WorldWideScience

Sample records for heterogeneous atmospheric chemistry

  1. Evaluated kinetic and photochemical data for atmospheric chemistry: Volume V – heterogeneous reactions on solid substrates

    Directory of Open Access Journals (Sweden)

    J. N. Crowley

    2010-09-01

    Full Text Available This article, the fifth in the ACP journal series, presents data evaluated by the IUPAC Subcommittee on Gas Kinetic Data Evaluation for Atmospheric Chemistry. It covers the heterogeneous processes on surfaces of solid particles present in the atmosphere, for which uptake coefficients and adsorption parameters have been presented on the IUPAC website in 2010. The article consists of an introduction and guide to the evaluation, giving a unifying framework for parameterisation of atmospheric heterogeneous processes. We provide summary sheets containing the recommended uptake parameters for the evaluated processes. Four substantial appendices contain detailed data sheets for each process considered for ice, mineral dust, sulfuric acid hydrate and nitric acid hydrate surfaces, which provide information upon which the recommendations are made.

  2. Heterogeneous chemistry and reaction dynamics of the atmospheric oxidants, O3, NO3, and OH, on organic surfaces

    OpenAIRE

    Chapleski, Robert C.; Zhang, Yafen; Troya, Diego; Morris, John R.

    2015-01-01

    Heterogeneous chemistry of the most important atmospheric oxidants, O3, NO3, and OH, plays a central role in regulating atmospheric gas concentrations, processing aerosols, and aging materials. Recent experimental and computational studies have begun to reveal the detailed reaction mechanisms and kinetics for gas-phase O3, NO3, and OH when they impinge on organic surfaces. Through new research approaches that merge the fields of traditional surface science with atmospheric chemistry, research...

  3. The effects of heterogeneous reactions on atmospheric chemistry and aerosol properties

    Science.gov (United States)

    Wei, Chao; Carmichael, Gregory; Su, Hang; Cheng, Yafang

    2017-04-01

    A new aerosol module is developed for the STEM model (the Sulfur Transport and dEposition Model) to better understand the chemical aging of dust during long range transport and assess the impact of heterogeneous reactions on tropospheric chemistry. The new aerosol module is verified and first applied in a box model, and then coupled into the 3-Dimentional STEM model. In the new aerosol model, a nonequilibrium (dynamic or kinetic) approach to treat gas-to-particle conversion is employed to replace the equilibrium method in STEM model. Meanwhile, a new numerical method solving the aerosol dynamics equation is introduced into the dynamic aerosol model for its improved computational efficiency and high accuracy. Compared with the equilibrium method, the new dynamic approach is found to provide better results on predicating the different hygroscopicity and chemical aging patterns as a function of size. The current modeling study also takes advantage of new findings from laboratory experiments about heterogeneous reactions on mineral oxides and dust particles, in order to consider the complexity of surface chemistry (such as surface saturation, coating and relative humidity). Modeling results show that the impacts of mineralogy and relative humidity on heterogeneous reactions are significant and should be considered in atmospheric chemistry modeling with first priority. The new dynamic approach for gas-to-particle conversion and RH-dependent heterogeneous uptake of HNO3 improve the model performance in term of aerosol predictions under different conditions. It is shown that these improvements change the modeled nitrate and sulfate concentrations, but also modify their size distributions significantly.

  4. Heterogeneous chemistry and reaction dynamics of the atmospheric oxidants, O3, NO3, and OH, on organic surfaces.

    Science.gov (United States)

    Chapleski, Robert C; Zhang, Yafen; Troya, Diego; Morris, John R

    2016-07-07

    Heterogeneous chemistry of the most important atmospheric oxidants, O3, NO3, and OH, plays a central role in regulating atmospheric gas concentrations, processing aerosols, and aging materials. Recent experimental and computational studies have begun to reveal the detailed reaction mechanisms and kinetics for gas-phase O3, NO3, and OH when they impinge on organic surfaces. Through new research approaches that merge the fields of traditional surface science with atmospheric chemistry, researchers are developing an understanding for how surface structure and functionality affect interfacial chemistry with this class of highly oxidizing pollutants. Together with future research initiatives, these studies will provide a more complete description of atmospheric chemistry and help others more accurately predict the properties of aerosols, the environmental impact of interfacial oxidation, and the concentrations of tropospheric gases.

  5. Modeling atmospheric mineral aerosol chemistry to predict heterogeneous photooxidation of SO2

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    Z. Yu

    2017-08-01

    Full Text Available The photocatalytic ability of airborne mineral dust particles is known to heterogeneously promote SO2 oxidation, but prediction of this phenomenon is not fully taken into account by current models. In this study, the Atmospheric Mineral Aerosol Reaction (AMAR model was developed to capture the influence of air-suspended mineral dust particles on sulfate formation in various environments. In the model, SO2 oxidation proceeds in three phases including the gas phase, the inorganic-salted aqueous phase (non-dust phase, and the dust phase. Dust chemistry is described as the absorption–desorption kinetics of SO2 and NOx (partitioning between the gas phase and the multilayer coated dust. The reaction of absorbed SO2 on dust particles occurs via two major paths: autoxidation of SO2 in open air and photocatalytic mechanisms under UV light. The kinetic mechanism of autoxidation was first leveraged using controlled indoor chamber data in the presence of Arizona Test Dust (ATD particles without UV light, and then extended to photochemistry. With UV light, SO2 photooxidation was promoted by surface oxidants (OH radicals that are generated via the photocatalysis of semiconducting metal oxides (electron–hole theory of ATD particles. This photocatalytic rate constant was derived from the integration of the combinational product of the dust absorbance spectrum and wave-dependent actinic flux for the full range of wavelengths of the light source. The predicted concentrations of sulfate and nitrate using the AMAR model agreed well with outdoor chamber data that were produced under natural sunlight. For seven consecutive hours of photooxidation of SO2 in an outdoor chamber, dust chemistry at the low NOx level was attributed to 55 % of total sulfate (56 ppb SO2, 290 µg m−3 ATD, and NOx less than 5 ppb. At high NOx ( >  50 ppb of NOx with low hydrocarbons, sulfate formation was also greatly promoted by dust chemistry, but it was suppressed by

  6. Modeling atmospheric mineral aerosol chemistry to predict heterogeneous photooxidation of SO2

    Science.gov (United States)

    Yu, Zechen; Jang, Myoseon; Park, Jiyeon

    2017-08-01

    The photocatalytic ability of airborne mineral dust particles is known to heterogeneously promote SO2 oxidation, but prediction of this phenomenon is not fully taken into account by current models. In this study, the Atmospheric Mineral Aerosol Reaction (AMAR) model was developed to capture the influence of air-suspended mineral dust particles on sulfate formation in various environments. In the model, SO2 oxidation proceeds in three phases including the gas phase, the inorganic-salted aqueous phase (non-dust phase), and the dust phase. Dust chemistry is described as the absorption-desorption kinetics of SO2 and NOx (partitioning between the gas phase and the multilayer coated dust). The reaction of absorbed SO2 on dust particles occurs via two major paths: autoxidation of SO2 in open air and photocatalytic mechanisms under UV light. The kinetic mechanism of autoxidation was first leveraged using controlled indoor chamber data in the presence of Arizona Test Dust (ATD) particles without UV light, and then extended to photochemistry. With UV light, SO2 photooxidation was promoted by surface oxidants (OH radicals) that are generated via the photocatalysis of semiconducting metal oxides (electron-hole theory) of ATD particles. This photocatalytic rate constant was derived from the integration of the combinational product of the dust absorbance spectrum and wave-dependent actinic flux for the full range of wavelengths of the light source. The predicted concentrations of sulfate and nitrate using the AMAR model agreed well with outdoor chamber data that were produced under natural sunlight. For seven consecutive hours of photooxidation of SO2 in an outdoor chamber, dust chemistry at the low NOx level was attributed to 55 % of total sulfate (56 ppb SO2, 290 µg m-3 ATD, and NOx less than 5 ppb). At high NOx ( > 50 ppb of NOx with low hydrocarbons), sulfate formation was also greatly promoted by dust chemistry, but it was suppressed by the competition between NO2 and SO2

  7. Evaluated kinetic and photochemical data for atmospheric chemistry: Volume VI – heterogeneous reactions with liquid substrates

    Directory of Open Access Journals (Sweden)

    M. Ammann

    2013-08-01

    Full Text Available This article, the sixth in the ACP journal series, presents data evaluated by the IUPAC Task Group on Atmospheric Chemical Kinetic Data Evaluation. It covers the heterogeneous processes involving liquid particles present in the atmosphere with an emphasis on those relevant for the upper troposphere/lower stratosphere and the marine boundary layer, for which uptake coefficients and adsorption parameters have been presented on the IUPAC website since 2009. The article consists of an introduction and guide to the evaluation, giving a unifying framework for parameterisation of atmospheric heterogeneous processes. We provide summary sheets containing the recommended uptake parameters for the evaluated processes. The experimental data on which the recommendations are based are provided in data sheets in separate appendices for the four surfaces considered: liquid water, deliquesced halide salts, other aqueous electrolytes and sulfuric acid.

  8. Microphysics and heterogeneous chemistry in aircraft plumes - high sensitivity on local meteorology and atmospheric composition

    Directory of Open Access Journals (Sweden)

    S. K. Meilinger

    2005-01-01

    Full Text Available An aircraft plume model has been developed on the basis of two coupled trajectory box models. Two boxes, one for plume and one for background conditions, are coupled by means of a mixing parameterization based on turbulence theory. The model considers comprehensive gas phase chemistry for the tropopause region including acetone, ethane and their oxidation products. Heterogeneous halogen, N2O5 and HOx chemistry on various types of background and aircraft-induced aerosols (liquid and ice is considered, using state-of-the-art solubility dependent uptake coefficients for liquid phase reactions. The microphysical scheme allows for coagulation, gas-diffusive particle growth and evaporation, so that the particle development from 1s after emission to several days can be simulated. Model results are shown, studying emissions into the upper troposphere as well as into the lowermost stratosphere for contrail and non-contrail conditions. We show the microphysical and chemical evolution of spreading plumes and use the concept of mean plume encounter time, tl, to define effective emission and perturbation indices (EEIs and EPIs for the North Atlantic Flight Corridor (NAFC showing EEI(NOy and EPI(O3 for various background conditions, such as relative humidity, local time of emission, and seasonal variations. Our results show a high sensitivity of EEI and EPIs on the exact conditions under which emissions take place. The difference of EEIs with and without considering plume processes indicates that these processes cannot be neglected.

  9. Single Particle Studies of Heterogeneous Atmospheric Chemistry on Aluminum Oxide Particles in a Quadrupole Trap

    Science.gov (United States)

    2000-03-01

    species of atmospheric importance are also available in permeation tubes, including S02, N02, NH3 , and many halocarbons. 3.5 Alumina Samples and Their...2) over a 20 cm optical path. A catalytic scrubber removes ozone from the reference beam path, and a four-way teflon valve interchanges scrubbed and

  10. Untangling the Chemical Evolution of Titan's Atmosphere and Surface -- From Homogeneous to Heterogeneous Chemistry

    Energy Technology Data Exchange (ETDEWEB)

    Kaiser, Ralf I.; Maksyutenko, Pavlo; Ennis, Courtney; Zhang, Fangtong; Gu, Xibin; Krishtal, Sergey P.; Mebel, Alexander M.; Kostko, Oleg; Ahmed, Musahid

    2010-03-16

    The arrival of the Cassini-Huygens probe at Saturn's moon Titan - the only Solar System body besides Earth and Venus with a solid surface and a thick atmosphere with a pressure of 1.4 atm at surface level - in 2004 opened up a new chapter in the history of Solar System exploration. The mission revealed Titan as a world with striking Earth-like landscapes involving hydrocarbon lakes and seas as well as sand dunes and lava-like features interspersed with craters and icy mountains of hitherto unknown chemical composition. The discovery of a dynamic atmosphere and active weather system illustrates further the similarities between Titan and Earth. The aerosol-based haze layers, which give Titan its orange-brownish color, are not only Titan's most prominent optically visible features, but also play a crucial role in determining Titan's thermal structure and chemistry. These smog-like haze layers are thought to be very similar to those that were present in Earth's atmosphere before life developed more than 3.8 billion years ago, absorbing the destructive ultraviolet radiation from the Sun, thus acting as 'prebiotic ozone' to preserve astrobiologically important molecules on Titan. Compared to Earth, Titan's low surface temperature of 94 K and the absence of liquid water preclude the evolution of biological chemistry as we know it. Exactly because of these low temperatures, Titan provides us with a unique prebiotic 'atmospheric laboratory' yielding vital clues - at the frozen stage - on the likely chemical composition of the atmosphere of the primitive Earth. However, the underlying chemical processes, which initiate the haze formation from simple molecules, have been not understood well to date.

  11. Atmospheric pseudohalogen chemistry

    OpenAIRE

    Lary, D. J.

    2004-01-01

    There are at least three reasons why hydrogen cyanide is likely to be significant for atmospheric chemistry. The first is well known, HCN is a product and marker of biomass burning. However, if a detailed ion chemistry of lightning is considered then it is almost certain than in addition to lightning producing NOx, it also produces HOx and HCN. Unlike NOx and HOx, HCN is long-lived and could therefore ...

  12. Atmospheric and aerosol chemistry

    Energy Technology Data Exchange (ETDEWEB)

    McNeill, V. Faye [Columbia Univ., New York, NY (United States). Dept. of Chemical Engineering; Ariya, Parisa A. (ed.) [McGill Univ. Montreal, QC (Canada). Dept. of Chemistry; McGill Univ. Montreal, QC (Canada). Dept. of Atmospheric and Oceanic Sciences

    2014-09-01

    This series presents critical reviews of the present position and future trends in modern chemical research. Short and concise reports on chemistry, each written by the world renowned experts. Still valid and useful after 5 or 10 years. More information as well as the electronic version of the whole content available at: springerlink.com. Christian George, Barbara D'Anna, Hartmut Herrmann, Christian Weller, Veronica Vaida, D. J. Donaldson, Thorsten Bartels-Rausch, Markus Ammann Emerging Areas in Atmospheric Photochemistry. Lisa Whalley, Daniel Stone, Dwayne Heard New Insights into the Tropospheric Oxidation of Isoprene: Combining Field Measurements, Laboratory Studies, Chemical Modelling and Quantum Theory. Neil M. Donahue, Allen L. Robinson, Erica R. Trump, Ilona Riipinen, Jesse H. Kroll Volatility and Aging of Atmospheric Organic Aerosol. P. A. Ariya, G. Kos, R. Mortazavi, E. D. Hudson, V. Kanthasamy, N. Eltouny, J. Sun, C. Wilde Bio-Organic Materials in the Atmosphere and Snow: Measurement and Characterization V. Faye McNeill, Neha Sareen, Allison N. Schwier Surface-Active Organics in Atmospheric Aerosols.

  13. The oleic acid-ozone heterogeneous reaction system: products, kinetics, secondary chemistry, and atmospheric implications of a model system – a review

    Directory of Open Access Journals (Sweden)

    J. Zahardis

    2007-01-01

    Full Text Available The heterogeneous processing of organic aerosols by trace oxidants has many implications to atmospheric chemistry and climate regulation. This review covers a model heterogeneous reaction system (HRS: the oleic acid-ozone HRS and other reaction systems featuring fatty acids, and their derivatives. The analysis of the commonly observed aldehyde and organic acid products of ozonolysis (azelaic acid, nonanoic acid, 9-oxononanoic acid, nonanal is described. The relative product yields are noted and explained by the observation of secondary chemical reactions. The secondary reaction products arising from reactive Criegee intermediates are mainly peroxidic, notably secondary ozonides and α-acyloxyalkyl hydroperoxide oligomers and polymers, and their formation is in accord with solution and liquid-phase ozonolysis. These highly oxygenated products are of low volatility and hydrophilic which may enhance the ability of particles to act as cloud condensation nuclei (CCN. The kinetic description of this HRS is critically reviewed. Most kinetic studies suggest this oxidative processing is either a near surface reaction that is limited by the diffusion of ozone or a surface based reaction. Internally mixed particles and coatings represent the next stage in the progression towards more realistic proxies of tropospheric organic aerosols and a description of the products and the kinetics resulting from the ozonolysis of these proxies, which are based on fatty acids or their derivatives, is presented. Finally, the main atmospheric implications of oxidative processing of particulate containing fatty acids are presented. These implications include the extended lifetime of unsaturated species in the troposphere facilitated by the presence of solids, semi-solids or viscous phases, and an enhanced rate of ozone uptake by particulate unsaturates compared to corresponding gas-phase organics. Ozonolysis of oleic acid enhances its CCN activity, which implies that

  14. Organic chemistry in Titan's atmosphere

    Science.gov (United States)

    Scattergood, T.

    1982-01-01

    Laboratory photochemical simulations and other types of chemical simulations are discussed. The chemistry of methane, which is the major known constituent of Titan's atmosphere was examined with stress on what can be learned from photochemistry and particle irradiation. The composition of dust that comprises the haze layer was determined. Isotope fractionation in planetary atmospheres is also discussed.

  15. Measuring Heterogeneous Reaction Rates with ATR-FTIR Spectroscopy to Evaluate Chemical Fates in an Atmospheric Environment: A Physical Chemistry and Environmental Chemistry Laboratory Experiment

    Science.gov (United States)

    Roberts, Jason E.; Zeng, Guang; Maron, Marta K.; Mach, Mindy; Dwebi, Iman; Liu, Yong

    2016-01-01

    This paper reports an undergraduate laboratory experiment to measure heterogeneous liquid/gas reaction kinetics (ozone-oleic acid and ozone-phenothrin) using a flow reactor coupled to an attenuated total reflectance-Fourier transform infrared (ATR-FTIR) spectrometer. The experiment is specially designed for an upper-level undergraduate Physical…

  16. Atmospheric chemistry over southern Africa

    Science.gov (United States)

    Gatebe, Charles K.; Levy, Robert C.; Thompson, Anne M.

    2012-03-01

    Changing Chemistry in a Changing Climate: Human and Natural Impacts Over Southern Africa (C4-SAR); Midrand, South Africa, 31 May to 3 June 2011 During the southern African dry season, regional haze from mixed industrial pollution, biomass burning aerosol and gases from domestic and grassland fires, and biogenic sources from plants and soils is worsened by a semipermanent atmospheric gyre over the subcontinent. These factors were a driver of several major international field campaigns in the 1990s and early 2000s and attracted many scientists to the region. Some researchers were interested in understanding fundamental processes governing chemistry of the atmosphere and interaction with climate change. Others found favorable conditions for evaluating satellite- derived measurements of atmospheric properties and a changing land surface. With that background in mind a workshop on atmospheric chemistry was held in South Africa. Sponsored by the International Commission on Atmospheric Chemistry and Global Pollution (ICACGP; http://www.icacgp.org/), the workshop received generous support from Eskom, the South African power utility; and the Climatology Research Group of the University of the Witwatersrand, Johannesburg, South Africa.

  17. Atmospheric Chemistry Over Southern Africa

    Science.gov (United States)

    Gatebe, Charles K.; Levy, Robert C.; Thompson, Anne M.

    2011-01-01

    During the southern African dry season, regional haze from mixed industrial pollution, biomass burning aerosol and gases from domestic and grassland fires, and biogenic sources from plants and soils is worsened by a semi-permanent atmosphere gyre over the subcontinent. These factors were a driver of several major international field campaigns in the 1990s and early 2000s, and attracted many scientists to the region. Some researchers were interested in understanding fundamental processes governing chemistry of the atmosphere and interaction with climate change. Others found favorable conditions for evaluating satellite-derived measurements of atmospheric properties and a changing land surface. With that background in mind a workshop on atmospheric chemistry was held in South Africa. Sponsored by the International Commission for Atmospheric Chemistry and Global Pollution (ICACGP; http://www.icacgp.org/), the workshop received generous support from the South African power utility, Eskom, and the Climatology Research Group of the University of the Witwatersrand, Johannesburg, South Africa. The purpose of the workshop was to review some earlier findings as well as more recent findings on southern African climate vulnerability, chemical changes due to urbanization, land-use modification, and how these factors interact. Originally proposed by John Burrows, president of ICACGP, the workshop was the first ICACGP regional workshop to study the interaction of air pollution with global chemical and climate change. Organized locally by the University of the Witwatersrand, the workshop attracted more than 60 delegates from South Africa, Mozambique, Botswana, Zimbabwe, France, Germany, Canada, and the United States. More than 30 presentations were given, exploring both retrospective and prospective aspects of the science. In several talks, attention was focused on southern African chemistry, atmospheric pollution monitoring, and climate processes as they were studied in the field

  18. Introductory lecture: atmospheric chemistry in the Anthropocene.

    Science.gov (United States)

    Finlayson-Pitts, Barbara J

    2017-08-24

    The term "Anthropocene" was coined by Professor Paul Crutzen in 2000 to describe an unprecedented era in which anthropogenic activities are impacting planet Earth on a global scale. Greatly increased emissions into the atmosphere, reflecting the advent of the Industrial Revolution, have caused significant changes in both the lower and upper atmosphere. Atmospheric reactions of the anthropogenic emissions and of those with biogenic compounds have significant impacts on human health, visibility, climate and weather. Two activities that have had particularly large impacts on the troposphere are fossil fuel combustion and agriculture, both associated with a burgeoning population. Emissions are also changing due to alterations in land use. This paper describes some of the tropospheric chemistry associated with the Anthropocene, with emphasis on areas having large uncertainties. These include heterogeneous chemistry such as those of oxides of nitrogen and the neonicotinoid pesticides, reactions at liquid interfaces, organic oxidations and particle formation, the role of sulfur compounds in the Anthropocene and biogenic-anthropogenic interactions. A clear and quantitative understanding of the connections between emissions, reactions, deposition and atmospheric composition is central to developing appropriate cost-effective strategies for minimizing the impacts of anthropogenic activities. The evolving nature of emissions in the Anthropocene places atmospheric chemistry at the fulcrum of determining human health and welfare in the future.

  19. Atmospheric Chemistry and Air Pollution

    Directory of Open Access Journals (Sweden)

    Jeffrey S. Gaffney

    2003-01-01

    Full Text Available Atmospheric chemistry is an important discipline for understanding air pollution and its impacts. This mini-review gives a brief history of air pollution and presents an overview of some of the basic photochemistry involved in the production of ozone and other oxidants in the atmosphere. Urban air quality issues are reviewed with a specific focus on ozone and other oxidants, primary and secondary aerosols, alternative fuels, and the potential for chlorine releases to amplify oxidant chemistry in industrial areas. Regional air pollution issues such as acid rain, long-range transport of aerosols and visibility loss, and the connections of aerosols to ozone and peroxyacetyl nitrate chemistry are examined. Finally, the potential impacts of air pollutants on the global-scale radiative balances of gases and aerosols are discussed briefly.

  20. Atmospheric Chemistry of Micrometeoritic Organic Compounds

    Science.gov (United States)

    Kress, M. E.; Belle, C. L.; Pevyhouse, A. R.; Iraci, L. T.

    2011-01-01

    Micrometeorites approx.100 m in diameter deliver most of the Earth s annual accumulation of extraterrestrial material. These small particles are so strongly heated upon atmospheric entry that most of their volatile content is vaporized. Here we present preliminary results from two sets of experiments to investigate the fate of the organic fraction of micrometeorites. In the first set of experiments, 300 m particles of a CM carbonaceous chondrite were subject to flash pyrolysis, simulating atmospheric entry. In addition to CO and CO2, many organic compounds were released, including functionalized benzenes, hydrocarbons, and small polycyclic aromatic hydrocarbons. In the second set of experiments, we subjected two of these compounds to conditions that simulate the heterogeneous chemistry of Earth s upper atmosphere. We find evidence that meteor-derived compounds can follow reaction pathways leading to the formation of more complex organic compounds.

  1. Impact of aircraft emissions on the atmospheric chemistry

    Energy Technology Data Exchange (ETDEWEB)

    Dameris, M.; Sausen, R.; Grewe, V.; Koehler, I.; Ponater, M. [Deutsche Forschungs- und Versuchsanstalt fuer Luft- und Raumfahrt e.V., Oberpfaffenhofen (Germany). Inst. fuer Physik der Atmosphaere; Steil, B. [Max-Planck-Inst. fuer Meteorologie, Hamburg (Germany); Bruehl, Ch. [Max-Planck-Inst. fuer Chemie (Otto-Hahn-Institut), Mainz (Germany)

    1997-12-31

    A hierarchy of models of different complexity has been applied to estimate the impact of aircraft NO{sub x} emissions on atmospheric chemistry. The global circulation model ECHAM3 has been coupled with two types of chemistry modules. The first of these describes only a simplified (linear) NO{sub x} and HNO{sub 3} chemistry while the second one is a comprehensive chemistry module (CHEM), describing tropospheric and stratospheric chemistry including photochemical reactions and heterogeneous reactions on sulphate aerosols and PSCs. The module CHEM has been coupled either off-line or with feedback via the ozone concentration. First results of multilayer integrations (over decades) are discussed. (author) 27 refs.

  2. Global atmospheric chemistry - which air matters

    Science.gov (United States)

    Prather, Michael J.; Zhu, Xin; Flynn, Clare M.; Strode, Sarah A.; Rodriguez, Jose M.; Steenrod, Stephen D.; Liu, Junhua; Lamarque, Jean-Francois; Fiore, Arlene M.; Horowitz, Larry W.; Mao, Jingqiu; Murray, Lee T.; Shindell, Drew T.; Wofsy, Steven C.

    2017-07-01

    An approach for analysis and modeling of global atmospheric chemistry is developed for application to measurements that provide a tropospheric climatology of those heterogeneously distributed, reactive species that control the loss of methane and the production and loss of ozone. We identify key species (e.g., O3, NOx, HNO3, HNO4, C2H3NO5, H2O, HOOH, CH3OOH, HCHO, CO, CH4, C2H6, acetaldehyde, acetone) and presume that they can be measured simultaneously in air parcels on the scale of a few km horizontally and a few tenths of a km vertically. As a first step, six global models have prepared such climatologies sampled at the modeled resolution for August with emphasis on the vast central Pacific Ocean basin. Objectives of this paper are to identify and characterize differences in model-generated reactivities as well as species covariances that could readily be discriminated with an unbiased climatology. A primary tool is comparison of multidimensional probability densities of key species weighted by the mass of such parcels or frequency of occurrence as well as by the reactivity of the parcels with respect to methane and ozone. The reactivity-weighted probabilities tell us which parcels matter in this case, and this method shows skill in differentiating among the models' chemistry. Testing 100 km scale models with 2 km measurements using these tools also addresses a core question about model resolution and whether fine-scale atmospheric structures matter to the overall ozone and methane budget. A new method enabling these six global chemistry-climate models to ingest an externally sourced climatology and then compute air parcel reactivity is demonstrated. Such an objective climatology containing these key species is anticipated from the NASA Atmospheric Tomography (ATom) aircraft mission (2015-2020), executing profiles over the Pacific and Atlantic Ocean basins. This modeling study addresses a core part of the design of ATom.

  3. Frontiers in Atmospheric Chemistry Modelling

    Science.gov (United States)

    Colette, Augustin; Bessagnet, Bertrand; Meleux, Frederik; Rouïl, Laurence

    2013-04-01

    The first pan-European kilometre-scale atmospheric chemistry simulation is introduced. The continental-scale air pollution episode of January 2009 is modelled with the CHIMERE offline chemistry-transport model with a massive grid of 2 million horizontal points, performed on 2000 CPU of a high performance computing system hosted by the Research and Technology Computing Center at the French Alternative Energies and Atomic Energy Commission (CCRT/CEA). Besides the technical challenge, which demonstrated the robustness of the selected air quality model, we discuss the added value in terms of air pollution modelling and decision support. The comparison with in-situ observations shows that model biases are significantly improved despite some spurious added spatial variability attributed to shortcomings in the emission downscaling process and coarse resolution of the meteorological fields. The increased spatial resolution is clearly beneficial for the detection of exceedances and exposure modelling. We reveal small scale air pollution patterns that highlight the contribution of city plumes to background air pollution levels. Up to a factor 5 underestimation of the fraction of population exposed to detrimental levels of pollution can be obtained with a coarse simulation if subgrid scale correction such as urban increments are ignored. This experiment opens new perspectives for environmental decision making. After two decades of efforts to reduce air pollutant emissions across Europe, the challenge is now to find the optimal trade-off between national and local air quality management strategies. While the first approach is based on sectoral strategies and energy policies, the later builds upon new alternatives such as urban development. The strategies, the decision pathways and the involvement of individual citizen differ, and a compromise based on cost and efficiency must be found. We illustrated how high performance computing in atmospheric science can contribute to this

  4. Spectroscopic Studies of Atmospheric Aerosol Chemistry

    Science.gov (United States)

    Wamsley, R.; Leather, K.; Horn, A. B.; Percival, C.

    2008-12-01

    Particles are ubiquitous in the troposphere and are involved in chemical and physical processes affecting the composition of the atmosphere, climate, cloud albedo and human health (Finlayson-Pitts and Pitts, 2000). Organic species, such as alcohols, carboxylic acids, ketones, aldehydes, aromatics, alkenes and alkanes, originate both from anthropogenic and natural sources and comprise a large component of atmospheric particles. Gas-phase species, such as ozone, can oxidize these organics, changing the particle's oxygen-to carbon ratio and potentially altering its hygroscopicity, viscosity, morphology and reactivity. One reaction in particular, that between ozone and oleic acid, has been the focus of several recent studies and extensively researched by Ziemann (2005). Oleic acid reacts readily with ozone and has a low vapor pressure making this reaction convenient to study in the laboratory and has become the benchmark for studying heterogeneous reactions representing the oxidative processing of atmospheric organic aerosols. A critical source of uncertainty in reactivity estimates is a lack of understanding of the mechanism through which some VOCs are oxidized. This knowledge gap is especially critical for aromatic compounds. Because the intermediate reaction steps and products of aromatics oxidation are unknown, chemical mechanisms incorporate parameters estimated from environmental chamber experiments to represent their overall contribution to ozone formation, e.g. Volkamer et al. ( 2006). Previous studies of uncertainties in incremental reactivity estimates for VOCs found that the representation of aromatics chemistry contributed significantly to the estimated 40 - 50% uncertainties in the incremental reactivities of common aromatic compounds Carter et al. (2002). This study shows development of an effective IR method that can monitor the reaction and hence obtain the kinetics of the ozonolysis of an aromatic compound in the aerosol phase. The development of such

  5. Global atmospheric chemistry – which air matters

    Directory of Open Access Journals (Sweden)

    M. J. Prather

    2017-07-01

    Full Text Available An approach for analysis and modeling of global atmospheric chemistry is developed for application to measurements that provide a tropospheric climatology of those heterogeneously distributed, reactive species that control the loss of methane and the production and loss of ozone. We identify key species (e.g., O3, NOx, HNO3, HNO4, C2H3NO5, H2O, HOOH, CH3OOH, HCHO, CO, CH4, C2H6, acetaldehyde, acetone and presume that they can be measured simultaneously in air parcels on the scale of a few km horizontally and a few tenths of a km vertically. As a first step, six global models have prepared such climatologies sampled at the modeled resolution for August with emphasis on the vast central Pacific Ocean basin. Objectives of this paper are to identify and characterize differences in model-generated reactivities as well as species covariances that could readily be discriminated with an unbiased climatology. A primary tool is comparison of multidimensional probability densities of key species weighted by the mass of such parcels or frequency of occurrence as well as by the reactivity of the parcels with respect to methane and ozone. The reactivity-weighted probabilities tell us which parcels matter in this case, and this method shows skill in differentiating among the models' chemistry. Testing 100 km scale models with 2 km measurements using these tools also addresses a core question about model resolution and whether fine-scale atmospheric structures matter to the overall ozone and methane budget. A new method enabling these six global chemistry–climate models to ingest an externally sourced climatology and then compute air parcel reactivity is demonstrated. Such an objective climatology containing these key species is anticipated from the NASA Atmospheric Tomography (ATom aircraft mission (2015–2020, executing profiles over the Pacific and Atlantic Ocean basins. This modeling study addresses a core part of the design of ATom.

  6. 1997 Atmospheric Chemistry Colloquium for Emerging Senior Scientists

    Energy Technology Data Exchange (ETDEWEB)

    Paul H. Wine

    1998-11-23

    DOE's Atmospheric Chemistry Program is providing partial funding for the Atmospheric Chemistry Colloquium for Emerging Senior Scientists (ACCESS) and FY 1997 Gordon Research Conference in Atmospheric Chemistry

  7. Impact of Amazonian deforestation on atmospheric chemistry

    NARCIS (Netherlands)

    Ganzeveld, L.N.; Lelieveld, J.

    2004-01-01

    A single-column chemistry and climate model has been used to study the impact of deforestation in the Amazon Basin on atmospheric chemistry. Over deforested areas, daytime ozone deposition generally decreases strongly except when surface wetness decreases through reduced precipitation, whereas

  8. Heterogeneous reactions of volatile organic compounds in the atmosphere

    Science.gov (United States)

    Shen, Xiaoli; Zhao, Yue; Chen, Zhongming; Huang, Dao

    2013-04-01

    Volatile organic compounds (VOCs) are of central importance in the atmosphere because of their close relation to air quality and climate change. As a significant sink for VOCs, the fate of VOCs via heterogeneous reactions may explain the big gap between field and model studies. These reactions play as yet unclear but potentially crucial role in atmospheric processes. In order to better evaluate this reaction pathway, we present the first specific review for the progress of heterogeneous reaction studies on VOCs, including carbonyl compounds, organic acids, alcohols, and so on. Our review focuses on the processes for heterogeneous reactions of VOCs under varying experimental conditions, as well as their implications for trace gas and HOx budget, secondary organic aerosol (SOA) formation, physicochemical properties of aerosols, and human health. Finally, we propose the future direction for laboratory studies of heterogeneous chemistry of VOCs that should be carried out under more atmospherically relevant conditions, with a special emphasis on the effects of relative humidity and illumination, the multicomponent reaction systems, and reactivity of aged and authentic particles. In particular, more reliable uptake coefficients, based on the abundant elaborate laboratory studies, appropriate calibration, and logical choice criterion, are urgently required in atmospheric models.

  9. Monsoon Circulations and Tropical Heterogeneous Chlorine Chemistry in the Stratosphere

    Science.gov (United States)

    Kinnison, Doug; Solomon, Susan; Garcia, Rolando; Bandoro, Justin; Wilka, Catherine; Neeley, Ryan, III; Schmidt, Anja; Barnes, John; Vernier, Jean-Paul; Höpfner, Michael; Mills, Michael

    2017-04-01

    Heterogeneous chlorine chemistry on and in liquid polar stratospheric particles is thought to play a significant role in polar and subpolar ozone depletion. Previous studies have not provided evidence for heterogeneous chlorine chemistry occurring in the tropical stratosphere. Using the current best understanding of liquid stratospheric particle chemistry in a state-of-the-art numerical model, we examine whether such processes should be expected to affect tropical composition, particularly at and slightly above the cold tropical tropopause, in association with the Asian and North American summer (June-July-August) monsoons. The Specified Dynamics version of the Community Earth System Model version 1 (CESM1) Whole Atmosphere Community Climate Model (WACCM) is used in this study. This model is nudged to externally specified dynamical fields for temperature, zonal and meridional winds, and surface pressure fields from the NASA Modern Era Retrospective Analysis for Research and Applications (MERRA). Model simulations suggest that transport processes associated with the summer monsoons bring increased abundances of hydrochloric acid (HCl) into contact with liquid sulfate aerosols in the cold tropical lowermost stratosphere, leading to heterogeneous chemical activation of chlorine species. The calculations indicate that the spatial and seasonal distributions of chlorine monoxide (ClO) and chlorine nitrate (ClONO2) near the monsoon regions of the northern hemisphere tropical and subtropical lowermost stratosphere could provide indicators of heterogeneous chlorine processing. In the model, these processes impact the local ozone budget and decrease ozone abundances, implying a chemical contribution to longer-term northern tropical ozone profile changes at 16-19 km.

  10. Chemistry of Planetary Atmospheres: Insights and Prospects

    Science.gov (United States)

    Yung, Yuk

    2015-11-01

    Using observations from the Mariners, Pioneers, Vikings, Voyagers, Pioneer Venus, Galileo, Venus Express, Curiosity, Cassini, New Horizons, and numerous observatories both in orbit of Earth and on the ground, I will give a survey of the major chemical processes that control the composition of planetary atmospheres. For the first time since the beginning of the space age, we understand the chemistry of planetary atmospheres ranging from the primitive atmospheres of the giant planets to the highly evolved atmospheres of terrestrial planets and small bodies. Our understanding can be distilled into three important ideas: (1) The stability of planetary atmospheres against escape of their constituents to space, (2) the role of equilibrium chemistry in determining the partitioning of chemical species, and (3) the role of disequilibrium chemistry, which produces drastic departures from equilibrium chemistry. To these three ideas we must also add a fourth: the role of biochemistry at Earth's surface, which makes its atmospheric chemistry unique in the cosmochemical environment. Only in the Earth's atmosphere do strong reducing and oxidizing species coexist to such a degree. For example, nitrogen species in the Earth's atmosphere span eight oxidation states from ammonia to nitric acid. Much of the Earth's atmospheric chemistry consists of reactions initiated by the degradation of biologically produced molecules. Life uses solar energy to drive chemical reactions that would otherwise not occur; it represents a kind of photochemistry that is special to Earth, at least within the Solar System. It remains to be seen how many worlds like Earth there are beyond the Solar System, especially as we are now exploring the exoplanets using Kepler, TESS, HST, Spitzer, soon to be launched missions such as JWST and WFIRST, and ground-based telescopes. The atmospheres of the Solar System provide a benchmark for studying exoplanets, which in turn serve to test and extend our current

  11. Organic chemistry in the atmosphere. [laboratory modeling of Titan atmosphere

    Science.gov (United States)

    Sagan, C.

    1974-01-01

    The existence of an at least moderately complex organic chemistry on Titan is stipulated based on clear evidence of methane, and at least presumptive evidence of hydrogen in its atmosphere. The ratio of methane to hydrogen is the highest of any atmosphere in the solar system. Irradiation of hydrogen/methane mixtures produces aromatic and aliphatic hydrocarbons. A very reasonable hypothesis assumes that the red cloud cover of Titan is made of organic chemicals. Two-carbon hydrocarbons experimentally produced from irradiated mixtures of methane, ammonia, water, and hydrogen bear out the possible organic chemistry of the Titanian environment.

  12. 1999 Gordon Research Conference on Atmospheric Chemistry

    Energy Technology Data Exchange (ETDEWEB)

    Storm, C.

    2000-08-01

    The Gordon Research Conference (GRC) on Atmospheric Chemistry was held at Salve Regina University in Newport, Rhode Island, June 13-18, 1999. The conference was well attended with 151 participants. The attendees represented the spectrum of endeavor in this field coming from academia, industry, and government laboratories, both US and foreign scientists, senior researchers, young investigators, and students.

  13. Investigation of Heterogeneous Atmospheric Chlorine Chemistry: Modeling and Environmental Chamber Studies Authors: Cameron B. Faxon, Lea Hildebrandt Ruiz, and David Allen University of Texas at Austin, McKetta Department of Chemical Engineering

    Science.gov (United States)

    Faxon, C. B.; Hildebrandt Ruiz, L.; Allen, D.

    2013-12-01

    Previous work has shown that gas phase atomic chlorine radicals (Cl*) can influence tropospheric photochemistry, including concentrations of volatile organic compound (VOC) and ozone. These radicals are produced through both gas phase and heterogeneous pathways. This work presents computational and experimental investigation into the heterogeneous reactions of chloride aerosols. An overview of a sensitivity analysis of the physical parameters involved in the heterogeneous production of nitryl chloride (ClNO2) (R1-R5) will comprise the computational work presented. NO2(g) + NO3(g) ↔ N2O5(g) (R1) N2O5(aq) ↔ N2O5(aq) (R2) N2O5(aq) ↔ NO2+(aq) + NO3-(aq) (R3) NO2+(aq) + H2O(aq) → H3O+(aq) + HNO3(aq) (R4a) NO2+(aq) + Cl- → ClNO2 + H2O(aq) (R4b) NO3-(aq) + H+ ↔ HNO3+(aq) (R5) Relative parameters include the reactive uptake coefficient, ClNO2 yield, particle surface area, and gas phase concentrations of VOCs and NOx. The sensitivity analysis results were generated through photochemical box modeling and focus on the production of ClNO2 and impacts to ozone production. Results were compared to a base case scenario in which all heterogeneous reactions were absent. Parameter values reaching the upper limits reported in the literature were tested, and results indicate that ClNO2 chemistry can potentially change peak O3 concentrations by -10.5% to 27%. NOx availability was also found to play an important role. Experimental results of the heterogeneous reaction between OH* and particulate chloride (R6-R7) will also be discussed. The mechanism is shown below, and OH***Cl- represents an intermediate species forming at the particle surface. OH(g) + Cl-(aq) → OH***Cl-(aq) (R6) 2OH***Cl-(aq) → Cl2,g + 2OH-(aq) (R7) Environmental chamber experiments involving the exposure of NaCl aerosol particles to typical atmospheric conditions (HOx, NOx, O3 and UV radiation) were performed. A 10 cubic meter teflon reaction chamber equipped with UV lights was used to contain the

  14. FinROSE - middle atmospheric chemistry transport model

    Energy Technology Data Exchange (ETDEWEB)

    Damski, J.; Thoelix, L.; Backman, L. (Research and Development, Finnish Meteorological Inst., Helsinki (FI)); Taalas, P. (Regional and Technical Cooperation for Development Dept. World Meteorological Organization, Geneve (CH)); Kulmala, M. (Helsinki Univ. (FI). Div. of Atmospheric Sciences)

    2007-07-01

    The development and performance of a three-dimensional global middle atmospheric chemistry transport model FinROSE is described. The FinROSE chemistry transport model includes a numerical scheme for stratospheric chemistry with parameterizations for heterogeneous processing on polar stratospheric clouds (PSC) and on liquid binary aerosols together with a parameterisation of large nitric acid trihydrate particles (i.e. NAT-rocks) and PSC sedimentation. The total number of trace species in the model is 34 and the total number of gas-phase reactions, photodissociation processes and heterogeneous reactions is about 150. The model is forced by external wind and temperature fields. The simulations are normally performed in a 5 deg x 10 deg (lat. x long.) grid from the surface up to around 0.1 hPa, with a vertical resolution of ca. 1.5 km in the stratosphere. Long-term simulations (40 to 50 years) have been done using winds and temperatures from ECMWF ERA40 analyses. The performance of the model in describing the stratospheric composition and chemistry is shown and evaluated in this paper. In general, the FinROSE results show a good comparison with measured total ozone. Also the timing, the depth and the deepening of the Antarctic ozone hole, and the responsible processes are captured well in the model simulations. (orig.)

  15. Chemistry in the clouds: the role of aerosols in atmospheric chemistry.

    Science.gov (United States)

    Reid, Jonathan P; Sayer, Robert M

    2002-01-01

    Ever since the discovery of the ozone hole over the Antarctic and the recognition of the damaging effects of acid rain, the role of atmospheric aerosol particles in determining the chemical balance of the atmosphere has received much attention. Aerosol particles produced in combustion can also have a deleterious effect on human health. In this article we review the chemistry that can occur on aerosol particles, particularly on aqueous based aerosols in the troposphere. The sources, transformation and loss mechanisms of atmospheric aerosol will be discussed. In particular, we will focus on the role of chemical transformation on aerosol particles in promoting reactions that would otherwise be too slow in the homogeneous atmospheric gas phase. Heterogeneous reaction mechanisms of some key chemical reactions will be described. Recent observations of a high organic content of tropospheric aerosol particles will be described and a model of organic coated aerosols will be reviewed.

  16. Atmospheric Prebiotic Chemistry and Organic Hazes

    Science.gov (United States)

    Trainer, Melissa G.

    2012-01-01

    Earth's atmospheric composition at the time of the origin of life is not known, but it has often been suggested that chemical transformation of reactive species in the atmosphere was a significant source of pre biotic organic molecules. Experimental and theoretical studies over the past half century have shown that atmospheric synthesis can yield molecules such as amino acids and nucleobases, but these processes are very sensitive to gas composition and energy source. Abiotic synthesis of organic molecules is more productive in reduced atmospheres, yet the primitive Earth may not have been as reducing as earlier workers assumed, and recent research has reflected this shift in thinking. This work provides a survey of the range of chemical products that can be produced given a set of atmospheric conditions, with a particular focus on recent reports. Intertwined with the discussion of atmospheric synthesis is the consideration of an organic haze layer, which has been suggested as a possible ultraviolet shield on the anoxic early Earth. Since such a haze layer - if formed - would serve as a reservoir for organic molecules, the chemical composition of the aerosol should be closely examined. The results highlighted here show that a variety of products can be formed in mildly reducing or even neutral atmospheres, demonstrating that contributions of atmospheric synthesis to the organic inventory on early Earth should not be discounted. This review intends to bridge current knowledge of the range of possible atmospheric conditions in the prebiotic environment and pathways for synthesis under such conditions by examining the possible products of organic chemistry in the early atmosphere.

  17. Atmospheric Composition Change: Climate-Chemistry Interactions

    Science.gov (United States)

    Isaksen, I.S.A.; Granier, C.; Myhre, G.; Bernsten, T. K.; Dalsoren, S. B.; Gauss, S.; Klimont, Z.; Benestad, R.; Bousquet, P.; Collins, W.; hide

    2011-01-01

    Chemically active climate compounds are either primary compounds such as methane (CH4), removed by oxidation in the atmosphere, or secondary compounds such as ozone (O3), sulfate and organic aerosols, formed and removed in the atmosphere. Man-induced climate-chemistry interaction is a two-way process: Emissions of pollutants change the atmospheric composition contributing to climate change through the aforementioned climate components, and climate change, through changes in temperature, dynamics, the hydrological cycle, atmospheric stability, and biosphere-atmosphere interactions, affects the atmospheric composition and oxidation processes in the troposphere. Here we present progress in our understanding of processes of importance for climate-chemistry interactions, and their contributions to changes in atmospheric composition and climate forcing. A key factor is the oxidation potential involving compounds such as O3 and the hydroxyl radical (OH). Reported studies represent both current and future changes. Reported results include new estimates of radiative forcing based on extensive model studies of chemically active climate compounds such as O3, and of particles inducing both direct and indirect effects. Through EU projects such as ACCENT, QUANTIFY, and the AEROCOM project, extensive studies on regional and sector-wise differences in the impact on atmospheric distribution are performed. Studies have shown that land-based emissions have a different effect on climate than ship and aircraft emissions, and different measures are needed to reduce the climate impact. Several areas where climate change can affect the tropospheric oxidation process and the chemical composition are identified. This can take place through enhanced stratospheric-tropospheric exchange of ozone, more frequent periods with stable conditions favouring pollution build up over industrial areas, enhanced temperature-induced biogenic emissions, methane releases from permafrost thawing, and enhanced

  18. Coupled Atmospheric Chemistry Schemes for Modeling Regional and Global Atmospheric Chemistry

    Science.gov (United States)

    Saunders, E.; Stockwell, W. R.

    2016-12-01

    Atmospheric chemistry models require chemical reaction mechanisms to simulate the production of air pollution. GACM (Global Atmospheric Chemistry Mechanism) is intended for use in global scale atmospheric chemistry models to provide chemical boundary conditions for regional scale simulations by models such as CMAQ. GACM includes additional chemistry for marine environments while reducing its treatment of the chemistry needed for highly polluted urban regions. This keeps GACM's size small enough to allow it to be used efficiently in global models. GACM's chemistry of volatile organic compounds (VOC) is highly compatible with the VOC chemistry in RACM2 allowing a global model with GACM to provide VOC boundary conditions to a regional scale model with RACM2 with reduced error. The GACM-RACM2 system of mechanisms should yield more accurate forecasts by regional air quality models such as CMAQ. Chemical box models coupled with the regional and global atmospheric chemistry mechanisms (RACM2 & GACM) will be used to make simulations of tropospheric ozone, nitric oxides, and volatile organic compounds that are produced in regional and global domains. The simulations will focus on the Los Angeles' South Coast Air Basin (SoCAB) where the Pacific Ocean meets a highly polluted urban area. These two mechanisms will be compared on the basis of simulated ozone concentrations over this marine-urban region. Simulations made with the more established RACM2 will be compared with simulations made with the newer GACM. In addition WRF-Chem will be used to simulate how RACM2 will produce regional simulations of tropospheric ozone and NOx, which can be further, analyzed for air quality impacts. Both the regional and global model in WRF-Chem will be used to predict how the concentrations of ozone and nitrogen oxides change over land and ocean. The air quality model simulation results will be applied to EPA's BenMAP-CE (Environmental Benefits Mapping & Analysis Program-Community Edition

  19. Heterogeneous Chemistry: Understanding Aerosol/Oxidant Interactions

    Energy Technology Data Exchange (ETDEWEB)

    Joyce E. Penner

    2005-03-14

    Global radiative forcing of nitrate and ammonium aerosols has mostly been estimated from aerosol concentrations calculated at thermodynamic equilibrium or using approximate treatments for their uptake by aerosols. In this study, a more accurate hybrid dynamical approach (DYN) was used to simulate the uptake of nitrate and ammonium by aerosols and the interaction with tropospheric reactive nitrogen chemistry in a three-dimensional global aerosol and chemistry model, IMPACT, which also treats sulfate, sea salt and mineral dust aerosol. 43% of the global annual average nitrate aerosol burden, 0.16 TgN, and 92% of the global annual average ammonium aerosol burden, 0.29 TgN, exist in the fine mode (D<1.25 {micro}m) that scatters most efficiently. Results from an equilibrium calculation differ significantly from those of DYN since the fraction of fine-mode nitrate to total nitrate (gas plus aerosol) is 9.8%, compared to 13% in DYN. Our results suggest that the estimates of aerosol forcing from equilibrium concentrations will be underestimated. We also show that two common approaches used to treat nitrate and ammonium in aerosol in global models, including the first-order gas-to-particle approximation based on uptake coefficients (UPTAKE) and a hybrid method that combines the former with an equilibrium model (HYB), significantly overpredict the nitrate uptake by aerosols especially that by coarse particles, resulting in total nitrate aerosol burdens higher than that in DYN by +106% and +47%, respectively. Thus, nitrate aerosol in the coarse mode calculated by HYB is 0.18 Tg N, a factor of 2 more than that in DYN (0.086 Tg N). Excessive formation of the coarse-mode nitrate in HYB leads to near surface nitrate concentrations in the fine mode lower than that in DYN by up to 50% over continents. In addition, near-surface HNO{sub 3} and NO{sub x} concentrations are underpredicted by HYB by up to 90% and 5%, respectively. UPTAKE overpredicts the NO{sub x} burden by 56% and near

  20. Surface Chemistry in Heterogeneous Catalysis: An Emerging Discipline.

    Science.gov (United States)

    White, J. M.; Campbell, Charles T.

    1980-01-01

    Provides background data on surface chemistry as an emerging discipline. Highlights the important role which surfaces play in catalysis by focusing on the catalyzed oxidation of carbon monoxide. Provides a demonstration of how surfaces exert their influences in heterogeneous phenomena and illustrates how experimental problems in this field are…

  1. Coordination chemistry in the design of heterogeneous photocatalysts.

    Science.gov (United States)

    Gao, Chao; Wang, Jin; Xu, Hangxun; Xiong, Yujie

    2017-05-22

    Heterogeneous catalysts have been widely used for photocatalysis, which is a highly important process for energy conversion, owing to their merits such as easy separation of catalysts from the reaction products and applicability to continuous chemical industry and recyclability. Yet, homogenous photocatalysis receives tremendous attention as it can offer a higher activity and selectivity with atomically dispersed catalytic sites and tunable light absorption. For this reason, there is a major trend to combine the advantages of both homogeneous and heterogeneous photocatalysts, in which coordination chemistry plays a role as the bridge. In this article, we aim to provide the first systematic review to give a clear picture of the recent progress from taking advantage of coordination chemistry. We specifically summarize the role of coordination chemistry as a versatile tool to engineer catalytically active sites, tune light harvesting and maneuver charge kinetics in heterogeneous photocatalysis. We then elaborate on the common fundamentals behind various materials systems, together with key spectroscopic characterization techniques and remaining challenges in this field. The typical applications of coordination chemistry in heterogeneous photocatalysis, including proton reduction, water oxidation, carbon dioxide reduction and organic reactions, are highlighted.

  2. EDITORIAL: Ice in the environment: connections to atmospheric chemistry Ice in the environment: connections to atmospheric chemistry

    Science.gov (United States)

    McNeill, V. Faye; Hastings, Meredith G.

    2008-12-01

    Ice in the environment, whether in the form of ice particles in clouds or sea ice and snow at the Earth's surface, has a profound influence on atmospheric composition and climate. The interaction of trace atmospheric gases with snow and sea ice surfaces largely controls atmospheric composition in polar regions. The heterogeneous chemistry of ice particles in clouds also plays critical roles in polar stratospheric ozone depletion and in tropospheric chemistry. A quantitative physical understanding of the interactions of snow and ice with trace gases is critical for predicting the effects of climate change on atmospheric composition, for the interpretation of ice core chemical records, and for modeling atmospheric chemistry. The motivation behind this focus issue of Environmental Research Letters (ERL), and the special session at the Fall 2007 meeting of the American Geophysical Union that generated it, was to enhance communication and interactions among field and laboratory scientists and modelers working in this area. Members of these three groups are each working toward a mutual goal of understanding and quantifying the connections between the chemistry of snow and ice in the environment and atmospheric composition, and communication and collaboration across these traditional disciplinary boundaries pose a challenge for the community. We are pleased to present new work from several current leaders in the field and laboratory communities in this focus issue. Topics include the interaction of organics and mercury with snow and ice surfaces, halogen activation from halide ice, and the emissions of reactive nitrogen oxides from snow. Novel experimental techniques are presented that make progress towards overcoming the experimental challenges of quantifying the chemistry of realistic snow samples and ice chemistry at temperatures relevant to the polar boundary layer. Several of the papers in this issue also touch on one of the significant gaps in our current

  3. Atmospheric chemistry and physics from air pollution to climate change

    CERN Document Server

    Seinfeld, John H

    2016-01-01

    Expanded and updated with new findings and new features Since the second edition of Seinfeld and Pandis’ classic textbook, significant progress has taken place in the field of atmospheric chemistry and physics, particularly in the areas of tropospheric chemistry, aerosols, and the science of climate change. A new edition of this comprehensive work has been developed by the renowned author team. Atmospheric Chemistry and Physics, 3rd Edition, as the previous two editions have done, provides a rigorous and comprehensive treatment of the chemistry and physics of the atmosphere – including the chemistry of the stratosphere and troposphere, aerosol physics and chemistry, atmospheric new particle formation, physical meteorology, cloud physics, global climate, statistical analysis of data, and mathematical chemical/transport models of the atmosphere. Each of these topics is covered in detail and in each area the central results are developed from first principles. In this way the reader gains a significant un...

  4. Heterogeneous catalytic materials solid state chemistry, surface chemistry and catalytic behaviour

    CERN Document Server

    Busca, Guido

    2014-01-01

    Heterogeneous Catalytic Materials discusses experimental methods and the latest developments in three areas of research: heterogeneous catalysis; surface chemistry; and the chemistry of catalysts. Catalytic materials are those solids that allow the chemical reaction to occur efficiently and cost-effectively. This book provides you with all necessary information to synthesize, characterize, and relate the properties of a catalyst to its behavior, enabling you to select the appropriate catalyst for the process and reactor system. Oxides (used both as catalysts and as supports for cata

  5. Impact of Land Surface Heterogeneity on Mesoscale Atmospheric Dispersion

    Science.gov (United States)

    Wu, Yuling; Nair, Udaysankar S.; Pielke, Roger A., Sr.; McNider, Richard T.; Christopher, Sundar A.; Anantharaj, Valentine G.

    2009-01-01

    Prior numerical modelling studies show that atmospheric dispersion is sensitive to surface heterogeneities, but past studies do not consider the impact of a realistic distribution of surface heterogeneities on mesoscale atmospheric dispersion. While these focussed on dispersion in the convective boundary layer, the present work also considers dispersion in the nocturnal boundary layer and above. Using a Lagrangian particle dispersion model (LPDM) coupled to the Eulerian Regional Atmospheric Modeling System (RAMS), the impact of topographic, vegetation, and soil moisture heterogeneities on daytime and nighttime atmospheric dispersion is examined. In addition, the sensitivity to the use of Moderate Resolution Imaging Spectroradiometer (MODIS)-derived spatial distributions of vegetation characteristics on atmospheric dispersion is also studied. The impact of vegetation and terrain heterogeneities on atmospheric dispersion is strongly modulated by soil moisture, with the nature of dispersion switching from non-Gaussian to near- Gaussian behaviour for wetter soils (fraction of saturation soil moisture content exceeding 40%). For drier soil moisture conditions, vegetation heterogeneity produces differential heating and the formation of mesoscale circulation patterns that are primarily responsible for non-Gaussian dispersion patterns. Nighttime dispersion is very sensitive to topographic, vegetation, soil moisture, and soil type heterogeneity and is distinctly non-Gaussian for heterogeneous land-surface conditions. Sensitivity studies show that soil type and vegetation heterogeneities have the most dramatic impact on atmospheric dispersion. To provide more skillful dispersion calculations, we recommend the utilisation of satellite-derived vegetation characteristics coupled with data assimilation techniques that constrain soil-vegetation-atmosphere transfer (SVAT) models to generate realistic spatial distributions of surface energy fluxes.

  6. Metal-free heterogeneous catalysis for sustainable chemistry.

    Science.gov (United States)

    Su, Dang Sheng; Zhang, Jian; Frank, Benjamin; Thomas, Arne; Wang, Xinchen; Paraknowitsch, Jens; Schlögl, Robert

    2010-02-22

    The current established catalytic processes used in chemical industries use metals, in many cases precious metals, or metal oxides as catalysts. These are often energy-consuming and not highly selective, wasting resources and producing greenhouse gases. Metal-free heterogeneous catalysis using carbon or carbon nitride is an interesting alternative to some current industrialized chemical processes. Carbon and carbon nitride combine environmental acceptability with inexhaustible resources and allow a favorable management of energy with good thermal conductivity. Owing to lower reaction temperatures and increased selectivity, these catalysts could be candidates for green chemistry with low emission and an efficient use of the chemical feedstock. This Review highlights some recent promising activities and developments in heterogeneous catalysis using only carbon and carbon nitride as catalysts. The state-of-the-art and future challenges of metal-free heterogeneous catalysis are also discussed.

  7. IceBridge Atmospheric Chemistry L1B Data

    Data.gov (United States)

    National Aeronautics and Space Administration — The IceBridge Atmospheric Chemistry L1B Data set (ICHEM1B) contains measurements acquired over Antarctica using the AVOCET differential Non-Dispersive Infrared...

  8. Heterogeneous chemistry in aircraft wakes: Constraints for uptake coefficients

    Science.gov (United States)

    KäRcher, B.

    1997-08-01

    Recent in situ measurements in subsonic and supersonic aircraft plumes show the presence of high aerosol abundances. Given the large initial surface areas of the exhaust particles (volatile aerosols, soot, and ice) of 103-105 μm2 cm-3 or more, heterogeneous processing can potentially become important. Based on an analytical model to predict the temporal evolution of the surface areas, the potential for heterogeneous chemistry during the lifetime of single aircraft wakes is investigated. The model surface areas are constrained by plume observations and compared to numerical simulations of aerosol formation and growth. Efficient heterogeneous processing on volatile aerosols and soot on timescales below 1 day generally requires uptake coefficients ≳0.003-0.007, depending on the specific surface area of soot. For low available surface areas and slow reactions, the lifetime of emitted exhaust species sensitively depends on the wake mixing properties. Shutting off uptake by volatile particles inhibits heterogeneous processing unless high soot surface areas and reaction probabilities are prescribed. Depending on the lifetime of ice contrails, uptake coefficients ≳0.1 are required for rapid uptake of exhaust species on the ice particles. This lower limit becomes relaxed if contrails are long-lived or develop into persistent cirrus or polar stratospheric clouds, rendering activation of chlorine potentially important. The model is applied to investigate the uptake of gaseous HNO2 and SO2 by the observed particles in the plume of the Concorde in the lower stratosphere.

  9. Comparison of multiple atmospheric chemistry schemes in C-IFS

    Science.gov (United States)

    Flemming, Johannes; Huijnen, Vincent; Arteta, Joaquim; Stein, Olaf; Inness, Antje; Josse, Beatrice; Schultz, Martin; Peuch, Vincent-Henri

    2013-04-01

    As part of the MACCII -project (EU-FP7) ECMWF's integrated forecast system (IFS) is being extended by modules for chemistry, deposition and emission of reactive gases. This integration of the chemistry complements the integration of aerosol processes in IFS (Composition-IFS). C-IFS provides global forecasts and analysis of atmospheric composition. Its main motivation is to utilize the IFS for the assimilation of satellite observation of atmospheric composition. Furthermore, the integration of chemistry packages directly into IFS will achieve better consistency in terms of the treatment of physical processes and has the potential for simulating interactions between atmospheric composition and meteorology. Atmospheric chemistry in C-IFS can be represented by the modified CB05 scheme as implemented in the TM5 model and the RACMOBUS scheme as implemented in the MOCAGE model. An implementation of the scheme of the MOZART 3.5 model is ongoing. We will present the latest progress in the development and application of C-IFS. We will focus on the comparison of the different chemistry schemes in an otherwise identical C-IFS model setup (emissions, meteorology) as well as in their original Chemistry and Transport Model setup.

  10. Coupling non-linear optical spectroscopy and surface chemistry: Towards new insights in atmospheric chemistry and aerosols

    Science.gov (United States)

    Abdelmonem, Ahmed; Lützenkirchen, Johannes

    2017-04-01

    For decades, the observation of atmospheric processes in general and ice nucleation in particular bridged the scales from macroscopic to microscopic levels. They delivered a wide variety of results in cloud microphysics, particularly concerning the ice nucleation ability of atmospheric aerosol particles [1]. The surface properties of an ice-nucleating particle (INP) play a major role in its ice nucleation ability. This role is not well explored in terms of water/INP-surface molecular-level interactions. For example, we found recently that surface-charge induced templating hampers ice nucleation [2]. Aging of an INP in a cloud may change its surface properties and hence its ice nucleation efficiency. To improve our understanding of heterogeneous ice nucleation, we combine chemical and optical surface techniques to probe the change in surface properties of an INP and the corresponding water structuring on it, respectively. The presentation will show the different scenarios after aging of an INP in a cloud and the impact on its ice nucleation ability. References 1. Hoose, C. and O. Mohler, Heterogeneous ice nucleation on atmospheric aerosols: a review of results from laboratory experiments. Atmospheric Chemistry and Physics, 2012. 12(20): p. 9817-9854. 2. Abdelmonem, A., et al., Surface charge-induced orientation of interfacial water suppresses heterogeneous ice nucleation on α-alumina (0001). Angewandte Chemie (Submitted), 2017.

  11. The Essential Role for Laboratory Studies in Atmospheric Chemistry

    Energy Technology Data Exchange (ETDEWEB)

    Burkholder, James B. [National Oceanic and Atmospheric Administration (NOAA), Boulder, CO (United States); Abbatt, Jonathan P. D. [Univ. of Toronto, ON (Canada); Barnes, Ian [Univ. of Wuppertal (Germany); Roberts, James M. [National Oceanic and Atmospheric Administration (NOAA), Boulder, CO (United States); Melamed, Megan L. [Univ. of Colorado, Boulder, CO (United States); Ammann, Markus [Paul Scherrer Inst. (PSI), Villigen (Switzerland); Bertram, Allan K. [Univ. of British Columbia, Vancouver, BC (Canada); Cappa, Christopher D. [Univ. of California, Davis, CA (United States); Carlton, Annmarie G. [Univ. of California, Irvine, CA (United States); Carpenter, Lucy J. [Univ. of York (United Kingdom); Crowley, John N. [Max Planck Inst. of Chemistry, Mainz (Germany); Dubowski, Yael [Technion-Israel Inst. of Tech., Haifa (Israel); George, Christian [Univ. of Lyon (France); Heard, Dwayne E. [Univ. of Leeds (United Kingdom); Herrmann, Hartmut [Leibniz Inst. for Tropospheric Research (ITR), Leipzig (Germany); Keutsch, Frank N. [Harvard Univ., Cambridge, MA (United States); Kroll, Jesse H. [Massachusetts Inst. of Technology (MIT), Cambridge, MA (United States); McNeill, V. Faye [Columbia Univ., New York, NY (United States); Ng, Nga Lee [Georgia Inst. of Technology, Atlanta, GA (United States); Nizkorodov, Sergey A. [Univ. of California, Irvine, CA (United States); Orlando, John J. [National Center for Atmospheric Research, Boulder, CO (United States); Percival, Carl J. [Univ. of Manchester (United Kingdom); Picquet-Varrault, Bénédicte [Inst. Pierre-Simon Laplace, Creteil (France); Rudich, Yinon [Weizmann Inst. of Science, Rehovot (Israel); Seakins, Paul W. [Univ. of Leeds (United Kingdom); Surratt, Jason D. [Univ. of North Carolina, Chapel Hill, NC (United States); Tanimoto, Hiroshi [National Inst. for Environmental Studies, Tsukuba (Japan); Thornton, Joel A. [Univ. of Washington, Seattle, WA (United States); Tong, Zhu [Peking Univ., Beijing (China); Tyndall, Geoffrey S. [National Center for Atmospheric Research, Boulder, CO (United States); Wahner, Andreas [Forschungszentrum Julich (Germany); Weschler, Charles J. [Rutgers Univ., Piscataway, NJ (United States); Wilson, Kevin R. [Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States); Ziemann, Paul J. [Univ. of Colorado, Boulder, CO (United States)

    2017-02-07

    Laboratory studies of atmospheric chemistry characterize the nature of atmospherically relevant processes down to the molecular level, providing fundamental information used to assess how human activities drive environmental phenomena such as climate change, urban air pollution, ecosystem health, indoor air quality, and stratospheric ozone depletion. Laboratory studies have a central role in addressing the incomplete fundamental knowledge of atmospheric chemistry. This paper highlights the evolving science needs for this community and emphasizes how our knowledge is far from complete, hindering our ability to predict the future state of our atmosphere and to respond to emerging global environmental change issues. Finally, laboratory studies provide rich opportunities to expand our understanding of the atmosphere via collaborative research with the modeling and field measurement communities, and with neighboring disciplines.

  12. Global atmospheric chemistry of CFC-123

    Science.gov (United States)

    Prinn, Ronald G.; Golombek, Amram

    1990-01-01

    The compound 1,1-dichloro--2,2,2-trifluoroethane (CFC-123) has been proposed as an industrial substitute for trichlorofluoromethane (CFC-11). The chemical destruction rates of CFC-123 by various processes is calculated here using a three-dimensional global model of the atmosphere, and it is confirmed that the chief sink of CFC-123 is destruction by OH radicals below 12 km, accounting for 88 percent of its loss. The calculated destruction rate is greatest in the equatorial region below 2 km. The calculated steady-state lifetime of CFC-123 is 1.5 years, much shorter than that of CFC-11, the destruction of which is largely confined to the stratosphere. For equal rates of CFC-123 and CFC-11 emission to the atmosphere, the molar content in the atmosphere and the injection rate of chlorine into the stratosphere are, respectively, 48 and 14 times greater for CFC-11 than for CFC-123 in steady state.

  13. Indoex : chemistry of the Indian Ocean atmosphere

    NARCIS (Netherlands)

    Laat, A.T.J. de

    2000-01-01

    NDOEX (INDian Ocean EXperiment) was large international measurement campaign focussing on measuring radiation in, and the chemical compisition of, the Indian Ocean Atmosphere during northern hemisphere winter. One of the reasons to measure in this region was the specific and unique

  14. Global atmospheric chemistry of CFC-123.

    Science.gov (United States)

    Prinn, R G; Golombek, A

    1990-03-01

    THE compound 1,1-dichloro-2,2,2-trifluoroethane (CFC-123), which is potentially usable as a foam-blowing agent in the plastics industry, an aerosol propellant and a refrigerant, has been proposed as an industrial substitute for trichlorofluoromethane (CFC-11), the use of which is increasingly restricted because of its effects on the ozone layer and on climate(1-3). It is expected that CFC-123, although like CFC-11 an absorber of infrared radiation, will be less stable in the atmosphere because of its expected reaction with OH radicals in the troposphere. Using a three-dimensional global model of the atmosphere, we have calculated the chemical destruction rates of CFC-123 by various processes, confirming that the chief sink is destruction by OH radicals below 12 km, which accounts for 88% of its loss. The calculated destruction rate is greatest in the equatorial region below 2 km. The calculated steady-state lifetime of CFC-123 is 1.5 years, based on the best available estimate of the rate constant of the reaction with OH. This lifetime is very much shorter than that of CFC-11, the destruction of which is largely confined to the stratosphere. For equal rates (by mass) of CFC-123 and CFC-11 emission to the atmosphere, the molar content in the atmosphere and the injection rate of chlorine into the stratosphere are, respectively, 48 and 14 times greater for CFC-11 than for CFC-123 in steady-state.

  15. Heterogeneous reactions important in atmospheric ozone depletion: a theoretical perspective.

    Science.gov (United States)

    Bianco, Roberto; Hynes, James T

    2006-02-01

    Theoretical studies of the mechanisms of several heterogeneous reactions involving ClONO(2), H(2)O, HCl, HBr, and H(2)SO(4) important in atmospheric ozone depletion are described, focused primarily on reactions on aqueous aerosol surfaces. Among the insights obtained is the active chemical participation of the surface water molecules in several of these reactions. The general methodology adopted allows reduction of these complex chemical problems to meaningful model systems amenable to quantum chemical calculations.

  16. Aspects of the atmospheric chemistry of amides.

    Science.gov (United States)

    Barnes, Ian; Solignac, Geraldine; Mellouki, Abdelwahid; Becker, Karl H

    2010-12-17

    The gas-phase reactions of six amides, formamide, N-methyl formamide, N,N-dimethyl formamide, acetamide, N-methyl acetamide and N,N-dimethyl acetamide with the atmospheric oxidants OH radicals and Cl atoms, but in a number of cases also with NO(3) radicals and ozone, are presented and discussed. Kinetic and mechanistic information available from previous experimental work is combined with new kinetic and product information from this study, obtained in a photoreactor using in situ FTIR spectrometry, to elucidate the gas-phase photooxidation mechanisms of the amides and assess potential environmental implications.

  17. Organic chemistry in a CO2 rich early Earth atmosphere

    Science.gov (United States)

    Fleury, Benjamin; Carrasco, Nathalie; Millan, Maëva; Vettier, Ludovic; Szopa, Cyril

    2017-12-01

    The emergence of life on the Earth has required a prior organic chemistry leading to the formation of prebiotic molecules. The origin and the evolution of the organic matter on the early Earth is not yet firmly understood. Several hypothesis, possibly complementary, are considered. They can be divided in two categories: endogenous and exogenous sources. In this work we investigate the contribution of a specific endogenous source: the organic chemistry occurring in the ionosphere of the early Earth where the significant VUV contribution of the young Sun involved an efficient formation of reactive species. We address the issue whether this chemistry can lead to the formation of complex organic compounds with CO2 as only source of carbon in an early atmosphere made of N2, CO2 and H2, by mimicking experimentally this type of chemistry using a low pressure plasma reactor. By analyzing the gaseous phase composition, we strictly identified the formation of H2O, NH3, N2O and C2N2. The formation of a solid organic phase is also observed, confirming the possibility to trigger organic chemistry in the upper atmosphere of the early Earth. The identification of Nitrogen-bearing chemical functions in the solid highlights the possibility for an efficient ionospheric chemistry to provide prebiotic material on the early Earth.

  18. Effects of Deep Convection on Atmospheric Chemistry

    Science.gov (United States)

    Pickering, Kenneth E.

    2007-01-01

    This presentation will trace the important research developments of the last 20+ years in defining the roles of deep convection in tropospheric chemistry. The role of deep convection in vertically redistributing trace gases was first verified through field experiments conducted in 1985. The consequences of deep convection have been noted in many other field programs conducted in subsequent years. Modeling efforts predicted that deep convection occurring over polluted continental regions would cause downstream enhancements in photochemical ozone production in the middle and upper troposphere due to the vertical redistribution of ozone precursors. Particularly large post-convective enhancements of ozone production were estimated for convection occurring over regions of pollution from biomass burning and urban areas. These estimates were verified by measurements taken downstream of biomass burning regions of South America. Models also indicate that convective transport of pristine marine boundary layer air causes decreases in ozone production rates in the upper troposphere and that convective downdrafts bring ozone into the boundary layer where it can be destroyed more rapidly. Additional consequences of deep convection are perturbation of photolysis rates, effective wet scavenging of soluble species, nucleation of new particles in convective outflow, and the potential fix stratosphere-troposphere exchange in thunderstorm anvils. The remainder of the talk will focus on production of NO by lightning, its subsequent transport within convective clouds . and its effects on downwind ozone production. Recent applications of cloud/chemistry model simulations combined with anvil NO and lightning flash observations in estimating NO Introduction per flash will be described. These cloud-resolving case-study simulations of convective transport and lightning NO production in different environments have yielded results which are directly applicable to the design of lightning

  19. Stability of the Martian atmosphere: Is heterogeneous catalysis essential?

    Science.gov (United States)

    Atreya, Sushil K.; Gu, Zhen Gang

    1994-01-01

    A comprehensive homogeneous gas phase photochemical model is developed to study the problem of stability of the Martian atmosphere. The one-dimensional model extends from the ground up to 220 km, passing through the homopause at 125 km. The model thus couples the lower (neutral) atmosphere to the ionosphere above which provides significant downward flux of carbon monoxide and oxygen atoms. It is concluded on the basic of currently accepted values for globally and seasonally averaged water vapor abundance, dust opacity and the middle atmospheric eddy mixing coefficient, as well as the relevant laboratory data (particularly the temperature dependence of CO2 absorption cross section and the rate constant for CO+OH reaction), that the rate of re-formation of carbon dioxide exceeds its photolytic destruction rate by about 40%. Furthermore, it is found that this result is virtually independent of the choice of eddy mixing coefficient, unless its value in the middle atmosphere exceeds 10(exp 8) sq cm/sec or is far smaller than 10(exp 5)sq cm/sec, or the dust opacity, unless it exceeds unity, or the water vapor mixing ratio at the surface, unless it is far smaller (less than or = 1 ppm) or far greater (greater than or = 500 ppm) than the average value (approximately 150 ppm). Since none of these extremes represent globally and seasonally averaged conditions on Mars, we propose that the present model requires existence of a mechanism to throttle down the recycling rate of carbon dioxide on Mars. Therefore, it is suggested that a heterogeneous process which provides a sink to the species that participate in the recycling of CO2, i.e., H2O, H2O2, OH, CO or O, in particular, may be necessary to bring about the balance between the CO2 recycling rate and its photolytic destruction rate. Aerosols of dust or ice (pure or doped water or carbon dioxide ice present in the atmosphere of Mars) can provide the appropriate adsorption sites for the above heterogeneous process. Despite our

  20. Ozone Depletion, UVB and Atmospheric Chemistry

    Science.gov (United States)

    Stolarski, Richard S.

    1999-01-01

    The primary constituents of the Earth's atmosphere are molecular nitrogen and molecular oxygen. Ozone is created when ultraviolet light from the sun photodissociates molecular oxygen into two oxygen atoms. The oxygen atoms undergo many collisions but eventually combine with a molecular oxygen to form ozone (O3). The ozone molecules absorb ultraviolet solar radiation, primarily in the wavelength region between 200 and 300 nanometers, resulting in the dissociation of ozone back into atomic oxygen and molecular oxygen. The oxygen atom reattaches to an O2 molecule, reforming ozone which can then absorb another ultraviolet photon. This sequence goes back and forth between atomic oxygen and ozone, each time absorbing a uv photon, until the oxygen atom collides with and ozone molecule to reform two oxygen molecules.

  1. Atmospheric chemistry of hydrofluorocarbons and hydrochlorofluorocarbons

    Energy Technology Data Exchange (ETDEWEB)

    Sehested, J.

    1995-03-01

    Pulse radiolysis coupled with a time resolved UV absorption detection system and a FTIR spectrometer coupled to a 140 l reaction chamber was used to study the degradation of HCFCs and HFCs in the atmosphere. Reaction rates for a series of reactions of HFCs and HCFCs were investigated: F + RH, R + O{sub 2} + RO{sub 2} + NO, and RO{sub 2} + NO{sub 2} + M, together with UV absorption spectra of the halogenated alkyl (R) and halogenated alkyl peroxy radicals (RO{sub 2}). The products following the self reactions for RO{sub 2} radicals for RO{sub 2} = CF{sub 3}CF{sub 2}O{sub 2}, CF{sub 2}HCF{sub 2}O{sub 2}, CF{sub 3}CH{sub 2}O{sub 2}, CFH{sub 2}CFHO{sub 2}, CF{sub 3}O{sub 2}, and CF{sub 3}C(O)O{sub 2} were investigated by the FTIR setup. The results show that the self reaction of halogenated peroxy radicals give the alkoxy radical, RO, as product. The atmospheric fate of these radicals were C-C bond cleavage for CF{sub 3}CF{sub 2}O, CHF{sub 2}CF{sub 2}O, CFH{sub 2}CHFO, and CF{sub 3}C(O)O; while CF{sub 3}CH{sub 2}O radicals rect with O{sub 2} to give CF{sub 3}CHO and HO{sub 2}. the reaction between CFH{sub 2}O{sub 2} and HO{sub 2} was shown to give 29{+-}7 % CH{sub 2}FCOOH and 72{+-}11 % HCOF as the carbon containing products. (Abstract Truncated)

  2. Skill in forecasting extreme ozone pollution episodes with a global atmospheric chemistry model

    Science.gov (United States)

    Schnell, J. L.; Holmes, C. D.; Jangam, A.; Prather, M. J.

    2014-08-01

    From the ensemble of stations that monitor surface air quality over the United States and Europe, we identify extreme ozone pollution events and find that they occur predominantly in clustered, multiday episodes with spatial extents of more than 1000 km. Such scales are amenable to forecasting with current global atmospheric chemistry models. We develop an objective mapping algorithm that uses the heterogeneous observations of the individual surface sites to calculate surface ozone averaged over 1° by 1° grid cells, matching the resolution of a global model. Air quality extreme (AQX) events are identified locally as statistical extremes of the ozone climatology and not as air quality exceedances. With the University of California, Irvine chemistry-transport model (UCI CTM) we find there is skill in hindcasting these extreme episodes, and thus identify a new diagnostic using global chemistry-climate models (CCMs) to identify changes in the characteristics of extreme pollution episodes in a warming climate.

  3. Exoplanetary Atmospheres-Chemistry, Formation Conditions, and Habitability.

    Science.gov (United States)

    Madhusudhan, Nikku; Agúndez, Marcelino; Moses, Julianne I; Hu, Yongyun

    2016-12-01

    Characterizing the atmospheres of extrasolar planets is the new frontier in exoplanetary science. The last two decades of exoplanet discoveries have revealed that exoplanets are very common and extremely diverse in their orbital and bulk properties. We now enter a new era as we begin to investigate the chemical diversity of exoplanets, their atmospheric and interior processes, and their formation conditions. Recent developments in the field have led to unprecedented advancements in our understanding of atmospheric chemistry of exoplanets and the implications for their formation conditions. We review these developments in the present work. We review in detail the theory of atmospheric chemistry in all classes of exoplanets discovered to date, from highly irradiated gas giants, ice giants, and super-Earths, to directly imaged giant planets at large orbital separations. We then review the observational detections of chemical species in exoplanetary atmospheres of these various types using different methods, including transit spectroscopy, Doppler spectroscopy, and direct imaging. In addition to chemical detections, we discuss the advances in determining chemical abundances in these atmospheres and how such abundances are being used to constrain exoplanetary formation conditions and migration mechanisms. Finally, we review recent theoretical work on the atmospheres of habitable exoplanets, followed by a discussion of future outlook of the field.

  4. Research for the advancement of green chemistry practice: Studies in atmospheric and educational chemistry

    Science.gov (United States)

    Cullipher, Steven Gene

    Green chemistry is a philosophy of chemistry that emphasizes a decreasing dependence on limited non-renewable resources and an increasing focus on preventing pollution byproducts of the chemical industry. In short, it is the discipline of chemistry practiced through the lens of environmental stewardship. In an effort to advance the practice of green chemistry, three studies will be described that have ramifications for the practice. The first study examines the atmospheric oxidation of a hydrofluorinated ether, a third-generation CFC replacement compound with primarily unknown atmospheric degradation products. Determination of these products has the potential to impact decisions on refrigerant usage in the future. The second study examines chemistry students' development of understanding benefits-costs-risks analysis when presented with two real-world scenarios: refrigerant choice and fuel choice. By studying how benefits-costs-risks thinking develops, curricular materials and instructional approaches can be designed to better foster the development of an ability that is both necessary for green chemists and important in daily decision-making for non-chemists. The final study uses eye tracking technology to examine students' abilities to interpret molecular properties from structural information in the context of global warming. Such abilities are fundamental if chemists are to appropriately assess risks and hazards of chemistry practice.

  5. An Overview of Atmospheric Chemistry and Air Quality Modeling

    Science.gov (United States)

    Johnson, Matthew S.

    2017-01-01

    This presentation will include my personal research experience and an overview of atmospheric chemistry and air quality modeling to the participants of the NASA Student Airborne Research Program (SARP 2017). The presentation will also provide examples on ways to apply airborne observations for chemical transport (CTM) and air quality (AQ) model evaluation. CTM and AQ models are important tools in understanding tropospheric-stratospheric composition, atmospheric chemistry processes, meteorology, and air quality. This presentation will focus on how NASA scientist currently apply CTM and AQ models to better understand these topics. Finally, the importance of airborne observation in evaluating these topics and how in situ and remote sensing observations can be used to evaluate and improve CTM and AQ model predictions will be highlighted.

  6. Evaluated kinetic and photochemical data for atmospheric chemistry

    Science.gov (United States)

    Baulch, D. L.; Cox, R. A.; Hampson, R. F., Jr.; Kerr, J. A.; Troe, J.; Watson, R. T.

    1980-01-01

    This paper contains a critical evaluation of the kinetics and photochemistry of gas phase chemical reactions of neutral species involved in middle atmosphere chemistry (10-55 km altitude). Data sheets have been prepared for 148 thermal and photochemical reactions, containing summaries of the available experimental data with notes giving details of the experimental procedures. For each reaction a preferred value of the rate coefficient at 298 K is given together with a temperature dependency where possible. The selection of the preferred value is discussed, and estimates of the accuracies of the rate coefficients and temperature coefficients have been made for each reaction. The data sheets are intended to provide the basic physical chemical data needed as input for calculations which model atmospheric chemistry. A table summarizing the preferred rate data is provided, together with an appendix listing the available data on enthalpies of formation of the reactant and product species.

  7. Concluding remarks: Faraday Discussion on chemistry in the urban atmosphere.

    Science.gov (United States)

    Jimenez, Jose L

    2016-07-18

    This article summarises the Concluding remarks from the Faraday Discussion on Chemistry in the Urban Atmosphere. The following themes are addressed: (a) new results that inform our understanding of the evolving sources and composition of the urban atmosphere ("News"); (b) results that identify gaps in our understanding that necessitate further work ("Gaps"); (c) the emerging instrumentation revolution and some of the challenges that it brings; (d) the structural issues of insufficient support for the analysis of field campaigns; and (e) some important areas that were missing from this Faraday Discussion and that should receive an increasing focus in the future.

  8. Recent Discoveries and Future Challenges in Atmospheric Organic Chemistry.

    Science.gov (United States)

    Glasius, Marianne; Goldstein, Allen H

    2016-03-15

    Earth's atmosphere contains a multitude of organic compounds, which differ by orders of magnitude regarding fundamental properties such as volatility, reactivity, and propensity to form cloud droplets, affecting their impact on global climate and human health. Despite recent major research efforts and advances, there are still substantial gaps in understanding of atmospheric organic chemistry, hampering efforts to understand, model, and mitigate environmental problems such as aerosol formation in both polluted urban and more pristine regions. The analytical toolbox available for chemists to study atmospheric organic components has expanded considerably during the past decade, opening new windows into speciation, time resolution and detection of reactive and semivolatile compounds at low concentrations. This has provided unprecedented opportunities, but also unveiled new scientific challenges. Specific groundbreaking examples include the role of epoxides in aerosol formation especially from isoprene, the importance of highly oxidized, reactive organics in air-surface processes (whether atmosphere-biosphere exchange or aerosols), as well as the extent of interactions of anthropogenic and biogenic emissions and the resulting impact on atmospheric organic chemistry.

  9. Report to the International Global Atmospheric Chemistry Project

    Energy Technology Data Exchange (ETDEWEB)

    Reisdorf, Jill [University Corporation for Atmospheric Research (UCAR/CPAESS), Boulder, CO (United States); Wiedinmyer, Christine [National Center for Atmospheric Research (NCAR/ACOM), Boulder, CO (United States)

    2017-04-21

    IGAC’s mission is to facilitate atmospheric chemistry research towards a sustainable world. This is achieved through IGAC’s three focal activities: fostering community, building capacity, and providing leadership. A key component to achieving IGAC’s mission is its developing early career program. These scientists join an international network early in their career that puts the cogs in motion to further facilitate atmospheric chemistry research at an international level for years to come. IGAC’s Science Conference is a primary mechanism for IGAC to build cooperation and disseminate scientific information across its international community. The first IGAC Science Conference was held in 1993 in Eilat, Israel. Since then, IGAC has successfully held fourteen science conferences, consistently becoming a biennial conference starting in 2002. The biennial IGAC Science Conference is regarded as THE international conference on atmospheric chemistry and participation in the conference is typically in the range of 350-650 participants. Since 2004, IGAC has included an Early Career Scientists Program as part of the conference to foster the next generation of scientists. IGAC believes, and has seen, that by allowing scientists to form an international network of colleagues early in their career that future international collaborations in atmospheric chemistry are enhanced. The 2016 IGAC Science Conference Early Career Program consisted of numerous events throughout the week giving these scientists the opportunity to not only create a community amongst themselves, but to also engage and build relationships with senior scientists. In order to support the Early Career Scientists Program, IGAC sought funding from international, regional and local organizations to provide Travel Grants to the conference based on an assessment of both need and merit. This conference summary reports on outcomes of the 2016 IGAC Science Conference and the Early Career Program, which included

  10. Micro-physics of aircraft-generated aerosols and their potential impact on heterogeneous plume chemistry

    Energy Technology Data Exchange (ETDEWEB)

    Kaercher, B.; Luo, B.P. [Muenchen Univ., Freising (Germany). Lehrstuhl fuer Bioklimatologie und Immissionsforschung

    1997-12-31

    Answers are attempted to give to open questions concerning physico-chemical processes in near-field aircraft plumes, with emphasis on their potential impact on subsequent heterogeneous chemistry. Research issues concerning the nucleation of aerosols and their interactions among themselves and with exhaust gases are summarized. Microphysical properties of contrail ice particles, formation of liquid ternary mixtures, and nucleation of nitric acid trihydrate particles in contrails are examined and possible implications for heterogeneous plume chemistry are discussed. (author) 19 refs.

  11. Systematic evaluation of atmospheric chemistry-transport model CHIMERE

    Science.gov (United States)

    Khvorostyanov, Dmitry; Menut, Laurent; Mailler, Sylvain; Siour, Guillaume; Couvidat, Florian; Bessagnet, Bertrand; Turquety, Solene

    2017-04-01

    Regional-scale atmospheric chemistry-transport models (CTM) are used to develop air quality regulatory measures, to support environmentally sensitive decisions in the industry, and to address variety of scientific questions involving the atmospheric composition. Model performance evaluation with measurement data is critical to understand their limits and the degree of confidence in model results. CHIMERE CTM (http://www.lmd.polytechnique.fr/chimere/) is a French national tool for operational forecast and decision support and is widely used in the international research community in various areas of atmospheric chemistry and physics, climate, and environment (http://www.lmd.polytechnique.fr/chimere/CW-articles.php). This work presents the model evaluation framework applied systematically to the new CHIMERE CTM versions in the course of the continuous model development. The framework uses three of the four CTM evaluation types identified by the Environmental Protection Agency (EPA) and the American Meteorological Society (AMS): operational, diagnostic, and dynamic. It allows to compare the overall model performance in subsequent model versions (operational evaluation), identify specific processes and/or model inputs that could be improved (diagnostic evaluation), and test the model sensitivity to the changes in air quality, such as emission reductions and meteorological events (dynamic evaluation). The observation datasets currently used for the evaluation are: EMEP (surface concentrations), AERONET (optical depths), and WOUDC (ozone sounding profiles). The framework is implemented as an automated processing chain and allows interactive exploration of the results via a web interface.

  12. Molecular dynamics study on mechanism of preformed particle gel transporting through nanopores: Surface chemistry and heterogeneity

    Science.gov (United States)

    Cui, Peng; Zhang, Heng; Ma, Ying; Hao, Qingquan; Liu, Gang; Sun, Jichao; Yuan, Shiling

    2017-10-01

    The translocation behavior of preformed particle gel (PPG) in porous media is crucial for its application in enhanced oil recovery. By means of non-equilibrium molecular dynamics simulation, the translocation mechanism of PPG confined in different silica nanopores were investigated. The influence of surface chemistry and chemical heterogeneity of silica nanopore on the translocation process was revealed. As the degree of surface hydroxylation increases and the heterogeneity decreases, the pulling force needed to drive PPG decreases. We infer that the nanopore's surface (i.e. surface chemistry and heterogeneity) affects the translocation of PPG indirectly by forming different hydration layers.

  13. Atmosphere-surface interactions over polar oceans and heterogeneous surfaces

    Energy Technology Data Exchange (ETDEWEB)

    Vihma, T.

    1995-12-31

    Processes of interaction between the atmospheric boundary layer and the planetary surface have been studied with special emphasis on polar ocean surfaces: the open ocean, leads, polynyas and sea ice. The local exchange of momentum, heat and moisture has been studied experimentally both in the Weddell Sea and in the Greenland Sea. Exchange processes over heterogeneous surfaces are addressed by modelling studies. Over a homogeneous surface, the local turbulent fluxes can be reasonably well estimated using an iterative flux-profile scheme based on the Monin-Obukhov similarity theory. In the Greenland Sea, the near-surface air temperature and the generally small turbulent fluxes over the open ocean were affected by the sea surface temperature fronts. Over the sea ice cover in the Weddell Sea, the turbulent sensible heat flux was generally downwards, and together with an upward oceanic heat flux through the ice it compensated the heat loss from the surface via long-wave radiation. The wind dominated on time scales of days, while the current became important on longer time scales. The drift dynamics showed apparent spatial differences between the eastern and western regions, as well as between the Antarctic Circumpolar Current and the rest of the Weddell Sea. Inertial motion was present in regions of low ice concentration. The surface heterogeneity, arising e.g. from roughness or temperature distribution, poses a problem for the parameterization of surface exchange processes in large-scale models. In the case of neutral flow over a heterogeneous terrain, an effective roughness length can be used to parameterize the roughness effects

  14. Heterogeneous chemistry of trichloroacetyl chloride in the atmosphere

    Energy Technology Data Exchange (ETDEWEB)

    George, C.; Mirabel, P.; Ponche, J.L. [Laboratoire de Physico-Chimie de l`Atmosphere, Strasbourg (France); Lagrange, J.; Lagrange, P.; Pallares, C. [Laboratoire de Cinetique et Analyse, Strasbourg (France)

    1994-01-20

    This article investigates the effects of anthropogenic releases of partially and fully halogenated hydrocarbons on the stratospheric ozone layer. Experiments using direct measurements of the reaction rates of hydrolysis and direct uptake of trichloroacetyl chlorides by water droplets are described. 32 refs., 9 figs., 3 tabs.

  15. Atmospheric Chemistry of CH3CH2OCH3

    DEFF Research Database (Denmark)

    Andersen, Mads Peter Sulbæk; Bjørn Svendsen, Sissel; Østerstrøm, Freja From

    2017-01-01

    The atmospheric chemistry of methyl ethyl ether, CH3CH2OCH3, was examined using FT-IR/relative-rate methods. Hydroxyl radical and chlorine atom rate coefficients of k(CH3CH2OCH3+OH) = (7.53 ± 2.86) × 10−12 cm3 molecule−1 s−1 and k(CH3CH2OCH3+Cl) = (2.35 ± 0.43) × 10−10 cm3 molecule−1 s−1 were...

  16. A study of aqueous phase reactions relevant for atmospheric chemistry

    Energy Technology Data Exchange (ETDEWEB)

    Loegager, T.

    1993-12-31

    The subject of this thesis being aqueous phase atmospheric chemistry, species of atmospheric relevance such ad ozone (O{sub 3}) ferrous ion (Fe{sup 2+}), the ferryl ion (FeO{sup 2+}), hydrogen perioxide (H{sub 2}O{sub 2}), the nitrite and nitrate ion and their acids, peroxynitrous acid (ONOOH), peroxynitric acid (O{sub 2}NOOH), and the radicals {sub a}{sup -}{sub q}, H, OH, HO{sub 2}/O{sub 2}{sup -}, NO{sub 2}, NO{sub 3}, NO{sub 3}{sup =}, and SO{sub 4}{sup -}, have all been studied. The ai has been to study spectra, extinction coefficients, specific rate constants, kinetic mechanisms, and pK`s using the stopped-flow and pulse radiolysis techniques, combined with an indispensable chemical kinetics simulations program. (au).

  17. The global change research center atmospheric chemistry model

    Energy Technology Data Exchange (ETDEWEB)

    Moraes, Jr., Francis Perry [Oregon Graduate Inst. of Science and Technology, Portland, OR (United States)

    1995-01-01

    This work outlines the development of a new model of the chemistry of the natural atmosphere. The model is 2.5-dimensional, having spatial coordinates height, latitude, and, the half-dimension, land and ocean. The model spans both the troposphere and stratosphere, although the troposphere is emphasized and the stratosphere is simple and incomplete. The chemistry in the model includes the Ox, HOx, NOx, and methane cycles in a highly modular fashion which allows model users great flexibility in selecting simulation parameters. A detailed modeled sensitivity analysis is also presented. A key aspect of the model is its inclusion of clouds. The model uses current understanding of the distribution and optical thickness of clouds to determine the true radiation distribution in the atmosphere. As a result, detailed studies of the radiative effects of clouds on the distribution of both oxidant concentrations and trace gas removal are possible. This work presents a beginning of this study with model results and discussion of cloud effects on the hydroxyl radical.

  18. Chemistry of Atmospheric Aerosols at Pacifichem 2015 Congress

    Energy Technology Data Exchange (ETDEWEB)

    Nizkorodov, Sergey [Univ. of California, Irvine, CA (United States)

    2016-12-28

    This grant was used to provide participant support for a symposium entitled “Chemistry of Atmospheric Aerosols” at the 2015 International Chemical Congress of Pacific Basin Societies (Pacifichem) that took place in Honolulu, Hawaii, USA, on December 15-20, 2015. The objective was to help attract both distinguished scientists as well as more junior researchers, including graduate students, to this international symposium by reducing the financial barrier for its attendance. It was the second time a symposium devoted to Atmospheric Aerosols was part of the Pacifichem program. This symposium provided a unique opportunity for the scientists from different countries to gather in one place and discuss the cutting edge advances in the cross-disciplinary areas of aerosol research. To achieve the highest possible impact, the PI and the symposium co-organizers actively advertised the symposium by e-mail and by announcements at other conferences. A number of people responded, and the end result was a very busy program with about 100 oral and poster presentation described in the attached PDF file. Presentations by invited speakers occupied approximately 30% of time in each of the sessions. In addition to the invited speakers, each session also had contributed presentations, including those by graduate students and postdoctoral researchers. This symposium gathered established aerosol chemists from a number of countries including United States, Canada, China, Japan, Korea, Australia, Brazil, Hongkong, Switzerland, France, and Germany. There were plenty of time for the attendees to discuss new ideas and potential collaborations both during the oral sessions and at the poster sessions of the symposium. The symposium was very beneficial to graduate student researchers, postdoctoral fellows, and junior researchers whose prior exposure to international aerosol chemistry science had been limited. The symposium provided junior researchers with a much broader perspective of aerosol

  19. Collaborative Research. Atmospheric Pressure Microplasma Chemistry-Photon Synergies

    Energy Technology Data Exchange (ETDEWEB)

    Park, Sung-Jin [Univ. of Illinois, Urbana, IL (United States); Eden, James Gary [Univ. of Illinois, Urbana, IL (United States)

    2015-12-01

    Combining the effects of low temperature, atmospheric pressure microplasmas and microplasma photon sources offers the promise of greatly expanding the range of applications for each of them. The plasma sources create active chemical species and these can be activated further by the addition of photons and the associated photochemistry. There are many ways to combine the effects of plasma chemistry and photochemistry, especially if there are multiple phases present. This project combined the construction of appropriate test experimental systems, various spectroscopic diagnostics and mathematical modeling. Through a continuous discussion and co-design process with the UC-Berkeley Team, we have successfully completed the fabrication and testing of all components for a microplasma array-assisted system designed for photon-activated plasma chemistry research. Microcavity plasma lamps capable of generating more than 20 mW/cm2 at 172 nm (Xe dimer) were fabricated with a custom form factor to mate to the plasma chemistry setup, and a lamp was current being installed by the Berkeley team so as to investigate plasma chemistry-photon synergies at a higher photon energy (~7.2 eV) as compared to the UVA treatment that is afforded by UV LEDs operating at 365 nm. In particular, motivated by the promising results from the Berkeley team with UVA treatment, we also produced the first generation of lamps that can generate photons in the 300-370 nm wavelength range. Another set of experiments, conducted under the auspices of this grant, involved the use of plasma microjet arrays. The combination of the photons and excited radicals produced by the plasma column resulted in broad area deactivation of bacteria.

  20. ALMA observations of Titan's atmospheric chemistry and seasonal variation

    Science.gov (United States)

    Cordiner, Martin

    2017-04-01

    Titan is the largest moon of Saturn, with a thick (1.45 bar) atmosphere composed primarily of molecular nitrogen and methane. Photochemistry in Titan's upper atmosphere results in the production of a wide range of organic molecules, including hydrocarbons, nitriles and aromatics, some of which could be of pre-biotic relevance. Thus, we obtain insights into the possible molecular inventories of primitive (reducing) planetary atmospheres. Titan's atmosphere also provides a unique laboratory for testing our understanding of fundamental processes involving the chemistry and spectroscopy of complex organic molecules. In this talk, results will be presented from our studies using the Atacama Large Millimeter/submillimeter Array (ALMA) during the period 2012-2015, focussing in particular on the detection and mapping of emission from various nitrile species. By combining data from multiple ALMA observations, our spectra have reached an unprecedented sensitivity level, enabling the first spectroscopic detection and mapping of C2H3CN (vinyl cyanide) on Titan. Liquid-phase simulations of Titan's seas indicate that vinyl cyanide molecules could combine to form vesicle membranes (similar to the cells of terrestrial biology), and the astrobiological implications of this discovery will be discussed. Furthermore, ALMA observations provide instantaneous snapshot mapping of Titan's entire Earth-facing hemisphere, for gases inaccessible to previous instruments. Combined with complementary data obtained from the Cassini Saturn orbiter, as well as theoretical models and laboratory studies, our observed, seasonally variable, spatially resolved abundance patterns are capable of providing new insights into photochemical production and transport in primitive planetary atmospheres in the Solar System and beyond.

  1. Clays as mineral dust aerosol: An integrated approach to studying climate, atmospheric chemistry, and biogeochemical effects of atmospheric clay minerals in an undergraduate research laboratory

    Science.gov (United States)

    Hatch, C. D.; Crane, C. C.; Harris, K. J.; Thompson, C. E.; Miles, M. K.; Weingold, R. M.; Bucuti, T.

    2011-12-01

    Entrained mineral dust aerosol accounts for 45% of the global annual atmospheric aerosol load and can have a significant influence on important environmental issues, including climate, atmospheric chemistry, cloud formation, biogeochemical processes, visibility, and human health. 70% of all mineral aerosol mass originating from Africa consists of layered aluminosilicates, including illite, kaolinite, and montmorillonite clays. Clay minerals are a largely neglected component of mineral aerosol, yet they have unique physiochemical properties, including a high reactive surface area, large cation exchange capacities, small particle sizes, and a relatively large capacity to take up adsorbed water, resulting in expansion of clay layers (and a larger reactive surface area for heterogeneous interactions) in some cases. An integrated laboratory research approach has been implemented at Hendrix College, a Primarily Undergraduate Institution, in which undergraduate students are involved in independent and interdisciplinary research projects that relate the chemical aging processes (heterogeneous chemistry) of clay minerals as a major component of mineral aerosol to their effects on climate (water adsorption), atmospheric chemistry (trace gas uptake), and biogeochemistry (iron dissolution and phytoplankton biomarker studies). Preliminary results and future directions will be reported.

  2. Laboratory studies of nitrate radical chemistry - application to atmospheric processes

    Energy Technology Data Exchange (ETDEWEB)

    Noremsaune, Ingse

    1997-12-31

    This thesis studies atmospheric chemistry and tries in particular to fill gaps in the data base of atmospheric reactions. It studies the nitrate radical reactions with chloroethenes and with but-2-yne (2-butyne). The mechanisms and rate coefficients for the NO{sub 3}-initiated degradation of the chloroethenes and 2-butyne were investigated by means of the static reaction chamber and the fast flow-discharge technique. The reactions between the nitrate radical and the chloroethenes were studied at atmospheric pressure in a reaction chamber with synthetic air as bath gas. FTIR (Fourier Transform InfraRed spectroscopy) spectroscopy was used to follow the reactions and to identify the products. Products were observed for the reactions with (E)-1,2-dichloroethene and tetrachloroethene, although the absorption bands are weak. The alkyl peroxynitrate and nitrate compounds form very strong and characteristic absorption bands. The rate coefficients for the reactions between NO{sub 3} and the chloroethenes were investigated at room temperature by three different methods. The results are given in tables. 132 refs., 44 figs., 21 tabs.

  3. Disequilibrium Chemistry and Photochemical Hazes in Temperate Jupiter Atmospheres

    Science.gov (United States)

    Gao, Peter; Zahnle, Kevin; Marley, Mark; Morley, Caroline

    2018-01-01

    Probing the chemical composition and aerosol content of "temperate Jupiters" - young, Jupiter-like worlds with effective temperatures between 400 and 800 K with no direct analogues in our own Solar System - may be possible with the James Webb Space Telescope and its direct imaging capabilities. The relatively low temperatures of these exoplanets, as compared to hot Jupiters, means that disequilibrium processes such as eddy mixing and photochemistry could play a dominant role in determining the composition of their atmospheres. In this work we use a photochemical model and a cloud microphysics model to investigate the impact of disequilibrium processes. We find that the resulting model atmospheres may be significantly different from one predicted by equilibrium chemistry. For example, upward transport of CO from depth leads to the formation of large amounts of CO2, such that observed CO2 abundances may not scale with metallicity the same way as in equilibrium models. In addition, formation of sulfur hazes from H2S loss could lead to UV heating of the atmosphere, and increased albedos at red-optical wavelengths. Our results show that disequilibrium models may be necessary to interpret future observations of these cool objects.

  4. Nitrate chemistry in the snow and atmosphere at Summit, Greenland

    Science.gov (United States)

    Fibiger, D. L.; Hastings, M. G.; Dibb, J. E.; Nenes, A.; Chen, D.

    2013-12-01

    Atmospheric nitrate deposition to snow surfaces results from reactions of NOx (NO + NO2) with oxidants to produce HNO3. There has been enormous interest in using the isotopic composition of nitrate in ice cores to trace past NOx chemistry and sources. With the rapid cycling of NO and NO2, the oxygen isotopic signal reflects the oxidants that NOx reacts with to form nitrate, while the nitrogen isotopes could contain information about the NOx sources. In two spring/summer field seasons at Summit, Greenland (May-June 2010 and 2011), surface snow was collected at high time resolution and was measured for the complete N and O isotopic composition of nitrate. The oxygen isotopes (δ18O and Δ17O = δ17O - 0.52*δ18O) display the same very strong linear relationship (Δ17O = 0.46 * δ18O - 6.9, R2 = 0.9) in both seasons. This relationship indicates that there is very little photolysis of the nitrate at Summit and an unaltered nitrate signal is preserved in the snowpack. In addition, a suite of atmospheric measurements was made at Summit and none of the constituents measured show any correlation with concentration or isotopes of nitrate in the snow. This indicates that local chemistry is not contributing significantly to the nitrate in the snow. The combination of nitrogen and oxygen isotopes provides a richer picture of the data. There are three nitrate signatures that contribute to total nitrate deposition to Summit in both seasons. These sources can be described by the following isotopic compositions: δ15N, Δ17O, δ18O (per mil vs. air N2 or VSMOW): (1) -8, 27, 74 (2) 6, 40, 100 and (3) 16, 0, 23. While the same three nitrate sources are contributing in the two years, there is a very different balance of importance in 2010 compared to 2011. With limited source δ15N data it is difficult to assign each point to a specific NOx source, however the complete isotopic composition, atmospheric measurements and differences between the two seasons allow for tentative source

  5. Coupled Surface-Atmosphere Chemistry of the Martian Peroxide and Perchlorate Oxidants

    Science.gov (United States)

    Atreya, Sushil K.; Wilson, Eric; Encrenaz, Thérèse; Kaiser, Ralf; Mahaffy, Paul

    2017-04-01

    Oxidants play a significant role in planetary habitability. On Mars, while they can be a source of nutrients, they can also destroy surface organics. They may also impact the atmospheric trace gas chemistry. Hydrogen peroxide was first detected in the martian atmosphere in 2003 [1,2], and perchlorates were detected in the surface in 2008 in the polar region [3] and 2012 in the equatorial region [4,5]. Global and seasonal maps of hydrogen peroxide have been generated from regular observations since 2003 [6], while all indications are that perchlorates are ubiquitous on Mars. Homogeneous gas phase chemistry can generally explain the observed atmospheric hydrogen peroxide, but the magnitude of seasonal variation poses a challenge. Heterogeneous chemistry involving airborne dust lifted from the surface and triboelectric processes [6,7] may play a role. Perchlorate formation on Mars is poorly understood, but one thing is clear that the same atmospheric process that works reasonably well for terrestrial perchlorates fails at Mars. An alternative proposal to perchlorate formation in an ancient aqueous environment is an initiation throughout the history of Mars in the surface by radiolysis to source gaseous ClO2 to the atmosphere with subsequent further oxidation [8]. This talk will discuss the current status of oxidant chemistry on Mars in the above context and provide directions for future laboratory and modeling studies. References: [1] Encrenaz, T., et al. (2004) Icarus 170, 424. [2] Clancy, R.T., et al. (2004) Icarus 168, 116. [3] Hecht, M.H., et al. (2009) Science, 325(5936), 64, doi:10.1126/science.1172466. [4] Glavin, D.P., et al. (2013) JGR Planets 118, 1955, doi:10.1002/jgre.20144. [5] Ming, D.W., et al. (2014) Science, 343(6169), doi:10.1126/science.1245267. [6] Encrenaz, T., et al. (2015) A&A. 578, A127 (12pp), DOI: 10.1051/0004-6361/201425448. [7] Atreya, S.K., et al. (2006) Astrobiology 6 (no. 3), 439. [8] Wilson, E.H. et al., (2016) JGR Planets, doi: 10

  6. TROPOLITE, on the path of atmospheric chemistry made simple

    Science.gov (United States)

    Maresi, Luca; Van Der Meulen, Wencke; Vink, Rob

    2014-10-01

    Accurate, reliable and stable long term measurements of Earth's Atmospheric Chemistry from Space are currently done by complex instruments, whose mass is in excess of 100 Kg. TROPOMI is the more recent instrument being developed jointly by ESA and NSO and due for launch in 2015. TROPOMI, consisting of four spectrometers ranging from UV to SWIR, is paving the way to the development of high performance spectrometers that will compose the backbone of the European Copernicus system. The objective of TROPOMI is to measure trace gases with an accuracy one order of magnitude better of what is currently done from Space. While teams of engineers are still busy finalizing TROPOMI, ESA, NSO, and TNO have launched an initiative along a different development axis: to explore the possibility of a lighter version of TROPOMI, to address a market valuing a cost effective instrument for Atmospheric Chemistry. TROPOLITE, as it is dubbed, leverages on all the technology developments and the lessons learnt from TROPOMI, but with the clear objective of a design to cost solution. Furthermore, mass and power of the instrument shall be within the envelope of a payload of a small satellite, namely 20kg and 30W and possibly within a volume of 20 x 20 x 40 cm3. The scope of TROPOLITE is to address a larger user base that is interested in an affordable instrument to perform from a small satellite some specific tasks relevant to Air Quality and/or Climate. The paper, after a short overview of the TROPOMI design and current status, presents the design philosophy of TROPOLITE, and shows what are the technologies and processes stemming from the experience gained with TROPOMI that make possible a simplified, but still very performing, version of TROPOMI. A comparison in terms of performance and functionalities of the two instruments is discussed. Finally, the development plan from the current development status of TROPOLITE up to Qualification Model is presented.

  7. Recent advances in heterogeneous selective oxidation catalysis for sustainable chemistry.

    Science.gov (United States)

    Guo, Zhen; Liu, Bin; Zhang, Qinghong; Deng, Weiping; Wang, Ye; Yang, Yanhui

    2014-05-21

    Oxidation catalysis not only plays a crucial role in the current chemical industry for the production of key intermediates such as alcohols, epoxides, aldehydes, ketones and organic acids, but also will contribute to the establishment of novel green and sustainable chemical processes. This review is devoted to dealing with selective oxidation reactions, which are important from the viewpoint of green and sustainable chemistry and still remain challenging. Actually, some well-known highly challenging chemical reactions involve selective oxidation reactions, such as the selective oxidation of methane by oxygen. On the other hand some important oxidation reactions, such as the aerobic oxidation of alcohols in the liquid phase and the preferential oxidation of carbon monoxide in hydrogen, have attracted much attention in recent years because of their high significance in green or energy chemistry. This article summarizes recent advances in the development of new catalytic materials or novel catalytic systems for these challenging oxidation reactions. A deep scientific understanding of the mechanisms, active species and active structures for these systems are also discussed. Furthermore, connections among these distinct catalytic oxidation systems are highlighted, to gain insight for the breakthrough in rational design of efficient catalytic systems for challenging oxidation reactions.

  8. Chemistry of atmospheric nucleation: on the recent advances on precursor characterization and atmospheric cluster composition in connection with atmospheric new particle formation.

    Science.gov (United States)

    Kulmala, M; Petäjä, T; Ehn, M; Thornton, J; Sipilä, M; Worsnop, D R; Kerminen, V-M

    2014-01-01

    The recent development in measurement techniques and theoretical understanding has enabled us to study atmospheric vapor, cluster and nanoparticle concentrations, dynamics, and their connection to atmospheric nucleation. Here we present a summary of the chemistry of atmospheric clustering, growing nanoparticles, and their precursors. In this work, we focus particularly on atmospheric gas-to-particle conversion and recent progress in its understanding.

  9. The effects of atmospheric chemistry on radiation budget in the Community Earth Systems Model

    Science.gov (United States)

    Choi, Y.; Czader, B.; Diao, L.; Rodriguez, J.; Jeong, G.

    2013-12-01

    The Community Earth Systems Model (CESM)-Whole Atmosphere Community Climate Model (WACCM) simulations were performed to study the impact of atmospheric chemistry on the radiation budget over the surface within a weather prediction time scale. The secondary goal is to get a simplified and optimized chemistry module for the short time period. Three different chemistry modules were utilized to represent tropospheric and stratospheric chemistry, which differ in how their reactions and species are represented: (1) simplified tropospheric and stratospheric chemistry (approximately 30 species), (2) simplified tropospheric chemistry and comprehensive stratospheric chemistry from the Model of Ozone and Related Chemical Tracers, version 3 (MOZART-3, approximately 60 species), and (3) comprehensive tropospheric and stratospheric chemistry (MOZART-4, approximately 120 species). Our results indicate the different details in chemistry treatment from these model components affect the surface temperature and impact the radiation budget.

  10. Importance of sulfate radical anion formation and chemistry in heterogeneous OH oxidation of sodium methyl sulfate, the smallest organosulfate

    Directory of Open Access Journals (Sweden)

    K. C. Kwong

    2018-02-01

    Full Text Available Organosulfates are important organosulfur compounds present in atmospheric particles. While the abundance, composition, and formation mechanisms of organosulfates have been extensively investigated, it remains unclear how they transform and evolve throughout their atmospheric lifetime. To acquire a fundamental understanding of how organosulfates chemically transform in the atmosphere, this work investigates the heterogeneous OH radical-initiated oxidation of sodium methyl sulfate (CH3SO4Na droplets, the smallest organosulfate detected in atmospheric particles, using an aerosol flow tube reactor at a high relative humidity (RH of 85 %. Aerosol mass spectra measured by a soft atmospheric pressure ionization source (direct analysis in real time, DART coupled with a high-resolution mass spectrometer showed that neither functionalization nor fragmentation products are detected. Instead, the ion signal intensity of the bisulfate ion (HSO4− has been found to increase significantly after OH oxidation. We postulate that sodium methyl sulfate tends to fragment into a formaldehyde (CH2O and a sulfate radical anion (SO4 ⋅ − upon OH oxidation. The formaldehyde is likely partitioned back to the gas phase due to its high volatility. The sulfate radical anion, similar to OH radical, can abstract a hydrogen atom from neighboring sodium methyl sulfate to form the bisulfate ion, contributing to the secondary chemistry. Kinetic measurements show that the heterogeneous OH reaction rate constant, k, is (3.79 ± 0.19  ×  10−13 cm3 molecule−1 s−1 with an effective OH uptake coefficient, γeff, of 0.17 ± 0.03. While about 40 % of sodium methyl sulfate is being oxidized at the maximum OH exposure (1.27  ×  1012 molecule cm−3 s, only a 3 % decrease in particle diameter is observed. This can be attributed to a small fraction of particle mass lost via the formation and volatilization of formaldehyde. Overall, we

  11. New directions: Mineral dust and ozone - Heterogeneous chemistry

    Science.gov (United States)

    Ramachandran, S.

    2015-04-01

    Aerosols, the tiny solid or liquid particles suspended in air and produced from natural sources and anthropogenic activities, continue to contribute the largest uncertainty to radiative forcing (IPCC, 2013). Aerosol particles give rise to radiative forcing directly through scattering and absorption of solar and infrared radiation in the atmosphere. Aerosols also give rise to indirect radiative forcing by modifying the cloud optical properties and lifetimes. Among the aerosol species mineral dust and black carbon cause a warming (positive forcing) while sulphate and sea salt cause a cooling (negative forcing) of the Earth-atmosphere system. In tropics and sub-tropics mineral dust is a major contributor to aerosol loading and optical thickness. The global source strength of dust aerosol varies significantly on spatial and temporal scales. The source regions of dust are mainly deserts, dry lake beds, and semi-arid regions, in addition to drier regions where vegetation has been reduced or soil surfaces that are disturbed by man made activities. Anthropogenic activities mainly related to agriculture such as harvesting, ploughing, overgrazing, and cement production and transport also produce mineral dust. An estimated 2500 terragram (Tg, 1012 g) of mineral dust is emitted into the atmosphere per year, and dominates the aerosol mass over continental regions in south Asia and China accounting for ∼35% of the total aerosol mass (IPCC, 2013). In India, dust is prevalent throughout the north and western India during the year and peaks during premonsoon season.

  12. Interrelation of chemistry and process design in biodiesel manufacturing by heterogeneous catalysis

    NARCIS (Netherlands)

    Dimian, A.C.; Srokol, Z.W.; Mittelmeijer-Hazeleger, M.C.; Rothenberg, G.

    2010-01-01

    The pros and cons of using heterogeneous catalysis for biodiesel manufacturing are introduced, and explained from a chemistry and engineering viewpoint. Transesterification reactions of various feed types are then compared in batch and continuous process operation modes. The results show that the

  13. Appendix C: First Global Observations of Atmospheric COClF from the Atmospheric Chemistry Experiment Mission

    Science.gov (United States)

    Fu, Djian; Boone, Chris D.; Bernath, Peter F.; Walker, Kaley A.; Rinsland, Curtis P.; Weisenstein, Debra K.; Manney, Gloria L.

    2009-01-01

    Carbonyl chlorofluoride (COCIF) is an important reservoir of chlorine and Fluorine in the Earth's atmosphere. Satellite-based remote sensing measurements of COCIF, obtained by Received in revised form the Atmospheric Chemistry Experiment (ACE) for a time period spanning February 2004 through April 2007, have been used in a global distribution study. There is a strong Accepted 18 February 2009 source region for COCIF in the tropical stratosphere near 27 km. A layer of enhanced COCIF spans the low- to mid-stratosphere over all latitudes, with volume mixing ratios of 40-100 parts Per trillion by volume, largest in the tropics and decreasing toward the poles. The COCIF volume mixing ratio profiles are nearly zonally symmetric, but they exhibit a small hemispheric asymmetry that likely arises from a hemispheric asymmetry in the parent molecule CCl3F. Comparisons are made with a set of in situ stratospheric measurements from the mid-1980s and with predictions from a 2-D model.

  14. Electrodynamic balance-mass spectrometry of single particles as a new platform for atmospheric chemistry research

    Science.gov (United States)

    Birdsall, Adam W.; Krieger, Ulrich K.; Keutsch, Frank N.

    2018-01-01

    New analytical techniques are needed to improve our understanding of the intertwined physical and chemical processes that affect the composition of aerosol particles in the Earth's atmosphere, such as gas-particle partitioning and homogenous or heterogeneous chemistry, and their ultimate relation to air quality and climate. We describe a new laboratory setup that couples an electrodynamic balance (EDB) to a mass spectrometer (MS). The EDB stores a single laboratory-generated particle in an electric field under atmospheric conditions for an arbitrarily long length of time. The particle is then transferred via gas flow to an ionization region that vaporizes and ionizes the analyte molecules before MS measurement. We demonstrate the feasibility of the technique by tracking evaporation of polyethylene glycol molecules and finding agreement with a kinetic model. Fitting data to the kinetic model also allows determination of vapor pressures to within a factor of 2. This EDB-MS system can be used to study fundamental chemical and physical processes involving particles that are difficult to isolate and study with other techniques. The results of such measurements can be used to improve our understanding of atmospheric particles.

  15. EPR approaches to heterogeneous catalysis. The chemistry of titanium in heterogeneous catalysts and photocatalysts.

    Science.gov (United States)

    Morra, Elena; Giamello, Elio; Chiesa, Mario

    2017-07-01

    Paramagnetic species are often involved in catalytic or photocatalytic reactions occurring at the solid-gas interface of heterogeneous catalysts. In this contribution we will provide an overview of the wealth and breadth of information that can be obtained from EPR in the characterization of paramagnetic species in such systems, illustrating the advantages that modern pulsed EPR methodologies can offer in monitoring the elementary processes occurring within the coordination sphere of surface transition-metal ions. To do so we selected three representative systems, where titanium ions in low oxidation states act as active catalytic sites, trying to outline the methodological approaches which characterize the application of EPR techniques and the questions that can be answered and addressed relative to the characterization of heterogeneous catalytic materials. Copyright © 2017 Elsevier Inc. All rights reserved.

  16. EPR approaches to heterogeneous catalysis. The chemistry of titanium in heterogeneous catalysts and photocatalysts

    Science.gov (United States)

    Morra, Elena; Giamello, Elio; Chiesa, Mario

    2017-07-01

    Paramagnetic species are often involved in catalytic or photocatalytic reactions occurring at the solid-gas interface of heterogeneous catalysts. In this contribution we will provide an overview of the wealth and breadth of information that can be obtained from EPR in the characterization of paramagnetic species in such systems, illustrating the advantages that modern pulsed EPR methodologies can offer in monitoring the elementary processes occurring within the coordination sphere of surface transition-metal ions. To do so we selected three representative systems, where titanium ions in low oxidation states act as active catalytic sites, trying to outline the methodological approaches which characterize the application of EPR techniques and the questions that can be answered and addressed relative to the characterization of heterogeneous catalytic materials.

  17. Laboratory Investigations of Heterogeneous Chemistry Important to Ozone Depletion in the Stratosphere

    Science.gov (United States)

    Zhang, Renyi

    Results of laboratory investigations of heterogeneous chemistry important to ozone depletion in the stratosphere are presented. Thermodynamic properties (such as melting points, enthalpies of fusion, etc.) for acids which are present in the stratosphere (HCl, HNO_3 , and H_2SO_4 ) are studied using laboratory-assembled apparatus of electrical conductivity and differential thermal analysis and using a commercial differential scanning calorimeter (DSC). Vapor pressures and infrared spectra of liquid and supercooled solutions, and of liquid-solid and solid -solid coexistence mixtures for the HCl/H_2 O and H_2SO_4 /H_2O binary systems are investigated. Equilibrium constants and standard enthalpies of formation for the pure crystalline hydrates of those acids as well as their corresponding liquid compositions are determined from the vapor pressure and calorimetric data. A theoretical approach, which allows determination of vapor pressures for two adjacent hydrates in thermodynamic equilibrium and for the coexistence systems involving a hydrate and ice in a binary system, is presented in terms of chemical equilibrium principles and compared with the experimental data for thermodynamic consistence. Vapor pressures of HNO_3 and HCl over H_2SO_4 /HNO_3/H_2 O and H_2SO_4 /HCl/H_2O solutions as well as over H_2SO_4/HNO _3/HCl/H_2O solutions are also measured in order to predict incorporation of stratospheric acids into the background sulfate aerosols. From the data, the Henry's law solubility constants for those systems are determined and the equilibrium compositions of aqueous stratospheric aerosols are predicted as a function of ambient temperature and mixing ratios of H_2 O and HNO_3. The results indicate that at the low temperatures characteristic of the stratosphere at high latitudes in the winter and spring, the HNO_3 content reaches levels of the order of 10% wt in the background sulfate aerosols. The results also reveal that the amount of dissolved HCl in the

  18. Size-resolved aqueous-phase atmospheric chemistry in a three-dimensional chemical transport model

    Science.gov (United States)

    Fahey, K. M.; Pandis, S. N.

    2003-11-01

    Three-dimensional chemical transport models typically include a bulk description of aqueous-phase atmospheric chemistry. Previously, this bulk description has been shown to be often inadequate in predicting sulfate production. The pH of the bulk mixture does not adequately describe the pH of the typically heterogeneous droplet population found in clouds and fogs. This often leads to an inability of bulk models to predict sulfate production when pH-dependent production pathways are important. A more accurate size-resolved aqueous-phase chemistry model, however, has long been considered infeasible for incorporation in a three-dimensional chemical transport model because of high computational costs. Here we investigate the feasibility of adding a computationally efficient size-resolved aqueous-phase chemistry module (Variable Size Resolution Model (VSRM)) to a three-dimensional model (the latest version of the Comprehensive Air Quality Model with extensions (PMCAMx)). The VSRM treats mass transfer between the gas phase and the different droplet populations and executes bulk or two-section size-resolved chemistry calculations in each step on the basis of the chemical environment of each computational cell. A fall air pollution episode in California's South Coast Air Basin is simulated, and model predictions are compared to observations. In an environment where clouds or fogs are present, the model without aqueous-phase chemistry severely underpredicts secondary sulfate formation. In cases where there is a high potential for sulfate production and widely varying composition across the droplet spectrum (over the ocean and near the coast), there is a significant increase in sulfate production over bulk predictions with the activation of a size-resolved aqueous-phase chemistry module. Unfortunately, measurements were only available at inland sites, where the difference between bulk and size-resolved sulfate predictions was small. The effects of other uncertainties on

  19. Hydrogen chloride heterogeneous chemistry on frozen water particles in subsonic aircraft plume. Laboratory studies and modelling

    Energy Technology Data Exchange (ETDEWEB)

    Persiantseva, N.V.; Popovitcheva, O.B.; Rakhimova, T.V. [Moscow State Univ. (Russian Federation)

    1997-12-31

    Heterogeneous chemistry of HCl, as a main reservoir of chlorine content gases, has been considered after plume cooling and ice particle formation. The HCl, HNO{sub 3}, N{sub 2}O{sub 5} uptake efficiencies by frozen water were obtained in a Knudsen-cell flow reactor at the subsonic cruise conditions. The formation of ice particles in the plume of subsonic aircraft is simulated to describe the kinetics of gaseous HCl loss due to heterogeneous processes. It is shown that the HCl uptake by frozen water particles may play an important role in the gaseous HCl depletion in the aircraft plume. (author) 14 refs.

  20. Non-OH chemistry in oxidation flow reactors for the study of atmospheric chemistry systematically examined by modeling

    OpenAIRE

    Peng, Zhe; Day, Douglas A.; Ortega, Amber M.; Palm, Brett B.; Hu, Weiwei; Stark, Harald; Li, Rui; Tsigaridis, Kostas; Brune, William H.; Jimenez, Jose L.

    2016-01-01

    Oxidation flow reactors (OFRs) using low-pressure Hg lamp emission at 185 and 254 nm produce OH radicals efficiently and are widely used in atmospheric chemistry and other fields. However, knowledge of detailed OFR chemistry is limited, allowing speculation in the literature about whether some non-OH reactants, including several not relevant for tropospheric chemistry, may play an important role in these OFRs. These non-OH reactants are UV radiation, O(1D), O(3P), and O3. In...

  1. Validation of ozone measurements from the Atmospheric Chemistry Experiment (ACE

    Directory of Open Access Journals (Sweden)

    E. Dupuy

    2009-01-01

    Full Text Available This paper presents extensive {bias determination} analyses of ozone observations from the Atmospheric Chemistry Experiment (ACE satellite instruments: the ACE Fourier Transform Spectrometer (ACE-FTS and the Measurement of Aerosol Extinction in the Stratosphere and Troposphere Retrieved by Occultation (ACE-MAESTRO instrument. Here we compare the latest ozone data products from ACE-FTS and ACE-MAESTRO with coincident observations from nearly 20 satellite-borne, airborne, balloon-borne and ground-based instruments, by analysing volume mixing ratio profiles and partial column densities. The ACE-FTS version 2.2 Ozone Update product reports more ozone than most correlative measurements from the upper troposphere to the lower mesosphere. At altitude levels from 16 to 44 km, the average values of the mean relative differences are nearly all within +1 to +8%. At higher altitudes (45–60 km, the ACE-FTS ozone amounts are significantly larger than those of the comparison instruments, with mean relative differences of up to +40% (about +20% on average. For the ACE-MAESTRO version 1.2 ozone data product, mean relative differences are within ±10% (average values within ±6% between 18 and 40 km for both the sunrise and sunset measurements. At higher altitudes (~35–55 km, systematic biases of opposite sign are found between the ACE-MAESTRO sunrise and sunset observations. While ozone amounts derived from the ACE-MAESTRO sunrise occultation data are often smaller than the coincident observations (with mean relative differences down to −10%, the sunset occultation profiles for ACE-MAESTRO show results that are qualitatively similar to ACE-FTS, indicating a large positive bias (mean relative differences within +10 to +30% in the 45–55 km altitude range. In contrast, there is no significant systematic difference in bias found for the ACE-FTS sunrise and sunset measurements.

  2. A comparison of atmospheric composition using the Carbon Bond and Regional Atmospheric Chemistry Mechanisms

    Science.gov (United States)

    Sarwar, G.; Godowitch, J.; Henderson, B. H.; Fahey, K.; Pouliot, G.; Hutzell, W. T.; Mathur, R.; Kang, D.; Goliff, W. S.; Stockwell, W. R.

    2013-10-01

    We incorporate the recently developed Regional Atmospheric Chemistry Mechanism (version 2, RACM2) into the Community Multiscale Air Quality modeling system for comparison with the existing 2005 Carbon Bond mechanism with updated toluene chemistry (CB05TU). Compared to CB05TU, RACM2 enhances the domain-wide monthly mean hydroxyl radical concentrations by 46% and nitric acid by 26%. However, it reduces hydrogen peroxide by 2%, peroxyacetic acid by 94%, methyl hydrogen peroxide by 19%, peroxyacetyl nitrate by 40%, and organic nitrate by 41%. RACM2 enhances ozone compared to CB05TU at all ambient levels. Although it exhibited greater overestimates at lower observed concentrations, it displayed an improved performance at higher observed concentrations. The RACM2 ozone predictions are also supported by increased ozone production efficiency that agrees better with observations. Compared to CB05TU, RACM2 enhances the domain-wide monthly mean sulfate by 10%, nitrate by 6%, ammonium by 10%, anthropogenic secondary organic aerosols by 42%, biogenic secondary organic aerosols by 5%, and in-cloud secondary organic aerosols by 7%. Increased inorganic and organic aerosols with RACM2 agree better with observed data. Any air pollution control strategies developed using the two mechanisms do not differ appreciably.

  3. A comparison of atmospheric composition using the Carbon Bond and Regional Atmospheric Chemistry Mechanisms

    Directory of Open Access Journals (Sweden)

    G. Sarwar

    2013-10-01

    Full Text Available We incorporate the recently developed Regional Atmospheric Chemistry Mechanism (version 2, RACM2 into the Community Multiscale Air Quality modeling system for comparison with the existing 2005 Carbon Bond mechanism with updated toluene chemistry (CB05TU. Compared to CB05TU, RACM2 enhances the domain-wide monthly mean hydroxyl radical concentrations by 46% and nitric acid by 26%. However, it reduces hydrogen peroxide by 2%, peroxyacetic acid by 94%, methyl hydrogen peroxide by 19%, peroxyacetyl nitrate by 40%, and organic nitrate by 41%. RACM2 enhances ozone compared to CB05TU at all ambient levels. Although it exhibited greater overestimates at lower observed concentrations, it displayed an improved performance at higher observed concentrations. The RACM2 ozone predictions are also supported by increased ozone production efficiency that agrees better with observations. Compared to CB05TU, RACM2 enhances the domain-wide monthly mean sulfate by 10%, nitrate by 6%, ammonium by 10%, anthropogenic secondary organic aerosols by 42%, biogenic secondary organic aerosols by 5%, and in-cloud secondary organic aerosols by 7%. Increased inorganic and organic aerosols with RACM2 agree better with observed data. Any air pollution control strategies developed using the two mechanisms do not differ appreciably.

  4. The Chemistry of Atmosphere-Forest Exchange (CAFE) Model - Part 2: Application to BEARPEX-2007 observations

    National Research Council Canada - National Science Library

    G. M. Wolfe; J. A. Thornton; N. C. Bouvier-Brown; A. H. Goldstein; J.-H. Park; M. McKay; D. M. Matross; J. Mao; W. H. Brune; B. W. LaFranchi; E. C. Browne; K.-E. Min; P. J. Wooldridge; R. C. Cohen; J. D. Crounse; I. C. Faloona; J. B. Gilman; W. C. Kuster; J. A. de Gouw; A. Huisman; F. N. Keutsch

    2011-01-01

    In a companion paper, we introduced the Chemistry of Atmosphere-Forest Exchange (CAFE) model, a vertically-resolved 1-D chemical transport model designed to probe the details of near-surface reactive gas exchange...

  5. The impact of Future Land Use and Land Cover Changes on Atmospheric Chemistry-Climate Interactions

    NARCIS (Netherlands)

    Ganzeveld, L.N.; Bouwman, L.

    2010-01-01

    To demonstrate potential future consequences of land cover and land use changes beyond those for physical climate and the carbon cycle, we present an analysis of large-scale impacts of land cover and land use changes on atmospheric chemistry using the chemistry-climate model EMAC (ECHAM5/MESSy

  6. Using high-frequency sampling to detect effects of atmospheric pollutants on stream chemistry

    Science.gov (United States)

    Stephen D. Sebestyen; James B. Shanley; Elizabeth W. Boyer

    2009-01-01

    We combined information from long-term (weekly over many years) and short-term (high-frequency during rainfall and snowmelt events) stream water sampling efforts to understand how atmospheric deposition affects stream chemistry. Water samples were collected at the Sleepers River Research Watershed, VT, a temperate upland forest site that receives elevated atmospheric...

  7. The Development of a Combined Search for a Heterogeneous Chemistry Database

    Directory of Open Access Journals (Sweden)

    Lulu Jiang

    2015-05-01

    Full Text Available A combined search, which joins a slow molecule structure search with a fast compound property search, results in more accurate search results and has been applied in several chemistry databases. However, the problems of search speed differences and combining the two separate search results are two major challenges. In this paper, two kinds of search strategies, synchronous search and asynchronous search, are proposed to solve these problems in the heterogeneous structure database and the property database found in ChemDB, a chemistry database owned by the Institute of Process Engineering, CAS. Their advantages and disadvantages under different conditions are discussed in detail. Furthermore, we applied these two searches to ChemDB and used them to screen for potential molecules that can work as CO2 absorbents. The results reveal that this combined search discovers reasonable target molecules within an acceptable time frame.

  8. Cation Chemistry in Titan's Upper Atmosphere and its Influence on Tholin Formation

    Science.gov (United States)

    Dubois, D.; Carrasco, N.; Jovanovic, L.; Vettier, L.

    2017-09-01

    Titan is the only moon in our solar system to have a thick atmosphere. This atmosphere is made of molecular nitrogen and methane. These molecules are broken apart and dissociated in the upper atmosphere, and can then start an intense and complex organic chemistry. This chemistry can be neutral species, or ions. The ions are studied here, in particular the cations, which have been shown to be present in the ionosphere. To investigate this, we turn to laboratory simulations, and reproduce ionosphere conditions using a plasma reactor. We then compare our results with actual Cassini-INMS (Ion Neutral Mass Spectrometer) data obtained at Titan.

  9. News from Online: In a Planet, Not a Test Tube: Atmospheric Chemistry

    Science.gov (United States)

    Michalovic, Mark

    2003-04-01

    Atmospheric chemistry covers many topics including the gas laws, chemical reactions, kinetics, and catalysis. The article reviews some of the materials available online for teaching chemistry through exploration of the atmosphere. Included are web sites dealing with ozone depletion caused by chlorofluorocarbons and the green house effect and global warming related to the presence of naturally-occurring and human-made compounds in the air. Also covered are materials dealing with the extraterrestrial chemistry in the atmospheres of other worlds, including Venus with its choking, high-pressure carbon dioxide and sulfuric acid atmosphere and Saturn's moon Titan, whose dense nitrogen blanket harbors hydrocarbons and other compounds thought necessary for life to develop.

  10. A photochemical reactor for studies of atmospheric chemistry

    DEFF Research Database (Denmark)

    Nilsson, Elna Johanna Kristina; Eskebjerg, Carsten; Johnson, Matthew Stanley

    2009-01-01

    A photochemical reactor for studies of atmospheric kinetics and spectroscopy has been built at the Copenhagen Center for Atmospheric Research. The reactor consists of a vacuum FTIR spectrometer coupled to a 100 L quartz cylinder by multipass optics mounted on electropolished stainless steel end...

  11. Experimental and Theoretical Studies of Atmosphereic Inorganic Chlorine Chemistry

    Science.gov (United States)

    Sander, Stanley P.; Friedl, Randall R.

    1993-01-01

    Over the last five years substantial progress has been made in defining the realm of new chlorine chemistry in the polar stratosphere. Application of existing experimental techniques to potentially important chlorine-containing compounds has yielded quantitative kinetic and spectroscopic data as well as qualitative mechanistic insights into the relevant reactions.

  12. Results of an interactively coupled atmospheric chemistry – general circulation model: Comparison with observations

    Directory of Open Access Journals (Sweden)

    R. Hein

    Full Text Available The coupled climate-chemistry model ECHAM4.L39(DLR/CHEM is presented which enables a simultaneous treatment of meteorology and atmospheric chemistry and their feedbacks. This is the first model which interactively combines a general circulation model with a chemical model, employing most of the important reactions and species necessary to describe the stratospheric and upper tropospheric ozone chemistry, and which is computationally fast enough to allow long-term integrations with currently available computer resources. This is possible as the model time-step used for the chemistry can be chosen as large as the integration time-step for the dynamics. Vertically the atmosphere is discretized by 39 levels from the surface up to the top layer which is centred at 10 hPa, with a relatively high vertical resolution of approximately 700 m near the extra-tropical tropopause. We present the results of a control simulation representing recent conditions (1990 and compare it to available observations. The focus is on investigations of stratospheric dynamics and chemistry relevant to describe the stratospheric ozone layer. ECHAM4.L39(DLR/CHEM reproduces main features of stratospheric dynamics in the arctic vortex region, including stratospheric warming events. This constitutes a major improvement compared to earlier model versions. However, apparent shortcomings in Antarctic circulation and temperatures persist. The seasonal and interannual variability of the ozone layer is simulated in accordance with observations. Activation and deactivation of chlorine in the polar stratospheric vortices and their inter-hemispheric differences are reproduced. Considering methane oxidation as part of the dynamic-chemistry feedback results in an improved representation of the spatial distribution of stratospheric water vapour concentrations. The current model constitutes a powerful tool to investigate, for instance, the combined direct and indirect effects of anthropogenic

  13. Atmospheric Chemistry from Space: Present Status and Future Plans

    Science.gov (United States)

    Schoeberl, Mark R.; Einaudi, Franco (Technical Monitor)

    2001-01-01

    One of the unqualified successes of the earth observation program is NASA's continuing monitoring of the ozone layer from space. This activity began in the early 70's with research instruments and continues to this day with the TOMS instrument series and the Upper Atmosphere Research Satellite. In the near future, NASA will be launching the EOS Aura spacecraft (launch mid-2003) which will continue our study of the chemical processes that produce stratospheric ozone depletion. In addition, Aura will begin the first global study of lower atmospheric air pollution including urban ozone, aerosols, nitrogen oxides and carbon monoxide. Atmospheric air pollution measurements from earth orbit involve the development of very high precision spectrometer technologies that have never been flown in space. Farther into the future, lower atmospheric ozone and aerosols may be monitored by space based lidars in low earth orbit, by sensors in geostationary orbit and by continuous limb observations instrument from the Lagrange point L2.

  14. Vesper - Venus Chemistry and Dynamics Orbiter - A NASA Discovery Mission Proposal: Submillimeter Investigation of Atmospheric Chemistry and Dynamics

    Science.gov (United States)

    Chin, Gordon

    2011-01-01

    Vesper conducts a focused investigation of the chemistry and dynamics of the middle atmosphere of our sister planet- from the base of the global cloud cover to the lower thermosphere. The middle atmosphere controls the stability of the Venus climate system. Vesper determines what processes maintain the atmospheric chemical stability, cause observed variability of chemical composition, control the escape of water, and drive the extreme super-rotation. The Vesper science investigation provides a unique perspective on the Earth environment due to the similarities in the middle atmosphere processes of both Venus and the Earth. Understanding key distinctions and similarities between Venus and Earth will increase our knowledge of how terrestrial planets evolve along different paths from nearly identical initial conditions.

  15. Single-Site Heterogeneous Catalysts: Innovations, Advantages, and Future Potential in Green Chemistry and Sustainable Technology

    Science.gov (United States)

    Raja, Robert; Thomas, John Meurig

    The advantages that flow from the availability of single-site heterogeneous catalysts are many. They facilitate the determination of the kinetics and mechanism of catalytic turnover and render accessible the energetics of various intermediates. More importantly, it is possible to prepare soluble molecular fragments that circumscribe the single site, thus enabling a direct comparison to be made between the catalytic performance of the same active site when functioning as a heterogeneous or a homogeneous catalyst. Our approach adopts the principles and practices of solid-state chemistry, augmented by lessons derived from enzymology, as well as computational chemistry. We have succeeded in designing a range of new catalysts to effect, inter alia, shape-selective, regioselective, bifunctional, and enantioselective catalytic conversions. In particular, large fractions of these catalysts are ideally suited for the era of clean technology in which single-step and/or solvent-free processes abound, and in which benign oxidants such as air or oxygen and inexpensive nanoporous materials are employed.

  16. The influence of small-scale variations in isoprene concentrations on atmospheric chemistry over a tropical rainforest

    Directory of Open Access Journals (Sweden)

    T. A. M. Pugh

    2011-05-01

    Full Text Available Biogenic volatile organic compounds (BVOCs such as isoprene constitute a large proportion of the global atmospheric oxidant sink. Their reactions in the atmosphere contribute to processes such as ozone production and secondary organic aerosol formation. However, over the tropical rainforest, where 50 % of the global emissions of BVOCs are believed to occur, atmospheric chemistry models have been unable to simulate concurrently the measured daytime concentration of isoprene and that of its principal oxidant, hydroxyl (OH. One reason for this model-measurement discrepancy may be incomplete mixing of isoprene within the convective boundary layer, leading to patchiness or segregation in isoprene and OH mixing ratios and average concentrations that appear to be incompatible with each other. One way of capturing this effect in models of atmospheric chemistry is to use a reduced effective rate constant for their reaction. Recent studies comparing atmospheric chemistry global/box models with field measurements have suggested that this effective rate reduction may be as large as 50 %; which is at the upper limit of that calculated using large eddy simulation models. To date there has only been one field campaign worldwide that has reported co-located measurements of isoprene and OH at the necessary temporal resolution to calculate the segregation of these compounds. However many campaigns have recorded sufficiently high resolution isoprene measurements to capture the small-scale fluctuations in its concentration. Assuming uniform distributions of other OH production and loss processes, we use a box model of atmospheric chemistry, constrained by the spectrum of isoprene concentrations measured, as a virtual instrument, to estimate the variability in OH at a point and hence, to estimate the segregation intensity of isoprene and OH from high-frequency isoprene time series. The method successfully reproduces the only directly observed segregation, using

  17. NASA's Upper Atmosphere Research Program (UARP) and Atmospheric Chemistry Modeling and Analysis Program (ACMAP): Research Summaries 1997-1999

    Science.gov (United States)

    Kurylo, M. J.; DeCola, P. L.; Kaye, J. A.

    2000-01-01

    Under the mandate contained in the FY 1976 NASA Authorization Act, the National Aeronautics and Space Administration (NASA) has developed and is implementing a comprehensive program of research, technology development, and monitoring of the Earth's upper atmosphere, with emphasis on the upper troposphere and stratosphere. This program aims at expanding our chemical and physical understanding to permit both the quantitative analysis of current perturbations as well as the assessment of possible future changes in this important region of our environment. It is carried out jointly by the Upper Atmosphere Research Program (UARP) and the Atmospheric Chemistry Modeling and Analysis Program (ACMAP), both managed within the Research Division in the Office of Earth Science at NASA. Significant contributions to this effort have also been provided by the Atmospheric Effects of Aviation Project (AEAP) of NASA's Office of Aero-Space Technology. The long-term objectives of the present program are to perform research to: understand the physics, chemistry, and transport processes of the upper troposphere and the stratosphere and their control on the distribution of atmospheric chemical species such as ozone; assess possible perturbations to the composition of the atmosphere caused by human activities and natural phenomena (with a specific emphasis on trace gas geographical distributions, sources, and sinks and the role of trace gases in defining the chemical composition of the upper atmosphere); understand the processes affecting the distributions of radiatively active species in the atmosphere, and the importance of chemical-radiative-dynamical feedbacks on the meteorology and climatology of the stratosphere and troposphere; and understand ozone production, loss, and recovery in an atmosphere with increasing abundances of greenhouse gases. The current report is composed of two parts. Part 1 summarizes the objectives, status, and accomplishments of the research tasks supported

  18. Seasonal changes in Titan's middle-atmosphere chemistry and dynamics

    Science.gov (United States)

    Teanby, N. A.; Irwin, P. G. J.; Nixon, C. A.; de Kok, R.; Vinatier, S.; Coustenis, A.; Sefton-Nash, E.; Calcutt, S. B.; Flasar, F. M.

    2013-09-01

    Titan is the largest satellite of Saturn and is the only moon in our solar system with a significant atmo- sphere. Titan's middle-atmosphere (stratosphere and mesosphere) circulation usually comprises a single hemisphere to hemisphere meridional circulation cell, with upwelling air in the summer hemisphere and sub- siding air at the winter pole with an associated winter polar vortex. Titan has an axial tilt (obliquity) of 26.7°, so during its 29.5 Earth year annual cycle pronounced seasonal effects are encountered as the relative solar insolation in each hemisphere changes. The most dramatic of these changes is the reversal in global meridional circulation as the peak solar heating switches hemispheres after an equinox. Titan's northern spring equinox occurred in August 2009, and since then many middle-atmosphere changes have been observed by Cassini that were previously impossible to study (1,2,3,4). Here we present a detailed analysis of the post equinox changes in middle-atmosphere temperature and composition measured with Cassini's Composite InfraRed Spectrometer (CIRS), use these to infer changes in atmospheric circulation, and explore implications for atmospheric photochemical and dynamical processes. Our results show that the meridional circulation has now reversed (1).

  19. Non-Equilibrium Thermodynamic Chemistry and the Composition of the Atmosphere of Mars

    Science.gov (United States)

    Levine, J. S.; Summers, M. E.

    2003-01-01

    A high priority objective of the Mars Exploration Program is to Determine if life exists today (MEPAG Goal I, Objective A). The measurement of gases of biogenic origin may be an approach to detect the presence of microbial life on the surface or subsurface of Mars. Chemical thermodynamic calculations indicate that on both Earth and Mars, certain gases should exist in extremely low concentrations, if at all. Microbial metabolic activity is an important non-equilibrium chemistry process on Earth, and if microbial life exists on Mars, may be an important nonequilibrium chemistry process on Mars. The non-equilibrium chemistry of the atmosphere of Mars is discussed in this paper.

  20. A numerical study for global atmospheric transport-chemistry problems

    NARCIS (Netherlands)

    E.J. Spee (Edwin); J.G. Verwer (Jan); P.M. de Zeeuw (Paul); J.G. Blom (Joke); W. Hundsdorfer (Willem)

    1998-01-01

    htmlabstractAtmospheric air quality modeling relies in part on numerical simulation. Required numerical simulations are often hampered by lack of computer capacity and computational speed. This problem is most severe in the field of global modeling where transport and exchange of trace constituents

  1. Isoprene nitrates: preparation, separation, identification, yields, and atmospheric chemistry

    Directory of Open Access Journals (Sweden)

    A. L. Lockwood

    2010-07-01

    Full Text Available Isoprene is an important atmospheric volatile organic compound involved in ozone production and NOx (NO+NO2 sequestration and transport. Isoprene reaction with OH in the presence of NO can form either isoprene hydroxy nitrates ("isoprene nitrates" or convert NO to NO2 which can photolyze to form ozone. While it has been shown that isoprene nitrate production can represent an important sink for NOx in forest impacted environments, there is little experimental knowledge of the relative importance of the individual isoprene nitrate isomers, each of which has a different fate and reactivity. In this work, we have identified the 8 individual isomers and determined their total and individual production yields. The overall yield of isoprene nitrates at atmospheric pressure and 295 K was found to be 0.070(+0.025/−0.015. Three isomers, representing nitrates resulting from OH addition to a terminal carbon, represent 90% of the total IN yield. We also determined the ozone rate constants for three of the isomers, and have calculated their atmospheric lifetimes, which range from ~1–2 h, making their oxidation products likely more important as atmospheric organic nitrates and sinks for nitrogen.

  2. Atmospheric chemistry of CH3CHF2 (HFC-152a)

    DEFF Research Database (Denmark)

    Taketani, Fumikazu; Nakayama, Tomoki; Takahashi, Kenshi

    2005-01-01

    Smog chamber/Fourier transform infrared (FTIR) and laser-induced fluorescence (LIF) spectroscopic techniques were used to study the atmospheric degradation of CH3CHF2. The kinetics and products of the Cl(2P(3/2)) (denoted Cl) atom- and the OH radical-initiated oxidation of CH3CHF2 in 700 Torr...

  3. Strong atmospheric chemistry feedback to climate warming from Arctic methane emissions

    Science.gov (United States)

    Isaksen, Ivar S.A.; Gauss, Michael; Myhre, Gunnar; Walter Anthony, Katey M.; Ruppel, Carolyn

    2011-01-01

    The magnitude and feedbacks of future methane release from the Arctic region are unknown. Despite limited documentation of potential future releases associated with thawing permafrost and degassing methane hydrates, the large potential for future methane releases calls for improved understanding of the interaction of a changing climate with processes in the Arctic and chemical feedbacks in the atmosphere. Here we apply a “state of the art” atmospheric chemistry transport model to show that large emissions of CH4 would likely have an unexpectedly large impact on the chemical composition of the atmosphere and on radiative forcing (RF). The indirect contribution to RF of additional methane emission is particularly important. It is shown that if global methane emissions were to increase by factors of 2.5 and 5.2 above current emissions, the indirect contributions to RF would be about 250% and 400%, respectively, of the RF that can be attributed to directly emitted methane alone. Assuming several hypothetical scenarios of CH4 release associated with permafrost thaw, shallow marine hydrate degassing, and submarine landslides, we find a strong positive feedback on RF through atmospheric chemistry. In particular, the impact of CH4 is enhanced through increase of its lifetime, and of atmospheric abundances of ozone, stratospheric water vapor, and CO2 as a result of atmospheric chemical processes. Despite uncertainties in emission scenarios, our results provide a better understanding of the feedbacks in the atmospheric chemistry that would amplify climate warming.

  4. Coordinating interdisciplinary and international research through CATCH (The Cryosphere and ATmospheric CHemistry)

    Science.gov (United States)

    Thomas, Jennie L.; Murphy, Jennifer; Bartels-Rausch, Thorsten; Frey, Markus; McNeill, V. Faye; Shepson, Paul; Pratt, Kerri; Douglas, Tom; Willis, Megan; Abbatt, Jon; Jones, Anna; Anastasio, Cort; Matrai, Patricia; Nomura, Daiki; Kim, Kitae; Melamed, Megan L.

    2017-04-01

    CATCH is a new international activity co-sponsored by IGAC (International Global Atmospheric Chemistry) and SOLAS (Surface Ocean - Lower Atmosphere Study). As an emerging international activity established in 2016, the CATCH mission is to facilitate atmospheric chemistry research within the international community, with a focus on natural processes specific to cold regions of the Earth. Cryospheric processes are known to be important for atmospheric chemistry in the Polar regions as well as other cold regions, such as continental snowpack. These processes are strongly linked to global and local environmental change, for example, through changes in snow and sea ice cover and aerosol processing in cold regions. CATCH aims to coordinate and encourage international/interdisciplinary cooperation between scientists in order to better understand and predict: - The impacts of physical, chemical, biological, and ecological changes in sea ice and snow on atmospheric chemistry; - Aerosol formation and processing in cold regions; - Changes in the cryosphere that alter feedbacks between climate change and atmospheric chemistry; - Ice core records of global environmental change; - Cold region aerosols as cloud condensation nuclei and their impacts on cloud properties; - Impacts of microbiology on the biogeochemical cycling of elements in cold environments; and - Changes in cold region atmospheric gases and aerosols due to industrialization and climate change. In this presentation, the ways for linking modeling and measurements including observations in the Arctic through CATCH in the future will be explored. CATCH is seeking participation and guidance and engagement from the community, including how to best link to existing efforts, to meet these objectives and to define future directions.

  5. A heterogeneous chemistry model for acid rain`s effect on ozone

    Energy Technology Data Exchange (ETDEWEB)

    Ye, Tao [Univ. of New York, Stonybrook, NY (United States)

    1995-11-01

    A computer model for simulating heterogeneous reactions in cloud is developed to determine the S(IV) species` effect on ozone. Crutzen claims that NO{sub x}, HO{sub x} families and H{sub 2}CO in the troposphere can decrease ozone by 5 to 10%. However, is this claim valid for a SO{sub x} polluted atmosphere? The SO{sub x} family reacts with the ozone destroyers. These reactions seem to be significant enough to reduce the H{sub 2}CO`s destructive effect on ozone.

  6. Application of physical adsorption thermodynamics to heterogeneous chemistry on polar stratospheric clouds

    Science.gov (United States)

    Elliott, Scott; Turco, Richard P.; Toon, Owen B.; Hamill, Patrick

    1991-01-01

    Laboratory isotherms for the binding of several nonheterogeneously active atmospheric gases and for HCl to water ice are translated into adsorptive equilibrium constants and surface enthalpies. Extrapolation to polar conditions through the Clausius Clapeyron relation yields coverage estimates below the percent level for N2, Ar, CO2, and CO, suggesting that the crystal faces of type II stratospheric cloud particles may be regarded as clean with respect to these species. For HCl, and perhaps HF and HNO3, estimates rise to several percent, and the adsorbed layer may offer acid or proton sources alternate to the bulk solid for heterogeneous reactions with stratospheric nitrates. Measurements are lacking for many key atmospheric molecules on water ice, and almost entirely for nitric acid trihydrate as substrate. Adsorptive equilibria enter into gas to particle mass flux descriptions, and the binding energy determines rates for desorption of, and encounter between, potential surface reactants.

  7. Observational Constraints on the Chemistry and Dynamics of Exoplanet Atmospheres

    Science.gov (United States)

    Charbonneau, David

    2008-09-01

    The observational study of the atmospheres of exoplanets is now well underway, despite the fact that astronomers have not yet imaged these bodies directly. These advances are enabled by the discovery of planetary systems that are viewed nearly edge-on to our line-of-sight, such that the star and planet undergo periodic mutual eclipses. When the planet transits in front of the star, starlight passing through the outer scale heights of the atmosphere is attenuated in a wavelength-dependent fashion that encodes information about the atoms, molecules, and condensates that are present. Observations spanning times of secondary eclipse, when the planet passes out of view behind the star, permit the direct study of the planetary thermal emission and estimates of the dayside temperatures. Furthermore, by inverting the time-dependent changes in brightness as features on the planet rotate in and out of view, we have constructed longitudinally-resolved temperature maps. I will review these various rich datasets, which challenge our understanding of the atmospheres of Jovian planets under strong irradiation.

  8. Composition and Chemistry of the Neutral Atmosphere of Venus

    Science.gov (United States)

    Marcq, Emmanuel; Mills, Franklin P.; Parkinson, Christopher D.; Vandaele, Ann Carine

    2018-02-01

    This paper deals with the composition and chemical processes occurring in the neutral atmosphere of Venus. Since the last synthesis, observers as well as modellers have emphasised the spatial and temporal variability of minor species, going beyond a static and uniform picture that may have prevailed in the past. The outline of this paper acknowledges this situation and follows closely the different dimensions along which variability in composition can be observed: vertical, latitudinal, longitudinal, temporal. The strong differences between the atmosphere below and above the cloud layers also dictate the structure of this paper. Observational constraints, obtained from both Earth and Venus Express, as well as 1D, 2D and 3D models results obtained since 1997 are also extensively referred and commented by the authors. An non-exhaustive list of topics included follows: modelled and observed latitudinal and vertical profiles of CO and OCS below the clouds of Venus; vertical profiles of CO and SO2 above the clouds as observed by solar occultation and modelled; temporal and spatial variability of sulphur oxides above the clouds. As a conclusion, open questions and topics of interest for further studies are discussed.

  9. On the numerical treatment of problems in atmospheric chemistry

    Energy Technology Data Exchange (ETDEWEB)

    Aro, Colin J. [Univ. of California, Davis, CA (United States)

    1995-09-01

    Atmospheric chemical-radiative-transport (CRT) models are vital in performing research on atmospheric chemical change. Even with the enormous computing capability delivered by massively parallel systems, extended three dimensional CRT simulations are still not computationally feasible. The major obstacle in a CRT model is the nonlinear ODE system describing the chemical kinetics in the model. These ODE systems are usually very stiff and account for anywhere from 75% to 90% of the CPU time required to run a CRT model. In this study, a simple explicit class of time stepping method is developed and demonstrated to be useful in treating chemical ODE systems without the use of a Jacobian matrix. These methods, called preconditioned time differencing methods, are tested on small mathematically idealized problems, box model problems, and full 2-D and 3-D CRT models. The methods are found to be both fast and memory efficient. Studies are performed on both vector and parallel systems. The preconditioned time differencing methods are established as a viable alternative to the more common backward differentiation formulas in terms of CPU speed across architectural platforms.

  10. On the atmospheric chemistry of NO2 - O3 systems : a laboratory study

    NARCIS (Netherlands)

    Verhees, P.W.C.

    1986-01-01

    In this dissertation a laboratory study dealing with the atmospheric chemistry of NO 2 -O 3 systems is described. Knowledge of this system is relevant for a better

  11. Modelling iodide – iodate speciation in atmospheric aerosol: Contributions of inorganic and organic iodine chemistry

    Directory of Open Access Journals (Sweden)

    S. Pechtl

    2007-01-01

    Full Text Available The speciation of iodine in atmospheric aerosol is currently poorly understood. Models predict negligible iodide concentrations but accumulation of iodate in aerosol, both of which is not confirmed by recent measurements. We present an updated aqueous phase iodine chemistry scheme for use in atmospheric chemistry models and discuss sensitivity studies with the marine boundary layer model MISTRA. These studies show that iodate can be reduced in acidic aerosol by inorganic reactions, i.e., iodate does not necessarily accumulate in particles. Furthermore, the transformation of particulate iodide to volatile iodine species likely has been overestimated in previous model studies due to negligence of collision-induced upper limits for the reaction rates. However, inorganic reaction cycles still do not seem to be sufficient to reproduce the observed range of iodide – iodate speciation in atmospheric aerosol. Therefore, we also investigate the effects of the recently suggested reaction of HOI with dissolved organic matter to produce iodide. If this reaction is fast enough to compete with the inorganic mechanism, it would not only directly lead to enhanced iodide concentrations but, indirectly via speed-up of the inorganic iodate reduction cycles, also to a decrease in iodate concentrations. Hence, according to our model studies, organic iodine chemistry, combined with inorganic reaction cycles, is able to reproduce observations. The presented chemistry cycles are highly dependent on pH and thus offer an explanation for the large observed variability of the iodide – iodate speciation in atmospheric aerosol.

  12. Bunsen conference 1999. Atmospheric physical chemistry; Bunsentagung 1999. Physikalische Chemie der Atmosphaere

    Energy Technology Data Exchange (ETDEWEB)

    Crutzen, P.J.; Zellner, R. [comps.

    2000-07-01

    The main subject of the 1999 Bunsen conference was atmospheric physical chemistry. There were lectures and posters on measurement and distribution of atmospheric trace gases, photochemical reactions in the different parts of the atmosphere, natural and anthropogenic emissions resulting from biomass combustion, thermodynamics and microphysics of aerosol, and air pollution abatement. [German] Die Bunsentagung 1999 beschaeftigte sich mit dem Thema Physikalische Chemie der Atmosphaere. Themen der Vortraege und Poster waren u.a. die Messung und Verteilung von Spurengasen in der Atmosphaere, photochemische Reaktionen in den verschiedenen Schichten der Atmosphaere, natuerliche und anthropogene Emissionen durch Verbrennung von Biomasse, Thermodynamik und Microphysik von Aerosolen und Klimaschutz.

  13. The atmospheric chemistry box model CAABA/MECCA-3.0

    Directory of Open Access Journals (Sweden)

    R. Sander

    2011-05-01

    Full Text Available We present version 3.0 of the atmospheric chemistry box model CAABA/MECCA. In addition to a complete update of the rate coefficients to the most recent recommendations, a number of new features have been added: chemistry in multiple aerosol size bins; automatic multiple simulations reaching steady-state conditions; Monte-Carlo simulations with randomly varied rate coefficients within their experimental uncertainties; calculations along Lagrangian trajectories; mercury chemistry; more detailed isoprene chemistry; tagging of isotopically labeled species. Further changes have been implemented to make the code more user-friendly and to facilitate the analysis of the model results. Like earlier versions, CAABA/MECCA-3.0 is a community model published under the GNU General Public License.

  14. Ten years of measurements from the Atmospheric Chemistry Experiment Satellite Mission

    Science.gov (United States)

    Walker, Kaley; McElroy, C. Thomas; Bernath, Peter F.; Boone, Chris

    Recently, the Canadian-led Atmospheric Chemistry Experiment (ACE) satellite mission has completed a decade of measurements from orbit. This Canadian-led scientific satellite uses infrared and UV-visible spectroscopy to investigate the chemistry and dynamics of the Earth's atmosphere. The primary instrument on-board, the ACE Fourier Transform Spectrometer (ACE-FTS) is a high-resolution (0.02 cm (-1) ) FTS operating between 750 and 4400 cm (-1) . It also contains two filtered imagers (0.525 and 1.02 microns) to measure atmospheric extinction due to clouds and aerosols. The second instrument is a dual UV-visible-NIR spectrophotometer called ACE-MAESTRO (Measurements of Aerosol Extinction in the Stratosphere and Troposphere Retrieved by Occultation) which extends the ACE wavelength coverage to the 280-1030 nm spectral region. The ACE instruments make solar occultation measurements from which altitude profiles of atmospheric trace gas species, temperature and pressure are retrieved. The 650 km altitude, 74 degree circular orbit provides global measurement coverage with a focus on the Arctic and Antarctic regions. These results are being used for studies relating to ozone depletion, climate-chemistry coupling and air pollution. As well, the decade long time series has been used to investigate trends in atmospheric constituents. This presentation will give an overview of the mission status and will provide a survey of the scientific results obtained from ACE.

  15. Trends in the chemistry of atmospheric deposition and surface waters in the Lake Maggiore catchment

    Directory of Open Access Journals (Sweden)

    M. Rogora

    2001-01-01

    Full Text Available The Lake Maggiore catchment is the area of Italy most affected by acid deposition. Trend analysis was performed on long-term (15-30 years series of chemical analyses of atmospheric deposition, four small rivers draining forested catchments and four high mountain lakes. An improvement in the quality of atmospheric deposition was detected, due to decreasing sulphate concentration and increasing pH. Similar trends were also found in high mountain lakes and in small rivers. Atmospheric deposition, however, is still providing a large and steady flux of nitrogen compounds (nitrate and ammonium which is causing increasing nitrogen saturation in forest ecosystems and increasing nitrate levels in rivers. Besides atmospheric deposition, an important factor controlling water acidification and recovery is the weathering of rocks and soils which may be influenced by climate warming. A further factor is the episodic deposition of Saharan calcareous dust which contributes significantly to base cation deposition. Keywords: trend, atmospheric deposition, nitrogen, stream water chemistry.

  16. Impacts of heterogeneous chemistry on heavy pollution in the JJJ (Beijing-Tianjin-Hebei) region

    Science.gov (United States)

    Tang, Yu Jia; Xian Liu, Bao; Sun, Feng; Wang, Li Hua; Zhang, Da Wei; Yin, Wen Jun; Zhang, Meng; Ma, Junwen

    2017-04-01

    The NO2 heterogeneous reaction on soot surfaces was incorporated into the WRF-Chem model to assess the impacts of the heterogeneous chemistry on the concentrations of HONO, HOx, O3, NO3-, and NH4+ in the JJJ (Beijing-Tianjin-Hebei) region. Results showed that the soot redox process with a γ value of 10-4 at night and the soot heterogeneous photochemistry with the γ formula of JNO2/10 in the daytime yielded a nighttime HONO increase of 0.4-1.8 ppb and a percentage enhancement of 10%-50% for HOx, 2%-6% for O3, 5%-21% for NO3-, and 6%-17% for NH4+ in the major cities of the JJJ region. The HONO simulations in this case were reasonable compared with observations in Beijing. Minor enhancements were found for HONO, HOx, O3, NO3-, and NH4+, with a maximum increase of 0.2 ppb for HONO and ≤ 6% for HOx, O3, NO3-, and NH4+ when γ was ≤ 10-5. When γ was increased to 10-3, produced are a nighttime maximum enhancement of 8.6 ppb for HONO, and a maximum percentage enhancement of 79% for HOx, 17% for O3, 211% for NO3-, and 152% for NH4+. This case considerably overestimated HONO and NO3- concentrations in Beijing in most cases. The soot surface area per unit volume of air (As) was another key parameter for the NO2 heterogeneous reaction on soot. The As values showed a sharp decrease from 3×103 μm2 cm-3 near the ground to 6×102 μm2 cm-3 at 200 m at night. Although the surface areas of major aerosol components at nighttime were  three times larger than that of those in the daytime, the surface area fractions of the major aerosol components showed minor variations between day and night. The surface area fractions of NO3-, SO42-, and soot were 32%-36%, 25%-28%, and 25%-26%, respectively.

  17. Non-OH Chemistry in Oxidation Flow Reactors for the Study of Atmospheric Chemistry Systematically Examined by Modeling

    Science.gov (United States)

    Peng, Zhe; Day, Douglas A.; Ortega, Amber M.; Palm, Brett B.; Hu, Weiwei; Stark, Harald; Li, Rui; Tsigaridis, Kostas; Brune, William H.; Jimenez, Jose L.

    2016-01-01

    Oxidation flow reactors (OFRs) using low-pressure Hg lamp emission at 185 and 254 nm produce OH radicals efficiently and are widely used in atmospheric chemistry and other fields. However, knowledge of detailed OFR chemistry is limited, allowing speculation in the literature about whether some non-OH reactants, including several not relevant for tropospheric chemistry, may play an important role in these OFRs. These non-OH reactants are UV radiation, O(1D), O(3P), and O3. In this study, we investigate the relative importance of other reactants to OH for the fate of reactant species in OFR under a wide range of conditions via box modeling. The relative importance of non-OH species is less sensitive to UV light intensity than to relative humidity (RH) and external OH reactivity (OHRext), as both non-OH reactants and OH scale roughly proportional to UV intensity. We show that for field studies in forested regions and also the urban area of Los Angeles, reactants of atmospheric interest are predominantly consumed by OH. We find that O(1D), O(3P), and O3 have relative contributions to VOC consumption that are similar or lower than in the troposphere. The impact of O atoms can be neglected under most conditions in both OFR and troposphere. Under pathological OFR conditions of low RH and/or high OHRext, the importance of non-OH reactants is enhanced because OH is suppressed. Some biogenics can have substantial destructions by O3, and photolysis at non-tropospheric wavelengths (185 and 254 nm) may also play a significant role in the degradation of some aromatics under pathological conditions. Working under low O2 with the OFR185 mode allows OH to completely dominate over O3 reactions even for the biogenic species most reactive with O3. Non-tropospheric VOC photolysis may have been a problem in some laboratory and source studies, but can be avoided or lessened in future studies by diluting source emissions and working at lower precursor concentrations in lab studies, and by

  18. Importance of heterogeneous processes to tropospheric chemistry - Studies with a one-dimensional model

    Science.gov (United States)

    Turco, R. P.; Toon, O. B.; Whitten, R. C.; Keesee, R. G.; Hamill, P.

    1982-01-01

    A one-dimensional, time-dependent model of tropospheric air composition is developed which incorporates several heterogeneous physical and chemical processes. The model includes the interaction of gases, aerosols, and hydrometeors through the physical mechanisms of nucleation, condensation, evaporation, coagulation, coalescence, and deliquescence. Precipitation, sedimentation, and dry deposition act to remove material from the atmosphere, while chemical transformations occur both in the vapor and the condensed phases. The model also incorporates the sources and vertical diffusion of gases and particles, as well as changes in the solar intensity caused by light-scattering from aerosols and clouds. Preliminary simulations made using this model indicate that rainout and washout processes strongly influence the distributions of tropospheric gases and aerosols under certain conditions.

  19. Controls of Polysaccharide Chemistry on the Kinetics and Thermodynamics of Heterogeneous Calcium Carbonate Nucleation

    Science.gov (United States)

    Giuffre, A. J.; Han, N.; Dove, P. M.

    2011-12-01

    Polysaccharide fibrils control the orientation of calcium carbonate (CaCO3) biominerals. Good examples are found in the multilayered extracellular mucilaginous sheath of green algae and cyanobacteria and in specialized vesicles inside coccolithophorids. More complex organisms such as arthropods and mollusks form biomineralized exoskeletons and shells that consist of insoluble polysaccharides and soluble acid-rich proteins. In these structures, CaCO3 mineral orientation occurs along fibers of the polysaccharide chitin. This raises the question of whether polysaccharide chemistry has specific roles in directing biomineralization. The last three decades of research show that acidic proteins influence CaCO3 polymorph selection, crystallographic orientation, and nucleation and growth rates but little is known about the function of polysaccharides. In fact, polysaccharides are long considered an inert component of organic frameworks. In this experimental investigation, we test the hypothesis that polysaccharides have chemistry-specific influences on calcification by measuring the kinetics of calcite nucleation onto three types of polysaccharide films under controlled solution compositions. Characterized polysaccharides of simple repeating monomer sequences were chosen as model compounds to represent the major carbohydrates seen in microbial and calcifying environments: 1) alginic acid with carboxyl groups, 2) hyaluronic acid with alternating carboxyl and acetylamine groups, and 3) chitosan with amine and acetylamine groups. Biosubstrates were prepared by electrodeposition of these compounds as thin gel-like films onto gold-coated silicon wafers. Using a flow-through cell, heterogeneous nucleation rates of calcite were measured for a suite of supersaturation conditions. These rate data were compared to similar measurements for carboxyl- and hydroxyl-terminated self-assembled monolayers. Calcite nucleation rates onto the three polysaccharides vary by a factor of 400x

  20. Analysis of coherent structures and atmosphere-canopy coupling strength during the CABINEX field campaign: implications for atmospheric chemistry

    Science.gov (United States)

    Steiner, A. L.; Pressley, S. N.; Botros, A.; Jones, E.; Chung, S. H.; Edburg, S. L.

    2011-07-01

    Intermittent coherent structures can be responsible for a large fraction of the chemical exchange between the vegetation canopy and the atmosphere. Quantifying their contribution to fluxes is necessary to interpret measurements of trace gases and aerosols within and above forest canopies. The primary objective of the Community Atmosphere-Biosphere Interactions Experiment (CABINEX) field campaign (10 July 2009 to 9 August 2009) was to study the chemistry of volatile organic compounds (VOC) within and above a forest canopy. In this manuscript, we provide an analysis of coherent structures and canopy-atmosphere exchange during CABINEX to support in-canopy gradient measurements of VOC. We quantify the number and duration of coherent structure events and their percent contribution to momentum and heat fluxes with two methods: (1) quadrant-hole analysis and (2) wavelet analysis. Despite differences in the duration and number of events, both methods predict that coherent structures contribute 40-50 % to total momentum fluxes and 44-65 % to total heat fluxes during the CABINEX campaign. Contributions associated with coherent structures are slightly greater under stable rather than unstable conditions. By comparing heat fluxes within and above the canopy, we determine the degree of coupling between upper canopy and atmosphere and find that they are coupled to the majority of the campaign time period. Uncoupled canopy-atmosphere events occur in the early morning (04:00-08:00 LT) approximately 30 % of the time. This study confirms that coherent structures contribute significantly to the exchange of heat and momentum between the canopy and atmosphere at the CABINEX site, and indicates the need to include these transport processes when studying the mixing and chemical reactions of trace gases and aerosols between a forest canopy and the atmosphere.

  1. Atmospheric Chemistry of (CF3)2CF-C≡N

    DEFF Research Database (Denmark)

    Andersen, Mads Peter Sulbæk; Kyte, Mildrid; Thirstrup Andersen, Simone

    2017-01-01

    FTIR/smog chamber experiments and ab initio quantum calculations were performed to investigate the atmospheric chemistry of (CF3)2CFCN, a proposed replacement compound for the industrially important sulfur hexafluoride, SF6. The present study determined k(Cl + (CF3)2CFCN) = (2.33 ± 0.87) × 10–17, k......(OH + (CF3)2CFCN) = (1.45 ± 0.25) × 10–15, and k(O3 + (CF3)2CFCN) ≤ 6 × 10–24 cm3 molecule–1 s–1, respectively, in 700 Torr of N2 or air diluent at 296 ± 2 K. The main atmospheric sink for (CF3)2CFCN was determined to be reaction with OH radicals. Quantum chemistry calculations, supported by experimental...

  2. Atmospheric chemistry, sources and sinks of carbon suboxide, C3O2

    Science.gov (United States)

    Keßel, Stephan; Cabrera-Perez, David; Horowitz, Abraham; Veres, Patrick R.; Sander, Rolf; Taraborrelli, Domenico; Tucceri, Maria; Crowley, John N.; Pozzer, Andrea; Stönner, Christof; Vereecken, Luc; Lelieveld, Jos; Williams, Jonathan

    2017-07-01

    Carbon suboxide, O = C = C = C = O, has been detected in ambient air samples and has the potential to be a noxious pollutant and oxidant precursor; however, its lifetime and fate in the atmosphere are largely unknown. In this work, we collect an extensive set of studies on the atmospheric chemistry of C3O2. Rate coefficients for the reactions of C3O2 with OH radicals and ozone were determined as kOH = (2.6 ± 0.5) × 10-12 cm3 molecule-1 s-1 at 295 K (independent of pressure between ˜ 25 and 1000 mbar) and kO3 Henry's law solubility and hydrolysis rate constant) were also investigated, enabling its photodissociation lifetime and hydrolysis rates, respectively, to be assessed. The role of C3O2 in the atmosphere was examined using in situ measurements, an analysis of the atmospheric sources and sinks and simulation with the EMAC atmospheric chemistry-general circulation model. The results indicate sub-pptv levels at the Earth's surface, up to about 10 pptv in regions with relatively strong sources, e.g. influenced by biomass burning, and a mean lifetime of ˜ 3.2 days. These predictions carry considerable uncertainty, as more measurement data are needed to determine ambient concentrations and constrain the source strengths.

  3. Heterogeneous chemistry of NO{sub 3} in clouds and fogs

    Energy Technology Data Exchange (ETDEWEB)

    Rudich, Y.; Talukdar, R.K.; Fox, R. [NOAA, Aeronomy Lab., Boulder (United States)] [and others

    1996-10-01

    The heterogeneous reactions of the nitrate free radical (NO{sub 3}) an important nighttime oxidant in the lower troposphere, in clouds and fogs are unexplored. Therefore, the uptake coefficients ({gamma}) of NO{sub 3} onto pure water and other dilute solutions were measured. The product of Henry`s law constant, H, and diffusion coefficient D{sub {ell}}, for NO{sub 3} in water was calculated to be H{radical}D{sub {ell}} = (1.9{plus_minus}0.2)x10{sup -3} M atm{sup -1} cm s-{sup 1/2} and H , was determined to be 0.6{plus_minus}0.3 M atm{sup -1}. Uptake of NO{sub 3} on pure water is interpreted as due to reaction of NO{sub 3(aq)} with H{sub 2}O{sub ({ell})} to produce HNO{sub 3} and OH in the liquid phase. Details of these measurements and the implications of these findings to the chemistry of NO{sub 3} in the troposphere will discussed.

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

    Science.gov (United States)

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

    2015-05-14

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

  5. Validation of NO2 and NO from the Atmospheric Chemistry Experiment (ACE)

    OpenAIRE

    Kerzenmacher, T.; M. A. Wolff; Strong, K.; Dupuy, E.; Walker, K. A.; Amekudzi, L.K.; Batchelor, R. L.; Bernath, P. F.; Berthet, G; Blumenstock, T.; Boone, C. D.; Bramstedt, K.; Brogniez, C.; Brohede, S.; Burrows, J. P.

    2008-01-01

    Vertical profiles of NO2 and NO have been obtained from solar occultation measurements by the Atmospheric Chemistry Experiment (ACE), using an infrared Fourier Transform Spectrometer (ACE-FTS) and (for NO2) an ultraviolet-visible-near-infrared spectrometer, MAESTRO (Measurement of Aerosol Extinction in the Stratosphere and Troposphere Retrieved by Occultation). In this paper, the quality of the ACE-FTS version 2.2 NO2 and NO and the MAESTRO version 1.2 NO2 data are assess...

  6. Collaborative Research: Atmospheric Pressure Microplasma Chemistry-Photon Synergies Final Report

    Energy Technology Data Exchange (ETDEWEB)

    Graves, David [Univ. of California, Berkeley, CA (United States)

    2017-02-07

    Combining the effects of low temperature, atmospheric pressure microplasmas and microplasma photon sources shows greatly expanded range of applications of each of them. The plasma sources create active chemical species and these can be activated further by addition of photons and associated photochemistry. There are many ways to combine the effects of plasma chemistry and photochemistry, especially if there are multiple phases present. The project combines construction of appropriate test experimental systems, various spectroscopic diagnostics and mathematical modeling.

  7. Kinetic and photochemical data for atmospheric chemistry reactions of the nitrogen oxides

    Science.gov (United States)

    Hampson, R. F., Jr.

    1980-01-01

    Data sheets for thermal and photochemical reactions of importance in the atmospheric chemistry of the nitrogen oxides are presented. For each reaction the available experimental data are summarized and critically evaluated, and a preferred value of the rate coefficient is given. The selection of the preferred value is discussed and an estimate of its accuracy is given. For the photochemical process, the data are summarized, and preferred for the photoabsorption cross section and primary quantum yields are given.

  8. Determination of the smoke-plume heights with scanning lidar using alternative functions for establishing the atmospheric heterogeneity locations

    Science.gov (United States)

    Vladimir A. Kovalev; Alexander Petkov; Cyle Wold; Wei Min Hao

    2010-01-01

    Data-processing techniques for the scanning lidar data are considered that allow determining the upper and lower boundaries of the smoke plume or smoke layering in the vicinity of wildfires. The task is fulfilled by utilizing the Atmospheric Heterogeneity Height Indicator (AHHI). The AHHI is a histogram, which shows a number of heterogeneity events defined by scanning...

  9. WRF-Chem model predictions of the regional impacts of N2O5 heterogeneous processes on night-time chemistry over north-western Europe

    Science.gov (United States)

    Lowe, D.; Archer-Nicholls, S.; Morgan, W.; Allan, J.; Utembe, S.; Ouyang, B.; Aruffo, E.; Le Breton, M.; Zaveri, R. A.; Di Carlo, P.; Percival, C.; Coe, H.; Jones, R.; McFiggans, G.

    2015-02-01

    Chemical modelling studies have been conducted over north-western Europe in summer conditions, showing that night-time dinitrogen pentoxide (N2O5) heterogeneous reactive uptake is important regionally in modulating particulate nitrate and has a~modest influence on oxidative chemistry. Results from Weather Research and Forecasting model with Chemistry (WRF-Chem) model simulations, run with a detailed volatile organic compound (VOC) gas-phase chemistry scheme and the Model for Simulating Aerosol Interactions and Chemistry (MOSAIC) sectional aerosol scheme, were compared with a series of airborne gas and particulate measurements made over the UK in July 2010. Modelled mixing ratios of key gas-phase species were reasonably accurate (correlations with measurements of 0.7-0.9 for NO2 and O3). However modelled loadings of particulate species were less accurate (correlation with measurements for particulate sulfate and ammonium were between 0.0 and 0.6). Sulfate mass loadings were particularly low (modelled means of 0.5-0.7 μg kg-1air, compared with measurements of 1.0-1.5 μg kg-1air). Two flights from the campaign were used as test cases - one with low relative humidity (RH) (60-70%), the other with high RH (80-90%). N2O5 heterogeneous chemistry was found to not be important in the low-RH test case; but in the high-RH test case it had a strong effect and significantly improved the agreement between modelled and measured NO3 and N2O5. When the model failed to capture atmospheric RH correctly, the modelled NO3 and N2O5 mixing ratios for these flights differed significantly from the measurements. This demonstrates that, for regional modelling which involves heterogeneous processes, it is essential to capture the ambient temperature and water vapour profiles. The night-time NO3 oxidation of VOCs across the whole region was found to be 100-300 times slower than the daytime OH oxidation of these compounds. The difference in contribution was less for alkenes (× 80) and

  10. WRF-Chem model predictions of the regional impacts of N2O5 heterogeneous processes on night-time chemistry over north-western Europe

    Directory of Open Access Journals (Sweden)

    D. Lowe

    2015-02-01

    Full Text Available Chemical modelling studies have been conducted over north-western Europe in summer conditions, showing that night-time dinitrogen pentoxide (N2O5 heterogeneous reactive uptake is important regionally in modulating particulate nitrate and has a~modest influence on oxidative chemistry. Results from Weather Research and Forecasting model with Chemistry (WRF-Chem model simulations, run with a detailed volatile organic compound (VOC gas-phase chemistry scheme and the Model for Simulating Aerosol Interactions and Chemistry (MOSAIC sectional aerosol scheme, were compared with a series of airborne gas and particulate measurements made over the UK in July 2010. Modelled mixing ratios of key gas-phase species were reasonably accurate (correlations with measurements of 0.7–0.9 for NO2 and O3. However modelled loadings of particulate species were less accurate (correlation with measurements for particulate sulfate and ammonium were between 0.0 and 0.6. Sulfate mass loadings were particularly low (modelled means of 0.5–0.7 μg kg−1air, compared with measurements of 1.0–1.5 μg kg−1air. Two flights from the campaign were used as test cases – one with low relative humidity (RH (60–70%, the other with high RH (80–90%. N2O5 heterogeneous chemistry was found to not be important in the low-RH test case; but in the high-RH test case it had a strong effect and significantly improved the agreement between modelled and measured NO3 and N2O5. When the model failed to capture atmospheric RH correctly, the modelled NO3 and N2O5 mixing ratios for these flights differed significantly from the measurements. This demonstrates that, for regional modelling which involves heterogeneous processes, it is essential to capture the ambient temperature and water vapour profiles. The night-time NO3 oxidation of VOCs across the whole region was found to be 100–300 times slower than the daytime OH oxidation of these compounds. The difference in contribution was less

  11. Predicting Complex Organic Mixture Atmospheric Chemistry Using Computer-Generated Reaction Models

    Science.gov (United States)

    Klein, M. T.; Broadbelt, L. J.; Mazurek, M. A.

    2001-12-01

    New measurement and chemical characterization technologies now offer unprecedented capabilities for detecting and describing atmospheric organic matter at the molecular level. As a result, very detailed and extensive chemical inventories are produced routinely in atmospheric field measurements of organic compounds found in the vapor and condensed phases (particles, cloud and fog droplets). Hundreds of organic compounds can constitute the complex chemical mixtures observed for these types of samples, exhibiting a wide spectrum of physical properties such as molecular weight, polarity, pH, and chemical reactivity. The central challenge is describing chemically the complex organic aerosol mixture in a useable fashion that can be linked to predictive models. However, the great compositional complexity of organic aerosols engenders a need for the modeling of the reaction chemistry of these compounds in atmospheric chemical models. On a mechanistic level, atmospheric reactions of organic compounds can involve a network of a very large number of chemical species and reactions. Deriving such large molecular kinetic models by hand is a tedious and time-consuming process. However, such models are usually built upon a few basic chemical principles tempered with the model builder's observations, experience, and intuition that can be summarized as a set of rules. This suggests that given an algorithmic framework, computers (information technology) may be used to apply these chemical principles and rules, thereby building a kinetic model. The framework for this model building process has been developed by means of graph theory. A molecule, which is a set of atoms connected by bonds, may be conceptualized as a set of vertices connected by edges, or to be more precise, a graph. The bond breaking and forming for a reaction can be represented compactly in the form of a matrix operator formally called the "reaction matrix". The addition of the reaction matrix operator to the reduced

  12. Variational data assimilation schemes for transport and transformation models of atmospheric chemistry

    Science.gov (United States)

    Penenko, Alexey; Penenko, Vladimir; Tsvetova, Elena; Antokhin, Pavel

    2016-04-01

    The work is devoted to data assimilation algorithm for atmospheric chemistry transport and transformation models. In the work a control function is introduced into the model source term (emission rate) to provide flexibility to adjust to data. This function is evaluated as the constrained minimum of the target functional combining a control function norm with a norm of the misfit between measured data and its model-simulated analog. Transport and transformation processes model is acting as a constraint. The constrained minimization problem is solved with Euler-Lagrange variational principle [1] which allows reducing it to a system of direct, adjoint and control function estimate relations. This provides a physically-plausible structure of the resulting analysis without model error covariance matrices that are sought within conventional approaches to data assimilation. High dimensionality of the atmospheric chemistry models and a real-time mode of operation demand for computational efficiency of the data assimilation algorithms. Computational issues with complicated models can be solved by using a splitting technique. Within this approach a complex model is split to a set of relatively independent simpler models equipped with a coupling procedure. In a fine-grained approach data assimilation is carried out quasi-independently on the separate splitting stages with shared measurement data [2]. In integrated schemes data assimilation is carried out with respect to the split model as a whole. We compare the two approaches both theoretically and numerically. Data assimilation on the transport stage is carried out with a direct algorithm without iterations. Different algorithms to assimilate data on nonlinear transformation stage are compared. In the work we compare data assimilation results for both artificial and real measurement data. With these data we study the impact of transformation processes and data assimilation to the performance of the modeling system [3]. The

  13. The Unsolved Mysteries of Atmospheric Chemistry for High School Students and Teachers

    Science.gov (United States)

    Simonich, S. L.

    2011-12-01

    The grant "CAREER: New Molecular Markers of Asian Air Emissions - Anthropogenic Semi-Volatile Organic Compounds" (ATM-0239823) was funded by NSF from 2003-2008. The CAREER proposal described the integration of research and outreach education activities in the field of atmospheric chemistry, specifically atmospheric measurements and atmospheric transport. The primary objective of the research was to identify anthropogenic semi-volatile organic compounds (SOCs) that could be used as molecular markers for Asian air emissions and trans-Pacific atmospheric transport. The outreach education activity was integrated with the research by developing curriculum to introduce underrepresented minority high school students, and their teachers, to atmospheric chemistry and atmospheric measurements through Oregon State University's National Institute of Environmental Health Sciences funded Hydroville Curriculum Project (http://www.hydroville.org/iaq_resources). A curriculum was developed to allow students to assume the role of "Air Quality Scientist" and measure air temperature, air flow, relative humidity, CO, CO2, O3, and volatile organic compounds in out-door and in-door air. The students gained an understanding of atmospheric transport and compared measured concentrations to recommended guidelines. In addition, the outreach education activities included the development of the "Unsolved Mysteries of Human Health" website (http://www.unsolvedmysteries.oregonstate.edu/), including a specific module on the research conducted under the CAREER grant (http://www.unsolvedmysteries.oregonstate.edu /Gas-Chromatography-Mass-Spectrometry-Overview). The PI of the CAREER proposal, Dr. Staci Massey Simonich, is now a full professor at Oregon State University. To date, she has published over 50 peer-review journal articles, as well as mentored 9 undergraduate students, 20 graduate students, 3 post-doctoral scholars, and 3 international visiting scientists in her laboratory.

  14. Failures and limitations of quantum chemistry for two key problems in the atmospheric chemistry of peroxy radicals

    Science.gov (United States)

    Dibble, Theodore S.

    Quantum chemical calculations have obtained significant and useful information about chemical reactions relevant to atmospheric chemistry. This article reviews two problems for which it would seem that such calculations could readily provide a great deal of helpful information, but for which that potential has not been fully realized. The first is the formation of alkylnitrates (RONO 2) from the reaction of peroxy radicals (ROO rad ) with NO. Several studies of this process have been carried out, but most clearly yielded unphysical results due to methodological pitfalls. The one study which appears valid [Zhao, Y., Houk, K.N., Olson, L.P., 2004. Mechanisms of peroxynitrous acid and methyl peroxynitrite, ROONO (R=H, Me), rearrangements: a conformation-dependent homolytic dissociation. Journal of Physical Chemistry A 108, 5864-5871] suggests an indirect route between ROONO and RONO 2, and implies that statistical rate theory will be insufficient to understand the yields of RONO 2. The second problem discussed here is the competition between radical production and disproportionation in the self-reaction of organic peroxy radicals, for which only one quantum chemical study has found a plausible mechanism connecting reactants with products.

  15. Response of middle atmosphere chemistry and dynamics to volcanically elevated sulfate aerosol: Three-dimensional coupled model simulations

    Science.gov (United States)

    Al-Saadi, Jassim A.; Pierce, R. Bradley; Fairlie, T. Duncan; Kleb, Mary M.; Eckman, Richard S.; Grose, William L.; Natarajan, Murali; Olson, Jennifer R.

    2001-11-01

    The NASA Langley Research Center Interactive Modeling Project for Atmospheric Chemistry and Transport (IMPACT) model has been used to examine the response of the middle atmosphere to a large tropical stratospheric injection of sulfate aerosol, such as that following the June 1991 eruption of Mount Pinatubo. The influence of elevated aerosol on heterogeneous chemical processing was simulated using a three-dimensional climatology of surface area density (SAD)developed using observations made from the Halogen Occultation Experiment, Stratospheric Aerosol and Gas Experiment II, and Stratospheric Aerosol Measurement satellite instruments beginning in June 1991. Radiative effects of the elevated aerosol were represented by monthly mean zonally averaged heating perturbations obtained from a study conducted with the European Center/Hamburg (ECHAM4) general circulation model combined with an observationally derived set of aerosol parameters. Two elevated-aerosol simulations were integrated for 31/2 years following the volcanic injection. One simulation included only the aerosol radiative perturbation, and one simulation included both the radiative perturbation and the elevated SAD. These perturbation simulations are compared with multiple-year control simulations to isolate relative contributions of transport and heterogeneous chemical processing. Significance of modeled responses is assessed through comparison with interannual variability. Dynamical and photochemical contributions to ozone decreases are of comparable magnitude. Important stratospheric chemical/dynamical feedback effects are shown, as ozone reductions modulate aerosol-induced heating by up to 10% in the lower stratosphere and 25% in the middle stratosphere. Dynamically induced changes in chemical constituents which propagate into the upper stratosphere are still pronounced at the end of the simulations.

  16. A synthesis of atmospheric mercury depletion event chemistry linking atmosphere, snow and water

    Science.gov (United States)

    Steffen, A.; Douglas, T.; Amyot, M.; Ariya, P.; Aspmo, K.; Berg, T.; Bottenheim, J.; Brooks, S.; Cobbett, F.; Dastoor, A.; Dommergue, A.; Ebinghaus, R.; Ferrari, C.; Gardfeldt, K.; Goodsite, M. E.; Lean, D.; Poulain, A.; Scherz, C.; Skov, H.; Sommar, J.; Temme, C.

    2007-07-01

    It was discovered in 1995 that, during the spring time, unexpectedly low concentrations of gaseous elemental mercury (GEM) occurred in the Arctic air. This was surprising for a pollutant known to have a long residence time in the atmosphere; however conditions appeared to exist in the Arctic that promoted this depletion of mercury (Hg). This phenomenon is termed atmospheric mercury depletion events (AMDEs) and its discovery has revolutionized our understanding of the cycling of Hg in Polar Regions while stimulating a significant amount of research to understand its impact to this fragile ecosystem. Shortly after the discovery was made in Canada, AMDEs were confirmed to occur throughout the Arctic, sub-Artic and Antarctic coasts. It is now known that, through a series of photochemically initiated reactions involving halogens, GEM is converted to a more reactive species and is subsequently associated to particles in the air and/or deposited to the polar environment. AMDEs are a means by which Hg is transferred from the atmosphere to the environment that was previously unknown. In this article we review the history of Hg in Polar Regions, the methods used to collect Hg in different environmental media, research results of the current understanding of AMDEs from field, laboratory and modeling work, how Hg cycles around the environment after AMDEs, gaps in our current knowledge and the future impacts that AMDEs may have on polar environments. The research presented has shown that while considerable improvements in methodology to measure Hg have been made the main limitation remains knowing the speciation of Hg in the various media. The processes that drive AMDEs and how they occur are discussed. As well, the roles that the snow pack, oceans, fresh water and the sea ice play in the cycling of Hg are presented. It has been found that deposition of Hg from AMDEs occurs at marine coasts and not far inland and that a fraction of the deposited Hg does not remain in the same

  17. Modeling Top of Atmosphere Radiance over Heterogeneous Non-Lambertian Rugged Terrain

    Directory of Open Access Journals (Sweden)

    Alijafar Mousivand

    2015-06-01

    Full Text Available Topography affects the fraction of direct and diffuse radiation received on a pixel and changes the sun–target–sensor geometry, resulting in variations in the observed radiance. Retrieval of surface–atmosphere properties from top of atmosphere radiance may need to account for topographic effects. This study investigates how such effects can be taken into account for top of atmosphere radiance modeling. In this paper, a system for top of atmosphere radiance modeling over heterogeneous non-Lambertian rugged terrain through radiative transfer modeling is presented. The paper proposes an extension of “the four-stream radiative transfer theory” (Verhoef and Bach 2003, 2007 and 2012 mainly aimed at representing topography-induced contributions to the top of atmosphere radiance modeling. A detailed account for BRDF effects, adjacency effects and topography effects on the radiance modeling is given, in which sky-view factor and non-Lambertian reflected radiance from adjacent slopes are modeled precisely. The paper also provides a new formulation to derive the atmospheric coefficients from MODTRAN with only two model runs, to make it more computationally efficient and also avoiding the use of zero surface albedo as used in the four-stream radiative transfer theory. The modeling begins with four surface reflectance factors calculated by the Soil–Leaf–Canopy radiative transfer model SLC at the top of canopy and propagates them through the effects of the atmosphere, which is explained by six atmospheric coefficients, derived from MODTRAN radiative transfer code. The top of the atmosphere radiance is then convolved with the sensor characteristics to generate sensor-like radiance. Using a composite dataset, it has been shown that neglecting sky view factor and/or terrain reflected radiance can cause uncertainty in the forward TOA radiance modeling up to 5 (mW/m2·sr·nm. It has also been shown that this level of uncertainty can be translated

  18. Heterogeneous ice nucleation and water uptake by field-collected atmospheric particles below 273 K

    Science.gov (United States)

    Wang, Bingbing; Laskin, Alexander; Roedel, Tobias; Gilles, Mary K.; Moffet, Ryan C.; Tivanski, Alexei V.; Knopf, Daniel A.

    2012-09-01

    Ice formation induced by atmospheric particles through heterogeneous nucleation is not well understood. Onset conditions for heterogeneous ice nucleation and water uptake by particles collected in Los Angeles and Mexico City were determined as a function of temperature (200-273 K) and relative humidity with respect to ice (RHice). Four dominant particle types were identified including soot associated with organics, soot with organic and inorganics, inorganic particles of marine origin coated with organic material, and Pb/Zn-containing particles apportioned to emissions relevant to waste incineration. Single particle characterization was provided by micro-spectroscopic analyses using computer controlled scanning electron microscopy with energy dispersive analysis of X-rays (CCSEM/EDX) and scanning transmission X-ray microscopy with near edge X-ray absorption fine structure spectroscopy (STXM/NEXAFS). Above 230 K, significant differences in onsets of water uptake and immersion freezing of different particle types were observed. Below 230 K, particles exhibited high deposition ice nucleation efficiencies and formed ice atRHicewell below homogeneous ice nucleation limits. The data suggest that water uptake and immersion freezing are more sensitive to changes in particle chemical composition compared to deposition ice nucleation. The data demonstrate that anthropogenic and marine influenced particles, exhibiting various chemical and physical properties, possess distinctly different ice nucleation efficiencies and can serve as efficient IN at atmospheric conditions typical for cirrus and mixed-phase clouds.

  19. Aqueous organic chemistry in the atmosphere: sources and chemical processing of organic aerosols.

    Science.gov (United States)

    McNeill, V Faye

    2015-02-03

    Over the past decade, it has become clear that aqueous chemical processes occurring in cloud droplets and wet atmospheric particles are an important source of organic atmospheric particulate matter. Reactions of water-soluble volatile (or semivolatile) organic gases (VOCs or SVOCs) in these aqueous media lead to the formation of highly oxidized organic particulate matter (secondary organic aerosol; SOA) and key tracer species, such as organosulfates. These processes are often driven by a combination of anthropogenic and biogenic emissions, and therefore their accurate representation in models is important for effective air quality management. Despite considerable progress, mechanistic understanding of some key aqueous processes is still lacking, and these pathways are incompletely represented in 3D atmospheric chemistry and air quality models. In this article, the concepts, historical context, and current state of the science of aqueous pathways of SOA formation are discussed.

  20. Atmospheric chemistry of perfluorinated carboxylic acids: Reaction with OH radicals and atmospheric lifetimes

    DEFF Research Database (Denmark)

    Hurley, MD; Andersen, Mads Peter Sulbæk; Wallington, TJ

    2004-01-01

    Relative rate techniques were used to study the kinetics of the reactions of OH radicals with a homologous series of perfluorinated acids, F(CF2)(n)COOH (n = 1, 2, 3, 4), in 700 Torr of air at 296 +/- 2 K. For n > 1, the length of the F(CF2)(n) group had no discernible impact on the reactivity.......03 Torr(-1), 0.41 +/- 0.04 Torr(-1), and 0.46 +/- 0.05 Torr(-1) for n = 1, 2, 3. 4, respectively. Atmospheric lifetimes of F(CF2)(n)COOH with respect to reaction with OH radicals are estimated to be approximately 230 days for n = 1 and 130 days for n > 1. Reaction with OH radicals is a minor atmospheric...... of the molecule. For n = 1, k(OH + F(CF2)(n)COOH) = (9.35 +/- 2.08) x 10(-14) cm(3) molecule(-1) s(-1). For n = 2-4, k(OH + F(CF2)(n)COOH) = (1.69 +/- 0.22) x 10(-13) cm(3) molecule(-1) s(-1). Dimerization constants for 2F(CF2)(n)COOH = (F(CF2)(n)COOH)(2) were determined to be 0.32 +/- 0.03 Torr(-1), 0.30 +/- 0...

  1. Heterogeneous Reactions between Toluene and NO2on Mineral Particles under Simulated Atmospheric Conditions.

    Science.gov (United States)

    Niu, Hejingying; Li, Kezhi; Chu, Biwu; Su, Wenkang; Li, Junhua

    2017-09-05

    Heterogeneous reactions between organic and inorganic gases with aerosols are important for the study of smog occurrence and development. In this study, heterogeneous reactions between toluene and NO 2 with three atmospheric mineral particles in the presence or absence of UV light were investigated. The three mineral particles were SiO 2 , α-Fe 2 O 3 , and BS (butlerite and szmolnokite). In a dark environment, benzaldehyde was produced on α-Fe 2 O 3 . For BS, nitrotoluene and benzaldehyde were obtained. No aromatic products were produced in the absence of NO 2 in the system. In the presence of UV irradiation, benzaldehyde was detected on the SiO 2 surface. Identical products were produced in the presence and absence of UV light over α-Fe 2 O 3 and BS. UV light promoted nitrite to nitrate on mineral particles surface. On the basisi of the X-ray photoelectron spectroscopy (XPS) results, a portion of BS was reduced from Fe 3+ to Fe 2+ with the adsorption of toluene or the reaction with toluene and NO 2 . Sulfate may play a key role in the generation of nitrotoluene on BS particles. From this research, the heterogeneous reactions between organic and inorganic gases with aerosols that occur during smog events will be better understood.

  2. A synthesis of atmospheric mercury depletion event chemistry in the atmosphere and snow

    Science.gov (United States)

    Steffen, A.; Douglas, T.; Amyot, M.; Ariya, P.; Aspmo, K.; Berg, T.; Bottenheim, J.; Brooks, S.; Cobbett, F.; Dastoor, A.; Dommergue, A.; Ebinghaus, R.; Ferrari, C.; Gardfeldt, K.; Goodsite, M. E.; Lean, D.; Poulain, A. J.; Scherz, C.; Skov, H.; Sommar, J.; Temme, C.

    2008-03-01

    It was discovered in 1995 that, during the spring time, unexpectedly low concentrations of gaseous elemental mercury (GEM) occurred in the Arctic air. This was surprising for a pollutant known to have a long residence time in the atmosphere; however conditions appeared to exist in the Arctic that promoted this depletion of mercury (Hg). This phenomenon is termed atmospheric mercury depletion events (AMDEs) and its discovery has revolutionized our understanding of the cycling of Hg in Polar Regions while stimulating a significant amount of research to understand its impact to this fragile ecosystem. Shortly after the discovery was made in Canada, AMDEs were confirmed to occur throughout the Arctic, sub-Artic and Antarctic coasts. It is now known that, through a series of photochemically initiated reactions involving halogens, GEM is converted to a more reactive species and is subsequently associated to particles in the air and/or deposited to the polar environment. AMDEs are a means by which Hg is transferred from the atmosphere to the environment that was previously unknown. In this article we review Hg research taken place in Polar Regions pertaining to AMDEs, the methods used to collect Hg in different environmental media, research results of the current understanding of AMDEs from field, laboratory and modeling work, how Hg cycles around the environment after AMDEs, gaps in our current knowledge and the future impacts that AMDEs may have on polar environments. The research presented has shown that while considerable improvements in methodology to measure Hg have been made but the main limitation remains knowing the speciation of Hg in the various media. The processes that drive AMDEs and how they occur are discussed. As well, the role that the snow pack and the sea ice play in the cycling of Hg is presented. It has been found that deposition of Hg from AMDEs occurs at marine coasts and not far inland and that a fraction of the deposited Hg does not remain in the

  3. A synthesis of atmospheric mercury depletion event chemistry in the atmosphere and snow

    Directory of Open Access Journals (Sweden)

    A. J. Poulain

    2008-03-01

    Full Text Available It was discovered in 1995 that, during the spring time, unexpectedly low concentrations of gaseous elemental mercury (GEM occurred in the Arctic air. This was surprising for a pollutant known to have a long residence time in the atmosphere; however conditions appeared to exist in the Arctic that promoted this depletion of mercury (Hg. This phenomenon is termed atmospheric mercury depletion events (AMDEs and its discovery has revolutionized our understanding of the cycling of Hg in Polar Regions while stimulating a significant amount of research to understand its impact to this fragile ecosystem. Shortly after the discovery was made in Canada, AMDEs were confirmed to occur throughout the Arctic, sub-Artic and Antarctic coasts. It is now known that, through a series of photochemically initiated reactions involving halogens, GEM is converted to a more reactive species and is subsequently associated to particles in the air and/or deposited to the polar environment. AMDEs are a means by which Hg is transferred from the atmosphere to the environment that was previously unknown. In this article we review Hg research taken place in Polar Regions pertaining to AMDEs, the methods used to collect Hg in different environmental media, research results of the current understanding of AMDEs from field, laboratory and modeling work, how Hg cycles around the environment after AMDEs, gaps in our current knowledge and the future impacts that AMDEs may have on polar environments. The research presented has shown that while considerable improvements in methodology to measure Hg have been made but the main limitation remains knowing the speciation of Hg in the various media. The processes that drive AMDEs and how they occur are discussed. As well, the role that the snow pack and the sea ice play in the cycling of Hg is presented. It has been found that deposition of Hg from AMDEs occurs at marine coasts and not far inland and that a fraction of the deposited Hg does

  4. 2011 Arctic ozone depletion as seen by ESA-ENVISAT Atmospheric-Chemistry sensors

    Science.gov (United States)

    Brizzi, G.; Niro, F.; Saavedra de Miguel, L.; Dehn, A.; Scarpino, G.; Fehr, T.; von Kuhlmann, R.

    2011-12-01

    Three Atmospheric-Chemistry sensors on-board the ENVISAT satellite (GOMOS, MIPAS, and SCIAMACHY) sound the Earth's atmosphere since about nine years and provide to the science community three separated, but complementary data sets of the most interesting atmospheric trace gases. These extended and coherent data sets, generated with ESA operational processors, give a historical overview over seasonal and long-term trends of geophysical parameters and allow investigating major atmospheric phenomena and natural events. During March 2011, ESA's satellite ENVISAT detected the severe ozone depletion above the Euro-Atlantic sector of the Northern Hemisphere. This record-breaking loss for the ozone layer over the North Pole was mainly caused by unusual polar vortex conditions characterized by very low temperatures in the Arctic stratosphere. This paper presents the chemical ozone depletion over the Arctic regions as detected by SCIAMACHY, MIPAS and GOMOS during spring of 2011. Global maps of total ozone column and vertical ozone profiles along the mission's lifetime clearly show the unprecedented Arctic ozone loss for 2011 with the subsequent migration of ozone depleted air masses towards lower latitudes. ENVISAT's atmospheric measurements reveal changes in the composition of the ozone-related chemical species and permit to point out the chemical correlations of the ozone distribution with nitrogen and chlorine compounds and with the evolution of stratospheric temperatures. The synergistic use of ESA operational data sets from the three instruments allows to closely monitor the occurrence and extension of seasonal ozone depletion events, and to draw a comprehensive picture of all chemistry processes involved in the full atmospheric range.

  5. The 1-way on-line coupled atmospheric chemistry model system MECO(n – Part 1: Description of the limited-area atmospheric chemistry model COSMO/MESSy

    Directory of Open Access Journals (Sweden)

    A. Kerkweg

    2012-01-01

    Full Text Available The numerical weather prediction model of the Consortium for Small Scale Modelling (COSMO, maintained by the German weather service (DWD, is connected with the Modular Earth Submodel System (MESSy. This effort is undertaken in preparation of a new, limited-area atmospheric chemistry model. Limited-area models require lateral boundary conditions for all prognostic variables. Therefore the quality of a regional chemistry model is expected to improve, if boundary conditions for the chemical constituents are provided by the driving model in consistence with the meteorological boundary conditions. The new developed model is as consistent as possible, with respect to atmospheric chemistry and related processes, with a previously developed global atmospheric chemistry general circulation model: the ECHAM/MESSy Atmospheric Chemistry (EMAC model. The combined system constitutes a new research tool, bridging the global to the meso-γ scale for atmospheric chemistry research. MESSy provides the infrastructure and includes, among others, the process and diagnostic submodels for atmospheric chemistry simulations. Furthermore, MESSy is highly flexible allowing model setups with tailor made complexity, depending on the scientific question. Here, the connection of the MESSy infrastructure to the COSMO model is documented and also the code changes required for the generalisation of regular MESSy submodels. Moreover, previously published prototype submodels for simplified tracer studies are generalised to be plugged-in and used in the global and the limited-area model. They are used to evaluate the TRACER interface implementation in the new COSMO/MESSy model system and the tracer transport characteristics, an important prerequisite for future atmospheric chemistry applications. A supplementary document with further details on the technical implementation of the MESSy interface into COSMO with a complete list of modifications to the COSMO code is provided.

  6. Stochastic fields method for sub-grid scale emission heterogeneity in mesoscale atmospheric dispersion models

    Directory of Open Access Journals (Sweden)

    M. Cassiani

    2010-01-01

    Full Text Available The stochastic fields method for turbulent reacting flows has been applied to the issue of sub-grid scale emission heterogeneity in a mesoscale model. This method is a solution technique for the probability density function (PDF transport equation and can be seen as a straightforward extension of currently used mesoscale dispersion models. It has been implemented in an existing mesoscale model and the results are compared with Large-Eddy Simulation (LES data devised to test specifically the effect of sub-grid scale emission heterogeneity on boundary layer concentration fluctuations. The sub-grid scale emission variability is assimilated in the model as a PDF of the emissions. The stochastic fields method shows excellent agreement with the LES data without adjustment of the constants used in the mesoscale model. The stochastic fields method is a stochastic solution of the transport equations for the concentration PDF of dispersing scalars, therefore it possesses the ability to handle chemistry of any complexity without the need to introduce additional closures for the high order statistics of chemical species. This study shows for the first time the feasibility of applying this method to mesoscale chemical transport models.

  7. Atmospheric deposition and lake chemistry trends at a high mountain site in the eastern Alps

    Directory of Open Access Journals (Sweden)

    Bertha THALER

    2000-02-01

    Full Text Available Records of atmospheric precipitation chemistry starting in 1983 and a series of limnological investigations at two high mountain reference lakes starting in 1988 enable us to describe the response of lake water chemistry to changes in precipitation chemistry and climate. The lakes are located at an altitude well above the timberline in a watershed composed of acidic rocks. Despite the observed reduction in the sulphur atmospheric deposition, the reference lakes showed no corresponding decline in sulphate concentrations, but a marked increase in the acid neutralising capacity was apparent. Changes of the seasonal distribution pattern of the precipitation amounts and a general increase of the air temperature have likely produced an increased weathering which increased the concentration of many inlake solutes and drove the lakes toward more buffered conditions. This phenomenon superimposed to changes like other physical factors (radiation, nutritional conditions and biological factors (enhanced production, competition, predation has produced in the last years greater modifications than merely those to be expected from the decreased acidic input.

  8. Radiative Impacts of Cloud Heterogeneity and Overlap in an Atmospheric General Circulation Model

    Science.gov (United States)

    Oreopoulos, L.; Lee, D.; Sud, Y. C.; Suarez, M. J.

    2012-01-01

    The radiative impacts of introducing horizontal heterogeneity of layer cloud condensate, and vertical overlap of condensate and cloud fraction are examined with the aid of a new radiation package operating in the GEOS-5 Atmospheric General Circulation Model. The impacts are examined in terms of diagnostic top-of-the-atmosphere shortwave (SW) and longwave (LW) cloud radiative effect (CRE) calculations for a range of assumptions and parameter specifications about the overlap. The investigation is conducted for two distinct cloud schemes, the one that comes with the standard GEOS-5 distribution, and another which has been recently used experimentally for its enhanced GEOS-5 distribution, and another which has been recently used experimentally for its enhanced cloud microphysical capabilities; both are coupled to a cloud generator allowing arbitrary cloud overlap specification. We find that cloud overlap radiative impacts are significantly stronger for the operational cloud scheme for which a change of cloud fraction overlap from maximum-random to generalized results to global changes of SW and LW CRE of approximately 4 Watts per square meter, and zonal changes of up to approximately 10 Watts per square meter. This is because of fewer occurrences compared to the other scheme of large layer cloud fractions and of multi-layer situations with large numbers of atmospheric being simultaneously cloudy, conditions that make overlap details more important. The impact on CRE of the details of condensate distribution overlap is much weaker. Once generalized overlap is adopted, both cloud schemes are only modestly sensitive to the exact values of the overlap parameters. We also find that if one of the CRE components is overestimated and the other underestimated, both cannot be driven towards observed values by adjustments to cloud condensate heterogeneity and overlap alone.

  9. Development of a fluidized bed agglomeration modeling methodology to include particle-level heterogeneities in ash chemistry and granular physics

    Science.gov (United States)

    Khadilkar, Aditi B.

    The utility of fluidized bed reactors for combustion and gasification can be enhanced if operational issues such as agglomeration are mitigated. The monetary and efficiency losses could be avoided through a mechanistic understanding of the agglomeration process and prediction of operational conditions that promote agglomeration. Pilot-scale experimentation prior to operation for each specific condition can be cumbersome and expensive. So the development of a mathematical model would aid predictions. With this motivation, the study comprised of the following model development stages- 1) development of an agglomeration modeling methodology based on binary particle collisions, 2) study of heterogeneities in ash chemical composition and gaseous atmosphere, 3) computation of a distribution of particle collision frequencies based on granular physics for a poly-disperse particle size distribution, 4) combining the ash chemistry and granular physics inputs to obtain agglomerate growth probabilities and 5) validation of the modeling methodology. The modeling methodology comprised of testing every binary particle collision in the system for sticking, based on the extent of dissipation of the particles' kinetic energy through viscous dissipation by slag-liquid (molten ash) covering the particles. In the modeling methodology developed in this study, thermodynamic equilibrium calculations are used to estimate the amount of slag-liquid in the system, and the changes in particle collision frequencies are accounted for by continuously tracking the number density of the various particle sizes. In this study, the heterogeneities in chemical composition of fuel ash were studied by separating the bulk fuel into particle classes that are rich in specific minerals. FactSage simulations were performed on two bituminous coals and an anthracite to understand the effect of particle-level heterogeneities on agglomeration. The mineral matter behavior of these constituent classes was studied

  10. Spatially resolved chemical imaging of individual atmospheric particles using nanoscale imaging mass spectrometry: Insighs into particle origin and chemistry

    Energy Technology Data Exchange (ETDEWEB)

    Ghosal, Sutapa; Weber, Peter K.; Laskin, Alexander

    2014-04-21

    Knowledge of the spatially-resolved composition of atmospheric particles is essential for differentiating between their surface versus bulk chemistry, understanding particle reactivity and the potential environmental impact. We demonstrate the application of nanometer-scale secondary ion mass spectrometry (Cameca NanoSIMS 50 ion probe) for 3D chemical imaging of individual atmospheric particles without any sample pre-treatment, such as the sectioning of particles. Use of NanoSIMS depth profile analysis enables elemental mapping of particles with nanometer spatial resolution over a broad of range of particle sizes. We have used this technique to probe spatially resolved composition of ambient particles collected during a field campaign in Mexico City. Particles collected during this campaign have been extensively characterized in the past using other particle analysis techniques and hence offer a unique opportunity for exploring the utility of depth resolved chemical imaging in ambient particle research. 1 Particles examined in this study include those collected during a pollution episode related to urban waste incineration as well as background particles from the same location prior to the episode. Particles from the pollution episode show substantial intra-particle compositional variability typical of particles resulting from multiple emission sources. In contrast, the background particles have relatively homogeneous compositions with enhanced presence of nitrogen, oxygen and chlorine at the particle surface. The observed surface enhancement of nitrogen and oxygen species is consistent with the presence of surface nitrates resulting from gas-particle heterogeneous interactions and is indicative of atmospheric ageing of the particles. The results presented here illustrate 3D characterization of ambient particles for insights into their chemical history.

  11. Analytical Models of Exoplanetary Atmospheres. III. Gaseous C-H-O-N Chemistry with Nine Molecules

    Science.gov (United States)

    Heng, Kevin; Tsai, Shang-Min

    2016-10-01

    We present novel, analytical, equilibrium-chemistry formulae for the abundances of molecules in hot exoplanetary atmospheres that include the carbon, oxygen, and nitrogen networks. Our hydrogen-dominated solutions involve acetylene (C2H2), ammonia (NH3), carbon dioxide (CO2), carbon monoxide (CO), ethylene (C2H4), hydrogen cyanide (HCN), methane (CH4), molecular nitrogen (N2), and water (H2O). By considering only the gas phase, we prove that the mixing ratio of carbon monoxide is governed by a decic equation (polynomial equation of 10 degrees). We validate our solutions against numerical calculations of equilibrium chemistry that perform Gibbs free energy minimization and demonstrate that they are accurate at the ˜ 1 % level for temperatures from 500 to 3000 K. In hydrogen-dominated atmospheres, the ratio of abundances of HCN to CH4 is nearly constant across a wide range of carbon-to-oxygen ratios, which makes it a robust diagnostic of the metallicity in the gas phase. Our validated formulae allow for the convenient benchmarking of chemical kinetics codes and provide an efficient way of enforcing chemical equilibrium in atmospheric retrieval calculations.

  12. CAM-chem: description and evaluation of interactive atmospheric chemistry in the Community Earth System Model

    Directory of Open Access Journals (Sweden)

    J.-F. Lamarque

    2012-03-01

    Full Text Available We discuss and evaluate the representation of atmospheric chemistry in the global Community Atmosphere Model (CAM version 4, the atmospheric component of the Community Earth System Model (CESM. We present a variety of configurations for the representation of tropospheric and stratospheric chemistry, wet removal, and online and offline meteorology. Results from simulations illustrating these configurations are compared with surface, aircraft and satellite observations. Major biases include a negative bias in the high-latitude CO distribution, a positive bias in upper-tropospheric/lower-stratospheric ozone, and a positive bias in summertime surface ozone (over the United States and Europe. The tropospheric net chemical ozone production varies significantly between configurations, partly related to variations in stratosphere-troposphere exchange. Aerosol optical depth tends to be underestimated over most regions, while comparison with aerosol surface measurements over the United States indicate reasonable results for sulfate , especially in the online simulation. Other aerosol species exhibit significant biases. Overall, the model-data comparison indicates that the offline simulation driven by GEOS5 meteorological analyses provides the best simulation, possibly due in part to the increased vertical resolution (52 levels instead of 26 for online dynamics. The CAM-chem code as described in this paper, along with all the necessary datasets needed to perform the simulations described here, are available for download at www.cesm.ucar.edu.

  13. Laboratory studies on N(2D) reactions of relevance to the chemistry of planetary atmospheres

    Science.gov (United States)

    Balucani, N.; Casavecchia, P.

    Molecular nitrogen is a very stable molecule, practically inert from a chemical point of view. For a nitrogen chemistry to occur in the planetary atmospheres which contain N2 , it is necessary to transform it into an active form, such as atoms or ions. As far as the production of atomic nitrogen in the upper atmospheres of planets (like Mars) or moons (like Titan) is concerned, several processes - as N2 dissociation induced by electron impact, EUV photolysis (λ fact, because N(4 S) atoms exhibit very low reactivity with closed-shell molecules and the probability of collision with an open-shell radical is small. Unfortunately laboratory experiments on the gas-phase reactions of N(2 D) have been lacking until recently, because of serious experimental difficulties in studying these reactive systems. Accurate kinetic data on the reactions of N(2 D) with the some molecules of relevance to the chemistry of planetary atmospheres have finally become available in the late 90's, but a better knowledge of the reactive behavior requires a dynamical investigation of N(2 D) reactions. The capability of generating intense continuous beams of N(2 D) achieved in our laboratory some years ago has opened up the possibility of studying the reactive scattering of this species under single collision conditions by means of the "crossed molecular beam" technique with mass spectrometric detection. Some examples of our experimental results will be illustrated, with particular attention to the reactions of N(2 D) with hydrocarbons (CH4 , C2 H2 and C2 H4 ) of relevance to the atmosphere of Titan, but also with other molecules of relevance to the atmospheres of Mars, Triton and Pluto.

  14. Heterogeneous Reactions of Polycyclic Aromatic Hydrocarbons on Atmospheric and Terrestrial Surfaces

    Science.gov (United States)

    Simonich, S. L.

    2014-12-01

    The heterogeneous reactions of five higher molecular weight polycyclic aromatic hydrocarbons (PAHs), benzo[a]pyrene-d12 (BaP-d12), benzo(k)fluoranthene-d12 (BkF-d12), benzo[g,h,i]perylene-d12 (BghiP-d12), dibenzo(a,i)pyrene-d14 (DBaiP-d14), and dibenzo[a,l]pyrene (DalP), with NO2, NO3/N2O5, O3, and OH radicals were investigated in a 7000 L indoor Teflon chamber. Quartz fiber filters (QFF) were used as the reaction surface and substrate and the analyses of parent PAHs and Nitro-PAH (NPAH) products was conducted using electron impact gas chromatographic mass spectrometry (GC/MS) and negative chemical ionization GC/MS. In parallel to the laboratory experiments, a theoretical study was conducted to assist in determining the formation of NPAH isomers based on the OH-radical initiated reaction. The thermodynamic stability of OH-PAH intermediates was used to indicate the position of highest electron density and the most stable NPAH products were synthesized to confirm their identity. NO2 and NO3/N2O5 were the most effective oxidizing agents in transforming PAHs deposited on filters to NPAHs, under the experimental conditions. Reaction of BaP-d12, BkF-d12 and BghiP-d12 resulted in the formation of several mono-nitro PAH isomer product, while the reaction of DalP and DaiP-d14 resulted in the formation of only one mono-nitro PAH isomer product. The direct-acting mutagenicity of the products increased the most after NO3/N2O5 exposure, particularly for BkF-d12 in which the formation of dinitro- PAHs was observed. In addition, the degradation of particulate matter (PM)-bound PAHs by heterogeneous reaction with OH radicals, O3, NO3/N2O5 was also studied. Ambient PM samples collected from Beijing, China and Riverside, California were exposed in an indoor chamber under simulated trans-Pacific atmospheric transport conditions and the formation of NPAHs was studied. NPAHs were most effectively formed during the NO3/N2O5 exposure and, for all exposures, there was no significant

  15. Prebiotic Chemistry and Atmospheric Warming of Early Earth by an Active Young Sun

    Science.gov (United States)

    Airapetian, V. S.; Glocer, A.; Gronoff, G.; Hebrard, E.; Danchi, W.

    2016-01-01

    Nitrogen is a critical ingredient of complex biological molecules. Molecular nitrogen, however, which was outgassed Into the Earth's early atmosphere, is relatively chemically inert and nitrogen fixation into more chemically reactive compounds requires high temperatures. Possible mechanisms of nitrogen fixation include lightning, atmospheric shock heating by meteorites, and solar ultraviolet radiation. Here we show that nitrogen fixation in the early terrestrial atmosphere can be explained by frequent and powerful coronal mass ejection events from the young Sun -- so-called superflares. Using magnetohydrodynamic simulations constrained by Kepler Space Telescope observations, we find that successive superflare ejections produce shocks that accelerate energetic particles, which would have compressed the early Earth's magnetosphere. The resulting extended polar cap openings provide pathways for energetic particles to penetrate into the atmosphere and, according to our atmospheric chemistry simulations, initiate reactions converting molecular nitrogen, carbon dioxide and methane to the potent greenhouse gas nitrous oxide as well as hydrogen cyanide, an essential compound for life. Furthermore, the destruction of N2, C02 and CH, suggests that these greenhouse gases cannot explain the stability of liquid water on the early Earth. Instead, we propose that the efficient formation of nitrous oxide could explain a warm early Earth.

  16. Active upper-atmosphere chemistry and dynamics from polar circulation reversal on Titan

    Science.gov (United States)

    Teanby, Nicholas A.; Irwin, Patrick G. J.; Nixon, Conor A.; de Kok, Remco; Vinatier, Sandrine; Coustenis, Athena; Sefton-Nash, Elliot; Calcutt, Simon B.; Flasar, F. Michael

    2012-11-01

    Saturn's moon Titan has a nitrogen atmosphere comparable to Earth's, with a surface pressure of 1.4 bar. Numerical models reproduce the tropospheric conditions very well but have trouble explaining the observed middle-atmosphere temperatures, composition and winds. The top of the middle-atmosphere circulation has been thought to lie at an altitude of 450 to 500 kilometres, where there is a layer of haze that appears to be separated from the main haze deck. This `detached' haze was previously explained as being due to the co-location of peak haze production and the limit of dynamical transport by the circulation's upper branch. Here we report a build-up of trace gases over the south pole approximately two years after observing the 2009 post-equinox circulation reversal, from which we conclude that middle-atmosphere circulation must extend to an altitude of at least 600 kilometres. The primary drivers of this circulation are summer-hemisphere heating of haze by absorption of solar radiation and winter-hemisphere cooling due to infrared emission by haze and trace gases; our results therefore imply that these effects are important well into the thermosphere (altitudes higher than 500 kilometres). This requires both active upper-atmosphere chemistry, consistent with the detection of high-complexity molecules and ions at altitudes greater than 950 kilometres, and an alternative explanation for the detached haze, such as a transition in haze particle growth from monomers to fractal structures.

  17. Active Upper-atmosphere Chemistry and Dynamics from Polar Circulation Reversal on Titan

    Science.gov (United States)

    Teanby, Nicholas A.; Irwin, Patrick Gerard Joseph; Nixon, Conor A.; DeKok, Remco; Vinatier, Sandrine; Coustenis, Athena; Sefton-Nash, Elliot; Calcutt, Simon B.; Flasar, Michael F.

    2012-01-01

    Saturn's moon Titan has a nitrogen atmosphere comparable to Earth's, with a surface pressure of 1.4 bar. Numerical models reproduce the tropospheric conditions very well but have trouble explaining the observed middle-atmosphere temperatures, composition and winds. The top of the middle-atmosphere circulation has been thought to lie at an altitude of 450 to 500 kilometres, where there is a layer of haze that appears to be separated from the main haze deck. This 'detached' haze was previously explained as being due to the colocation of peak haze production and the limit of dynamical transport by the circulation's upper branch. Herewe report a build-up of trace gases over the south pole approximately two years after observing the 2009 post-equinox circulation reversal, from which we conclude that middle-atmosphere circulation must extend to an altitude of at least 600 kilometres. The primary drivers of this circulation are summer-hemisphere heating of haze by absorption of solar radiation and winter-hemisphere cooling due to infrared emission by haze and trace gases; our results therefore imply that these effects are important well into the thermosphere (altitudes higher than 500 kilometres). This requires both active upper-atmosphere chemistry, consistent with the detection of high-complexity molecules and ions at altitudes greater than 950 kilometres, and an alternative explanation for the detached haze, such as a transition in haze particle growth from monomers to fractal structures.

  18. Validation of NO2 and NO from the Atmospheric Chemistry Experiment (ACE)

    OpenAIRE

    Schneider, M; Richter, A.; Ridolfi, M.; Raspollini, P.; Randall, C; J.-P. Pommereau; Piccolo, C.; Nowlan, C.; Notholt, J.; Nichitiu, F; Murtagh, D.; Mikuteit, S.; Melo, S.; McLinden, C. A.; McElroy, C. T.

    2008-01-01

    Vertical profiles of NO2 and NO have been obtained from solar occultation measurements by the Atmospheric Chemistry Experiment (ACE), using an infrared Fourier Transform Spectrometer (ACE-FTS) and (for NO2) an ultraviolet-visible-near-infrared spectrometer, MAESTRO (Measurement of Aerosol Extinction in the Stratosphere and Troposphere Retrieved by Occultation). In this paper, the quality of the ACE-FTS version 2.2 NO2 and NO and the MAESTRO version 1.2 NO2 data are assessed using other solar ...

  19. Results of an interactively coupled atmospheric chemistry - general circulation model. Comparison with observations

    Energy Technology Data Exchange (ETDEWEB)

    Hein, R.; Dameris, M.; Schnadt, C. [and others

    2000-01-01

    An interactively coupled climate-chemistry model which enables a simultaneous treatment of meteorology and atmospheric chemistry and their feedbacks is presented. This is the first model, which interactively combines a general circulation model based on primitive equations with a rather complex model of stratospheric and tropospheric chemistry, and which is computational efficient enough to allow long-term integrations with currently available computer resources. The applied model version extends from the Earth's surface up to 10 hPa with a relatively high number (39) of vertical levels. We present the results of a present-day (1990) simulation and compare it to available observations. We focus on stratospheric dynamics and chemistry relevant to describe the stratospheric ozone layer. The current model version ECHAM4.L39(DLR)/CHEM can realistically reproduce stratospheric dynamics in the Arctic vortex region, including stratospheric warming events. This constitutes a major improvement compared to formerly applied model versions. However, apparent shortcomings in Antarctic circulation and temperatures persist. The seasonal and interannual variability of the ozone layer is simulated in accordance with observations. Activation and deactivation of chlorine in the polar stratospheric vortices and their interhemispheric differences are reproduced. The consideration of the chemistry feedback on dynamics results in an improved representation of the spatial distribution of stratospheric water vapor concentrations, i.e., the simulated meriodional water vapor gradient in the stratosphere is realistic. The present model version constitutes a powerful tool to investigate, for instance, the combined direct and indirect effects of anthropogenic trace gas emissions, and the future evolution of the ozone layer. (orig.)

  20. Neutral and charged clusters in the atmosphere - Their importance and potential role in heterogeneous catalysis

    Science.gov (United States)

    Castleman, A. W., Jr.

    1982-01-01

    An assessment is presented of current knowledge concerning the role and importance of neutral and charged clusters in atmospheric heterogeneous catalysis, with a view to the recommendation of future studies needed for progress in the quantification of aerosol formation and catalytic reactivity. It is established that nucleation from the gaseous to the aerosol state commences via the formation of clusters among molecules participating in the phase-transformation process. Nucleation may proceed in some cases by way of the formation of prenucleation embryos, which then evolve through the energy barrier and undergo phase transformation. In other cases, cluster-cluster interaction among neutral particles or stagewise building of alternate-sign ion clusters may be important in the gas-to-particle conversion process.

  1. On the relationship between total ozone and atmospheric dynamics and chemistry at mid-latitudes – Part 1: Statistical models and spatial fingerprints of atmospheric dynamics and chemistry

    Directory of Open Access Journals (Sweden)

    L. Frossard

    2013-01-01

    Full Text Available We use statistical models for mean and extreme values of total column ozone to analyze "fingerprints" of atmospheric dynamics and chemistry on long-term ozone changes at northern and southern mid-latitudes on grid cell basis. At each grid cell, the r-largest order statistics method is used for the analysis of extreme events in low and high total ozone (termed ELOs and EHOs, respectively, and an autoregressive moving average (ARMA model is used for the corresponding mean value analysis. In order to describe the dynamical and chemical state of the atmosphere, the statistical models include important atmospheric covariates: the solar cycle, the Quasi-Biennial Oscillation (QBO, ozone depleting substances (ODS in terms of equivalent effective stratospheric chlorine (EESC, the North Atlantic Oscillation (NAO, the Antarctic Oscillation (AAO, the El Niño/Southern Oscillation (ENSO, and aerosol load after the volcanic eruptions of El Chichón and Mt. Pinatubo. The influence of the individual covariates on mean and extreme levels in total column ozone is derived on a grid cell basis. The results show that "fingerprints", i.e., significant influence, of dynamical and chemical features are captured in both the "bulk" and the tails of the statistical distribution of ozone, respectively described by mean values and EHOs/ELOs. While results for the solar cycle, QBO, and EESC are in good agreement with findings of earlier studies, unprecedented spatial fingerprints are retrieved for the dynamical covariates. Column ozone is enhanced over Labrador/Greenland, the North Atlantic sector and over the Norwegian Sea, but is reduced over Europe, Russia and the Eastern United States during the positive NAO phase, and vice-versa during the negative phase. The NAO's southern counterpart, the AAO, strongly influences column ozone at lower southern mid-latitudes, including the southern parts of South America and the Antarctic Peninsula, and the central southern mid

  2. Growth of atmospheric nano-particles by heterogeneous nucleation of organic vapor

    Science.gov (United States)

    Wang, J.; McGraw, R. L.; Kuang, C.

    2013-07-01

    Atmospheric aerosols play critical roles in air quality, public health, and visibility. In addition, they strongly influence climate by scattering solar radiation and by changing the reflectivity and lifetime of clouds. One major but still poorly understood source of atmospheric aerosols is new particle formation, which consists of the formation of thermodynamically stable clusters from trace gas molecules (homogeneous nucleation) followed by growth of these clusters to a detectable size (~3 nm). Because freshly nucleated clusters are most susceptible to loss due to high rate of coagulation with pre-existing aerosol population, the initial growth rate strongly influences the rate of new particle formation and ambient aerosol population. Whereas many field observations and modeling studies indicate that organics enhance the initial growth of the clusters and therefore new particle formation, thermodynamic considerations would suggest that the strong increase of equilibrium vapor concentration due to cluster surface curvature (Kelvin effect) may prevent ambient organics from condensing on these small clusters. Here, the contribution of organics to the initial cluster growth is described as heterogeneous nucleation of organic molecules onto these clusters. We find that the strong gradient in cluster population with respect to its size leads to positive cluster number flux. This positive flux drives the growth of clusters substantially smaller than the Kelvin diameter, conventionally considered the minimum particle size that can be grown through condensation. The conventional approach neglects the contribution from the cluster concentration gradient, and underestimates the cluster survival probabilities by a factor of up to 60 if early growth of clusters is due to both condensation of sulfuric acid and heterogeneous nucleation of organic vapors.

  3. NATO Advanced Study Institute on Pollutants from Combustion Formation and Impact on Atmospheric Chemistry

    CERN Document Server

    2000-01-01

    This volume is based on the lectures presented at the NATO Advanced Study Institute: (ASI) «Pollutants Formation from Combustion. Formation Mechanisms and Impact on th th Atmospheric Chemistry» held in Maratea, Italy, from 13 to 26 september 1998. Preservation of the environment is of increasing concern in individual countries but also at continental or world scales. The structure of a NATO ASI which involve lecturers and participants of different nationalities was thought as especially well suited to address environmental issues. As combustion is known to substantially contribute to the damaging of the atmosphere, it was natural to concentrate the ASI program on reviewing the currently available knowledge of the formation mechanisms of the main pollutants liberated by combustion systems. In most situations, pollutants are present as trace components and their formation and removal is strongly conditioned by the chemical reactions initiated by fuel consumption. Therefore specific lectures were aimed at defi...

  4. Nano-sized metabolic precursors for heterogeneous tumor-targeting strategy using bioorthogonal click chemistry in vivo.

    Science.gov (United States)

    Lee, Sangmin; Jung, Seulhee; Koo, Heebeom; Na, Jin Hee; Yoon, Hong Yeol; Shim, Man Kyu; Park, Jooho; Kim, Jong-Ho; Lee, Seulki; Pomper, Martin G; Kwon, Ick Chan; Ahn, Cheol-Hee; Kim, Kwangmeyung

    2017-12-01

    Herein, we developed nano-sized metabolic precursors (Nano-MPs) for new tumor-targeting strategy to overcome the intrinsic limitations of biological ligands such as the limited number of biological receptors and the heterogeneity in tumor tissues. We conjugated the azide group-containing metabolic precursors, triacetylated N-azidoacetyl-d-mannosamine to generation 4 poly(amidoamine) dendrimer backbone. The nano-sized dendrimer of Nano-MPs could generate azide groups on the surface of tumor cells homogeneously regardless of cell types via metabolic glycoengineering. Importantly, these exogenously generated 'artificial chemical receptors' containing azide groups could be used for bioorthogonal click chemistry, regardless of phenotypes of different tumor cells. Furthermore, in tumor-bearing mice models, Nano-MPs could be mainly localized at the target tumor tissues by the enhanced permeation and retention (EPR) effect, and they successfully generated azide groups on tumor cells in vivo after an intravenous injection. Finally, we showed that these azide groups on tumor tissues could be used as 'artificial chemical receptors' that were conjugated to bioorthogonal chemical group-containing liposomes via in vivo click chemistry in heterogeneous tumor-bearing mice. Therefore, overall results demonstrated that our nano-sized metabolic precursors could be extensively applied to new alternative tumor-targeting technique for molecular imaging and drug delivery system, regardless of the phenotype of heterogeneous tumor cells. Copyright © 2017 Elsevier Ltd. All rights reserved.

  5. Non-OH chemistry in oxidation flow reactors for the study of atmospheric chemistry systematically examined by modeling

    Science.gov (United States)

    Peng, Zhe; Day, Douglas A.; Ortega, Amber M.; Palm, Brett B.; Hu, Weiwei; Stark, Harald; Li, Rui; Tsigaridis, Kostas; Brune, William H.; Jimenez, Jose L.

    2016-04-01

    Oxidation flow reactors (OFRs) using low-pressure Hg lamp emission at 185 and 254 nm produce OH radicals efficiently and are widely used in atmospheric chemistry and other fields. However, knowledge of detailed OFR chemistry is limited, allowing speculation in the literature about whether some non-OH reactants, including several not relevant for tropospheric chemistry, may play an important role in these OFRs. These non-OH reactants are UV radiation, O(1D), O(3P), and O3. In this study, we investigate the relative importance of other reactants to OH for the fate of reactant species in OFR under a wide range of conditions via box modeling. The relative importance of non-OH species is less sensitive to UV light intensity than to water vapor mixing ratio (H2O) and external OH reactivity (OHRext), as both non-OH reactants and OH scale roughly proportionally to UV intensity. We show that for field studies in forested regions and also the urban area of Los Angeles, reactants of atmospheric interest are predominantly consumed by OH. We find that O(1D), O(3P), and O3 have relative contributions to volatile organic compound (VOC) consumption that are similar or lower than in the troposphere. The impact of O atoms can be neglected under most conditions in both OFR and troposphere. We define "riskier OFR conditions" as those with either low H2O ( 200 s-1 in OFR254). We strongly suggest avoiding such conditions as the importance of non-OH reactants can be substantial for the most sensitive species, although OH may still dominate under some riskier conditions, depending on the species present. Photolysis at non-tropospheric wavelengths (185 and 254 nm) may play a significant (> 20 %) role in the degradation of some aromatics, as well as some oxidation intermediates, under riskier reactor conditions, if the quantum yields are high. Under riskier conditions, some biogenics can have substantial destructions by O3, similarly to the troposphere. Working under low O2 (volume mixing

  6. Non-OH chemistry in oxidation flow reactors for the study of atmospheric chemistry systematically examined by modeling

    Directory of Open Access Journals (Sweden)

    Z. Peng

    2016-04-01

    Full Text Available Oxidation flow reactors (OFRs using low-pressure Hg lamp emission at 185 and 254 nm produce OH radicals efficiently and are widely used in atmospheric chemistry and other fields. However, knowledge of detailed OFR chemistry is limited, allowing speculation in the literature about whether some non-OH reactants, including several not relevant for tropospheric chemistry, may play an important role in these OFRs. These non-OH reactants are UV radiation, O(1D, O(3P, and O3. In this study, we investigate the relative importance of other reactants to OH for the fate of reactant species in OFR under a wide range of conditions via box modeling. The relative importance of non-OH species is less sensitive to UV light intensity than to water vapor mixing ratio (H2O and external OH reactivity (OHRext, as both non-OH reactants and OH scale roughly proportionally to UV intensity. We show that for field studies in forested regions and also the urban area of Los Angeles, reactants of atmospheric interest are predominantly consumed by OH. We find that O(1D, O(3P, and O3 have relative contributions to volatile organic compound (VOC consumption that are similar or lower than in the troposphere. The impact of O atoms can be neglected under most conditions in both OFR and troposphere. We define “riskier OFR conditions” as those with either low H2O (< 0.1 % or high OHRext ( ≥  100 s−1 in OFR185 and > 200 s−1 in OFR254. We strongly suggest avoiding such conditions as the importance of non-OH reactants can be substantial for the most sensitive species, although OH may still dominate under some riskier conditions, depending on the species present. Photolysis at non-tropospheric wavelengths (185 and 254 nm may play a significant (> 20 % role in the degradation of some aromatics, as well as some oxidation intermediates, under riskier reactor conditions, if the quantum yields are high. Under riskier conditions, some biogenics can have

  7. The Chemistry of Atmosphere-Forest Exchange (CAFE Model – Part 1: Model description and characterization

    Directory of Open Access Journals (Sweden)

    G. M. Wolfe

    2011-01-01

    Full Text Available We present the Chemistry of Atmosphere-Forest Exchange (CAFE model, a vertically-resolved 1-D chemical transport model designed to probe the details of near-surface reactive gas exchange. CAFE integrates all key processes, including turbulent diffusion, emission, deposition and chemistry, throughout the forest canopy and mixed layer. CAFE utilizes the Master Chemical Mechanism (MCM and is the first model of its kind to incorporate a suite of reactions for the oxidation of monoterpenes and sesquiterpenes, providing a more comprehensive description of the oxidative chemistry occurring within and above the forest. We use CAFE to simulate a young Ponderosa pine forest in the Sierra Nevada, CA. Utilizing meteorological constraints from the BEARPEX-2007 field campaign, we assess the sensitivity of modeled fluxes to parameterizations of diffusion, laminar sublayer resistance and radiation extinction. To characterize the general chemical environment of this forest, we also present modeled mixing ratio profiles of biogenic hydrocarbons, hydrogen oxides and reactive nitrogen. The vertical profiles of these species demonstrate a range of structures and gradients that reflect the interplay of physical and chemical processes within the forest canopy, which can influence net exchange.

  8. Do organic surface films on sea salt aerosols influence atmospheric chemistry? ─ a model study

    Directory of Open Access Journals (Sweden)

    R. von Glasow

    2007-11-01

    Full Text Available Organic material from the ocean's surface can be incorporated into sea salt aerosol particles often producing a surface film on the aerosol. Such an organic coating can reduce the mass transfer between the gas phase and the aerosol phase influencing sea salt chemistry in the marine atmosphere. To investigate these effects and their importance for the marine boundary layer (MBL we used the one-dimensional numerical model MISTRA. We considered the uncertainties regarding the magnitude of uptake reduction, the concentrations of organic compounds in sea salt aerosols and the oxidation rate of the organics to analyse the possible influence of organic surfactants on gas and liquid phase chemistry with a special focus on halogen chemistry. By assuming destruction rates for the organic coating based on laboratory measurements we get a rapid destruction of the organic monolayer within the first meters of the MBL. Larger organic initial concentrations lead to a longer lifetime of the coating but lead also to an unrealistically strong decrease of O3 concentrations as the organic film is destroyed by reaction with O3. The lifetime of the film is increased by assuming smaller reactive uptake coefficients for O3 or by assuming that a part of the organic surfactants react with OH. With regard to tropospheric chemistry we found that gas phase concentrations for chlorine and bromine species decreased due to the decreased mass transfer between gas phase and aerosol phase. Aqueous phase chlorine concentrations also decreased but aqueous phase bromine concentrations increased. Differences for gas phase concentrations are in general smaller than for liquid phase concentrations. The effect on gas phase NO2 or NO is very small (reduction less than 5% whereas liquid phase NO2 concentrations increased in some cases by nearly 100%. We list suggestions for further laboratory studies which are needed for improved model studies.

  9. Analysis of coherent structures during the 2009 CABINEX field campaign: Implications for atmospheric chemistry

    Science.gov (United States)

    Pressley, S. N.; Steiner, A. L.; Chung, S. H.; Edburg, S. L.; Jones, E.; Botros, A.

    2010-12-01

    Intermittent coherent structures are an important component of turbulent exchange of mass, momentum, and energy at the biosphere-atmosphere interface. Specifically, above forested canopies, coherent structures can be responsible for a large fraction of the exchange of trace gases and aerosols between the sub-canopy (ground surface), canopy and the atmosphere. This study quantifies the coherent structures and associated turbulence intensity at the canopy interface for the Community Atmosphere-Biosphere Interactions Experiment (CABINEX) field campaign (July 1 - Aug 10, 2009) at the University of Michigan Biological Station (UMBS), and determines the effect of coherent structures on canopy air-parcel residence times and importance for atmospheric chemistry. Two different methods of analysis are used to estimate the coherent exchange: 1) wavelet analysis and 2) quadrant-hole (Q-H) analysis (also referred to as conditional sampling). Wavelet analysis uses wavelet transforms to detect non-periodic signals with a variable duration. Using temperature ramp structures, the timing and magnitude of individual coherent ‘events’ can be evaluated over the duration of the campaign. Conversely, the Q-H analysis detects ‘events’ when │u'w'│≥ H×urmswrms, where H is a threshold parameter, u is the stream-wise velocity and w is the vertical velocity. Events are primarily comprised of high momentum air penetrating into the canopy (sweeps, u’> 0; w’0). Results from both techniques are compared under varying stability classes, and the number of events, total duration, and contribution to the total flux are analyzed for the full campaign. The contribution of coherent structures to the total canopy-atmosphere exchange is similar between the two methods, despite a greater number of events estimated from the Q-H analysis. These analyses improve the quantification of canopy mixing time at the UMBS site during CABINEX, and will aid in interpreting in-canopy processes

  10. Studies in Photochemical Smog Chemistry: I. Atmospheric Chemistry of Toluene. I. Analysis of Chemical Reaction Mechanisms for Photochemical Smog

    Science.gov (United States)

    Leone, Joseph Anthony

    This study focuses on two related topics in the gas phase organic chemistry of importance in urban air pollution. Part I describes an experimental and modeling effort aimed at developing a new explicit reaction mechanism for the atmospheric photooxidation of toluene. This mechanism is tested using experimental data from both indoor and outdoor smog chamber facilities. The predictions of the new reaction mechanism are found to be in good agreement with both sets of experimental data. Additional simulations performed with the new mechanism are used to investigate various mechanistic paths, and to gain insight into areas where our understanding is not complete. The outdoor experimental facility, which was built to provide the second set of experimental data, consists of a 65 cubic meter teflon smog chamber together with full instrumentation capable of measuring ozone, nitrogen dioxide, nitric oxide, peroxyacetyl nitrate (PAN), carbon monoxide, relative humidity, temperature, aerosol size distributions, and of course toluene and its photooxidation products. In Part II, we present a theoretical analysis of lumped chemical reaction mechanisms for photochemical smog. Included is a description of a new counter species analysis technique which can be used to analyze any complex chemical reaction mechanism. When applied to mechanisms for photochemical smog, this analysis is shown capable of providing answers to previously inaccessible questions such as the relative contributions of individual organics to photochemical ozone formation. The counter species analysis is applied to six existing mechanisms for photochemical smog to determine why they predict substantially different degrees of emission controls to achieve the same desired air quality under identical conditions. For each mechanism critical areas are identified that when altered bring the predictions of the various mechanisms into much closer agreement. Finally, a new lumped mechanism for photochemical smog is

  11. Atmospheric impact of the 1783–1784 Laki eruption: Part I Chemistry modelling

    Directory of Open Access Journals (Sweden)

    D. S. Stevenson

    2003-01-01

    Full Text Available Results from the first chemistry-transport model study of the impact of the 1783–1784 Laki fissure eruption (Iceland: 64°N, 17°W upon atmospheric composition are presented. The eruption released an estimated 61 Tg(S as SO2 into the troposphere and lower stratosphere. The model has a high resolution tropopause region, and detailed sulphur chemistry. The simulated SO2 plume spreads over much of the Northern Hemisphere, polewards of ~40°N. About 70% of the SO2 gas is directly deposited to the surface before it can be oxidised to sulphuric acid aerosol. The main SO2 oxidants, OH and H2O2, are depleted by up to 40% zonally, and the lifetime of SO2 consequently increases. Zonally averaged tropospheric SO2 concentrations over the first three months of the eruption exceed 20 ppbv, and sulphuric acid aerosol reaches ~2 ppbv. These compare to modelled pre-industrial/present-day values of 0.1/0.5 ppbv SO2 and 0.1/1.0 ppbv sulphate. A total sulphuric acid aerosol yield of 17–22 Tg(S is produced. The mean aerosol lifetime is 6–10 days, and the peak aerosol loading of the atmosphere is 1.4–1.7 Tg(S (equivalent to 5.9–7.1 Tg of hydrated sulphuric acid aerosol. These compare to modelled pre-industrial/present-day sulphate burdens of 0.28/0.81 Tg(S, and lifetimes of 6/5 days, respectively. Due to the relatively short atmospheric residence times of both SO2 and sulphate, the aerosol loading approximately mirrors the temporal evolution of emissions associated with the eruption. The model produces a reason-able simulation of the acid deposition found in Greenland ice cores. These results appear to be relatively insensitive to the vertical profile of emissions assumed, although if more of the emissions reached higher levels (>12 km, this would give longer lifetimes and larger aerosol yields. Introducing the emissions in episodes generates similar results to using monthly mean emissions, because the atmospheric lifetimes are similar to the repose periods

  12. The Development of a Combined Search for a Heterogeneous Chemistry Database

    National Research Council Canada - National Science Library

    Lulu Jiang; Yuehong Zhao; Bojun Xu; Hao Wen

    2015-01-01

    .... In this paper, two kinds of search strategies, synchronous search and asynchronous search, are proposed to solve these problems in the heterogeneous structure database and the property database found...

  13. CARBON-RICH GIANT PLANETS: ATMOSPHERIC CHEMISTRY, THERMAL INVERSIONS, SPECTRA, AND FORMATION CONDITIONS

    Energy Technology Data Exchange (ETDEWEB)

    Madhusudhan, Nikku [Department of Astrophysical Sciences, Princeton University, Princeton, NJ 08544 (United States); Mousis, Olivier [Institut UTINAM, CNRS-UMR 6213, Observatoire de Besancon, BP 1615, F-25010 Besancon Cedex (France); Johnson, Torrence V. [Jet Propulsion Laboratory, California Institute of Technology, Pasadena, CA 91109 (United States); Lunine, Jonathan I., E-mail: nmadhu@astro.princeton.edu [Department of Astronomy, Cornell University, Ithaca, NY 14853 (United States)

    2011-12-20

    The recent inference of a carbon-rich atmosphere, with C/O {>=} 1, in the hot Jupiter WASP-12b motivates the exotic new class of carbon-rich planets (CRPs). We report a detailed study of the atmospheric chemistry and spectroscopic signatures of carbon-rich giant (CRG) planets, the possibility of thermal inversions in their atmospheres, the compositions of icy planetesimals required for their formation via core accretion, and the apportionment of ices, rock, and volatiles in their envelopes. Our results show that CRG atmospheres probe a unique region in composition space, especially at high temperature (T). For atmospheres with C/O {>=} 1, and T {approx}> 1400 K in the observable atmosphere, most of the oxygen is bound up in CO, while H{sub 2}O is depleted and CH{sub 4} is enhanced by up to two or three orders of magnitude each, compared to equilibrium compositions with solar abundances (C/O = 0.54). These differences in the spectroscopically dominant species for the different C/O ratios cause equally distinct observable signatures in the spectra. As such, highly irradiated transiting giant exoplanets form ideal candidates to estimate atmospheric C/O ratios and to search for CRPs. We also find that the C/O ratio strongly affects the abundances of TiO and VO, which have been suggested to cause thermal inversions in highly irradiated hot Jupiter atmospheres. A C/O = 1 yields TiO and VO abundances of {approx}100 times lower than those obtained with equilibrium chemistry assuming solar abundances, at P {approx} 1 bar. Such a depletion is adequate to rule out thermal inversions due to TiO/VO even in the most highly irradiated hot Jupiters, such as WASP-12b. We estimate the compositions of the protoplanetary disk, the planetesimals, and the envelope of WASP-12b, and the mass of ices dissolved in the envelope, based on the observed atmospheric abundances. Adopting stellar abundances (C/O = 0.44) for the primordial disk composition and low-temperature formation conditions

  14. Spatial and temporal dynamics of stream chemistry in a forested watershed impacted by atmospheric deposition

    Science.gov (United States)

    Piatek, K. B.; Christopher, S. F.; Mitchell, M. J.

    2008-09-01

    We analyzed spatial and temporal dynamics of solute chemistry in a forest watershed impacted by atmospheric deposition in the Adirondack Mountains of New York State, USA. Spatial dynamics of solute chemistry and natural abundance isotopes of nitrate (15N and 18O) were examined in 6 locations and the watershed outlet in 2001 and 2002. Temporal dynamics were examined during 5 discharge periods: winter, snowmelt, spring, summer, and fall, which were based on discharge levels at the outlet. Solute concentrations were statistically significantly different (p≤0.05) among stream sampling locations and discharge periods, with no interaction effects. Groundwater sources located in upper watershed controlled stream chemistry at higher elevations with highest pH, Ca2+, sum of base cations, Si, NO3-, total N, and SO42- and lowest Al concentrations. Two low elevation wetlands had a substantial influence over stream chemistry at those locations contributing lowest NO3-, total N, and highest DOC and DON. Snowmelt exhibited among the lowest pH, sum of base cations, and SO42-, and highest NO3-, total N, DON, and total Al; snowmelt appeared to dilute groundwater, and flush stored soil-derived solutes. Summer discharge, composed mainly of groundwater, exhibited the lowest flow, among the highest Mg2+, Ca2+, and lowest DON, DOC, and total Al concentrations. Isotopic analysis together with patterns of NH4+ versus NO3- dynamics indicated that NO3- was microbial, generated in fall and accumulated in winter in upper watershed soils, and flushed to stream during high discharge events. Highest discharge in snowmelt 2001, a summer drought in 2002, and fall storms following the drought were further evaluated for their specific effects on stream chemistry. Snowmelt 2001 had the lowest pH and highest NO3-, base flow during summer drought had the lowest total Al, and storms in fall 2002 had highest SO42- of all periods, but all other solute concentrations were comparable to other discharge

  15. Simulation of comprehensive chemistry and atmospheric methane lifetime in the LGM with EMAC

    Science.gov (United States)

    Gromov, Sergey; Steil, Benedikt

    2017-04-01

    Past records of atmospheric methane (CH4) abundance/isotope composition may provide a substantial insight on C exchanges in the Earth System (ES). When simulated in the climate models, CH4 helps to identify climate parameters transitions via triggering of its different (natural) sources, with a proviso that its sinks are adequately represented in the model. The latter are still a matter of large uncertainty in the studies focussing on the interpretation of CH4 evolution throughout Last Glacial Maximum (LGM), judging the conferred span of tropospheric CH4 lifetime (λ) of 3-16 yr [1-4]. In this study, we attempt to: (i) deliver the most adequate estimate of the LGM atmospheric sink of CH4 in the EMAC AC-GCM [5] equipped with the comprehensive representation of atmospheric chemistry [6], (ii) reveal the ES and CH4 emission parameters that are most influential for λ and (iii) based on these findings, suggest a parameterisation for λ that may be consistently used in climate models. In pursuing (i) we have tuned the EMAC model for simulating LGM atmospheric chemistry state, including careful revisiting of the trace gases emissions from the biosphere, biomass burning/lightning source, etc. The latter affect the key simulated component bound with λ, viz. the abundance and distribution of the hydroxyl radicals (OH) which, upon reacting with CH4, constitute its main tropospheric sink. Our preliminary findings suggest that OH is buffered in the atmosphere in a similar fashion to preindustrial climate, which in line with the recent studies employing comprehensive chemistry mechanisms (e.g., [3]). The analysis in (ii) suggests that tropospheric λ values may be qualitatively described as a convolution of values typical for zonal domain with high and low photolytic recycling rates (i.e. tropics and extra-tropics), as in the latter a dependence of the zonal average λ value on the CH4 emission strength exists. We further use the extensive diagnostic in EMAC to infer the

  16. Compilation and analyses of emissions inventories for the NOAA atmospheric chemistry project. Progress report, August 1997

    Energy Technology Data Exchange (ETDEWEB)

    Benkovitz, C.M.

    1997-09-01

    Global inventories of anthropogenic emissions of oxides of nitrogen for circa 1985 and 1990 and non-methane volatile organic compounds (NMVOCs) for circa 1990 have been compiled by this project. Work on the inventories has been carried out under the umbrella of the Global Emissions Inventory Activity of the International Global Atmospheric Chemistry program. Global emissions of NOx for 1985 are estimated to be 21 Tg N/yr, with approximately 84% originating in the Northern Hemisphere. The global emissions for 1990 are 31 Tg N/yr for NOx and 173 Gg NMVOC/yr. Ongoing research activities for this project continue to address emissions of both NOx and NMVOCs. Future tasks include: evaluation of more detailed regional emissions estimates and update of the default 1990 inventories with the appropriate estimates; derivation of quantitative uncertainty estimates for the emission values; and development of emissions estimates for 1995.

  17. Partial Overhaul and Initial Parallel Optimization of KINETICS, a Coupled Dynamics and Chemistry Atmosphere Model

    Science.gov (United States)

    Nguyen, Howard; Willacy, Karen; Allen, Mark

    2012-01-01

    KINETICS is a coupled dynamics and chemistry atmosphere model that is data intensive and computationally demanding. The potential performance gain from using a supercomputer motivates the adaptation from a serial version to a parallelized one. Although the initial parallelization had been done, bottlenecks caused by an abundance of communication calls between processors led to an unfavorable drop in performance. Before starting on the parallel optimization process, a partial overhaul was required because a large emphasis was placed on streamlining the code for user convenience and revising the program to accommodate the new supercomputers at Caltech and JPL. After the first round of optimizations, the partial runtime was reduced by a factor of 23; however, performance gains are dependent on the size of the data, the number of processors requested, and the computer used.

  18. Multiple sulfur isotope geochemistry of Dharwar Supergroup, Southern India: Late Archean record of changing atmospheric chemistry

    Science.gov (United States)

    Mishima, Kaoru; Yamazaki, Rie; Satish-Kumar, Madhusoodhan; Ueno, Yuichiro; Hokada, Tomokazu; Toyoshima, Tsuyoshi

    2017-04-01

    Earth's tectonic and climatic systems may have changed fundamentally before the Great Oxidation Event (GOE) at about 2.3 Ga. Sulfur Mass Independent Fractionation (S-MIF) has demonstrated that Earth's atmosphere was virtually oxygen-free before the GOE. During 3.0 to 2.4 Ga, the change in Δ33S and Δ36S signals may reflect the perturbation of atmospheric chemistry, though the mechanisms of the change are uncertain. Here, we reported multiple sulfur isotopic studies of Archean volcano-sedimentary sequences of the Dharwar Supergroup, distributed in the Chitradurga Schist Belt (CSB), Southern India. New field mapping and zircon U-Pb dating allows us to reconstruct detailed lithostratigraphy of the Dharwar Supergroup. The lower unit consists of post-3.0 Ga conglomerate, stromatolitic carbonate, siliciclastics with diamictite, chert/BIF and pillowed basalt in ascending order, all of which are older than the 2676 Ma dacite dyke that had intruded into the lower unit. The upper unit unconformably overlies the pillow basalts at the top of the lower unit, and consists of conglomerate/sandstone with ∼2600 Ma detrital zircons, komatiitic basalt, BIF and siliciclastic sequence with mafic volcanics. Sulfur isotope analysis of extracted sulfides shows MIF signals (Δ33S > + 1 ‰) with clear Δ33S- Δ36S correlations. The lower group of the Dharwar Supergroup shows a Δ36S / Δ33S slope of -1.48, the middle group shows -1.16 and -1.07, and the upper group shows -0.94. Reassessment of all the Archean S-MIF records from sedimentary rocks indicates that the Δ36S / Δ33S slope systematically changed during the Archean period. The observed trend in the Indian section is similar to those of its Pilbara-Kaapvaal equivalents, thus it could reflect a global atmospheric signature. Moreover, the isotopic trend seems to correlate with mid-Archean glaciation. Thus, the Δ36S / Δ33S slope could be a useful tracer for atmospheric chemistry and its link with climate change before the GOE.

  19. An adaptive reduction algorithm for efficient chemical calculations in global atmospheric chemistry models

    Science.gov (United States)

    Santillana, Mauricio; Le Sager, Philippe; Jacob, Daniel J.; Brenner, Michael P.

    2010-11-01

    We present a computationally efficient adaptive method for calculating the time evolution of the concentrations of chemical species in global 3-D models of atmospheric chemistry. Our strategy consists of partitioning the computational domain into fast and slow regions for each chemical species at every time step. In each grid box, we group the fast species and solve for their concentration in a coupled fashion. Concentrations of the slow species are calculated using a simple semi-implicit formula. Separation of species between fast and slow is done on the fly based on their local production and loss rates. This allows for example to exclude short-lived volatile organic compounds (VOCs) and their oxidation products from chemical calculations in the remote troposphere where their concentrations are negligible, letting the simulation determine the exclusion domain and allowing species to drop out individually from the coupled chemical calculation as their production/loss rates decline. We applied our method to a 1-year simulation of global tropospheric ozone-NO x-VOC-aerosol chemistry using the GEOS-Chem model. Results show a 50% improvement in computational performance for the chemical solver, with no significant added error.

  20. The first results from HIRAC - the Highly Instrumented Reactor for Atmospheric Chemistry

    Science.gov (United States)

    Malkin, T. L.; Smith, S. C.; Goddard, A.; Glowacki, D. R.; Heemavibool, K.; Wada, R.; Winiberg, F.; Pilling, M. J.; Heard, D. E.; Seakins, P.

    2009-12-01

    The Highly Instrumented Reactor for Atmospheric Chemistry, HIRAC, is a recently commissioned stainless steel environmental chamber. Uniquely, the structure allows for simultaneous temperature and pressure variation and for the monitoring of radical species by Fluorescence Assay by Gas Expansion (FAGE) and Cavity Ring Down Spectroscopy (CRDS). HIRAC is cylindrical in shape with internal dimensions of 2.0 m long and 1.2 m diameter giving a total volume of ~2.25 m3. It is fitted with a broad range of instrumentation based on different detection techniques (detailed in the table below) to allow accurate monitoring of the chemistry occurring inside the chamber. Light for photochemical studies is be provided by lamps housed in eight quartz tubes mounted radially inside the reactive volume parallel to the chamber's principle axis providing a homogenous radiation profile. In this paper we present example of work relating to the three major objectives for HIRAC: 1) Mechanism development linked to the Master Chemical Mechanism - Measurements of pressure dependent OH and HO2 yields from the reaction of O3 with trans-2-butene and isoprene. 2) Field instrument development and calibration - Development of a CRDS system for measuring NO3 radicals inside HIRAC and the first pressure dependent calibrations of a FAGE HOx instrument. 3) Kinetics and Structural Activity Relationship (SAR) development - Relative rate studies of the reaction of Cl atoms with a series of acetates. The range of detection techniques employed in HIRAC and the species detected.

  1. Atmospheric deposition chemistry in a subalpine area of the Julian Alps, NW Slovenia

    Directory of Open Access Journals (Sweden)

    Gregor Muri

    2013-04-01

    Full Text Available Wet-only precipitation was collected in Rateče, a remote village in the outskirts of the Julian Alps (Nort-West Slovenia during 2003-2011, in order to characterise atmospheric deposition chemistry. The samples were collected on a daily basis and combined into weekly samples that were analysed for pH, conductivity and major anions and cations. Ammonium, nitrate and sulphate were the most abundant ions, exhibiting volume-weighted mean values (2003-2011 of 22, 17 and 17 µeq L–1, respectively. Furthermore, the trends of the major parameters in the precipitation were assessed using a simple linear regression. A significant downward trend of both nitrate and sulphate was observed, explained by evident reductions in NOx and SOx emissions in the region. The decline of nitrate and sulphate was also reflected in a significant and downward trend of conductivity. While the trend of ammonium could also be downward, the trends of other major ions were not significant. Atmospheric nitrogen deposition, representing inorganic forms of nitrogen (i.e., ammonium and nitrate, was calculated to examine potential threats that the deposition of nitrogen may cause on lake ecosystems. Nitrogen deposition in Rateče ranged from 5.5 to 9.5 kg N ha–1 yr–1. Although this was below the critical threshold that might cause an impact on surface waters, nitrogen deposition in the nearby Julian Alps, where sensitive mountain lakes are situated, might be higher and its impact on the ecosystem greater. In fact, several studies performed on water chemistry, sedimentary organic matter and stable isotopes in Slovenian mountain lakes have shown progressive changes in their water columns and sediments that can be attributed to nitrogen deposition.

  2. Natural versus anthropogenic inhalable aerosol chemistry of transboundary East Asian atmospheric outflows into western Japan.

    Science.gov (United States)

    Moreno, Teresa; Kojima, Tomoko; Querol, Xavier; Alastuey, Andrés; Amato, Fulvio; Gibbons, Wes

    2012-05-01

    The eastward transport of aerosols exported from mainland Asia strongly influences air quality in the Japanese archipelago. The bulk of the inhalable particulate matter (PM(10)) in these intrusions comprises either natural, desert-derived minerals (mostly supermicron silicates) or anthropogenic pollutants (mostly submicron sulphates), in various states of mixing. We analyse PM(10) collected in Kumamoto, SW Japan, during three contrasting types of aerosol intrusions, the first being dominated by desert PM which became increasingly mixed with anthropogenic components as time progressed, the second being a relatively minor event mixing fine, distal desert PM with anthropogenic materials, and the third being dominated by anthropogenic pollutants. Whereas the chemistry of the natural mineral component is characterised by "crustal" elements (Si, Al, Fe, Mg, K, Li, P, Sc, V, Rb, Sr, Zr, Th, lanthanoids), the anthropogenic component is rich in secondary inorganic compounds and more toxic metallic elements (NH(4)(+), SO(4)(2-), As, Pb, Cd, Cu, Zn, Sn, Bi, Sb, and Ge). Some desert-dust (Kosa) intrusions are more calcareous than others, implicating geologically different source areas, and contain enhanced levels of NO(3)(-), probably as supermicron Ca(NO(3))(2) particles produced by chemical reaction between NOx pollutants (mostly from industry and traffic) and carbonate during atmospheric transport. The overall trace element chemistry of aerosol intrusions into Kumamoto shows low V/Rb, low NO(3)(-)/SO(4)(2-), enhanced As levels, and unfractionated La/Ce values, which are all consistent with anthropogenic sources including coal emissions rather than those derived from the refining and combustion of oil fractionates. Geographically dispersed, residual sulphatic plumes of this nature mix with local traffic (revealed by OC and EC concentrations) and industrial emissions and dissipate only slowly, due to the dominance of submicron accumulation mode PM which is atmospherically

  3. Heterogeneous chemistry: a mechanism missing in current models to explain secondary inorganic aerosol formation during the January 2013 haze episode in North China

    Science.gov (United States)

    Zheng, B.; Zhang, Q.; Zhang, Y.; He, K. B.; Wang, K.; Zheng, G. J.; Duan, F. K.; Ma, Y. L.; Kimoto, T.

    2015-02-01

    Severe regional haze pollution events occurred in eastern and central China in January 2013, which had adverse effects on the environment and public health. Extremely high levels of particulate matter with aerodynamic diameter of 2.5 μm or less (PM2.5) with dominant components of sulfate and nitrate are responsible for the haze pollution. Although heterogeneous chemistry is thought to play an important role in the production of sulfate and nitrate during haze episodes, few studies have comprehensively evaluated the effect of heterogeneous chemistry on haze formation in China by using the 3-D models due to of a lack of treatments for heterogeneous reactions in most climate and chemical transport models. In this work, the WRF-CMAQ model with newly added heterogeneous reactions is applied to East Asia to evaluate the impacts of heterogeneous chemistry and the meteorological anomaly during January 2013 on regional haze formation. As the parameterization of heterogeneous reactions on different types of particles is not well established yet, we arbitrarily selected the uptake coefficients from reactions on dust particles and then conducted several sensitivity runs to find the value that can best match observations. The revised CMAQ with heterogeneous chemistry not only captures the magnitude and temporal variation of sulfate and nitrate, but also reproduces the enhancement of relative contribution of sulfate and nitrate to PM2.5 mass from clean days to polluted haze days. These results indicate the significant role of heterogeneous chemistry in regional haze formation and improve the understanding of the haze formation mechanisms during the January 2013 episode.

  4. Do vibrationally excited OH molecules affect middle and upper atmospheric chemistry?

    Directory of Open Access Journals (Sweden)

    T. von Clarmann

    2010-10-01

    Full Text Available Except for a few reactions involving electronically excited molecular or atomic oxygen or nitrogen, atmospheric chemistry modelling usually assumes that the temperature dependence of reaction rates is characterized by Arrhenius' law involving kinetic temperatures. It is known, however, that in the upper atmosphere the vibrational temperatures may exceed the kinetic temperatures by several hundreds of Kelvins. This excess energy has an impact on the reaction rates. We have used upper atmospheric OH populations and reaction rate coefficients for OH(v=0...9+O3 and OH(v=0...9+O to estimate the effective (i.e. population weighted reaction rates for various atmospheric conditions. We have found that the effective rate coefficient for OH(v=0...9+O3 can be larger by a factor of up to 1470 than that involving OH in its vibrational ground state only. At altitudes where vibrationally excited states of OH are highly populated, the OH reaction is a minor sink of Ox and O3 compared to other reactions involving, e.g., atomic oxygen. Thus the impact of vibrationally excited OH on the ozone or Ox sink remains small. Among quiescent atmospheres under investigation, the largest while still small (less than 0.1% effect was found for the polar winter upper stratosphere and mesosphere. The contribution of the reaction of vibrationally excited OH with ozone to the OH sink is largest in the upper polar winter stratosphere (up to 4%, while its effect on the HO2 source is larger in the lower thermosphere (up to 1.5% for polar winter and 2.5% for midlatitude night conditions. For OH(v=0...9+O the effective rate coefficients are lower by up to 11% than those involving OH in its vibrational ground state. The effects on the odd oxygen sink are negative and can reach −3% (midlatitudinal nighttime lowermost thermosphere, i.e. neglecting vibrational excitation overestimates the odd

  5. Climate change and atmospheric chemistry: how will the stratospheric ozone layer develop?

    Science.gov (United States)

    Dameris, Martin

    2010-10-25

    The discovery of the ozone hole over Antarctica in 1985 was a surprise for science. For a few years the reasons of the ozone hole was speculated about. Soon it was obvious that predominant meteorological conditions led to a specific situation developing in this part of the atmosphere: Very low temperatures initiate chemical processes that at the end cause extreme ozone depletion at altitudes of between about 15 and 30 km. So-called polar stratospheric clouds play a key role. Such clouds develop at temperatures below about 195 K. Heterogeneous chemical reactions on cloud particles initiate the destruction of ozone molecules. The future evolution of the ozone layer will not only depend on the further development of concentrations of ozone-depleting substances, but also significantly on climate change.

  6. Chemistry, spectroscopy and the role of supported vanadium oxides in heterogeneous catalysis

    NARCIS (Netherlands)

    Weckhuysen, B.M.; Keller, D.E.

    2003-01-01

    Supported vanadium oxide catalysts are active in a wide range of applications. In this review, an overview is given of the current knowledge available about vanadium oxide-based catalysts. The review starts with the importance of vanadium in heterogeneous catalysis, a discussion of the molecular

  7. Biomass burning in the tropics: impact on atmospheric chemistry and biogeochemical cycles.

    Science.gov (United States)

    Crutzen, P J; Andreae, M O

    1990-12-21

    Biomass burning is widespread, especially in the tropics. It serves to clear land for shifting cultivation, to convert forests to agricultural and pastoral lands, and to remove dry vegetation in order to promote agricultural productivity and the growth of higher yield grasses. Furthermore, much agricultural waste and fuel wood is being combusted, particularly in developing countries. Biomass containing 2 to 5 petagrams of carbon is burned annually (1 petagram = 10(15) grams), producing large amounts of trace gases and aerosol particles that play important roles in atmospheric chemistry and climate. Emissions of carbon monoxide and methane by biomass burning affect the oxidation efficiency of the atmosphere by reacting with hydroxyl radicals, and emissions of nitric oxide and hydrocarbons lead to high ozone concentrations in the tropics during the dry season. Large quantities of smoke particles are produced as well, and these can serve as cloud condensation nuclei. These particles may thus substantially influence cloud microphysical and optical properties, an effect that could have repercussions for the radiation budget and the hydrological cycle in the tropics. Widespread burning may also disturb biogeochemical cycles, especially that of nitrogen. About 50 percent of the nitrogen in the biomass fuel can be released as molecular nitrogen. This pyrdenitrification process causes a sizable loss of fixed nitrogen in tropical ecosystems, in the range of 10 to 20 teragrams per year (1 teragram = 10(12) grams).

  8. Molecular Chemistry of Atmospheric Brown Carbon Inferred from a Nationwide Biomass Burning Event

    Energy Technology Data Exchange (ETDEWEB)

    Lin, Peng; Bluvshtein, Nir; Rudich, Yinon; Nizkorodov, Sergey; Laskin, Julia; Laskin, Alexander

    2017-10-17

    Lag Ba'Omer, a nationwide bonfire festival in Israel, was chosen as a case study to investigate the influence of a major biomass burning event on the light absorption properties of atmospheric brown carbon (BrC). The chemical composition and optical properties of BrC chromophores were investigated using a high performance liquid chromatography (HPLC) platform coupled to photo diode array (PDA) and high resolution mass spectrometry (HRMS) detectors. Substantial increase of BrC light absorption coefficient was observed during the night-long biomass burning event. Most chromophores observed during the event were attributed to nitroaromatic compounds, comprising 28 elemental formulas of at least 63 structural isomers. The NAC, in combination, accounted for 50-80% of the total visible light absorption (> 400 nm) by solvent extractable BrC. The results highlight that NAC, particular nitrophenols, are important light absorption contributors of biomass burning organic aerosol (BBOA), suggesting that night time chemistry of ▪NO3 and N2O5 with particles may play a significant role in atmospheric transformations of BrC. Nitrophenols and related compounds were especially important chromophores of BBOA. The absorption spectra of the BrC chromophores are influenced by the extraction solvent and solution pH, implying that the aerosol acidity is an important factor controlling the light absorption properties of BrC.

  9. Atmospheric oxidation chemistry and ozone production: Results from SHARP 2009 in Houston, Texas

    Science.gov (United States)

    Ren, Xinrong; van Duin, Diana; Cazorla, Maria; Chen, Shuang; Mao, Jingqiu; Zhang, Li; Brune, William H.; Flynn, James H.; Grossberg, Nicole; Lefer, Barry L.; Rappenglück, Bernhard; Wong, Kam W.; Tsai, Catalina; Stutz, Jochen; Dibb, Jack E.; Thomas Jobson, B.; Luke, Winston T.; Kelley, Paul

    2013-06-01

    Ozone (O3) and secondary fine particles come from the atmospheric oxidation chemistry that involves the hydroxyl radical (OH) and hydroperoxyl radical (HO2), which are together called HOx. Radical precursors such as nitrous acid (HONO) and formaldehyde (HCHO) significantly affect the HOx budget in urban environments. These chemical processes connect surface anthropogenic and natural emissions to local and regional air pollution. Using the data collected during the Study of Houston Atmospheric Radical Precursors (SHARP) in spring 2009, we examine atmospheric oxidation chemistry and O3 production in this polluted urban environment. A numerical box model with five different chemical mechanisms was used to simulate the oxidation processes and thus OH and HO2 in this study. In general, the model reproduced the measured OH and HO2 with all five chemical mechanisms producing similar levels of OH and HO2, although midday OH was overpredicted and nighttime OH and HO2 were underpredicted. The calculated HOx production was dominated by HONO photolysis in the early morning and by the photolysis of O3 and oxygenated volatile organic compounds (OVOCs) in the midday. On average, the daily HOx production rate was 24.6 ppbv d-1, of which 30% was from O3 photolysis, 22% from HONO photolysis, 15% from the photolysis of OVOCs (other than HCHO), 14% from HCHO photolysis, and 13% from O3 reactions with alkenes. The O3 production was sensitive to volatile organic compounds (VOCs) in the early morning but was sensitive to NOx for most of afternoon. This is similar to the behavior observed in two previous summertime studies in Houston: the Texas Air Quality Study in 2000 (TexAQS 2000) and the TexAQS II Radical and Aerosol Measurement Project in 2006 (TRAMP 2006). Ozone production in SHARP exhibits a longer NOx-sensitive period than TexAQS 2000 and TRAMP 2006, indicating that NOx control may be an efficient approach for the O3 control in springtime for Houston. Results from this study

  10. Atmospheric chemistry of 4:2 fluorotelomer alcohol (n-C4F9CH2CH2OH)

    DEFF Research Database (Denmark)

    Andersen, Mads Peter Sulbæk; Nielsen, Ole John; Hurley, M. D.

    2005-01-01

    Smog chamber/FTIR techniques were used to study the Cl atom initiated oxidation of 4:2 fluorotelomer alcohol (C4F9CH2CH2OH, 4:2 FTOH) in the presence of NOx in 700 Torr of N-2/O-2 diluent at 296 K. Chemical activation effects play an important role in the atmospheric chemistry of the peroxy...

  11. Clouds and Chemistry in the Atmosphere of Extrasolar Planet HR8799b

    Energy Technology Data Exchange (ETDEWEB)

    Barman, T S; Macintosh, B A; Konopacky, Q M; Marois, C

    2011-03-21

    Using the integral field spectrograph OSIRIS, on the Keck II telescope, broad near-infrared H and K-band spectra of the young exoplanet HR8799b have been obtained. In addition, six new narrow-band photometric measurements have been taken across the H and K bands. These data are combined with previously published photometry for an analysis of the planet's atmospheric properties. Thick photospheric dust cloud opacity is invoked to explain the planet's red near-IR colors and relatively smooth near-IR spectrum. Strong water absorption is detected, indicating a Hydrogen-rich atmosphere. Only weak CH{sub 4} absorption is detected at K band, indicating efficient vertical mixing and a disequilibrium CO/CH{sub 4} ratio at photospheric depths. The H-band spectrum has a distinct triangular shape consistent with low surface gravity. New giant planet atmosphere models are compared to these data with best fitting bulk parameters, T{sub eff} = 1100K {+-} 100 and log(g) = 3.5 {+-} 0.5 (for solar composition). Given the observed luminosity (log L{sub obs}/L{sub {circle_dot}} {approx} -5.1), these values correspond to a radius of 0.75 R{sub Jup{sub 0.12}{sup +0.17}} and mass {approx} 0.72 M{sub Jup{sub -0.6}{sup +2.6}} - strikingly inconsistent with interior/evolution models. Enhanced metallicity (up to {approx} 10 x that of the Sun) along with thick clouds and non-equilibrium chemistry are likely required to reproduce the complete ensemble of spectroscopic and photometric data and the low effective temperatures (< 1000K) required by the evolution models.

  12. Ground-based Observations and Atmospheric Modelling of Energetic Electron Precipitation Effects on Antarctic Mesospheric Chemistry

    Science.gov (United States)

    Newnham, D.; Clilverd, M. A.; Horne, R. B.; Rodger, C. J.; Seppälä, A.; Verronen, P. T.; Andersson, M. E.; Marsh, D. R.; Hendrickx, K.; Megner, L. S.; Kovacs, T.; Feng, W.; Plane, J. M. C.

    2016-12-01

    The effect of energetic electron precipitation (EEP) on the seasonal and diurnal abundances of nitric oxide (NO) and ozone in the Antarctic middle atmosphere during March 2013 to July 2014 is investigated. Geomagnetic storm activity during this period, close to solar maximum, was driven primarily by impulsive coronal mass ejections. Near-continuous ground-based atmospheric measurements have been made by a passive millimetre-wave radiometer deployed at Halley station (75°37'S, 26°14'W, L = 4.6), Antarctica. This location is directly under the region of radiation-belt EEP, at the extremity of magnetospheric substorm-driven EEP, and deep within the polar vortex during Austral winter. Superposed epoch analyses of the ground based data, together with NO observations made by the Solar Occultation For Ice Experiment (SOFIE) onboard the Aeronomy of Ice in the Mesosphere (AIM) satellite, show enhanced mesospheric NO following moderate geomagnetic storms (Dst ≤ -50 nT). Measurements by co-located 30 MHz riometers indicate simultaneous increases in ionisation at 75-90 km directly above Halley when Kp index ≥ 4. Direct NO production by EEP in the upper mesosphere, versus downward transport of NO from the lower thermosphere, is evaluated using a new version of the Whole Atmosphere Community Climate Model incorporating the full Sodankylä Ion Neutral Chemistry Model (WACCM SIC). Model ionization rates are derived from the Polar orbiting Operational Environmental Satellites (POES) second generation Space Environment Monitor (SEM 2) Medium Energy Proton and Electron Detector instrument (MEPED). The model data are compared with observations to quantify the impact of EEP on stratospheric and mesospheric odd nitrogen (NOx), odd hydrogen (HOx), and ozone.

  13. Design of and initial results from a Highly Instrumented Reactor for Atmospheric Chemistry (HIRAC

    Directory of Open Access Journals (Sweden)

    D. R. Glowacki

    2007-10-01

    Full Text Available The design of a Highly Instrumented Reactor for Atmospheric Chemistry (HIRAC is described and initial results obtained from HIRAC are presented. The ability of HIRAC to perform in-situ laser-induced fluorescence detection of OH and HO2 radicals with the Fluorescence Assay by Gas Expansion (FAGE technique establishes it as internationally unique for a chamber of its size and pressure/temperature variable capabilities. In addition to the FAGE technique, HIRAC features a suite of analytical instrumentation, including: a multipass FTIR system; a conventional gas chromatography (GC instrument and a GC instrument for formaldehyde detection; NO/NO2, CO, O3, and H2O vapour analysers. Ray tracing simulations and NO2 actinometry have been utilized to develop a detailed model of the radiation field within HIRAC. Comparisons between the analysers and the FTIR coupled to HIRAC have been performed, and HIRAC has also been used to investigate pressure dependent kinetics of the chlorine atom reaction with ethene and the reaction of O3 and t-2-butene. The results obtained are in good agreement with literature recommendations and Master Chemical Mechanism predictions. HIRAC thereby offers a highly instrumented platform with the potential for: (1 high precision kinetics investigations over a range of atmospheric conditions; (2 detailed mechanism development, significantly enhanced according to its capability for measuring radicals; and (3 field instrument intercomparison, calibration, development, and investigations of instrument response at a range of atmospheric conditions.

  14. Aerosol Fragmentation Driven by Coupling of Acid-Base and Free-Radical Chemistry in the Heterogeneous Oxidation of Aqueous Citric Acid by OH Radicals.

    Science.gov (United States)

    Liu, Matthew J; Wiegel, Aaron A; Wilson, Kevin R; Houle, Frances A

    2017-08-10

    A key uncertainty in the heterogeneous oxidation of carboxylic acids by hydroxyl radicals (OH) in aqueous-phase aerosol is how the free-radical reaction pathways might be altered by acid-base chemistry. In particular, if acid-base reactions occur concurrently with acyloxy radical formation and unimolecular decomposition of alkoxy radicals, there is a possibility that differences in reaction pathways impact the partitioning of organic carbon between the gas and aqueous phases. To examine these questions, a kinetic model is developed for the OH-initiated oxidation of citric acid aerosol at high relative humidity. The reaction scheme, containing both free-radical and acid-base elementary reaction steps with physically validated rate coefficients, accurately predicts the experimentally observed molecular composition, particle size, and average elemental composition of the aerosol upon oxidation. The difference between the two reaction channels centers on the reactivity of carboxylic acid groups. Free-radical reactions mainly add functional groups to the carbon skeleton of neutral citric acid, because carboxylic acid moieties deactivate the unimolecular fragmentation of alkoxy radicals. In contrast, the conjugate carboxylate groups originating from acid-base equilibria activate both acyloxy radical formation and carbon-carbon bond scission of alkoxy radicals, leading to the formation of low molecular weight, highly oxidized products such as oxalic and mesoxalic acid. Subsequent hydration of carbonyl groups in the oxidized products increases the aerosol hygroscopicity and accelerates the substantial water uptake and volume growth that accompany oxidation. These results frame the oxidative lifecycle of atmospheric aerosol: it is governed by feedbacks between reactions that first increase the particle oxidation state, then eventually promote water uptake and acid-base chemistry. When coupled to free-radical reactions, acid-base channels lead to formation of low molecular

  15. he Impact of Primary Marine Aerosol on Atmospheric Chemistry, Radiation and Climate: A CCSM Model Development Study

    Energy Technology Data Exchange (ETDEWEB)

    Keene, William C. [University of Virginia; Long, Michael S. [University of Virginia

    2013-05-20

    This project examined the potential large-scale influence of marine aerosol cycling on atmospheric chemistry, physics and radiative transfer. Measurements indicate that the size-dependent generation of marine aerosols by wind waves at the ocean surface and the subsequent production and cycling of halogen-radicals are important but poorly constrained processes that influence climate regionally and globally. A reliable capacity to examine the role of marine aerosol in the global-scale atmospheric system requires that the important size-resolved chemical processes be treated explicitly. But the treatment of multiphase chemistry across the breadth of chemical scenarios encountered throughout the atmosphere is sensitive to the initial conditions and the precision of the solution method. This study examined this sensitivity, constrained it using high-resolution laboratory and field measurements, and deployed it in a coupled chemical-microphysical 3-D atmosphere model. First, laboratory measurements of fresh, unreacted marine aerosol were used to formulate a sea-state based marine aerosol source parameterization that captured the initial organic, inorganic, and physical conditions of the aerosol population. Second, a multiphase chemical mechanism, solved using the Max Planck Institute for Chemistry's MECCA (Module Efficiently Calculating the Chemistry of the Atmosphere) system, was benchmarked across a broad set of observed chemical and physical conditions in the marine atmosphere. Using these results, the mechanism was systematically reduced to maximize computational speed. Finally, the mechanism was coupled to the 3-mode modal aerosol version of the NCAR Community Atmosphere Model (CAM v3.6.33). Decadal-scale simulations with CAM v.3.6.33, were run both with and without reactive-halogen chemistry and with and without explicit treatment of particulate organic carbon in the marine aerosol source function. Simulated results were interpreted (1) to evaluate influences

  16. Polar Stratospheric Clouds and heterogeneous chemistry: Comparison between a 3D-CTM with detailed online PSC microphysics and CALIPSO observations

    Science.gov (United States)

    Viscardy, Sébastien; Errera, Quentin; Pitts, Michael C.; Poole, Lamont R.; Chabrillat, Simon; Daerden, Frank

    2013-04-01

    A 3-D Chemical Transport Model (CTM), with full stratospheric chemistry and driven by the ECMWF temperature and wind fields, has been coupled to a detailed PSC microphysical model to simulate polar winters. The formation and evolution of four types of PSC particles (STS, SAT, NAT, and ice) are described through relevant microphysical processes which alter interactively the nitric acid and water vapor concentrations of the atmosphere. Each particle type is described by a binned size distribution for the number density and chemical composition. This set-up allows for detailed calculation of optical properties and surface area densities used to compute the heterogeneous reaction rates. After comparing the evolution of the stratospheric chemical structure to satellite observations, we will investigate how the model reproduces the PSC coverage detected by CALIPSO. A comparison between the model and CALIPSO optical properties will be used to discuss the PSC composition. Finally, we aim at estimating the contribution of each PSC particle type to the chlorine activation.

  17. Global atmospheric sulfur budget under volcanically quiescent conditions: Aerosol-chemistry-climate model predictions and validation

    Science.gov (United States)

    Sheng, Jian-Xiong; Weisenstein, Debra K.; Luo, Bei-Ping; Rozanov, Eugene; Stenke, Andrea; Anet, Julien; Bingemer, Heinz; Peter, Thomas

    2015-01-01

    The global atmospheric sulfur budget and its emission dependence have been investigated using the coupled aerosol-chemistry-climate model SOCOL-AER. The aerosol module comprises gaseous and aqueous sulfur chemistry and comprehensive microphysics. The particle distribution is resolved by 40 size bins spanning radii from 0.39 nm to 3.2 μm, including size-dependent particle composition. Aerosol radiative properties required by the climate model are calculated online from the aerosol module. The model successfully reproduces main features of stratospheric aerosols under nonvolcanic conditions, including aerosol extinctions compared to Stratospheric Aerosol and Gas Experiment II (SAGE II) and Halogen Occultation Experiment, and size distributions compared to in situ measurements. The calculated stratospheric aerosol burden is 109 Gg of sulfur, matching the SAGE II-based estimate (112 Gg). In terms of fluxes through the tropopause, the stratospheric aerosol layer is due to about 43% primary tropospheric aerosol, 28% SO2, 23% carbonyl sulfide (OCS), 4% H2S, and 2% dimethyl sulfide (DMS). Turning off emissions of the short-lived species SO2, H2S, and DMS shows that OCS alone still establishes about 56% of the original stratospheric aerosol burden. Further sensitivity simulations reveal that anticipated increases in anthropogenic SO2 emissions in China and India have a larger influence on stratospheric aerosols than the same increase in Western Europe or the U.S., due to deep convection in the western Pacific region. However, even a doubling of Chinese and Indian emissions is predicted to increase the stratospheric background aerosol burden only by 9%. In contrast, small to moderate volcanic eruptions, such as that of Nabro in 2011, may easily double the stratospheric aerosol loading.

  18. Atmospheric chemistry of polycyclic aromatic compounds with special emphasis on nitro derivatives

    Energy Technology Data Exchange (ETDEWEB)

    Feilberg, A.

    2000-04-01

    Field measurements of polycyclic aromatic compounds (PAC) have been carried out at a semi-rural site and at an urban site. Correlation analyses, PAC indicators, and PAC ratios have been used to evaluate the importance of various sources of nitro-PAHs. A major source of nitro-PAHs is atmospheric transformation of PAHs initiated by OH radicals. Especially during long-range transport (LRT) of air pollution from Central Europe, the nitro-PAH composition in Denmark is dominated by nitro-PAHs formed in the atmosphere. Locally emitted nitro-PAHs are primarily from diesel vehicles. Levels of unsubstituted PAHs can also be strongly elevated in connection with LRT episodes. The ratio of 2-nitrofluoranthene relative to 1-nitropyrene is proposed as a measure of the relative photochemical age of particulate matter. Using this ratio, the relative mutagenicity of particle extracts appears to increase with increasing photochemical age. In connection with the field measurements, a method for measuring nitro-PAHs in particle extracts based on MS-MS detection has been developed. The atmospheric chemistry of nitronaphthalenes has been investigated with a smog chamber system combined with simulation with photochemical kinetics software. A methodology to implement gas-particle partitioning in a model based on chemical kinetics is described. Equilibrium constants (KP) for gas-particle partitioning of 1- and 2-nitronaphthalene have been determined. Mass transfer between the two phases appears to occur on a very short timescale. The gas phase photolysis of the nitronaphthalenes depends upon the molecular conformation. Significantly faster photolysis of 1-nitronaphthalene than of 2-nitronaphthalene is observed. The photochemistry of nitro-PAHs, and to some extent other PAC, associated with organic aerosols, has been studied with model systems simulating organic aerosol material. A number of aerosol constituents, including substituted phenols, benzaldehydes, and oxy-PAHs, are demonstrated to

  19. "Click Chemistry" Mediated Functional Microporous Organic Nanotube Networks for Heterogeneous Catalysis.

    Science.gov (United States)

    Yu, Wei; Zhou, Minghong; Wang, Tianqi; He, Zidong; Shi, Buyin; Xu, Yang; Huang, Kun

    2017-10-26

    The synthesis of azide functional microporous organic nanotube networks (N3-MONNs) via a Friedel-Crafts hyper-cross-linking reaction is reported. Subsequently, a general method for obtaining heterogeneous catalysts through a Cu-catalyzed alkyne-azide reaction is presented. The small-molecule catalysts such as 2,2,6,6,-tetramethylpiperidine-1-oyl and 4-(N,N-dimethylamino)pyridine can be anchored into the MONNs. Owing to the hierarchically porous structure and high surface area, these catalysts show high activity in selective oxidation of alcohols and acylation reaction, respectively.

  20. Sentinel-5 Precursor: First Copernicus Atmospheric Chemistry Mission ready for Launch

    Science.gov (United States)

    McMullan, Kevin; Nett, Herbert

    2017-04-01

    Sentinel-5 Precursor (S-5P) will be the first of a series of atmospheric chemistry missions to be launched within the European Commission's Copernicus (former GMES) Programme. With the current launch window of June 2017 and a nominal lifetime of 7 years, S-5P is expected to provide continuity in the availability of global atmospheric data products between its predecessor missions SCIAMACHY (Envisat) and OMI (AURA) and the future Sentinel-4 and -5 series. S-5P will deliver unique data regarding the sources and sinks of trace gases with a focus on the lower Troposphere including the planet boundary layer due to its enhanced spatial, temporal and spectral sampling capabilities as compared to its predecessors. The S-5P satellite will carry a single payload, TROPOMI (TROPOspheric Monitoring Instrument) which is jointly developed by The Netherlands and ESA. Covering spectral channels in the UV, visible, near- and short-wave infrared, it will measure various key species including tropospheric/stratospheric ozone, NO2, SO2, CO, CH4, CH2O as well as cloud and aerosol parameters. The S-5P Project successfully passed the Ground Segment Acceptance Review (GS-AR) and the satellite-level Qualification Acceptance Review (QAR) in March and April 2016, respectively. Remaining pre-launch tasks focus on the detailed planning of Phase E1 activities and the training of the operations teams. The paper includes descriptions of the S-5p spacecraft, the TROPOMI instrument, data products and applications, Level-1b and Level-2 processing, Ground Segment, launch preparation, launch and in-orbit commissioning and in-flight calibration and validation.

  1. Major Successes of Theory-and-Experiment-Combined Studies in Surface Chemistry and Heterogeneous Catalysis.

    Energy Technology Data Exchange (ETDEWEB)

    Somorjai, Gabor A.; Li, Yimin

    2009-11-21

    Experimental discoveries followed by theoretical interpretations that pave the way of further advances by experimentalists is a developing pattern in modern surface chemistry and catalysis. The revolution of modern surface science started with the development of surface-sensitive techniques such as LEED, XPS, AES, ISS and SIMS, in which the close collaboration between experimentalists and theorists led to the quantitative determination of surface structure and composition. The experimental discovery of the chemical activity of surface defects and the trends in the reactivity of transitional metals followed by the explanations from the theoretical studies led to the molecular level understanding of active sites in catalysis. The molecular level knowledge, in turn, provided a guide for experiments to search for new generation of catalysts. These and many other examples of successes in experiment-and-theory-combined studies demonstrate the importance of the collaboration between experimentalists and theorists in the development of modern surface science.

  2. Uncertainties in modelling heterogeneous chemistry and Arctic ozone depletion in the winter 2009/2010

    Directory of Open Access Journals (Sweden)

    I. Wohltmann

    2013-04-01

    Full Text Available Stratospheric chemistry and denitrification are simulated for the Arctic winter 2009/2010 with the Lagrangian Chemistry and Transport Model ATLAS. A number of sensitivity runs is used to explore the impact of uncertainties in chlorine activation and denitrification on the model results. In particular, the efficiency of chlorine activation on different types of liquid aerosol versus activation on nitric acid trihydrate clouds is examined. Additionally, the impact of changes in reaction rate coefficients, in the particle number density of polar stratospheric clouds, in supersaturation, temperature or the extent of denitrification is investigated. Results are compared to satellite measurements of MLS and ACE-FTS and to in-situ measurements onboard the Geophysica aircraft during the RECONCILE measurement campaign. It is shown that even large changes in the underlying assumptions have only a small impact on the modelled ozone loss, even though they can cause considerable differences in chemical evolution of other species and in denitrification. Differences in column ozone between the sensitivity runs stay below 10% at the end of the winter. Chlorine activation on liquid aerosols alone is able to explain the observed magnitude and morphology of the mixing ratios of active chlorine, reservoir gases and ozone. This is even true for binary aerosols (no uptake of HNO3 from the gas-phase allowed in the model. Differences in chlorine activation between sensitivity runs are within 30%. Current estimates of nitric acid trihydrate (NAT number density and supersaturation imply that, at least for this winter, NAT clouds play a relatively small role compared to liquid clouds in chlorine activation. The change between different reaction rate coefficients for liquid or solid clouds has only a minor impact on ozone loss and chlorine activation in our sensitivity runs.

  3. Description and evaluation of the Multiscale Online Nonhydrostatic AtmospheRe CHemistry model (NMMB-MONARCH) version 1.0: gas-phase chemistry at global scale

    Science.gov (United States)

    Badia, Alba; Jorba, Oriol; Voulgarakis, Apostolos; Dabdub, Donald; Pérez García-Pando, Carlos; Hilboll, Andreas; Gonçalves, María; Janjic, Zavisa

    2017-02-01

    This paper presents a comprehensive description and benchmark evaluation of the tropospheric gas-phase chemistry component of the Multiscale Online Nonhydrostatic AtmospheRe CHemistry model (NMMB-MONARCH), formerly known as NMMB/BSC-CTM, that can be run on both regional and global domains. Here, we provide an extensive evaluation of a global annual cycle simulation using a variety of background surface stations (EMEP, WDCGG and CASTNET), ozonesondes (WOUDC, CMD and SHADOZ), aircraft data (MOZAIC and several campaigns), and satellite observations (SCIAMACHY and MOPITT). We also include an extensive discussion of our results in comparison to other state-of-the-art models. We note that in this study, we omitted aerosol processes and some natural emissions (lightning and volcano emissions). The model shows a realistic oxidative capacity across the globe. The seasonal cycle for CO is fairly well represented at different locations (correlations around 0.3-0.7 in surface concentrations), although concentrations are underestimated in spring and winter in the Northern Hemisphere, and are overestimated throughout the year at 800 and 500 hPa in the Southern Hemisphere. Nitrogen species are well represented in almost all locations, particularly NO2 in Europe (root mean square error - RMSE - below 5 ppb). The modeled vertical distributions of NOx and HNO3 are in excellent agreement with the observed values and the spatial and seasonal trends of tropospheric NO2 columns correspond well to observations from SCIAMACHY, capturing the highly polluted areas and the biomass burning cycle throughout the year. Over Asia, the model underestimates NOx from March to August, probably due to an underestimation of NOx emissions in the region. Overall, the comparison of the modeled CO and NO2 with MOPITT and SCIAMACHY observations emphasizes the need for more accurate emission rates from anthropogenic and biomass burning sources (i.e., specification of temporal variability). The resulting

  4. Chemical kinetics and modeling of planetary atmospheres

    Science.gov (United States)

    Yung, Yuk L.

    1990-01-01

    A unified overview is presented for chemical kinetics and chemical modeling in planetary atmospheres. The recent major advances in the understanding of the chemistry of the terrestrial atmosphere make the study of planets more interesting and relevant. A deeper understanding suggests that the important chemical cycles have a universal character that connects the different planets and ultimately link together the origin and evolution of the solar system. The completeness (or incompleteness) of the data base for chemical kinetics in planetary atmospheres will always be judged by comparison with that for the terrestrial atmosphere. In the latter case, the chemistry of H, O, N, and Cl species is well understood. S chemistry is poorly understood. In the atmospheres of Jovian planets and Titan, the C-H chemistry of simple species (containing 2 or less C atoms) is fairly well understood. The chemistry of higher hydrocarbons and the C-N, P-N chemistry is much less understood. In the atmosphere of Venus, the dominant chemistry is that of chlorine and sulfur, and very little is known about C1-S coupled chemistry. A new frontier for chemical kinetics both in the Earth and planetary atmospheres is the study of heterogeneous reactions. The formation of the ozone hole on Earth, the ubiquitous photochemical haze on Venus and in the Jovian planets and Titan all testify to the importance of heterogeneous reactions. It remains a challenge to connect the gas phase chemistry to the production of aerosols.

  5. Evaluation of NO+ reagent ion chemistry for online measurements of atmospheric volatile organic compounds

    Science.gov (United States)

    Koss, Abigail R.; Warneke, Carsten; Yuan, Bin; Coggon, Matthew M.; Veres, Patrick R.; de Gouw, Joost A.

    2016-07-01

    NO+ chemical ionization mass spectrometry (NO+ CIMS) can achieve fast (1 Hz and faster) online measurement of trace atmospheric volatile organic compounds (VOCs) that cannot be ionized with H3O+ ions (e.g., in a PTR-MS or H3O+ CIMS instrument). Here we describe the adaptation of a high-resolution time-of-flight H3O+ CIMS instrument to use NO+ primary ion chemistry. We evaluate the NO+ technique with respect to compound specificity, sensitivity, and VOC species measured compared to H3O+. The evaluation is established by a series of experiments including laboratory investigation using a gas-chromatography (GC) interface, in situ measurement of urban air using a GC interface, and direct in situ measurement of urban air. The main findings are that (1) NO+ is useful for isomerically resolved measurements of carbonyl species; (2) NO+ can achieve sensitive detection of small (C4-C8) branched alkanes but is not unambiguous for most; and (3) compound-specific measurement of some alkanes, especially isopentane, methylpentane, and high-mass (C12-C15) n-alkanes, is possible with NO+. We also demonstrate fast in situ chemically specific measurements of C12 to C15 alkanes in ambient air.

  6. Chemical isolation in the Asian monsoon anticyclone observed in Atmospheric Chemistry Experiment (ACE-FTS data

    Directory of Open Access Journals (Sweden)

    M. Park

    2008-02-01

    Full Text Available Evidence of chemical isolation in the Asian monsoon anticyclone is presented using chemical constituents obtained from the Atmospheric Chemistry Experiment Fourier Transform Spectrometer instrument during summer (June–August of 2004–2006. Carbon monoxide (CO shows a broad maximum over the monsoon anticyclone region in the upper troposphere and lower stratosphere (UTLS; these enhanced CO values are associated with air pollution transported upward by convection, and confined by the strong anticyclonic circulation. Profiles inside the anticyclone show enhancement of tropospheric tracers CO, HCN, C2H6, and C2H2 between ~12 to 20 km, with maxima near 13–15 km. Strong correlations are observed among constituents, consistent with sources from near-surface pollution and biomass burning. Stratospheric tracers (O3, HNO3 and HCl exhibit decreased values inside the anticyclone between ~12–20 km. These observations are further evidence of transport of lower tropospheric air into the UTLS region, and isolation of air within the anticyclone. The relative enhancements of tropospheric species inside the anticyclone are closely related to the photochemical lifetime of the species, with strongest enhancement for shorter lived species. Vertical profiles of the ratio of C2H2/CO (used to measure the relative age of air suggest relatively rapid transport of fresh emissions up to the tropopause level inside the anticyclone.

  7. Changes in domestic heating fuel use in Greece: effects on atmospheric chemistry and radiation

    Science.gov (United States)

    Athanasopoulou, Eleni; Speyer, Orestis; Brunner, Dominik; Vogel, Heike; Vogel, Bernhard; Mihalopoulos, Nikolaos; Gerasopoulos, Evangelos

    2017-09-01

    For the past 8 years, Greece has been experiencing a major financial crisis which, among other side effects, has led to a shift in the fuel used for residential heating from fossil fuel towards biofuels, primarily wood. This study simulates the fate of the residential wood burning aerosol plume (RWB smog) and the implications on atmospheric chemistry and radiation, with the support of detailed aerosol characterization from measurements during the winter of 2013-2014 in Athens. The applied model system (TNO-MACC_II emissions and COSMO-ART model) and configuration used reproduces the measured frequent nighttime aerosol spikes (hourly PM10 > 75 µg m-3) and their chemical profile (carbonaceous components and ratios). Updated temporal and chemical RWB emission profiles, derived from measurements, were used, while the level of the model performance was tested for different heating demand (HD) conditions, resulting in better agreement with measurements for Tmin air pollution conditions is attributed to the timing of the smog plume appearance, both directly (longwave radiation increases during nighttime) and indirectly (the mild effect of the residual plume on solar radiation during the next day, due to removal and dispersion processes).

  8. Gas-surface interactions and heterogeneous chemistry on interstellar grains analogues

    Directory of Open Access Journals (Sweden)

    Cazaux S.

    2012-01-01

    Full Text Available Detailed laboratory studies and progress in surface science technique, have allowed in recent years the first experimental confirmation of surface reaction schemes, as introduced by Tielens, Hagen and Charnley [1,2]. In this paper, we review few heterogeneous processes which give routes to form elementary molecules considered as precursors for explaining the variety and richness of molecular species in the interstellar medium. Adsorption, diffusion and reaction processes are discussed. With emphasis on the experimental approaches, but also supported by theoretical developments, progresses in the understanding of the “catalytic role” of a dust grain surface in various physical conditions are described. Recent advances made on few important species (H2, H2O, CH3OH are used to illustrate basic properties and raise open questions.

  9. Chemistry?!

    Indian Academy of Sciences (India)

    Chemistry is the science of matter and of its transformations, and life is its highest expression. It provides structures endowed with properties and develops processes for the synthesis of structures. It plays a primordial role in our understanding of material phe- nomena, in our capability to act upon them, to modify them, to.

  10. Modeling and experimental validation of CO heterogeneous chemistry and electrochemistry in solid oxide fuel cells

    Energy Technology Data Exchange (ETDEWEB)

    Yurkiv, Vitaly

    2010-12-17

    In the present work experimental and numerical modeling studies of the heterogeneously catalyzed and electrochemical oxidation of CO at Nickel/yttria-stabilized zirconia (YSZ) solid oxide fuel cell (SOFC) anode systems were performed to evaluate elementary charge-transfer reaction mechanisms taking place at the three-phase boundary of CO/CO{sub 2} gas-phase, Ni electrode, and YSZ electrolyte. Temperature-programmed desorption and reaction experiments along with density functional theory calculations were performed to determine adsorption/desorption and surface diffusion kinetics as well as thermodynamic data for the CO/CO{sub 2}/Ni and CO/CO{sub 2}/YSZ systems. Based on these data elementary reaction based models with four different charge transfer mechanisms for the electrochemical CO oxidation were developed and applied in numerical simulations of literature experimental electrochemical data such as polarization curves and impedance spectra. Comparison between simulation and experiment demonstrated that only one of the four charge transfer mechanisms can consistently reproduce the electrochemical data over a wide range of operating temperatures and CO/CO{sub 2} gas compositions. (orig.) [German] In der vorliegenden Arbeit wurden experimentelle und numerische Untersuchungen zur heterogen katalysierten und elektrochemischen Oxidation von CO an Anodensystemen (bestehend aus Nickel und yttriumdotiertem Zirkoniumdioxid, YSZ) von Festoxidbrennstoffzellen (engl. Solid Oxide Fuel Cells, SOFCs) ausgefuehrt, um den mikroskopischen Mechanismus der an der CO/CO{sub 2}-Gasphase/Ni-Elektrode/YSZ-Elektrolyt- Dreiphasen-Grenzflaeche ablaufenden Ladungsuebertragungsreaktion aufzuklaeren. Temperaturprogrammierte Desorptionsmessungen (TPD) und Temperaturprogrammierte Reaktionsmessungen (TPR) sowie Dichtefunktionaltheorierechnungen wurden ausgefuehrt, um adsorptions-, desorptions- und reaktionskinetische sowie thermodynamische Daten fuer die CO/CO{sub 2}/Ni- und CO/CO{sub 2}/YSZ

  11. Hydrogeophysical imaging of deposit heterogeneity and groundwater chemistry changes during DNAPL source zone bioremediation

    Science.gov (United States)

    Chambers, J. E.; Wilkinson, P. B.; Wealthall, G. P.; Loke, M. H.; Dearden, R.; Wilson, R.; Allen, D.; Ogilvy, R. D.

    2010-10-01

    Robust characterization and monitoring of dense nonaqueous phase liquid (DNAPL) source zones is essential for designing effective remediation strategies, and for assessing the efficacy of treatment. In this study high-resolution cross-hole electrical resistivity tomography (ERT) was evaluated as a means of monitoring a field-scale in-situ bioremediation experiment, in which emulsified vegetable oil (EVO) electron donor was injected into a trichloroethene source zone. Baseline ERT scans delineated the geometry of the interface between the contaminated alluvial aquifer and the underlying mudstone bedrock, and also the extent of drilling-induced physical heterogeneity. Time-lapse ERT images revealed major preferential flow pathways in the source and plume zones, which were corroborated by multiple lines of evidence, including geochemical monitoring and hydraulic testing using high density multilevel sampler arrays within the geophysical imaging planes. These pathways were shown to control the spatial distribution of the injected EVO, and a bicarbonate buffer introduced into the cell for pH control. Resistivity signatures were observed within the preferential flow pathways that were consistent with elevated chloride levels, providing tentative evidence from ERT of the biodegradation of chlorinated solvents.

  12. Impact of Improvements in Volcanic Implementation on Atmospheric Chemistry and Climate in the GISS-E2 Model

    Science.gov (United States)

    Tsigaridis, Kostas; LeGrande, Allegra; Bauer, Susanne

    2015-01-01

    The representation of volcanic eruptions in climate models introduces some of the largest errors when evaluating historical simulations, partly due to the crude model parameterizations. We will show preliminary results from the Goddard Institute for Space Studies (GISS)-E2 model comparing traditional highly parameterized volcanic implementation (specified Aerosol Optical Depth, Effective Radius) to deploying the full aerosol microphysics module MATRIX and directly emitting SO2 allowing us the prognosically determine the chemistry and climate impact. We show a reasonable match in aerosol optical depth, effective radius, and forcing between the full aerosol implementation and reconstructions/observations of the Mt. Pinatubo 1991 eruption, with a few areas as targets for future improvement. This allows us to investigate not only the climate impact of the injection of volcanic aerosols, but also influences on regional water vapor, O3, and OH distributions. With the skill of the MATRIX volcano implementation established, we explore (1) how the height of the injection column of SO2 influence atmospheric chemistry and climate response, (2) how the initial condition of the atmosphere influences the climate and chemistry impact of the eruption with a particular focus on how ENSO and QBO and (3) how the coupled chemistry could mitigate the climate signal for much larger eruptions (i.e. the 1258 eruption, reconstructed to be approximately 10x Pinatubo). During each sensitivity experiment we assess the impact on profiles of water vapor, O3, and OH, and assess how the eruption impacts the budget of each.

  13. Trace gas retrievals for the ExoMars Trace Gas Orbiter Atmospheric Chemistry Suite mid-infrared solar occultation spectrometer

    Science.gov (United States)

    Olsen, K. S.; Montmessin, F.; Fedorova, A.; Trokhimovskiy, A.; Korablev, O.

    2017-09-01

    Here we present preparations for retrieving trace gas volume mixing ratio vertical profiles from the Atmospheric Chemistry Suite (ACS) mid-infrared channel operating in solar occultation mode. ACS is a cross-dispersion spectrometer on the ESA/Roscosmos ExoMars Trace Gas orbiter which entered Mars orbit in October 2016. It is mid-way through an aerobreaking compaign and science operations will commence around March 2o18.

  14. Modeling Top of Atmosphere Radiance over Heterogeneous Non-Lambertian Rugged Terrain

    NARCIS (Netherlands)

    Mousivand, A.; Verhoef, W.; Menenti, M.; Gorte, B.G.H.

    2015-01-01

    Topography affects the fraction of direct and diffuse radiation received on a pixel and changes the sun–target–sensor geometry, resulting in variations in the observed radiance. Retrieval of surface–atmosphere properties from top of atmosphere radiance may need to account for topographic effects.

  15. The Atmospheric Chemistry and Climate Model Intercomparison Project (ACCMIP): Overview and Description of Models, Simulations and Climate Diagnostics

    Science.gov (United States)

    Lamarque, J.-F.; Shindell, D. T.; Naik, V.; Plummer, D.; Josse, B.; Righi, M.; Rumbold, S. T.; Schulz, M.; Skeie, R. B.; Strode, S.; hide

    2013-01-01

    The Atmospheric Chemistry and Climate Model Intercomparison Project (ACCMIP) consists of a series of time slice experiments targeting the long-term changes in atmospheric composition between 1850 and 2100, with the goal of documenting composition changes and the associated radiative forcing. In this overview paper, we introduce the ACCMIP activity, the various simulations performed (with a requested set of 14) and the associated model output. The 16 ACCMIP models have a wide range of horizontal and vertical resolutions, vertical extent, chemistry schemes and interaction with radiation and clouds. While anthropogenic and biomass burning emissions were specified for all time slices in the ACCMIP protocol, it is found that the natural emissions are responsible for a significant range across models, mostly in the case of ozone precursors. The analysis of selected present-day climate diagnostics (precipitation, temperature, specific humidity and zonal wind) reveals biases consistent with state-of-the-art climate models. The model-to- model comparison of changes in temperature, specific humidity and zonal wind between 1850 and 2000 and between 2000 and 2100 indicates mostly consistent results. However, models that are clear outliers are different enough from the other models to significantly affect their simulation of atmospheric chemistry.

  16. The Reaction between Sodium Hydroxide and Atomic Hydrogen in Atmospheric and Flame Chemistry.

    Science.gov (United States)

    Gómez Martín, J C; Seaton, C; de Miranda, M P; Plane, J M C

    2017-10-12

    We report the first direct kinetic study of the gas-phase reaction NaOH + H → Na + H2O, which is central to the chemistry of sodium in the upper atmosphere and in flames. The reaction was studied in a fast flow tube, where NaOH was observed by multiphoton ionization and time-of-flight mass spectrometry, yielding k(NaOH + H, 230-298 K) = (3.8 ± 0.8) × 10(-11) cm(3) molecule (-1) s(-1) (at 2σ confidence level), showing no significant temperature dependence over the indicated temperature range and essentially in agreement with previous estimates of the rate constant in hydrogen-rich flames. We show, using theoretical trajectory calculations, that the unexpectedly slow, yet T-independent, rate coefficient for NaOH + H is explained by severe constraints in the angle of attack that H can make on NaOH to produce H2O. This reaction is also central to explaining Na-catalyzed flame inhibition, which has been proposed to occur via the sequence Na + OH (+ M) → NaOH followed by NaOH + H → Na + H2O, thereby effectively recombinating H and OH to H2O. RRKM calculations for the recombination of Na and OH yield k(Na + OH + N2, 300-2400 K) = 2.7 × 10(-29) (300/T)(1.2) cm(6) molecule(-2) s(-1), in agreement with a previous flash photolysis measurement at 653 K and Na-seeded flame studies in the 1800-2200 K range. These results therefore provide strong evidence to support the mechanism of flame inhibition by Na.

  17. Validation of NO2 and NO from the Atmospheric Chemistry Experiment (ACE

    Directory of Open Access Journals (Sweden)

    M. Schneider

    2008-10-01

    Full Text Available Vertical profiles of NO2 and NO have been obtained from solar occultation measurements by the Atmospheric Chemistry Experiment (ACE, using an infrared Fourier Transform Spectrometer (ACE-FTS and (for NO2 an ultraviolet-visible-near-infrared spectrometer, MAESTRO (Measurement of Aerosol Extinction in the Stratosphere and Troposphere Retrieved by Occultation. In this paper, the quality of the ACE-FTS version 2.2 NO2 and NO and the MAESTRO version 1.2 NO2 data are assessed using other solar occultation measurements (HALOE, SAGE II, SAGE III, POAM III, SCIAMACHY, stellar occultation measurements (GOMOS, limb measurements (MIPAS, OSIRIS, nadir measurements (SCIAMACHY, balloon-borne measurements (SPIRALE, SAOZ and ground-based measurements (UV-VIS, FTIR. Time differences between the comparison measurements were reduced using either a tight coincidence criterion, or where possible, chemical box models. ACE-FTS NO2 and NO and the MAESTRO NO2 are generally consistent with the correlative data. The ACE-FTS and MAESTRO NO2 volume mixing ratio (VMR profiles agree with the profiles from other satellite data sets to within about 20% between 25 and 40 km, with the exception of MIPAS ESA (for ACE-FTS and SAGE II (for ACE-FTS (sunrise and MAESTRO and suggest a negative bias between 23 and 40 km of about 10%. MAESTRO reports larger VMR values than the ACE-FTS. In comparisons with HALOE, ACE-FTS NO VMRs typically (on average agree to ±8% from 22 to 64 km and to +10% from 93 to 105 km, with maxima of 21% and 36%, respectively. Partial column comparisons for NO2 show that there is quite good agreement between the ACE instruments and the FTIRs, with a mean difference of +7.3% for ACE-FTS and +12.8% for MAESTRO.

  18. Response of an aerosol mass spectrometer to organonitrates and organosulfates and implications for atmospheric chemistry

    Science.gov (United States)

    Farmer, D. K.; Matsunaga, A.; Docherty, K. S.; Surratt, J. D.; Seinfeld, J. H.; Ziemann, P. J.; Jimenez, J. L.

    2010-01-01

    Organonitrates (ON) are important products of gas-phase oxidation of volatile organic compounds in the troposphere; some models predict, and laboratory studies show, the formation of large, multifunctional ON with vapor pressures low enough to partition to the particle phase. Organosulfates (OS) have also been recently detected in secondary organic aerosol. Despite their potential importance, ON and OS remain a nearly unexplored aspect of atmospheric chemistry because few studies have quantified particulate ON or OS in ambient air. We report the response of a high-resolution time-of-flight aerosol mass spectrometer (AMS) to aerosol ON and OS standards and mixtures. We quantify the potentially substantial underestimation of organic aerosol O/C, commonly used as a metric for aging, and N/C. Most of the ON-nitrogen appears as ions in the AMS, which are typically dominated by inorganic nitrate. Minor organonitrogen ions are observed although their identity and intensity vary between standards. We evaluate the potential for using fragment ratios, organonitrogen ions, ions, the ammonium balance of the nominally inorganic ions, and comparison to ion-chromatography instruments to constrain the concentrations of ON for ambient datasets, and apply these techniques to a field study in Riverside, CA. OS manifests as separate organic and sulfate components in the AMS with minimal organosulfur fragments and little difference in fragmentation from inorganic sulfate. The low thermal stability of ON and OS likely causes similar detection difficulties for other aerosol mass spectrometers using vaporization and/or ionization techniques with similar or larger energy, which has likely led to an underappreciation of these species. PMID:20194777

  19. Changes in domestic heating fuel use in Greece: effects on atmospheric chemistry and radiation

    Directory of Open Access Journals (Sweden)

    E. Athanasopoulou

    2017-09-01

    Full Text Available For the past 8 years, Greece has been experiencing a major financial crisis which, among other side effects, has led to a shift in the fuel used for residential heating from fossil fuel towards biofuels, primarily wood. This study simulates the fate of the residential wood burning aerosol plume (RWB smog and the implications on atmospheric chemistry and radiation, with the support of detailed aerosol characterization from measurements during the winter of 2013–2014 in Athens. The applied model system (TNO-MACC_II emissions and COSMO-ART model and configuration used reproduces the measured frequent nighttime aerosol spikes (hourly PM10  >  75 µg m−3 and their chemical profile (carbonaceous components and ratios. Updated temporal and chemical RWB emission profiles, derived from measurements, were used, while the level of the model performance was tested for different heating demand (HD conditions, resulting in better agreement with measurements for Tmin < 9 °C. Half of the aerosol mass over the Athens basin is organic in the submicron range, of which 80 % corresponds to RWB (average values during the smog period. Although organic particles are important light scatterers, the direct radiative cooling of the aerosol plume during wintertime is found low (monthly average forcing of –0.4 W m−2 at the surface, followed by a minor feedback to the concentration levels of aerosol species. The low radiative cooling of a period with such intense air pollution conditions is attributed to the timing of the smog plume appearance, both directly (longwave radiation increases during nighttime and indirectly (the mild effect of the residual plume on solar radiation during the next day, due to removal and dispersion processes.

  20. Afterglow chemistry of atmospheric-pressure helium-oxygen plasmas with humid air impurity

    Science.gov (United States)

    Murakami, Tomoyuki; Niemi, Kari; Gans, Timo; O'Connell, Deborah; Graham, William G.

    2014-04-01

    The formation of reactive species in the afterglow of a radio-frequency-driven atmospheric-pressure plasma in a fixed helium-oxygen feed gas mixture (He+0.5%O2) with humid air impurity (a few hundred ppm) is investigated by means of an extensive global plasma chemical kinetics model. As an original objective, we explore the effects of humid air impurity on the biologically relevant reactive species in an oxygen-dependent system. After a few milliseconds in the afterglow environment, the densities of atomic oxygen (O) decreases from 1015 to 1013 cm-3 and singlet delta molecular oxygen (O2(1D)) of the order of 1015 cm-3 decreases by a factor of two, while the ozone (O3) density increases from 1014 to 1015 cm-3. Electrons and oxygen ionic species, initially of the order of 1011 cm-3, recombine much faster on the time scale of some microseconds. The formation of atomic hydrogen (H), hydroxyl radical (OH), hydroperoxyl (HO2), hydrogen peroxide (H2O2), nitric oxide (NO) and nitric acid (HNO3) resulting from the humid air impurity as well as the influence on the afterglow chemistry is clarified with particular emphasis on the formation of dominant reactive oxygen species (ROS). The model suggests that the reactive species predominantly formed in the afterglow are major ROS O2(1D) and O3 (of the order of 1015 cm-3) and rather minor hydrogen- and nitrogen-based reactive species OH, H2O2, HNO3 and NO2/NO3, of which densities are comparable to the O-atom density (of the order of 1013 cm-3). Furthermore, the model quantitatively reproduces the experimental results of independent O and O3 density measurements.

  1. Organocatalysis: Key Trends in Green Synthetic Chemistry, Challenges, Scope towards Heterogenization, and Importance from Research and Industrial Point of View

    Directory of Open Access Journals (Sweden)

    Isak Rajjak Shaikh

    2014-01-01

    Full Text Available This paper purports to review catalysis, particularly the organocatalysis and its origin, key trends, challenges, examples, scope, and importance. The definition of organocatalyst corresponds to a low molecular weight organic molecule which in stoichiometric amounts catalyzes a chemical reaction. In this review, the use of the term heterogenized organocatalyst will be exclusively confined to a catalytic system containing an organic molecule immobilized onto some sort of support material and is responsible for accelerating a chemical reaction. Firstly, a brief description of the field is provided putting it in a green and sustainable perspective of chemistry. Next, research findings on the use of organocatalysts on various inorganic supports including nano(porousmaterials, nanoparticles, silica, and zeolite/zeolitic materials are scrutinized in brief. Then future scope, research directions, and academic and industrial applications will be outlined. A succinct account will summarize some of the research and developments in the field. This review tries to bring many outstanding researches together and shows the vitality of the organocatalysis through several aspects.

  2. A Safe Cooperative Framework for Atmospheric Science Missions with Multiple Heterogeneous UAS using Piecewise Bezier Curves

    Science.gov (United States)

    Mehdi, S. Bilal; Puig-Navarro, Javier; Choe, Ronald; Cichella, Venanzio; Hovakimyan, Naira; Chandarana, Meghan; Trujillo, Anna; Rothhaar, Paul M.; Tran, Loc; Neilan, James H.; hide

    2016-01-01

    Autonomous operation of UAS holds promise for greater productivity of atmospheric science missions. However, several challenges need to be overcome before such missions can be made autonomous. This paper presents a framework for safe autonomous operations of multiple vehicles, particularly suited for atmospheric science missions. The framework revolves around the use of piecewise Bezier curves for trajectory representation, which in conjunction with path-following and time-coordination algorithms, allows for safe coordinated operations of multiple vehicles.

  3. Heterogeneous Catalysis.

    Science.gov (United States)

    Miranda, R.

    1989-01-01

    Described is a heterogeneous catalysis course which has elements of materials processing embedded in the classical format of catalytic mechanisms and surface chemistry. A course outline and list of examples of recent review papers written by students are provided. (MVL)

  4. The nitrogen cycle: Atmosphere interactions

    Science.gov (United States)

    Levine, J. S.

    1984-01-01

    Atmospheric interactions involving the nitrogen species are varied and complex. These interactions include photochemical reactions, initiated by the absorption of solar photons and chemical kinetic reactions, which involve both homogeneous (gas-to-gas reactions) and heterogeneous (gas-to-particle) reactions. Another important atmospheric interaction is the production of nitrogen oxides by atmospheric lightning. The nitrogen cycle strongly couples the biosphere and atmosphere. Many nitrogen species are produced by biogenic processes. Once in the atmosphere nitrogen oxides are photochemically and chemically transformed to nitrates, which are returned to the biosphere via precipitation, dry deposition and aerosols to close the biosphere-atmosphere nitrogen cycle. The sources, sinks and photochemistry/chemistry of the nitrogen species; atmospheric nitrogen species; souces and sinks of nitrous oxide; sources; sinks and photochemistry/chemistry of ammonia; seasonal variation of the vertical distribution of ammonia in the troposphere; surface and atmospheric sources of the nitrogen species, and seasonal variation of ground level ammonia are summarized.

  5. Lightning-driven inner radiation belt energy deposition into the atmosphere: implications for ionisation-levels and neutral chemistry

    Directory of Open Access Journals (Sweden)

    C. J. Rodger

    2007-08-01

    Full Text Available Lightning-generated whistlers lead to coupling between the troposphere, the Van Allen radiation belts and the lower-ionosphere through Whistler-induced electron precipitation (WEP. Lightning produced whistlers interact with cyclotron resonant radiation belt electrons, leading to pitch-angle scattering into the bounce loss cone and precipitation into the atmosphere. Here we consider the relative significance of WEP to the lower ionosphere and atmosphere by contrasting WEP produced ionisation rate changes with those from Galactic Cosmic Radiation (GCR and solar photoionisation. During the day, WEP is never a significant source of ionisation in the lower ionosphere for any location or altitude. At nighttime, GCR is more significant than WEP at altitudes <68 km for all locations, above which WEP starts to dominate in North America and Central Europe. Between 75 and 80 km altitude WEP becomes more significant than GCR for the majority of spatial locations at which WEP deposits energy. The size of the regions in which WEP is the most important nighttime ionisation source peaks at ~80 km, depending on the relative contributions of WEP and nighttime solar Lyman-α. We also used the Sodankylä Ion Chemistry (SIC model to consider the atmospheric consequences of WEP, focusing on a case-study period. Previous studies have also shown that energetic particle precipitation can lead to large-scale changes in the chemical makeup of the neutral atmosphere by enhancing minor chemical species that play a key role in the ozone balance of the middle atmosphere. However, SIC modelling indicates that the neutral atmospheric changes driven by WEP are insignificant due to the short timescale of the WEP bursts. Overall we find that WEP is a significant energy input into some parts of the lower ionosphere, depending on the latitude/longitude and altitude, but does not play a significant role in the neutral chemistry of the mesosphere.

  6. Parameterization of dust emissions in the global atmospheric chemistry-climate model EMAC: impact of nudging and soil properties

    Directory of Open Access Journals (Sweden)

    M. Astitha

    2012-11-01

    Full Text Available Airborne desert dust influences radiative transfer, atmospheric chemistry and dynamics, as well as nutrient transport and deposition. It directly and indirectly affects climate on regional and global scales. Two versions of a parameterization scheme to compute desert dust emissions are incorporated into the atmospheric chemistry general circulation model EMAC (ECHAM5/MESSy2.41 Atmospheric Chemistry. One uses a globally uniform soil particle size distribution, whereas the other explicitly accounts for different soil textures worldwide. We have tested these two versions and investigated the sensitivity to input parameters, using remote sensing data from the Aerosol Robotic Network (AERONET and dust concentrations and deposition measurements from the AeroCom dust benchmark database (and others. The two versions are shown to produce similar atmospheric dust loads in the N-African region, while they deviate in the Asian, Middle Eastern and S-American regions. The dust outflow from Africa over the Atlantic Ocean is accurately simulated by both schemes, in magnitude, location and seasonality. Approximately 70% of the modelled annual deposition data and 70–75% of the modelled monthly aerosol optical depth (AOD in the Atlantic Ocean stations lay in the range 0.5 to 2 times the observations for all simulations. The two versions have similar performance, even though the total annual source differs by ~50%, which underscores the importance of transport and deposition processes (being the same for both versions. Even though the explicit soil particle size distribution is considered more realistic, the simpler scheme appears to perform better in several locations. This paper discusses the differences between the two versions of the dust emission scheme, focusing on their limitations and strengths in describing the global dust cycle and suggests possible future improvements.

  7. Stochastic fields method for sub-grid scale emission heterogeneity in mesoscale atmospheric dispersion models

    OpenAIRE

    M. Cassiani; Vinuesa, J.F.; Galmarini, S.; Denby, B

    2010-01-01

    The stochastic fields method for turbulent reacting flows has been applied to the issue of sub-grid scale emission heterogeneity in a mesoscale model. This method is a solution technique for the probability density function (PDF) transport equation and can be seen as a straightforward extension of currently used mesoscale dispersion models. It has been implemented in an existing mesoscale model and the results are compared with Large-Eddy Simulation (LES) data devised to test specifically the...

  8. Plants, Pollution and Public Engagement with Atmospheric Chemistry: Sharing the TEMPO Story Through Ozone Garden Activities

    Science.gov (United States)

    Reilly, L. G.; Pippin, M. R.; Malick, E.; Summers, D.; Dussault, M. E.; Wright, E. A.; Skelly, J.

    2016-12-01

    What do a snap-bean plant and a future NASA satellite instrument named TEMPO have in common? They are both indicators of the quality of the air we breathe. Scientists, educators, and museum and student collaborators of the Tropospheric Emissions: Monitoring Pollution (TEMPO) instrument team are developing a program model to engage learners of all ages via public ozone garden exhibits and associated activities. TEMPO, an ultraviolet and visible spectroscopy instrument due for launch on a geostationary host satellite between 2019 and 2021, will scan North America hourly to measure the major elements in the tropospheric ozone chemistry cycle, providing near real-time data with high temporal and spatial resolution. The TEMPO mission provides a unique opportunity to share the story of the effects of air quality on living organisms. A public ozone garden exhibit affords an accessible way to understand atmospheric science through a connection with nature, while providing a visual representation of the impact of ozone pollution on living organisms. A prototype ozone garden exhibit was established at the Virginia Living Museum in partnership with NASA Langley, and has served as a site to formatively evaluate garden planting and exhibit display protocols, hands-on interpretive activities, and citizen science data collection protocols for learners as young as 3 to 10 as well as older adults. The fun and engaging activities, optimized for adult-child interaction in informal or free-choice learning environments, are aimed at developing foundational science skills such as observing, comparing, classifying, and collecting and making sense of data in the context of thinking about air quality - all NGSS-emphasized scientific practices, as well as key capabilities for future contributing members of the citizen science community. As the launch of TEMPO approaches, a major public engagement effort will include disseminating this ozone garden exhibit and program model to a network of

  9. COMPILATION AND ANALYSES OF EMISSIONS INVENTORIES FOR THE NOAA ATMOSPHERIC CHEMISTRY PROJECT. PROGRESS REPORT, AUGUST 1997.

    Energy Technology Data Exchange (ETDEWEB)

    BENKOVITZ,C.M.

    1997-09-01

    Global inventories of anthropogenic emissions of oxides of nitrogen (NO{sub x}) for circa 1985 and 1990 and Non-Methane Volatile Organic Compounds (NMVOCs) for circa 1990 have been compiled by this project. Work on the inventories has been carried out under the umbrella of the Global Emissions Inventory Activity (GEIA) of the International Global Atmospheric Chemistry (IGAC) Program. The 1985 NO{sub x} inventory was compiled using default data sets of global emissions that were refined via the use of more detailed regional data sets; this inventory is being distributed to the scientific community at large as the GEIA Version 1A inventory. Global emissions of NO{sub x} for 1985 are estimated to be 21 Tg N y{sup -1}, with approximately 84% originating in the Northern Hemisphere. The 1990 inventories of NO{sub x} and NMVOCs were compiled using unified methodologies and data sets in collaboration with the Netherlands National Institute of Public Health and Environmental Protection (Rijksinstituut Voor Volksgezondheid en Milieuhygiene, RIVM) and the Division of Technology for Society of the Netherlands Organization for Applied Scientific Research, (IMW-TNO); these emissions will be used as the default estimates to be updated with more accurate regional data. The NMVOC inventory was gridded and speciated into 23 chemical categories. The resulting global emissions for 1990 are 31 Tg N yr{sup -1} for NO{sub x} and 173 Gg NMVOC yr{sup -1}. Emissions of NO{sub x} are highest in the populated and industrialized areas of eastern North America and across Europe, and in biomass burning areas of South America, Africa, and Asia. Emissions of NMVOCs are highest in biomass burning areas of South America, Africa, and Asia. The 1990 NO{sub x} emissions were gridded to 1{sup o} resolution using surrogate data, and were given seasonal, two-vertical-level resolution and speciated into NO and NO{sub 2} based on proportions derived from the 1985 GEIA Version 1B inventory. Global NMVOC

  10. Wildland fire emissions, carbon, and climate: Plume rise, atmospheric transport, and chemistry processes

    Science.gov (United States)

    Warren Heilman; Yongqiang Liu; Shawn Urbanski; Vladimir Kovalev; Robert Mickler

    2014-01-01

    This paper provides an overview and summary of the current state of knowledge regarding critical atmospheric processes that affect the distribution and concentrations of greenhouse gases and aerosols emitted from wildland fires or produced through subsequent chemical reactions in the atmosphere. These critical atmospheric processes include the dynamics of plume rise,...

  11. Atmospheric chemistry of two biodiesel model compounds: methyl propionate and ethyl acetate.

    Science.gov (United States)

    Andersen, Vibeke F; Berhanu, Tesfaye A; Nilsson, Elna J K; Jørgensen, Solvejg; Nielsen, Ole John; Wallington, Timothy J; Johnson, Matthew S

    2011-08-18

    The atmospheric chemistry of two C(4)H(8)O(2) isomers (methyl propionate and ethyl acetate) was investigated. With relative rate techniques in 980 mbar of air at 293 K the following rate constants were determined: k(C(2)H(5)C(O)OCH(3) + Cl) = (1.57 ± 0.23) × 10(-11), k(C(2)H(5)C(O)OCH(3) + OH) = (9.25 ± 1.27) × 10(-13), k(CH(3)C(O)OC(2)H(5) + Cl) = (1.76 ± 0.22) × 10(-11), and k(CH(3)C(O)OC(2)H(5) + OH) = (1.54 ± 0.22) × 10(-12) cm(3) molecule(-1) s(-1). The chlorine atom initiated oxidation of methyl propionate in 930 mbar of N(2)/O(2) diluent (with, and without, NO(x)) gave methyl pyruvate, propionic acid, acetaldehyde, formic acid, and formaldehyde as products. In experiments conducted in N(2) diluent the formation of CH(3)CHClC(O)OCH(3) and CH(3)CCl(2)C(O)OCH(3) was observed. From the observed product yields we conclude that the branching ratios for reaction of chlorine atoms with the CH(3)-, -CH(2)-, and -OCH(3) groups are 9 ± 2%, respectively. The chlorine atom initiated oxidation of ethyl acetate in N(2)/O(2) diluent gave acetic acid, acetic acid anhydride, acetic formic anhydride, formaldehyde, and, in the presence of NO(x), PAN. From the yield of these products we conclude that at least 41 ± 6% of the reaction of chlorine atoms with ethyl acetate occurs at the -CH(2)- group. The rate constants and branching ratios for reactions of OH radicals with methyl propionate and ethyl acetate were investigated theoretically using transition state theory. The stationary points along the oxidation pathways were optimized at the CCSD(T)/cc-pVTZ//BHandHLYP/aug-cc-pVTZ level of theory. The reaction of OH radicals with ethyl acetate was computed to occur essentially exclusively (∼99%) at the -CH(2)- group. In contrast, both methyl groups and the -CH(2)- group contribute appreciably in the reaction of OH with methyl propionate. Decomposition via the α-ester rearrangement (to give C(2)H(5)C(O)OH and a HCO radical) and reaction with O(2) (to give CH(3)CH(2)C

  12. A two-dimensional atmospheric chemistry modeling investigation of Earth's Phanerozoic O3 and near-surface ultraviolet radiation history

    Science.gov (United States)

    Harfoot, Michael B. J.; Beerling, David J.; Lomax, Barry H.; Pyle, John A.

    2007-04-01

    We use the Cambridge two-dimensional (2-D) chemistry-radiation transport model to investigate the implications for column O3 and near-surface ultraviolet radiation (UV), of variations in atmospheric O2 content over the Phanerozoic (last 540 Myr). Model results confirm some earlier 1-D model investigations showing that global annual mean O3 column increases monotonically with atmospheric O2. Sensitivity studies indicate that changes in temperature and N2O exert a minor influence on O3 relative to O2. We reconstructed Earth's O3 history by interpolating the modeled relationship between O3 and O2 onto two Phanerozoic O2 histories. Our results indicate that the largest variation in Phanerozoic column O3 occurred between 400 and 200 Myr ago, corresponding to a rise in atmospheric O2 to ˜1.5 times the present atmospheric level (PAL) and subsequent fall to ˜0.5 PAL. The O3 response to this O2 decline shows latitudinal differences, thinning most at high latitudes (30-40 Dobson units (1 DU = 0.001 atm cm) at 66°N) and least at low latitudes (5-10 DU at 9°N) where a "self-healing" effect is evident. This O3 depletion coincides with significant increases in the near-surface biologically active UV radiation at high latitudes, +28% as weighted by the Thimijan spectral weighting function. O3 and UV changes were exacerbated when we incorporated a direct feedback of the terrestrial biosphere on atmospheric chemistry, through enhanced N2O production as the climate switched from an icehouse to a greenhouse mode. On the basis of a summary of field and laboratory experimental evidence, we suggest that these UV radiation increases may have exerted subtle rather than catastrophic effects on ecosystem processes.

  13. Simulating atmospheric composition over a South-East Asian tropical rainforest: performance of a chemistry box model

    Directory of Open Access Journals (Sweden)

    T. A. M. Pugh

    2010-01-01

    Full Text Available Atmospheric composition and chemistry above tropical rainforests is currently not well established, particularly for south-east Asia. In order to examine our understanding of chemical processes in this region, the performance of a box model of atmospheric boundary layer chemistry is tested against measurements made at the top of the rainforest canopy near Danum Valley, Malaysian Borneo. Multi-variate optimisation against ambient concentration measurements was used to estimate average canopy-scale emissions for isoprene, total monoterpenes and nitric oxide. The excellent agreement between estimated values and measured fluxes of isoprene and total monoterpenes provides confidence in the overall modelling strategy, and suggests that this method may be applied where measured fluxes are not available, assuming that the local chemistry and mixing are adequately understood. The largest contributors to the optimisation cost function at the point of best-fit are OH (29%, NO (22% and total peroxy radicals (27%. Several factors affect the modelled VOC chemistry. In particular concentrations of methacrolein (MACR and methyl-vinyl ketone (MVK are substantially overestimated, and the hydroxyl radical (OH concentration is substantially underestimated; as has been seen before in tropical rainforest studies. It is shown that inclusion of dry deposition of MACR and MVK and wet deposition of species with high Henry's Law values substantially improves the fit of these oxidised species, whilst also substantially decreasing the OH sink. Increasing OH production arbitrarily, through a simple OH recycling mechanism , adversely affects the model fit for volatile organic compounds (VOCs. Given the constraints on isoprene flux provided by measurements, a substantial decrease in the rate of reaction of VOCs with OH is the only remaining option to explain the measurement/model discrepancy for OH. A reduction in the isoprene+OH rate constant of 50%, in conjunction with

  14. Simulating atmospheric composition over a South-East Asian tropical rainforest: performance of a chemistry box model

    Science.gov (United States)

    Pugh, T. A. M.; MacKenzie, A. R.; Hewitt, C. N.; Langford, B.; Edwards, P. M.; Furneaux, K. L.; Heard, D. E.; Hopkins, J. R.; Jones, C. E.; Karunaharan, A.; Lee, J.; Mills, G.; Misztal, P.; Moller, S.; Monks, P. S.; Whalley, L. K.

    2010-01-01

    Atmospheric composition and chemistry above tropical rainforests is currently not well established, particularly for south-east Asia. In order to examine our understanding of chemical processes in this region, the performance of a box model of atmospheric boundary layer chemistry is tested against measurements made at the top of the rainforest canopy near Danum Valley, Malaysian Borneo. Multi-variate optimisation against ambient concentration measurements was used to estimate average canopy-scale emissions for isoprene, total monoterpenes and nitric oxide. The excellent agreement between estimated values and measured fluxes of isoprene and total monoterpenes provides confidence in the overall modelling strategy, and suggests that this method may be applied where measured fluxes are not available, assuming that the local chemistry and mixing are adequately understood. The largest contributors to the optimisation cost function at the point of best-fit are OH (29%), NO (22%) and total peroxy radicals (27%). Several factors affect the modelled VOC chemistry. In particular concentrations of methacrolein (MACR) and methyl-vinyl ketone (MVK) are substantially overestimated, and the hydroxyl radical (OH) concentration is substantially underestimated; as has been seen before in tropical rainforest studies. It is shown that inclusion of dry deposition of MACR and MVK and wet deposition of species with high Henry's Law values substantially improves the fit of these oxidised species, whilst also substantially decreasing the OH sink. Increasing OH production arbitrarily, through a simple OH recycling mechanism , adversely affects the model fit for volatile organic compounds (VOCs). Given the constraints on isoprene flux provided by measurements, a substantial decrease in the rate of reaction of VOCs with OH is the only remaining option to explain the measurement/model discrepancy for OH. A reduction in the isoprene+OH rate constant of 50%, in conjunction with increased

  15. Simulating organic species with the global atmospheric chemistry general circulation model ECHAM5/MESSy1: a comparison of model results with observation

    NARCIS (Netherlands)

    Pozzer, A.; Jöckel, P.; Tost, H.; Sander, R.; Ganzeveld, L.N.; Kerkweg, A.; Lelieveld, J.

    2007-01-01

    The atmospheric-chemistry general circulation model ECHAM5/MESSy1 is evaluated with observations of different organic ozone precursors. This study continues a prior analysis which focused primarily on the representation of atmospheric dynamics and ozone. We use the results of the same reference

  16. The Chemistry of Atmosphere-Forest Exchange (CAFE Model – Part 2: Application to BEARPEX-2007 observations

    Directory of Open Access Journals (Sweden)

    G. M. Wolfe

    2011-02-01

    Full Text Available In a companion paper, we introduced the Chemistry of Atmosphere-Forest Exchange (CAFE model, a vertically-resolved 1-D chemical transport model designed to probe the details of near-surface reactive gas exchange. Here, we apply CAFE to noontime observations from the 2007 Biosphere Effects on Aerosols and Photochemistry Experiment (BEARPEX-2007. In this work we evaluate the CAFE modeling approach, demonstrate the significance of in-canopy chemistry for forest-atmosphere exchange and identify key shortcomings in the current understanding of intra-canopy processes.

    CAFE generally reproduces BEARPEX-2007 observations but requires an enhanced radical recycling mechanism to overcome a factor of 6 underestimate of hydroxyl (OH concentrations observed during a warm (~29 °C period. Modeled fluxes of acyl peroxy nitrates (APN are quite sensitive to gradients in chemical production and loss, demonstrating that chemistry may perturb forest-atmosphere exchange even when the chemical timescale is long relative to the canopy mixing timescale. The model underestimates peroxy acetyl nitrate (PAN fluxes by 50% and the exchange velocity by nearly a factor of three under warmer conditions, suggesting that near-surface APN sinks are underestimated relative to the sources. Nitric acid typically dominates gross dry N deposition at this site, though other reactive nitrogen (NOy species can comprise up to 28% of the N deposition budget under cooler conditions. Upward NO2 fluxes cause the net above-canopy NOy flux to be ~30% lower than the gross depositional flux. CAFE under-predicts ozone fluxes and exchange velocities by ~20%. Large uncertainty in the parameterization of cuticular and ground deposition precludes conclusive attribution of non-stomatal fluxes to chemistry or surface uptake. Model-measurement comparisons of vertical concentration gradients for several emitted species suggests that the lower canopy airspace may be

  17. Evaluated kinetic and photochemical data for atmospheric chemistry: Volume IV – gas phase reactions of organic halogen species

    Directory of Open Access Journals (Sweden)

    R. Atkinson

    2008-08-01

    Full Text Available This article, the fourth in the series, presents kinetic and photochemical data sheets evaluated by the IUPAC Subcommittee on Gas Kinetic Data Evaluation for Atmospheric Chemistry. It covers the gas phase and photochemical reactions of organic halogen species, which were last published in 1997, and were updated on the IUPAC website in 2006/07. The article consists of a summary sheet, containing the recommended kinetic parameters for the evaluated reactions, and four appendices containing the data sheets, which provide information upon which the recommendations are made.

  18. Evaluated kinetic and photochemical data for atmospheric chemistry: Volume I - gas phase reactions of Ox, HOx, NOx and SOx species

    Directory of Open Access Journals (Sweden)

    R. Atkinson

    2004-01-01

    Full Text Available This article, the first in the series, presents kinetic and photochemical data evaluated by the IUPAC Subcommittee on GasKinetic Data Evaluation for Atmospheric Chemistry. It covers the gas phase and photochemical reactions of Ox, HOx, NOx and SOx species, which were last published in 1997, and were updated on the IUPAC website in late 2001. The article consists of a summary sheet, containing the recommended kinetic parameters for the evaluated reactions, and five appendices containing the data sheets, which provide information upon which the recommendations are made.

  19. Evaluated kinetic and photochemical data for atmospheric chemistry: Volume II – gas phase reactions of organic species

    Directory of Open Access Journals (Sweden)

    R. Atkinson

    2006-01-01

    Full Text Available This article, the second in the series, presents kinetic and photochemical data evaluated by the IUPAC Subcommittee on Gas Kinetic Data Evaluation for Atmospheric Chemistry. It covers the gas phase and photochemical reactions of Organic species, which were last published in 1999, and were updated on the IUPAC website in late 2002, and subsequently during the preparation of this article. The article consists of a summary table of the recommended rate coefficients, containing the recommended kinetic parameters for the evaluated reactions, and eight appendices containing the data sheets, which provide information upon which the recommendations are made.

  20. Chemistry Simulations using the MERRA-2 Reanalysis with the GMI CTM and Replay in Support of the Atmospheric Composition Community

    Science.gov (United States)

    Oman, Luke D.; Strahan, Susan E.

    2017-01-01

    Simulations using reanalysis meteorological fields have long been used to understand the causes of atmospheric composition change in the recent past. Using the new MERRA-2 reanalysis, we are conducting chemistry simulations to create products covering 1980-2016 for the atmospheric composition community. These simulations use the Global Modeling Initiative (GMI) chemical mechanism in two different models: the GMI Chemical Transport Model (CTM) and the GEOS-5 model in Replay mode. Replay mode means an integration of the GEOS-5 general circulation model that is incrementally adjusted each time step toward the MERRA-2 reanalysis. The GMI CTM is a 1 deg x 1.25 deg simulation and the MERRA-2 GMI Replay simulation uses the native MERRA-2 grid of approximately 1/2 deg horizontal resolution on the cubed sphere. A specialized set of transport diagnostics is included in both runs to better understand trace gas transport and its variability in the recent past.

  1. The Canadian Arctic Atmospheric Chemistry Experiment (ACE) Validation Project: Overview and results from ten years of ACE operations

    Science.gov (United States)

    Walker, Kaley; Strong, Kimberly

    2014-05-01

    As of February 2014, the Canadian-led Atmospheric Chemistry Experiment (ACE) satellite mission has been making measurements of the Earth's atmosphere for ten years. As ACE operations have extended beyond the initial two-year mission, there is a continuing need to validate the trace gas data products from the ACE-Fourier Transform Spectrometer (ACE-FTS) and the Measurement of Aerosol Extinction in the Stratosphere and Troposphere Retrieved by Occultation (ACE-MAESTRO) instruments. Ground-based measurements provide critical data for the validation of satellite retrievals of trace gases and for the assessment of long-term stability of these measurements. In particular, validation comparisons are needed for ACE during Arctic springtime to understand better the measurements of species involved in stratospheric ozone chemistry. To this end, eleven Canadian Arctic Atmospheric Chemistry Experiment (ACE) Validation Campaigns have been conducted during the spring period (February - April in 2004 - 2014) at the Polar Environment Atmospheric Research Laboratory (PEARL) in Eureka, Nunavut (80°N, 86°W). This period coincides with the most chemically active time of year in the Arctic, as well as a significant number of satellite overpasses. A suite of as many as 12 ground-based instruments, as well as frequent balloon-borne ozonesonde and radiosonde launches, have been used in each campaign. These instruments include: a ground-based version of the ACE-FTS (PARIS - Portable Atmospheric Research Interferometric Spectrometer), a terrestrial version of the ACE-MAESTRO, a SunPhotoSpectrometer, two zenith-viewing UV-visible grating spectrometers, a Bomem DA8 Fourier transform spectrometer, a Bruker 125HR Fourier transform spectrometer, a Systeme d'Analyse par Observations Zenithales (SAOZ) instrument, and several Brewer spectrophotometers. In the past several years, these results have been used to validate the measurements by the ACE-FTS and ACE-MAESTRO instruments on SCISAT as well

  2. High Energy Radical Chemistry Formation of HCN- rich Atmospheres on early Earth

    Czech Academy of Sciences Publication Activity Database

    Ferus, Martin; Kubelík, Petr; Knížek, Antonín; Pastorek, Adam; Sutherland, J.D.; Civiš, Svatopluk

    2017-01-01

    Roč. 7, č. 1 (2017), č. článku 6275. ISSN 2045-2322 R&D Projects: GA ČR GA17-05076S; GA MŠk(CZ) LM2015083; GA MŠk LG15013 Grant - others:Akademie věd - GA AV ČR(CZ) R200401521 Institutional support: RVO:61388955 Keywords : high-power laser * transform emission-spectroscopy * induced dielectric-breakdown * prebiotic organic-synthesis * nucleobase formation Subject RIV: CF - Physical ; Theoretical Chemistry OBOR OECD: Physical chemistry Impact factor: 4.259, year: 2016

  3. Russian contribution to ExoMars Trace Gas Orbiter: Atmospheric Chemistry Suite (ACS)

    Science.gov (United States)

    Shakun, Alexey; Korablev, Oleg; Trokhimovskiy, Alexander; Grigoriev, Alexey; Anufreychik, Konstantin; Fedorova, Anna; Ignatiev, Nikolay; Ivanov, Yuriy; Moshkin, Boris; Kalinnikov, Yuriy; Montmessin, Franck

    2016-04-01

    Atmospheric Chemistry Suite (ACS) is a part of science payload of Trace Gas Orbiter (TGO), ExoMars mission. This project developed by European Space Agency (ESA) in collaboration with Russian Space Agency (Roscosmos). Russian contribution to ExoMars TGO is the Proton rocket and two science instruments ACS (three infrared spectrometers) and FREND (neutron detector). ACS consists of three infrared spectrometers (ACS/NIR, ACS/MIR and ACS/TIRVIM) capable to take spectral measurements from near to thermal infrared range simultaneously or separately. Spectrometric channels of ACS share common mechanical, electrical, and thermal interfaces. Electronic box (ACS/BE) provides to spectrometric channels power and data transfer interfaces. SpaceWire link is used for science data transfer and MIL-1553 link - for commanding and housekeeping data transfer. The NIR channel is an echelle spectrometer with acousto-optic tunable filter (AOTF) for the selection of diffraction orders. ACS NIR is capable to perform nadir and occultation observations. NIR covers the spectral range of 0.7-1.7 μm with resolving power of ~25000. NIR will perform unique for TGO instruments nightglow science (searching for O2, OH, NO nightglow emissions on Mars). From the 1.38 μm band NIR will do water vapour mapping in nadir and H2O vertical profiling in solar occultations. High resolution NIR measurements of 1.27 μm O2(a1Δg) dayglow will supply indirect ozone observations on the dayside on nadir. In solar occultation mode, the O2 vertical profiles will be measured from the surface (in case of low dust activity) to the 40 km altitude based on 0.76 μm absorption band. Together with MIR channel in solar occultation NIR will support the measurements of CO2 density profiles (based on 1.43 μm band) and aerosols characterization from 0.7 to 4 μm. The wide spectral range will allow not just determine aerosol particle sizes and density at different altitudes, but also distinguish between dust and ice particles

  4. A study of the dissociative recombination of CaO+ with electrons: Implications for Ca chemistry in the upper atmosphere

    Science.gov (United States)

    Bones, D. L.; Gerding, M.; Höffner, J.; Martín, Juan Carlos Gómez; Plane, J. M. C.

    2016-12-01

    The dissociative recombination of CaO+ ions with electrons has been studied in a flowing afterglow reactor. CaO+ was generated by the pulsed laser ablation of a Ca target, followed by entrainment in an Ar+ ion/electron plasma. A kinetic model describing the gas-phase chemistry and diffusion to the reactor walls was fitted to the experimental data, yielding a rate coefficient of (3.0 ± 1.0) × 10-7 cm3 molecule-1 s-1 at 295 K. This result has two atmospheric implications. First, the surprising observation that the Ca+/Fe+ ratio is 8 times larger than Ca/Fe between 90 and 100 km in the atmosphere can now be explained quantitatively by the known ion-molecule chemistry of these two metals. Second, the rate of neutralization of Ca+ ions in a descending sporadic E layer is fast enough to explain the often explosive growth of sporadic neutral Ca layers.

  5. Effect of spatial vegetation and relief heterogeneity on vertical CO2 fluxes between land surface and the atmosphere

    Science.gov (United States)

    Olchev, Alexander; Mukhartova, Yulia; Levashova, Natalia; Volkova, Elena

    2015-04-01

    The main goal of the study is to describe the influence of spatial vegetation and relief heterogeneity on turbulent CO2 fluxes between land surface and the atmosphere using a process-based two-dimensional turbulent exchange models. As a key area for this modeling study the hilly territory situated at the southern boundary of broadleaf forest community in European part of Russia (Tula region) was selected. The vegetation cover in the study region is mainly represented by mosaic of agricultural areas, grasslands, mires and groves that makes very difficult an adequate determining the local and regional CO2 fluxes using experimental methods only. Applied two two-dimensional models based on solution of the Navier-Stokes and continuity equations using the first-order and one-and-a-half order (TKE) closure schemes. Numerical scheme of the first-order closure model is based on the theory of contrast structures (Levashova et al 2005). For description of the plant canopy photosynthesis and respiration rates an aggregated approach based on the model of Ball et al (1987) in Leuning modification (1990, 1995), the Beer-Lambert equation for the description of solar radiation penetration within a plant canopy (Monsi, Saeki 1953), and also an algorithm describing the response of stomatal conductance of the leaves to incoming photosynthetically active radiation is used. All necessary input parameters describing the photosynthesis and respiration properties of different plants and soil types in the study region were obtained from the field measurements or taken from the literature. To quantify the possible effects of relief and vegetation heterogeneity on CO2 fluxes the three transects crossing the study area were chosen. For each transect the 2D patterns of wind speed components, turbulent exchange coefficients, CO2 concentrations and fluxes were calculated both for actual vegetation structure and for additional scenario assuming the total area deforestation. All modeling

  6. Advanced exploitation of Ground-Based measurements for Atmospheric Chemistry and Climate Applications "AGACC"

    OpenAIRE

    De Mazière, Martine; De Backer, Hugo; Carleer, Michel; Mahieu, Emmanuel; Clémer, Katrijn; Dils, Bart; Kruglanski, Michel; Hendrick, François; Hermans, Christian; Van Roozendael, Michel; Vigouroux, Corinne; Cheymol, Anne; De Bock, Veerle; Mangold, Alexander; Van Malderen, Roeland

    2011-01-01

    We live in an era in which human activities are causing significant changes to the atmospheric environment which result in local to global consequences on the ecosystems. Changes in the atmospheric composition impact our climate via chemical and dynamical feedback mechanisms; in many instances they also affect air quality, and the health of the biosphere. Monitoring and understanding those changes and their consequences is fundamental to establish adequate actions for adaptation to and mitiga...

  7. On the Surface Chemistry of Iron Oxides in Reactive Gas Atmospheres

    NARCIS (Netherlands)

    de Smit, Emiel; van Schooneveld, Matti M.; Cinquini, Fabrizio; Bluhm, Hendrik; Sautet, Phillippe; de Groot, Frank M. F.; Weckhuysen, Bert M.

    2011-01-01

    Heterogeneous catalysis is based on the generation and subsequent combination of chemical species retained on the surface of a catalytic solid. Elementary reaction steps, that is, the dissociation of reactants and association to products, take place at the solid–gas or solid–liquid interface.

  8. Global trend analysis of surface CO simulated using the global atmospheric chemistry general circulation model, EMAC (ECHAM5/MESSy)

    Science.gov (United States)

    Yoon, Jongmin; Pozzer, Andrea; Lelieveld, Jos

    2013-04-01

    Carbon monoxide (CO) is an important trace gas in tropospheric chemistry. It directly influences the concentration of tropospheric hydroxyl radical (OH), and therefore regulates the lifetimes of various tropospheric trace gases. Since anthropogenic activity produces about 60% of the annual global emission of the tropospheric CO, temporal trend analysis of surface CO is needed to understand the increasing (decreasing) influence of humans on the cleansing capacity of the atmosphere. In this study, the global trend of surface CO from 2001 to 2010 was estimated using the EMAC (ECHAM5/MESSy for Atmospheric Chemistry) model. The simulation is based on the emission scenario based on RCP8.5 (Representative Concentration Pathways). The global EMAC simulations of monthly surface CO are evaluated with monthly MOPITT (Measurements Of Pollution In The Troposphere) observations (i.e. MOP03TM), and the spatial correlations range from 0.87 to 0.97. The simulated trends are compared with the data from a global surface CO monitoring network, the World Data Centre for Greenhouse Gases (WDCGG), which includes also the NOAA/CMDL (Climate Monitoring and Diagnostic Laboratory of the National Oceanic and Atmospheric Administration) Cooperative Air Sampling Network. Over the United States and Western Europe, the significant decreases of surface CO are estimated at -49.7±2.7 and -38.6±2.7 ppbv per decade. In contrast, the surface CO increased by +12.4±10.2 and +7.2±3.7 ppbv per decade over South America and South Africa, respectively.

  9. The atmospheric chemistry general circulation model ECHAM5/MESSy1: consistent simulation of ozone from the surface to the mesosphere

    Directory of Open Access Journals (Sweden)

    P. Jöckel

    2006-01-01

    Full Text Available The new Modular Earth Submodel System (MESSy describes atmospheric chemistry and meteorological processes in a modular framework, following strict coding standards. It has been coupled to the ECHAM5 general circulation model, which has been slightly modified for this purpose. A 90-layer model setup up to 0.01 hPa was used at spectral T42 resolution to simulate the lower and middle atmosphere. With the high vertical resolution the model simulates the Quasi-Biennial Oscillation. The model meteorology has been tested to check the influence of the changes to ECHAM5 and the radiation interactions with the new representation of atmospheric composition. In the simulations presented here a Newtonian relaxation technique was applied in the tropospheric part of the domain to weakly nudge the model towards the analysed meteorology during the period 1998–2005. This allows an efficient and direct evaluation with satellite and in-situ data. It is shown that the tropospheric wave forcing of the stratosphere in the model suffices to reproduce major stratospheric warming events leading e.g. to the vortex split over Antarctica in 2002. Characteristic features such as dehydration and denitrification caused by the sedimentation of polar stratospheric cloud particles and ozone depletion during winter and spring are simulated well, although ozone loss in the lower polar stratosphere is slightly underestimated. The model realistically simulates stratosphere-troposphere exchange processes as indicated by comparisons with satellite and in situ measurements. The evaluation of tropospheric chemistry presented here focuses on the distributions of ozone, hydroxyl radicals, carbon monoxide and reactive nitrogen compounds. In spite of minor shortcomings, mostly related to the relatively coarse T42 resolution and the neglect of inter-annual changes in biomass burning emissions, the main characteristics of the trace gas distributions are generally reproduced well. The MESSy

  10. Study of the atmospheric chemistry of radon progeny in laboratory and real indoor atmospheres. Final project report

    Energy Technology Data Exchange (ETDEWEB)

    Hopke, P.K.

    1996-09-01

    This report completes Clarkson University`s study of the chemical and physical behavior of the {sup 218}Po atom immediately following its formation by the alpha decay of radon. Because small changes in size for activity in the sub-10 nm size range result in large changes in the delivered dose per unit exposure, this behavior must be understood if the exposure to radon progeny and it dose to the cells in the respiratory tract are to be fully assessed. In order to pursue this general goal, two areas of radon progeny behavior are being pursued; laboratory studies under controlled conditions to better understand the fundamental physical and chemical processes that affect the progeny`s atmospheric behavior and studies in actual indoor environments to develop a better assessment of the exposure of the occupants of that space to the size and concentration of the indoor radioactive aerosol. Thus, two sets of specific goals have been established for this project. The specific tasks of the controlled laboratory studies are (1) Determine the formation rates of {circ}OH radicals formed by the radiolysis of air following radon decay; (2) Examine the formation of particles by the radiolytic oxidation of substances like SO{sub 2}, ethylene, and H{sub 2}S to lower vapor pressure compounds and determine the role of gas phase additives such as H{sub 2}O and NH{sub 3} in determining the particle size; (3) Measure the rate of ion-induced nucleation using a thermal diffusion cloud chamber, and (4) Measure the neutralization rate of {sup 218}PoO{sub x}{sup +} in O{sub 2} at low radon concentrations.

  11. Role of Atmospheric Chemistry in the Climate Impacts of Stratospheric Volcanic Injections

    Science.gov (United States)

    Legrande, Allegra N.; Tsigaridis, Kostas; Bauer, Susanne E.

    2016-01-01

    The climate impact of a volcanic eruption is known to be dependent on the size, location and timing of the eruption. However, the chemistry and composition of the volcanic plume also control its impact on climate. It is not just sulfur dioxide gas, but also the coincident emissions of water, halogens and ash that influence the radiative and climate forcing of an eruption. Improvements in the capability of models to capture aerosol microphysics, and the inclusion of chemistry and aerosol microphysics modules in Earth system models, allow us to evaluate the interaction of composition and chemistry within volcanic plumes in a new way. These modeling efforts also illustrate the role of water vapor in controlling the chemical evolution, and hence climate impacts, of the plume. A growing realization of the importance of the chemical composition of volcanic plumes is leading to a more sophisticated and realistic representation of volcanic forcing in climate simulations, which in turn aids in reconciling simulations and proxy reconstructions of the climate impacts of past volcanic eruptions. More sophisticated simulations are expected to help, eventually, with predictions of the impact on the Earth system of any future large volcanic eruptions.

  12. Role of atmospheric chemistry in the climate impacts of stratospheric volcanic injections

    Science.gov (United States)

    Tsigaridis, Kostas; LeGrande, Allegra; Bauer, Susanne

    2017-04-01

    The climate impact of a volcanic eruption is known to be dependent on the size, location and timing of the eruption. However, the chemistry and composition of the volcanic plume also control its impact on climate. It is not just sulfur dioxide gas, but also the coincident emissions of water, halogens and ash that influence the radiative and climate forcing of an eruption. Improvements in the capability of models to capture aerosol microphysics, and the inclusion of chemistry and aerosol microphysics modules in Earth system models, allow us to evaluate the interaction of composition and chemistry within volcanic plumes in a new way. These modeling efforts also illustrate the role of water vapor in controlling the chemical evolution - and hence climate impacts - of the plume. A growing realization of the importance of the chemical composition of volcanic plumes is leading to a more sophisticated and realistic representation of volcanic forcing in climate simulations, which in turn aids in reconciling simulations and proxy reconstructions of the climate impacts of past volcanic eruptions. More sophisticated simulations are expected to help, eventually, with predictions of the impact on the Earth system of any future large volcanic eruptions. Such simulations will be presented, and the role of water in accelerating sulfate aerosol formation in the stratosphere will be demonstrated.

  13. Description and Evaluation of the Multiscale Online Nonhydrostatic AtmospheRe CHemistry Model (NMMB-MONARCH) Version 1.0: Gas-Phase Chemistry at Global Scale

    Science.gov (United States)

    Badia, Alba; Jorba, Oriol; Voulgarakis, Apostolos; Dabdub, Donald; Garcia-Pando, Carlos Perez; Hilboll, Andreas; Goncalves, Maria; Janjic, Zavisa

    2017-01-01

    This paper presents a comprehensive description and benchmark evaluation of the tropospheric gas-phase chemistry component of the Multiscale Online Nonhydrostatic AtmospheRe CHemistry model (NMMBMONARCH), formerly known as NMMB/BSC-CTM, that can be run on both regional and global domains. Here, we provide an extensive evaluation of a global annual cycle simulation using a variety of background surface stations (EMEP, WDCGG and CASTNET), ozonesondes (WOUDC, CMD and SHADOZ), aircraft data (MOZAIC and several campaigns), and satellite observations (SCIAMACHY and MOPITT).We also include an extensive discussion of our results in comparison to other state-of-the-art models. We note that in this study, we omitted aerosol processes and some natural emissions (lightning and volcano emissions). The model shows a realistic oxidative capacity across the globe. The seasonal cycle for CO is fairly well represented at different locations (correlations around 0.3-0.7 in surface concentrations), although concentrations are underestimated in spring and winter in the Northern Hemisphere, and are overestimated throughout the year at 800 and 500 hPa in the Southern Hemisphere. Nitrogen species are well represented in almost all locations, particularly NO2 in Europe (root mean square error - RMSE - below 5 ppb). The modeled vertical distributions of NOx and HNO3 are in excellent agreement with the observed values and the spatial and seasonal trends of tropospheric NO2 columns correspond well to observations from SCIAMACHY, capturing the highly polluted areas and the biomass burning cycle throughout the year. Over Asia, the model underestimates NOx from March to August, probably due to an underestimation of NOx emissions in the region. Overall, the comparison of the modeled CO and NO2 with MOPITT and SCIAMACHY observations emphasizes the need for more accurate emission rates from anthropogenic and biomass burning sources (i.e., specification of temporal variability).

  14. The influence of vegetation and relief heterogeneity on turbulent exchange of CO2 between land surface and the atmosphere

    Science.gov (United States)

    Mukhartova, Juliya; Levashova, Natalia; Volkova, Elena; Olchev, Alexander

    2016-04-01

    vegetation and land-use types are situated far enough from the domain boundaries. It enabled us to assume that near these boundaries the values of vertical and horizontal wind components are independent on x coordinate. To quantify the possible effects of relief and vegetation heterogeneity on CO2 fluxes the three transects crossing the study area were chosen. For each transect the 2D patterns of wind speed components, turbulent exchange coefficients, CO2 concentrations and fluxes were calculated. The modeled vertical CO2 fluxes were compared with the fluxes calculated without allowing for turbulent disturbances due to relief and vegetation heterogeneity. All modeling experiments were provided for different weather conditions. The results of modeling experiments for different transects under various meteorological conditions showed that relief and vegetation heterogeneity have a significant impact on CO2 fluxes within the atmospheric surface layer and their ignoring can results in uncertainties in flux estimations. This study was supported by the Russian Science Foundation (Grant 14-14-00956).

  15. Soil HONO Emissions and Its Potential Impact on the Atmospheric Chemistry and Nitrogen Cycle

    Science.gov (United States)

    Su, H.; Chen, C.; Zhang, Q.; Poeschl, U.; Cheng, Y.

    2014-12-01

    Hydroxyl radicals (OH) are a key species in atmospheric photochemistry. In the lower atmosphere, up to ~30% of the primary OH radical production is attributed to the photolysis of nitrous acid (HONO), and field observations suggest a large missing source of HONO. The dominant sources of N(III) in soil, however, are biological nitrification and denitrification processes, which produce nitrite ions from ammonium (by nitrifying microbes) as well as from nitrate (by denitrifying microbes). We show that soil nitrite can release HONO and explain the reported strength and diurnal variation of the missing source. The HONO emissions rates are estimated to be comparable to that of nitric oxide (NO) and could be an important source of atmospheric reactive nitrogen. Fertilized soils appear to be particularly strong sources of HONO. Thus, agricultural activities and land-use changes may strongly influence the oxidizing capacity of the atmosphere. A new HONO-DNDC model was developed to simulate the evolution of HONO emissions in agriculture ecosystems. Because of the widespread occurrence of nitrite-producing microbes and increasing N and acid deposition, the release of HONO from soil may also be important in natural environments, including forests and boreal regions. Reference: Su, H. et al., Soil Nitrite as a Source of Atmospheric HONO and OH Radicals, Science, 333, 1616-1618, 10.1126/science.1207687, 2011.

  16. DAVINCI: Deep Atmosphere Venus Investigation of Noble gases, Chemistry, and Imaging

    Science.gov (United States)

    Glaze, Lori S.; Garvin, James B.; Robertson, Brent; Johnson, Natasha M.; Amato, Michael J.; Thompson, Jessica; Goodloe, Colby; Everette, Dave

    2017-01-01

    DAVINCI is one of five Discovery-class missions selected by NASA in October 2015 for Phase A studies. Launching in November 2021 and arriving at Venus in June of 2023, DAVINCI would be the first U.S. entry probe to target Venus atmosphere in 45 years. DAVINCI is designed to study the chemical and isotopic composition of a complete cross-section of Venus atmosphere at a level of detail that has not been possible on earlier missions and to image the surface at optical wavelengths and process-relevant scales.

  17. A Transition from a Traditional to a Project-Like Physical Chemistry Laboratory via a Heterogeneous Catalysis Study.

    Science.gov (United States)

    Goldwasser, M. R.; Leal, O.

    1979-01-01

    Outlines an approach for instruction in a physical chemistry laboratory which combines traditional and project-like experiments. An outline of laboratory experiments and examples of project-like experiments are included. (BT)

  18. Impact of acid atmosphere deposition on soils : field monitoring and aluminum chemistry

    NARCIS (Netherlands)

    Mulder, J.

    1988-01-01

    The effect of acid atmospheric deposition on concentrations and transfer of major solutes in acid, sandy soils was studied. Emphasis was given to mobilization and transport of potentially toxic aluminum. Data on solute concentrations and fluxes in meteoric water as well as soil solutions

  19. The impact of dynamic processes on chemistry in atmospheric boundary layers over tropical and boreal forest

    NARCIS (Netherlands)

    Ouwersloot, H.G.

    2013-01-01

    Improving our knowledge of the atmospheric processes that drive climate and air quality is very relevant for society. The application of this knowledge enables us to predict and mitigate the effects of human induced perturbations to our environment. Key factors in the current and future climate

  20. Future changes in biogenic isoprene emissions: how might they affect regional and global atmospheric chemistry?

    Science.gov (United States)

    Christine Wiedinmyer; Xuexi Tie; Alex Guenther; Ron Neilson; Claire. Granier

    2006-01-01

    Isoprene is emitted from vegetation to the atmosphere in significant quantities, and it plays an important role in the reactions that control tropospheric oxidant concentrations. As future climatic and land-cover changes occur, the spatial and temporal variations, as well as the magnitude of these biogenic isoprene emissions, are expected to change. This paper presents...

  1. Atmospheric chemistry of Z- and E-CF3CH=CHCF3

    DEFF Research Database (Denmark)

    Østerstrøm, Freja From; Andersen, Simone Thirstrup; Sølling, Theis Ivan

    2017-01-01

    The atmospheric fates of Z- and E-CF3CH[double bond, length as m-dash]CHCF3 have been studied, investigating the kinetics and the products of the reactions of the two compounds with Cl atoms, OH radicals, OD radicals, and O3. FTIR smog chamber experiments measured: k(Cl + Z-CF3CH[double bond...

  2. Modelling atmospheric chemistry and long-range transport of emerging Asian pollutants

    CERN Document Server

    Wang, Kuo-Ying

    2008-01-01

    Modeling is a very important tool for scientific processes, requiring long-term dedication, desire, and continuous reflection. In this work, we discuss several aspects of modeling, and the reasons for doing it. We discuss two major modeling systems that have been built by us over the last 10 years. It is a long and arduous process but the reward of understanding can be enormous, as demonstrated in the examples shown in this work. We found that long-range transport of emerging Asian pollutants can be interpreted using a Lagrangian framework for wind analysis. More detailed processes still need to be modeled but an accurate representation of the wind structure is the most important thing above all others. Our long-term chemistry integrations reveal the capability of the IMS model in simulating tropospheric chemistry on a climate scale. These long-term integrations also show ways for further model development. Modeling is a quantitative process, and the understanding can be sustained only when theories are vigor...

  3. Reactions of Azine Anions with Nitrogen and Oxygen Atoms: Implications for Titan's Upper Atmosphere and Interstellar Chemistry.

    Science.gov (United States)

    Wang, Zhe-Chen; Cole, Callie A; Demarais, Nicholas J; Snow, Theodore P; Bierbaum, Veronica M

    2015-08-26

    Azines are important in many extraterrestrial environments, from the atmosphere of Titan to the interstellar medium. They have been implicated as possible carriers of the diffuse interstellar bands in astronomy, indicating their persistence in interstellar space. Most importantly, they constitute the basic building blocks of DNA and RNA, so their chemical reactivity in these environments has significant astrobiological implications. In addition, N and O atoms are widely observed in the ISM and in the ionospheres of planets and moons. However, the chemical reactions of molecular anions with abundant interstellar and atmospheric atomic species are largely unexplored. In this paper, gas-phase reactions of deprotonated anions of benzene, pyridine, pyridazine, pyrimidine, pyrazine, and s-triazine with N and O atoms are studied both experimentally and computationally. In all cases, the major reaction channel is associative electron detachment; these reactions are particularly important since they control the balance between negative ions and free electron densities. The reactions of the azine anions with N atoms exhibit larger rate constants than reactions of corresponding chain anions. The reactions of azine anions with O atoms are even more rapid, with complex product patterns for different reactants. The mechanisms are studied theoretically by employing density functional theory; spin conversion is found to be important in determining some product distributions. The rich gas-phase chemistry observed in this work provides a better understanding of ion-atom reactions and their contributions to ionospheric chemistry as well as the chemical processing that occurs in the boundary layers between diffuse and dense interstellar clouds.

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

    Science.gov (United States)

    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.

  5. Reaction Mechanisms on Multiwell Potential Energy Surfaces in Combustion (and Atmospheric) Chemistry.

    Science.gov (United States)

    Osborn, David L

    2017-05-05

    Chemical reactions occurring on a potential energy surface with multiple wells are ubiquitous in low-temperature combustion and in the oxidation of volatile organic compounds in Earth's atmosphere. The rich variety of structural isomerizations that compete with collisional stabilization makes characterizing such complex-forming reactions challenging. This review describes recent experimental and theoretical advances that deliver increasingly complete views of their reaction mechanisms. New methods for creating reactive intermediates coupled with multiplexed measurements provide many experimental observables simultaneously. Automated methods to explore potential energy surfaces can uncover hidden reactive pathways, and master equation methods enable a holistic treatment of both sequential and well-skipping pathways. Our ability to probe and understand nonequilibrium effects and reaction sequences is increasing. These advances provide the fundamental science base for predictive models of combustion and the atmosphere that are crucial to address global challenges.

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

    Energy Technology Data Exchange (ETDEWEB)

    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).

  7. Solar cosmic ray effects in atmospheric chemistry evidenced from ground- based measurements

    Science.gov (United States)

    Shumilov, O.; Kasatkina, E.; Turyansky, V.

    Solar protons with a relatively soft energy spectrum (E450 MeV) of Ground Level Event (GLE) type can penetrate below 30 km and cause neutron flow enhancement detected by ground-based neutron monitors. Atmospheric effects of such high-energy particles seem to be more pronounced and appeared variations of total content of some atmospheric parameters that can be detected by ground-based devices. It was shown earlier that some GLEs cause considerable ozone total content decreases (up to 25%), or so-called ozone "miniholes" at high latitudes. This work presents ground-based measurements of nitrogen dioxide (NO2) total content made at Murmansk, Kola Peninsula (corrected geomagnetic latitude: 64.8) during and after GLE of 2 May 1998. Nitrogen dioxide was measured by zenith viewing spectrophotometer in wavelength region between 435-450 nm. An increase (about of 20%) in total column of NO2 has been recorded after 2 May 1998 GLE by this facility. Model calculations based on gas phase photochemical theory quantitatively agree with observations. In addition to satellite measurements the information obtained by ground-based devices will be helpful to study atmospheric effects of cosmic ray events. This work was supported by the RFBR grants 01-05-64850 and 01-05-26226).

  8. Convective Dynamics and Disequilibrium Chemistry in the Atmospheres of Giant Planets and Brown Dwarfs

    Science.gov (United States)

    Bordwell, Baylee; Brown, Benjamin P.; Oishi, Jeffrey S.

    2018-02-01

    Disequilibrium chemical processes significantly affect the spectra of substellar objects. To study these effects, dynamical disequilibrium has been parameterized using the quench and eddy diffusion approximations, but little work has been done to explore how these approximations perform under realistic planetary conditions in different dynamical regimes. As a first step toward addressing this problem, we study the localized, small-scale convective dynamics of planetary atmospheres by direct numerical simulation of fully compressible hydrodynamics with reactive tracers using the Dedalus code. Using polytropically stratified, plane-parallel atmospheres in 2D and 3D, we explore the quenching behavior of different abstract chemical species as a function of the dynamical conditions of the atmosphere as parameterized by the Rayleigh number. We find that in both 2D and 3D, chemical species quench deeper than would be predicted based on simple mixing-length arguments. Instead, it is necessary to employ length scales based on the chemical equilibrium profile of the reacting species in order to predict quench points and perform chemical kinetics modeling in 1D. Based on the results of our simulations, we provide a new length scale, derived from the chemical scale height, that can be used to perform these calculations. This length scale is simple to calculate from known chemical data and makes reasonable predictions for our dynamical simulations.

  9. Tropospheric Ozone Changes, Radiative Forcing and Attribution to Emissions in the Atmospheric Chemistry and Climate Model Intercomparison Project (ACCMIP)

    Science.gov (United States)

    Stevenson, D.S.; Young, P.J.; Naik, V.; Lamarque, J.-F.; Shindell, D. T.; Voulgarakis, A.; Skeie, R. B.; Dalsoren, S. B.; Myhre, G.; Berntsen, T. K.; hide

    2013-01-01

    Ozone (O3) from 17 atmospheric chemistry models taking part in the Atmospheric Chemistry and Climate Model Intercomparison Project (ACCMIP) has been used to calculate tropospheric ozone radiative forcings (RFs). All models applied a common set of anthropogenic emissions, which are better constrained for the present-day than the past. Future anthropogenic emissions follow the four Representative Concentration Pathway (RCP) scenarios, which define a relatively narrow range of possible air pollution emissions. We calculate a value for the pre-industrial (1750) to present-day (2010) tropospheric ozone RF of 410 mW m-2. The model range of pre-industrial to present-day changes in O3 produces a spread (+/-1 standard deviation) in RFs of +/-17%. Three different radiation schemes were used - we find differences in RFs between schemes (for the same ozone fields) of +/-10 percent. Applying two different tropopause definitions gives differences in RFs of +/-3 percent. Given additional (unquantified) uncertainties associated with emissions, climate-chemistry interactions and land-use change, we estimate an overall uncertainty of +/-30 percent for the tropospheric ozone RF. Experiments carried out by a subset of six models attribute tropospheric ozone RF to increased emissions of methane (44+/-12 percent), nitrogen oxides (31 +/- 9 percent), carbon monoxide (15 +/- 3 percent) and non-methane volatile organic compounds (9 +/- 2 percent); earlier studies attributed more of the tropospheric ozone RF to methane and less to nitrogen oxides. Normalising RFs to changes in tropospheric column ozone, we find a global mean normalised RF of 42 mW m(-2) DU(-1), a value similar to previous work. Using normalised RFs and future tropospheric column ozone projections we calculate future tropospheric ozone RFs (mW m(-2); relative to 1750) for the four future scenarios (RCP2.6, RCP4.5, RCP6.0 and RCP8.5) of 350, 420, 370 and 460 (in 2030), and 200, 300, 280 and 600 (in 2100). Models show some

  10. Tropospheric ozone changes, radiative forcing and attribution to emissions in the Atmospheric Chemistry and Climate Model Intercomparison Project (ACCMIP

    Directory of Open Access Journals (Sweden)

    D. S. Stevenson

    2013-03-01

    Full Text Available Ozone (O3 from 17 atmospheric chemistry models taking part in the Atmospheric Chemistry and Climate Model Intercomparison Project (ACCMIP has been used to calculate tropospheric ozone radiative forcings (RFs. All models applied a common set of anthropogenic emissions, which are better constrained for the present-day than the past. Future anthropogenic emissions follow the four Representative Concentration Pathway (RCP scenarios, which define a relatively narrow range of possible air pollution emissions. We calculate a value for the pre-industrial (1750 to present-day (2010 tropospheric ozone RF of 410 mW m−2. The model range of pre-industrial to present-day changes in O3 produces a spread (±1 standard deviation in RFs of ±17%. Three different radiation schemes were used – we find differences in RFs between schemes (for the same ozone fields of ±10%. Applying two different tropopause definitions gives differences in RFs of ±3%. Given additional (unquantified uncertainties associated with emissions, climate-chemistry interactions and land-use change, we estimate an overall uncertainty of ±30% for the tropospheric ozone RF. Experiments carried out by a subset of six models attribute tropospheric ozone RF to increased emissions of methane (44±12%, nitrogen oxides (31 ± 9%, carbon monoxide (15 ± 3% and non-methane volatile organic compounds (9 ± 2%; earlier studies attributed more of the tropospheric ozone RF to methane and less to nitrogen oxides. Normalising RFs to changes in tropospheric column ozone, we find a global mean normalised RF of 42 mW m−2 DU−1, a value similar to previous work. Using normalised RFs and future tropospheric column ozone projections we calculate future tropospheric ozone RFs (mW m−2; relative to 1750 for the four future scenarios (RCP2.6, RCP4.5, RCP6.0 and RCP8.5 of 350, 420, 370 and 460 (in 2030, and 200, 300, 280 and 600 (in 2100. Models show some coherent responses of ozone to climate change

  11. Chemistry Simulations Using MERRA-2 Reanalysis with the GMI CTM and Replay in Support of the Atmospheric Composition Community

    Science.gov (United States)

    Oman, Luke D.; Strahan, Susan E.

    2016-01-01

    Simulations using reanalyzed meteorological conditions have been long used to understand causes of atmospheric composition change over the recent past. Using the new Modern-Era Retrospective analysis for Research and Applications, version 2 (MERRA-2) meteorology, chemistry simulations are being conducted to create products covering 1980-2016 for the atmospheric composition community. These simulations use the Global Modeling Initiative (GMI) chemical mechanism in two different models: the GMI Chemical Transport Model (CTM) and the GEOS-5 model developed Replay mode. Replay mode means an integration of the GEOS-5 general circulation model that is incrementally adjusted each time step toward the MERRA-2 analysis. The GMI CTM is a 1 x 1.25 simulation and the MERRA-2 GMI Replay simulation uses the native MERRA-2 approximately horizontal resolution on the cubed sphere. The Replay simulations is driven by the online use of key MERRA-2 meteorological variables (i.e. U, V, T, and surface pressure) with all other variables calculated in response to those variables. A specialized set of transport diagnostics is included in both runs to better understand trace gas transport and changes over the recent past.

  12. The Chemistry CATT-BRAMS model (CCATT-BRAMS 4.5: a regional atmospheric model system for integrated air quality and weather forecasting and research

    Directory of Open Access Journals (Sweden)

    K. M. Longo

    2013-09-01

    Full Text Available Coupled Chemistry Aerosol-Tracer Transport model to the Brazilian developments on the Regional Atmospheric Modeling System (CCATT-BRAMS, version 4.5 is an on-line regional chemical transport model designed for local and regional studies of atmospheric chemistry from the surface to the lower stratosphere suitable both for operational and research purposes. It includes gaseous/aqueous chemistry, photochemistry, scavenging and dry deposition. The CCATT-BRAMS model takes advantage of BRAMS-specific development for the tropics/subtropics as well as the recent availability of preprocessing tools for chemical mechanisms and fast codes for photolysis rates. BRAMS includes state-of-the-art physical parameterizations and dynamic formulations to simulate atmospheric circulations down to the meter. This on-line coupling of meteorology and chemistry allows the system to be used for simultaneous weather and chemical composition forecasts as well as potential feedback between the two. The entire system is made of three preprocessing software tools for user-defined chemical mechanisms, aerosol and trace gas emissions fields and the interpolation of initial and boundary conditions for meteorology and chemistry. In this paper, the model description is provided along with the evaluations performed by using observational data obtained from ground-based stations, instruments aboard aircrafts and retrieval from space remote sensing. The evaluation accounts for model applications at different scales from megacities and the Amazon Basin up to the intercontinental region of the Southern Hemisphere.

  13. Design of a new multi-phase experimental simulation chamber for atmospheric photosmog, aerosol and cloud chemistry research

    Directory of Open Access Journals (Sweden)

    J. Wang

    2011-11-01

    Full Text Available A new simulation chamber has been built at the Interuniversitary Laboratory of Atmospheric Systems (LISA. The CESAM chamber (French acronym for Experimental Multiphasic Atmospheric Simulation Chamber is designed to allow research in multiphase atmospheric (photo- chemistry which involves both gas phase and condensed phase processes including aerosol and cloud chemistry. CESAM has the potential to carry out variable temperature and pressure experiments under a very realistic artificial solar irradiation. It consists of a 4.2 m3 stainless steel vessel equipped with three high pressure xenon arc lamps which provides a controlled and steady environment. Initial characterization results, all carried out at 290–297 K under dry conditions, concerning lighting homogeneity, mixing efficiency, ozone lifetime, radical sources, NOy wall reactivity, particle loss rates, background PM, aerosol formation and cloud generation are given. Photolysis frequencies of NO2 and O3 related to chamber radiation system were found equal to (4.2 × 10−3 s−1 for JNO2 and (1.4 × 10−5 s−1 for JO1D which is comparable to the solar radiation in the boundary layer. An auxiliary mechanism describing NOy wall reactions has been developed. Its inclusion in the Master Chemical Mechanism allowed us to adequately model the results of experiments on the photo-oxidation of propene-NOx-Air mixtures. Aerosol yields for the α-pinene + O3 system chosen as a reference were determined and found in good agreement with previous studies. Particle lifetime in the chamber ranges from 10 h to 4 days depending on particle size distribution which indicates that the chamber can provide high quality data on aerosol aging processes and their effects. Being evacuable, it is possible to generate in this new chamber

  14. Global Sensitivity analysis of atmospheric chemistry models using emulator-based and emulator-free methods

    Science.gov (United States)

    Ryan, Edmund; Wild, Oliver; O'Connor, Fiona; Voulgarakis, Apostolos; Lee, Lindsay

    2017-04-01

    Carrying out global sensitivity analysis (GSA) for a numerical model is critical in determining which inputs (e.g. parameters, driving data) most affect the model output. This informs us of which inputs to include: (i) for model calibration; (ii) when quantifying the uncertainty in the output given the uncertainty in the inputs. It is also used to diagnose differences in outputs between models. GSA quantifies the sensitivity index (SI) of a particular input - the percentage of the total variability in the output attributed to the changes in that input - by averaging over the other inputs, rather than fixing the other inputs at particular values as done in one-at-a-time sensitivity analysis. Traditional means of computing the SIs involve running the model thousands of times, but this becomes infeasible when the computational cost is high. GSA methods which use a surrogate of the model, called an emulator, are popular as they typically require far fewer runs of the model. Here we consider methods that would further reduce the computational burden of sensitivity analysis. When the output of a model is non-scalar, it is standard practice with an emulator-based GSA method to build a separate emulator for each dimension of the output space. An alternative is to apply principal component analysis (PCA) to reduce the output dimension and then build an emulator for each of the transformed outputs. We consider here a global map of methane lifetimes from our chemistry models. This requires 2000 emulators for the emulator-based GSA methods, but only 10-50 emulators for the PCA-emulator hybrid approach, reducing the computation of the SIs from 1 hour to 3 minutes on a desktop computer. The other benefit of PCA is that the transformed outputs are orthogonal, and thus building separate emulators is appropriate. Results show that very similar maps of SIs are produced whether the emulator-only or emulator-PCA hybrid approach is used. Another avenue to reducing the computational

  15. Atmospheric chemistry of benzyl alcohol: kinetics and mechanism of reaction with OH radicals.

    Science.gov (United States)

    Bernard, François; Magneron, Isabelle; Eyglunent, Grégory; Daële, Véronique; Wallington, Timothy J; Hurley, Michael D; Mellouki, Abdelwahid

    2013-04-02

    The atmospheric oxidation of benzyl alcohol has been investigated using smog chambers at ICARE, FORD, and EUPHORE. The rate coefficient for reaction with OH radicals was measured and an upper limit for the reaction with ozone was established; kOH = (2.8 ± 0.4) × 10(-11) at 297 ± 3 K (averaged value including results from Harrison and Wells) and kO(3) < 2 × 10(-19) cm(3) molecule(-1) s(-1) at 299 K. The products of the OH radical initiated oxidation of benzyl alcohol in the presence of NOX were studied. Benzaldehyde, originating from H-abstraction from the -CH(2)OH group, was identified using in situ FTIR spectroscopy, HPLC-UV/FID, and GC-PID and quantified in a yield of (24 ± 5) %. Ring retaining products originating from OH-addition to the aromatic ring such as o-hydroxybenzylalcohol and o-dihydroxybenzene as well as ring-cleavage products such as glyoxal were also identified and quantified with molar yields of (22 ± 2)%, (10 ± 3)%, and (2.7 ± 0.7)%, respectively. Formaldehyde was observed with a molar yield of (27 ± 10)%. The results are discussed with respect to previous studies and the atmospheric oxidation mechanism of benzyl alcohol.

  16. The role and importance of ozone for atmospheric chemistry and methods for measuring its concentration

    Directory of Open Access Journals (Sweden)

    Marković Dragan M.

    2003-01-01

    Full Text Available Depending on where ozone resides, it can protect or harm life on Earth. The thin layer of ozone that surrounds Earth acts as a shield protecting the planet from irradiation by UV light. When it is close to the planet's surface, ozone is a powerful photochemical oxidant that damage, icons frescos, museum exhibits, rubber, plastic and all plant and animal life. Besides the basic properties of some methods for determining the ozone concentration in working and living conditions, this paper presents a detailed description of the electrochemical method. The basic properties of the electrochemical method are used in the construction of mobile equipment for determining the sum of oxidants in the atmosphere. The equipment was used for testing the determination of the ozone concentration in working rooms, where the concentration was at a high level and caused by UV radiation or electrostatic discharge. According to the obtained results, it can be concluded that this equipment for determining the ozone concentration in the atmosphere is very powerful and reproducible in measurements.

  17. Fine-Structure Measurements of Oxygen A Band Absorbance for Estimating the Thermodynamic Average Temperature of the Earth's Atmosphere: An Experiment in Physical and Environmental Chemistry

    Science.gov (United States)

    Myrick, M. L.; Greer, A. E.; Nieuwland, A.; Priore, R. J.; Scaffidi, J.; Andreatta, Daniele; Colavita, Paula

    2006-01-01

    The experiment describe the measures of the A band transitions of atmospheric oxygen, a rich series of rotation-electronic absorption lines falling in the deep red portion of the optical spectrum and clearly visible owing to attenuation of solar radiation. It combines pure physical chemistry with analytical and environmental science and provides a…

  18. The Atmospheric Chemistry and Canopy Exchange Simulation System (ACCESS: model description and application to a temperate deciduous forest canopy

    Directory of Open Access Journals (Sweden)

    R. D. Saylor

    2013-01-01

    Full Text Available Forest canopies are primary emission sources of biogenic volatile organic compounds (BVOCs and have the potential to significantly influence the formation and distribution of secondary organic aerosol (SOA mass. Biogenically-derived SOA formed as a result of emissions from the widespread forests across the globe may affect air quality in populated areas, degrade atmospheric visibility, and affect climate through direct and indirect forcings. In an effort to better understand the formation of SOA mass from forest emissions, a 1-D column model of the multiphase physical and chemical processes occurring within and just above a vegetative canopy is being developed. An initial, gas-phase-only version of this model, the Atmospheric Chemistry and Canopy Exchange Simulation System (ACCESS, includes processes accounting for the emission of BVOCs from the canopy, turbulent vertical transport within and above the canopy and throughout the height of the planetary boundary layer (PBL, near-explicit representation of chemical transformations, mixing with the background atmosphere and bi-directional exchange between the atmosphere and canopy and the atmosphere and forest floor. The model formulation of ACCESS is described in detail and results are presented for an initial application of the modeling system to Walker Branch Watershed, an isoprene-emission-dominated forest canopy in the southeastern United States which has been the focal point for previous chemical and micrometeorological studies. Model results of isoprene profiles and fluxes are found to be consistent with previous measurements made at the simulated site and with other measurements made in and above mixed deciduous forests in the southeastern United States. Sensitivity experiments are presented which explore how canopy concentrations and fluxes of gas-phase precursors of SOA are affected by background anthropogenic nitrogen oxides (NOx. Results from these experiments suggest that the

  19. Parameterized isoprene and monoterpene emissions from the boreal forest floor: Implementation into a 1D chemistry-transport model and investigation of the influence on atmospheric chemistry

    Science.gov (United States)

    Mogensen, Ditte; Aaltonen, Hermanni; Aalto, Juho; Bäck, Jaana; Kieloaho, Antti-Jussi; Gierens, Rosa; Smolander, Sampo; Kulmala, Markku; Boy, Michael

    2015-04-01

    Volatile organic compounds (VOCs) are emitted from the biosphere and can work as precursor gases for aerosol particles that can affect the climate (e.g. Makkonen et al., ACP, 2012). VOC emissions from needles and leaves have gained the most attention, however other parts of the ecosystem also have the ability to emit a vast amount of VOCs. This, often neglected, source can be important e.g. at periods where leaves are absent. Both sources and drivers related to forest floor emission of VOCs are currently limited. It is thought that the sources are mainly due to degradation of organic matter (Isidorov and Jdanova, Chemosphere, 2002), living roots (Asensio et al., Soil Biol. Biochem., 2008) and ground vegetation. The drivers are biotic (e.g. microbes) and abiotic (e.g. temperature and moisture). However, the relative importance of the sources and the drivers individually are currently poorly understood. Further, the relative importance of these factors is highly dependent on the tree species occupying the area of interest. The emission of isoprene and monoterpenes where measured from the boreal forest floor at the SMEAR II station in Southern Finland (Hari and Kulmala, Boreal Env. Res., 2005) during the snow-free period in 2010-2012. We used a dynamic method with 3 automated chambers analyzed by Proton Transfer Reaction - Mass Spectrometer (Aaltonen et al., Plant Soil, 2013). Using this data, we have developed empirical parameterizations for the emission of isoprene and monoterpenes from the forest floor. These parameterizations depends on abiotic factors, however, since the parameterizations are based on field measurements, biotic features are captured. Further, we have used the 1D chemistry-transport model SOSAA (Boy et al., ACP, 2011) to test the seasonal relative importance of inclusion of these parameterizations of the forest floor compared to the canopy crown emissions, on the atmospheric reactivity throughout the canopy.

  20. Long-term variations and trends in the simulation of the middle atmosphere 1980–2004 by the chemistry-climate model of the Meteorological Research Institute

    Directory of Open Access Journals (Sweden)

    M. Deushi

    2008-05-01

    Full Text Available A middle-atmosphere simulation of the past 25 years (from 1980 to 2004 has been performed with a chemistry-climate model (CCM of the Meteorological Research Institute (MRI under observed forcings of sea-surface temperature, greenhouse gases, halogens, volcanic aerosols, and solar irradiance variations. The dynamics module of MRI-CCM is a spectral global model truncated triangularly at a maximum wavenumber of 42 with 68 layers extending from the surface to 0.01 hPa (about 80 km, wherein the vertical spacing is 500 m from 100 to 10 hPa. The chemistry-transport module treats 51 species with 124 reactions including heterogeneous reactions. Transport of chemical species is based on a hybrid semi-Lagrangian scheme, which is a flux form in the vertical direction and an ordinary semi-Lagrangian form in the horizontal direction. The MRI-CCM used in this study reproduced a quasi-biennial oscillation (QBO of about a 20-month period for wind and ozone in the equatorial stratosphere. Multiple linear regression analysis with time lags for volcanic aerosols was performed on the zonal-mean quantities of the simulated result to separate the trend, the QBO, the El Chichón and Mount Pinatubo, the 11-year solar cycle, and the El Niño/Southern Oscillation (ENSO signals. It is found that MRI-CCM can more or less realistically reproduce observed trends of annual mean temperature and ozone, and those of total ozone in each month. MRI-CCM also reproduced the vertical multi-cell structures of tropical temperature, zonal-wind, and ozone associated with the QBO, and the mid-latitude total ozone QBO in each winter hemisphere. Solar irradiance variations of the 11-year cycle were found to affect radiation alone (not photodissociation because of an error in making the photolysis lookup table. Nevertheless, though the heights of the maximum temperature (ozone in the tropics are much higher (lower than observations, MRI-CCM could reproduce the second maxima of temperature and

  1. Development of a grid-independent GEOS-chem chemical transport model as an atmospheric chemistry module for Earth System Models

    Science.gov (United States)

    Long, M. S.; Yantosca, R.; Nielsen, J. E.; Keller, C. A.; da Silva, A.; Sulprizio, M. P.; Pawson, S.; Jacob, D. J.

    2014-11-01

    The GEOS-Chem global chemical transport model (CTM), used by a large atmospheric chemistry research community, has been re-engineered to also serve as an atmospheric chemistry module for Earth System Models (ESMs). This was done using an Earth System Modelling Framework (ESMF) interface that operates independently of the GEOS-Chem scientific code, permitting the exact same GEOS-Chem code to be used as an ESM module or as a stand-alone CTM. In this manner, the continual stream of updates contributed by the CTM user community is automatically passed on to the ESM module, which remains state-of-science and referenced to the latest version of the standard GEOS-Chem CTM. A major step in this re-engineering was to make GEOS-Chem grid-independent, i.e., capable of using any geophysical grid specified at run time. GEOS-Chem data "sockets" were also created for communication between modules and with external ESM code via the ESMF. The grid-independent, ESMF-compatible GEOS-Chem is now the standard version of the GEOS-Chem CTM. It has been implemented as an atmospheric chemistry module into the NASA GEOS-5 ESM. The coupled GEOS-5/GEOS-Chem system was tested for scalability and performance with a tropospheric oxidant-aerosol simulation (120 coupled species, 66 transported tracers) using 48-240 cores and MPI parallelization. Numerical experiments demonstrate that the GEOS-Chem chemistry module scales efficiently for the number of processors tested. Although inclusion of atmospheric chemistry in ESMs is computationally expensive, the excellent scalability of the chemistry module means that the relative cost goes down with increasing number of MPI processes.

  2. Development of a grid-independent GEOS-Chem chemical transport model (v9-02) as an atmospheric chemistry module for Earth system models

    Science.gov (United States)

    Long, M. S.; Yantosca, R.; Nielsen, J. E.; Keller, C. A.; da Silva, A.; Sulprizio, M. P.; Pawson, S.; Jacob, D. J.

    2015-03-01

    The GEOS-Chem global chemical transport model (CTM), used by a large atmospheric chemistry research community, has been re-engineered to also serve as an atmospheric chemistry module for Earth system models (ESMs). This was done using an Earth System Modeling Framework (ESMF) interface that operates independently of the GEOS-Chem scientific code, permitting the exact same GEOS-Chem code to be used as an ESM module or as a stand-alone CTM. In this manner, the continual stream of updates contributed by the CTM user community is automatically passed on to the ESM module, which remains state of science and referenced to the latest version of the standard GEOS-Chem CTM. A major step in this re-engineering was to make GEOS-Chem grid independent, i.e., capable of using any geophysical grid specified at run time. GEOS-Chem data sockets were also created for communication between modules and with external ESM code. The grid-independent, ESMF-compatible GEOS-Chem is now the standard version of the GEOS-Chem CTM. It has been implemented as an atmospheric chemistry module into the NASA GEOS-5 ESM. The coupled GEOS-5-GEOS-Chem system was tested for scalability and performance with a tropospheric oxidant-aerosol simulation (120 coupled species, 66 transported tracers) using 48-240 cores and message-passing interface (MPI) distributed-memory parallelization. Numerical experiments demonstrate that the GEOS-Chem chemistry module scales efficiently for the number of cores tested, with no degradation as the number of cores increases. Although inclusion of atmospheric chemistry in ESMs is computationally expensive, the excellent scalability of the chemistry module means that the relative cost goes down with increasing number of cores in a massively parallel environment.

  3. Plasma chemistry in an atmospheric pressure Ar/NH3 dielectric barrier discharge

    DEFF Research Database (Denmark)

    Fateev, A.; Leipold, F.; Kusano, Y.

    2005-01-01

    absorption spectroscopy was also employed for the detection of stable products in the exhaust gas. To clarify the different processes for ammonia decomposition, N-2(2 - 10%) was added to the plasma. Modeling of the chemical kinetics in an Ar/NH3 plasma was performed as well. The dominant stable products...... of an atmospheric pressure Ar/NH3 DBD are H-2, N-2 and N2H4. The hydrazine (N2H4) concentration in the plasma and in the exhaust gases at various ammonia concentrations and different discharge powers was measured. Thermal N2H4 decomposition into NH2 radicals may be used for NOx reduction processes....

  4. Atmospheric chemistry in the Arctic and subarctic - Influence of natural fires, industrial emissions, and stratospheric inputs

    Science.gov (United States)

    Wofsy, S. C.; Sachse, G. W.; Gregory, G. L.; Blake, D. R.; Bradshaw, J. D.; Sandholm, S. T.; Singh, H. B.; Barrick, J. A.; Harriss, R. C.; Talbot, R. W.

    1992-01-01

    Layers with enhanced concentrations of trace gases intercepted by the NASA Electra aircraft over Alaska during the Arctic Boundary Layer Expedition (ABLE 3A) in July-August 1988 are discussed. Haze layers apparently associated with boreal fires were enriched in hydrocarbons and NO(y), with emission factors corresponding closely to laboratory data for smoldering combustion. It is argued that atmospheric composition was strongly modified by wildfires during several periods of the ABLE 3A mission. The associated enhancement of NO(y) was smaller than observed for most other combustion processes but was nonetheless significant in the context of very low background concentrations. Ozone production in fire plumes was negligible. Ambient O3 was supplied by the stratosphere, with little direct input from midlatitude source during summer. It is argued that NO(y) was supplied about equally by the stratosphere and by wildfires. Hydrocarbons and CO appear to derive from biomass fires and from human activities.

  5. Comparison of the HadGEM2 climate-chemistry model against in situ and SCIAMACHY atmospheric methane data

    Directory of Open Access Journals (Sweden)

    G. D. Hayman

    2014-12-01

    Full Text Available Wetlands are a major emission source of methane (CH4 globally. In this study, we evaluate wetland emission estimates derived using the UK community land surface model (JULES, the Joint UK Land Earth Simulator against atmospheric observations of methane, including, for the first time, total methane columns derived from the SCIAMACHY instrument on board the ENVISAT satellite. Two JULES wetland emission estimates are investigated: (a from an offline run driven with Climatic Research Unit–National Centers for Environmental Prediction (CRU-NCEP meteorological data and (b from the same offline run in which the modelled wetland fractions are replaced with those derived from the Global Inundation Extent from Multi-Satellites (GIEMS remote sensing product. The mean annual emission assumed for each inventory (181 Tg CH4 per annum over the period 1999–2007 is in line with other recently published estimates. There are regional differences as the unconstrained JULES inventory gives significantly higher emissions in the Amazon (by ~36 Tg CH4 yr−1 and lower emissions in other regions (by up to 10 Tg CH4 yr−1 compared to the JULES estimates constrained with the GIEMS product. Using the UK Hadley Centre's Earth System model with atmospheric chemistry (HadGEM2, we evaluate these JULES wetland emissions against atmospheric observations of methane. We obtain improved agreement with the surface concentration measurements, especially at high northern latitudes, compared to previous HadGEM2 runs using the wetland emission data set of Fung et al. (1991. Although the modelled monthly atmospheric methane columns reproduce the large-scale patterns in the SCIAMACHY observations, they are biased low by 50 part per billion by volume (ppb. Replacing the HadGEM2 modelled concentrations above 300 hPa with HALOE–ACE assimilated TOMCAT output results in a significantly better agreement with the SCIAMACHY observations. The use of the GIEMS product to constrain the JULES

  6. Plant surface reactions: an opportunistic ozone defence mechanism impacting atmospheric chemistry

    Science.gov (United States)

    Jud, W.; Fischer, L.; Canaval, E.; Wohlfahrt, G.; Tissier, A.; Hansel, A.

    2016-01-01

    Elevated tropospheric ozone concentrations are considered a toxic threat to plants, responsible for global crop losses with associated economic costs of several billion dollars per year. Plant injuries have been linked to the uptake of ozone through stomatal pores and oxidative damage of the internal leaf tissue. But a striking question remains: can surface reactions limit the stomatal uptake of ozone and therefore reduce its detrimental effects to plants?In this laboratory study we could show that semi-volatile organic compounds exuded by the glandular trichomes of different Nicotiana tabacum varieties are an efficient ozone sink at the plant surface. In our experiments, different diterpenoid compounds were responsible for a strongly variety-dependent ozone uptake of plants under dark conditions, when stomatal pores are almost closed. Surface reactions of ozone were accompanied by a prompt release of oxygenated volatile organic compounds, which could be linked to the corresponding precursor compounds: ozonolysis cis-abienol (C20H34O) - a diterpenoid with two exocyclic double bonds - caused emissions of formaldehyde (HCHO) and methyl vinyl ketone (C4H6O). The ring-structured cembratrien-diols (C20H34O2) with three endocyclic double bonds need at least two ozonolysis steps to form volatile carbonyls such as 4-oxopentanal (C5H8O2), which we could observe in the gas phase, too.Fluid dynamic calculations were used to model ozone distribution in the diffusion-limited leaf boundary layer under daylight conditions. In the case of an ozone-reactive leaf surface, ozone gradients in the vicinity of stomatal pores are changed in such a way that the ozone flux through the open stomata is strongly reduced.Our results show that unsaturated semi-volatile compounds at the plant surface should be considered as a source of oxygenated volatile organic compounds, impacting gas phase chemistry, as well as efficient ozone sink improving the ozone tolerance of plants.

  7. Plant surface reactions: an opportunistic ozone defence mechanism impacting atmospheric chemistry

    Directory of Open Access Journals (Sweden)

    W. Jud

    2016-01-01

    Full Text Available Elevated tropospheric ozone concentrations are considered a toxic threat to plants, responsible for global crop losses with associated economic costs of several billion dollars per year. Plant injuries have been linked to the uptake of ozone through stomatal pores and oxidative damage of the internal leaf tissue. But a striking question remains: can surface reactions limit the stomatal uptake of ozone and therefore reduce its detrimental effects to plants?In this laboratory study we could show that semi-volatile organic compounds exuded by the glandular trichomes of different Nicotiana tabacum varieties are an efficient ozone sink at the plant surface. In our experiments, different diterpenoid compounds were responsible for a strongly variety-dependent ozone uptake of plants under dark conditions, when stomatal pores are almost closed. Surface reactions of ozone were accompanied by a prompt release of oxygenated volatile organic compounds, which could be linked to the corresponding precursor compounds: ozonolysis cis-abienol (C20H34O – a diterpenoid with two exocyclic double bonds – caused emissions of formaldehyde (HCHO and methyl vinyl ketone (C4H6O. The ring-structured cembratrien-diols (C20H34O2 with three endocyclic double bonds need at least two ozonolysis steps to form volatile carbonyls such as 4-oxopentanal (C5H8O2, which we could observe in the gas phase, too.Fluid dynamic calculations were used to model ozone distribution in the diffusion-limited leaf boundary layer under daylight conditions. In the case of an ozone-reactive leaf surface, ozone gradients in the vicinity of stomatal pores are changed in such a way that the ozone flux through the open stomata is strongly reduced.Our results show that unsaturated semi-volatile compounds at the plant surface should be considered as a source of oxygenated volatile organic compounds, impacting gas phase chemistry, as well as efficient ozone sink improving the ozone tolerance of plants.

  8. Peroxyacetic acid in urban and rural atmosphere: concentration, feedback on PAN-NOx cycle and implication on radical chemistry

    Directory of Open Access Journals (Sweden)

    J. L. Li

    2010-01-01

    kinetics analysis indicate that the formation and removal processes of H2O2 may be different from those of MHP and PAA. (iv Considering that PAA is the reservior of free radicals, its fate is expected to have an effect on the free radical budget in the atmosphere. A box model based on the CBM-IV mechanism has been performed to access its influence on the radical budget. We suggest that the detailed information on PAA in the atmosphere is of importance to better understand the free radical chemistry.

  9. A STUDY ON LEGIONELLA PNEUMOPHILA, WATER CHEMISTRY, AND ATMOSPHERIC CONDITIONS IN COOLING TOWERS AT THE SAVANNAH RIVER SITE

    Energy Technology Data Exchange (ETDEWEB)

    Smith, C.; Brigmon, R.

    2009-10-20

    elevated Legionella concentrations when the dew point temperature was high--a summertime occurrence. However, analysis of the three years of Legionella monitoring data of the 14 different SRS Cooling Towers demonstrated that elevated concentrations are observed at all temperatures and seasons. The objective of this study is to evaluate the ecology of L. pneumophila including serogroups and population densities, chemical, and atmospheric data, on cooling towers at SRS to determine whether relationships exist among water chemistry, and atmospheric conditions. The goal is to more fully understand the conditions which inhibit or encourage L. pneumophila growth and supply this data and associated recommendations to SRS Cooling Tower personnel for improved management of operation. Hopefully this information could then be used to help control L. pneumophila growth more effectively in SRS cooling tower water.

  10. Emission Spectroscopy of Atmospheric-Pressure Ball Plasmoids: Higher Energy Reveals a Rich Chemistry

    Science.gov (United States)

    Dubowsky, Scott E.; Rose, Amber Nicole; Glumac, Nick; McCall, Benjamin J.

    2017-06-01

    Ball plasmoids (self-sustaining spherical plasmas) are a particularly unique example of a non-equilibrium air plasma. These plasmoids have lifetimes on the order of hundreds of milliseconds without an external power source, however, current models dictate that a ball plasmoid should recombine in a millisecond or less. Ball plasmoids are considered to be a laboratory analogue of natural ball lightning, a phenomenon that has eluded scientific explanation for centuries. We are searching for the underlying physicochemical mechanism(s) by which ball plasmoids and (by extension) ball lightning are stabilized using a variety of diagnostic techniques. This presentation will focus on optical emission spectroscopy (OES) of ball plasmoid discharges between 190-850 nm. The previous generation of OES measurements of this system showed emission from only a few atomic and molecular species, however, the energy available for the discharges in these experiments was limited by the size of the capacitor banks and voltages to which the capacitor banks were charged. We are capable of generating plasmoids at much higher energies, and as a result we are the first to report a very rich chemistry previously not observed in ball plasmoids. We have identified signals from species including NO A^{2}Σ^{+}→X^{2}Π, OH A^{2}Σ^{+}→X^{2}Π, NH A^{3}Π→X^{3}Σ^{-}, AlO A^{2}Π→X^{2}Σ^{+}, NH^{+} B^{2}Δ→X^{2}Π, W I, Al I, Cu I, and H_{α}, all of which have not yet been reported for this system. Analysis of the emission spectra and fitting procedures will be discussed, rotational temperatures of constituent species will be reported, and theories of ball plasmoid stabilization based upon these new results will be presented. Versteegh, A.; Behringer, K.; Fantz, U.; Fussman, G.; Jüttner, B.; Noack, S. Plas. Sour. Sci. Technol. 2008, 17(2), 024014 Stephan, K. D.; Dumas, S.; Komala-Noor, L.; McMinn, J. Plas. Sour. Sci. Technol. 2013, 22(2), 025018

  11. Biogenic non-methane hydrocarbons (NMHC). Nature`s contribution to regional and global atmospheric chemistry

    Energy Technology Data Exchange (ETDEWEB)

    Klockow, D.; Hoffman, T. [Inst. of Spectrochemistry and Applied Spectroscopy, Dortmund (Germany)

    1995-12-31

    Terrestrial vegetation provides an important source of volatile hydrocarbons, especially isoprene, monoterpenes and in addition possibly sesquiterpenes as well as oxygenated compounds. Although there exist considerable uncertainties in the estimation of the magnitude of these biogenic NMHC emissions, it is generally accepted that the majority of global NMHC release is from natural and not from anthropogenic sources. Taking into consideration the high reactivity of the mostly unsaturated biogenic emissions, their impact on tropospheric processes can be assumed to be of great importance. Together with anthropogenic NO{sub x} emissions, the highly reactive natural alkenes can act as precursors in photochemical oxidant formation and contribute to regional-scale air pollution. Their oxidation in the atmosphere and the subsequent gas-to-particle conversion of the products lead to the formation of organic aerosols. Because of the formation of phytotoxic compounds, the interaction of the biogenic hydrocarbons with ozone inside or outside the leaves and needles of plants has been suggested to play a role in forest decline. (author)

  12. Palmitic Acid on Salt Subphases and in Mixed Monolayers of Cerebrosides: Application to Atmospheric Aerosol Chemistry

    Directory of Open Access Journals (Sweden)

    Ellen M. Adams

    2013-10-01

    Full Text Available Palmitic acid (PA has been found to be a major constituent in marine aerosols, and is commonly used to investigate organic containing atmospheric aerosols, and is therefore used here as a proxy system. Surface pressure-area isotherms (π-A, Brewster angle microscopy (BAM, and vibrational sum frequency generation (VSFG were used to observe a PA monolayer during film compression on subphases of ultrapure water, CaCl2 and MgCl2 aqueous solutions, and artificial seawater (ASW. π-A isotherms indicate that salt subphases alter the phase behavior of PA, and BAM further reveals that a condensation of the monolayer occurs when compared to pure water. VSFG spectra and BAM images show that Mg2+ and Ca2+ induce ordering of the PA acyl chains, and it was determined that the interaction of Mg2+ with the monolayer is weaker than Ca2+. π-A isotherms and BAM were also used to monitor mixed monolayers of PA and cerebroside, a simple glycolipid. Results reveal that PA also has a condensing effect on the cerebroside monolayer. Thermodynamic analysis indicates that attractive interactions between the two components exist; this may be due to hydrogen bonding of the galactose and carbonyl headgroups. BAM images of the collapse structures show that mixed monolayers of PA and cerebroside are miscible at all surface pressures. These results suggest that the surface morphology of organic-coated aerosols is influenced by the chemical composition of the aqueous core and the organic film itself.

  13. Organocatalysis: Key Trends in Green Synthetic Chemistry, Challenges, Scope towards Heterogenization, and Importance from Research and Industrial Point of View

    OpenAIRE

    Isak Rajjak Shaikh

    2014-01-01

    This paper purports to review catalysis, particularly the organocatalysis and its origin, key trends, challenges, examples, scope, and importance. The definition of organocatalyst corresponds to a low molecular weight organic molecule which in stoichiometric amounts catalyzes a chemical reaction. In this review, the use of the term heterogenized organocatalyst will be exclusively confined to a catalytic system containing an organic molecule immobilized onto some sort of support material and i...

  14. Prospects for Simulating Macromolecular Surfactant Chemistry at the Ocean-Atmosphere Boundary

    Energy Technology Data Exchange (ETDEWEB)

    Elliott, S.; Burrows, Susannah M.; Deal, C.; Liu, Xiaohong; Long, M.; Ogunro, O.; Russell, Lynn M.; Wingenter, O.

    2014-05-01

    Biogenic lipids and polymers are surveyed for their ability to adsorb at the water-air interfaces associated with bubbles, marine microlayers and particles in the overlying boundary layer. Representative ocean biogeochemical regimes are defined in order to estimate local concentrations for the major macromolecular classes. Surfactant equilibria and maximum excess are then derived based on a network of model compounds. Relative local coverage and upward mass transport follow directly, and specific chemical structures can be placed into regional rank order. Lipids and denatured protein-like polymers dominate at the selected locations. The assigned monolayer phase states are variable, whether assessed along bubbles or at the atmospheric spray droplet perimeter. Since oceanic film compositions prove to be irregular, effects on gas and organic transfer are expected to exhibit geographic dependence as well. Moreover, the core arguments extend across the sea-air interface into aerosol-cloud systems. Fundamental nascent chemical properties including mass to carbon ratio and density depend strongly on the geochemical state of source waters. High surface pressures may suppress the Kelvin effect, and marine organic hygroscopicities are almost entirely unconstrained. While bubble adsorption provides a well-known means for transporting lipidic or proteinaceous material into sea spray, the same cannot be said of polysaccharides. Carbohydrates tend to be strongly hydrophilic so that their excess carbon mass is low despite stacked polymeric geometries. Since sugars are abundant in the marine aerosol, gel-based mechanisms may be required to achieve uplift. Uncertainties in the surfactant logic distill to a global scale dearth of information regarding two dimensional kinetics and equilibria. Nonetheless simulations are recommended, to initiate the process of systems level quantification.

  15. Prospects for simulating macromolecular surfactant chemistry at the ocean-atmosphere boundary

    Science.gov (United States)

    Elliott, S.; Burrows, S. M.; Deal, C.; Liu, X.; Long, M.; Ogunro, O.; Russell, L. M.; Wingenter, O.

    2014-05-01

    Biogenic lipids and polymers are surveyed for their ability to adsorb at the water-air interfaces associated with bubbles, marine microlayers and particles in the overlying boundary layer. Representative ocean biogeochemical regimes are defined in order to estimate local concentrations for the major macromolecular classes. Surfactant equilibria and maximum excess are then derived based on a network of model compounds. Relative local coverage and upward mass transport follow directly, and specific chemical structures can be placed into regional rank order. Lipids and denatured protein-like polymers dominate at the selected locations. The assigned monolayer phase states are variable, whether assessed along bubbles or at the atmospheric spray droplet perimeter. Since oceanic film compositions prove to be irregular, effects on gas and organic transfer are expected to exhibit geographic dependence as well. Moreover, the core arguments extend across the sea-air interface into aerosol-cloud systems. Fundamental nascent chemical properties including mass to carbon ratio and density depend strongly on the geochemical state of source waters. High surface pressures may suppress the Kelvin effect, and marine organic hygroscopicities are almost entirely unconstrained. While bubble adsorption provides a well-known means for transporting lipidic or proteinaceous material into sea spray, the same cannot be said of polysaccharides. Carbohydrates tend to be strongly hydrophilic so that their excess carbon mass is low despite stacked polymeric geometries. Since sugars are abundant in the marine aerosol, gel-based mechanisms may be required to achieve uplift. Uncertainties distill to a global scale dearth of information regarding two dimensional kinetics and equilibria. Nonetheless simulations are recommended, to initiate the process of systems level quantification.

  16. Chemistry of riming: the retention of organic and inorganic atmospheric trace constituents

    Science.gov (United States)

    Jost, Alexander; Szakáll, Miklós; Diehl, Karoline; Mitra, Subir K.; Borrmann, Stephan

    2017-08-01

    During free fall in clouds, ice hydrometeors such as snowflakes and ice particles grow effectively by riming, i.e., the accretion of supercooled droplets. Volatile atmospheric trace constituents dissolved in the supercooled droplets may remain in ice during freezing or may be released back to the gas phase. This process is quantified by retention coefficients. Once in the ice phase the trace constituents may be vertically redistributed by scavenging and subsequent precipitation or by evaporation of these ice hydrometeors at high altitudes. Retention coefficients of the most dominant carboxylic acids and aldehydes found in cloud water were investigated in the Mainz vertical wind tunnel under dry-growth (surface temperature less than 0 °C) riming conditions which are typically prevailing in the mixed-phase zone of convective clouds (i.e., temperatures from -16 to -7 °C and a liquid water content (LWC) of 0. 9 ± 0. 2 g m-3). The mean retention coefficients of formic and acetic acids are found to be 0. 68 ± 0. 09 and 0. 63 ± 0. 19. Oxalic and malonic acids as well as formaldehyde show mean retention coefficients of 0. 97 ± 0. 06, 0. 98 ± 0. 08, and 0. 97 ± 0. 11, respectively. Application of a semi-empirical model on the present and earlier wind tunnel measurements reveals that retention coefficients can be well interpreted by the effective Henry's law constant accounting for solubility and dissociation. A parameterization for the retention coefficients has been derived for substances whose aqueous-phase kinetics are fast compared to mass transport timescales. For other cases, the semi-empirical model in combination with a kinetic approach is suited to determine the retention coefficients. These may be implemented in high-resolution cloud models.

  17. Development of an aerosol-chemistry transport model coupled to non-hydrostatic icosahedral atmospheric model (NICAM) through applying a stretched grid system to regional simulations around Japan

    Science.gov (United States)

    Goto, D.; Nakajima, T.; Masaki, S.

    2014-12-01

    Air pollution has a great impact on both climate change and human health. One effective way to tackle with these issues is a use of atmospheric aerosol-chemistry models with high-resolution in a global scale. For this purpose, we have developed an aerosol-chemistry model based on a global cloud-resolving model (GCRM), Nonhydrostatic Icosahedral Atmospheric Model (NICAM; Tomita and Satoh, Fluid. Dyn. Res. 2004; Satoh et al., J. Comput. Phys. 2008, PEPS, 2014) under MEXT/RECCA/SALSA project. In the present study, we have simulated aerosols and tropospheric ozone over Japan by our aerosol-chemistry model "NICAM-Chem" with a stretched-grid system of approximately 10 km resolution, for saving the computer resources. The aerosol and chemistry modules are based on Spectral Radiation-Transport Model for Aerosol Species (SPRINTARS; Takemura et al., J. Geophys. Res., 2005) and Chemical AGCM for Study of Atmospheric Environment and Radiative Forcing (CHASER; Sudo et al., J. Geophys. Res., 2002). We found that our model can generally reproduce both aerosols and ozone, in terms of temporal variations (daily variations of aerosols and diurnal variations of ozone). Under MEXT/RECCA/SALSA project, we also have used these results obtained by NICAM-Chem for the assessment of their impact on human health.

  18. A new Differential Optical Absorption Spectroscopy instrument to study atmospheric chemistry from a high-altitude unmanned aircraft

    Science.gov (United States)

    Stutz, Jochen; Werner, Bodo; Spolaor, Max; Scalone, Lisa; Festa, James; Tsai, Catalina; Cheung, Ross; Colosimo, Santo F.; Tricoli, Ugo; Raecke, Rasmus; Hossaini, Ryan; Chipperfield, Martyn P.; Feng, Wuhu; Gao, Ru-Shan; Hintsa, Eric J.; Elkins, James W.; Moore, Fred L.; Daube, Bruce; Pittman, Jasna; Wofsy, Steven; Pfeilsticker, Klaus

    2017-03-01

    Observations of atmospheric trace gases in the tropical upper troposphere (UT), tropical tropopause layer (TTL), and lower stratosphere (LS) require dedicated measurement platforms and instrumentation. Here we present a new limb-scanning Differential Optical Absorption Spectroscopy (DOAS) instrument developed for NASA's Global Hawk (GH) unmanned aerial system and deployed during the Airborne Tropical TRopopause EXperiment (ATTREX). The mini-DOAS system is designed for automatic operation under unpressurized and unheated conditions at 14-18 km altitude, collecting scattered sunlight in three wavelength windows: UV (301-387 nm), visible (410-525 nm), and near infrared (900-1700 nm). A telescope scanning unit allows selection of a viewing angle around the limb, as well as real-time correction of the aircraft pitch. Due to the high altitude, solar reference spectra are measured using diffusors and direct sunlight. The DOAS approach allows retrieval of slant column densities (SCDs) of O3, O4, NO2, and BrO with relative errors similar to other aircraft DOAS systems. Radiative transfer considerations show that the retrieval of trace gas mixing ratios from the observed SCD based on O4 observations, the most common approach for DOAS measurements, is inadequate for high-altitude observations. This is due to the frequent presence of low-altitude clouds, which shift the sensitivity of the O4 SCD into the lower atmosphere and make it highly dependent on cloud coverage. A newly developed technique that constrains the radiative transfer by comparing in situ and DOAS O3 observations overcomes this issue. Extensive sensitivity calculations show that the novel O3-scaling technique allows the retrieval of BrO and NO2 mixing ratios at high accuracies of 0.5 and 15 ppt, respectively. The BrO and NO2 mixing ratios and vertical profiles observed during ATTREX thus provide new insights into ozone and halogen chemistry in the UT, TTL, and LS.

  19. A kinetics study of the homogeneous and heterogeneous components of the HCl + ClONO2 reaction. [and its relevance to stratospheric chemistry

    Science.gov (United States)

    Friedl, Randall R.; Goble, James H.; Sander, Stanley P.

    1986-01-01

    The kinetics of the reaction HCl + ClONO2 to Cl2 + HNO3 were investigated at 298 K using a flow reactor with FTIR analysis to assess the importance of this reaction for stratospheric chemistry. The observed reaction was characteristic of a heterogeneous process; an upper limit of 5 x 10 to the -18th cu cm/molecule per s was obtained for the homogeneous gas phase rate constant. From calculations of the first order wall rate constant, estimates were made of the reaction rate on stratospheric aerosols. Because both HCl and ClONO2 need to be adsorbed on the particle surface, the reaction will be of negligible importance under most stratospheric conditions.

  20. Model development of dust emission and heterogeneous chemistry within the Community Multiscale Air Quality modeling system and its application over East Asia

    Science.gov (United States)

    Dong, Xinyi; Fu, Joshua S.; Huang, Kan; Tong, Daniel; Zhuang, Guoshun

    2016-07-01

    The Community Multiscale Air Quality (CMAQ) model has been further developed in terms of simulating natural wind-blown dust in this study, with a series of modifications aimed at improving the model's capability to predict the emission, transport, and chemical reactions of dust. The default parameterization of initial threshold friction velocity constants are revised to correct the double counting of the impact of soil moisture in CMAQ by the reanalysis of field experiment data; source-dependent speciation profiles for dust emission are derived based on local measurements for the Gobi and Taklamakan deserts in East Asia; and dust heterogeneous chemistry is also implemented. The improved dust module in the CMAQ is applied over East Asia for March and April from 2006 to 2010. The model evaluation result shows that the simulation bias of PM10 and aerosol optical depth (AOD) is reduced, respectively, from -55.42 and -31.97 % by the original CMAQ to -16.05 and -22.1 % by the revised CMAQ. Comparison with observations at the nearby Gobi stations of Duolun and Yulin indicates that applying a source-dependent profile helps reduce simulation bias for trace metals. Implementing heterogeneous chemistry also results in better agreement with observations for sulfur dioxide (SO2), sulfate (SO42-), nitric acid (HNO3), nitrous oxides (NOx), and nitrate (NO3-). The investigation of a severe dust storm episode from 19 to 21 March 2010 suggests that the revised CMAQ is capable of capturing the spatial distribution and temporal variation of dust. The model evaluation also indicates potential uncertainty within the excessive soil moisture used by meteorological simulation. The mass contribution of fine-mode particles in dust emission may be underestimated by 50 %. The revised CMAQ model provides a useful tool for future studies to investigate the emission, transport, and impact of wind-blown dust over East Asia and elsewhere.

  1. The weathering of organic carbon and pyrite sulfur in Earth's crust and its importance for regulating atmospheric composition, seawater chemistry, and stable isotope records

    Science.gov (United States)

    Reinhard, C. T.; Planavsky, N.; Bolton, E. W.

    2016-12-01

    Earth's crust stores extremely large reservoirs of organic carbon and pyrite sulfur, and transient or secular changes in the sizes of these reservoirs have the capacity to dramatically alter atmospheric composition, climate, seawater acid-base chemistry, and the propagation of isotopic signals into the geologic record. This talk will present and discuss new quantitative approaches toward better understanding the factors that control organic carbon and pyrite sulfur weathering under a wide range of Earth surface conditions, as well as their downstream effects on seawater chemistry, stability of atmospheric pO2, and conventional interpretations of stable carbon isotope mass balance during pivotal events in Earth's biogeochemical evolution. In particular, we will focus on (1) development of a weathering-driven scaling between atmospheric pO2 and geologic carbon isotope signals that explains the relative stability of marine δ13C through time and provides a mechanism for protracted negative δ13C excursions during transient increases in atmospheric pO2; (2) experimental and theoretical approaches aimed at better understanding the role of pyrite sulfur weathering in stabilizing atmospheric pO2; and (3) the importance of redox balance in the sedimentary rock cycle for controlling the marine carbonate system and atmospheric pCO2.

  2. ATMOSPHERIC CHEMISTRY FOR ASTROPHYSICISTS: A SELF-CONSISTENT FORMALISM AND ANALYTICAL SOLUTIONS FOR ARBITRARY C/O

    Energy Technology Data Exchange (ETDEWEB)

    Heng, Kevin; Tsai, Shang-Min [University of Bern, Center for Space and Habitability, Sidlerstrasse 5, CH-3012, Bern (Switzerland); Lyons, James R., E-mail: kevin.heng@csh.unibe.ch [Arizona State University, School of Earth and Space Exploration, Bateman Physical Sciences, Tempe, AZ 85287-1404 (United States)

    2016-01-10

    We present a self-consistent formalism for computing and understanding the atmospheric chemistry of exoplanets from the viewpoint of an astrophysicist. Starting from the first law of thermodynamics, we demonstrate that the van’t Hoff equation (which describes the equilibrium constant), Arrhenius equation (which describes the rate coefficients), and procedures associated with the Gibbs free energy (minimization, rescaling) have a common physical and mathematical origin. We address an ambiguity associated with the equilibrium constant, which is used to relate the forward and reverse rate coefficients, and restate its two definitions. By necessity, one of the equilibrium constants must be dimensionless and equate to an exponential function involving the Gibbs free energy, while the other is a ratio of rate coefficients and must therefore possess physical units. We demonstrate that the Arrhenius equation takes on a functional form that is more general than previously stated without recourse to tagging on ad hoc functional forms. Finally, we derive analytical models of chemical systems, in equilibrium, with carbon, hydrogen, and oxygen. We include acetylene and are able to reproduce several key trends, versus temperature and carbon-to-oxygen ratio, published in the literature. The rich variety of behavior that mixing ratios exhibit as a function of the carbon-to-oxygen ratio is merely the outcome of stoichiometric book-keeping and not the direct consequence of temperature or pressure variations.

  3. Compilation and analyses of emissions inventories for NOAA`s atmospheric chemistry project. Progress report, August 1997

    Energy Technology Data Exchange (ETDEWEB)

    Benkovitz, C.M.; Mubaraki, M.A.

    1997-09-01

    Global inventories of anthropogenic emissions of oxides of nitrogen (NO{sub x}) for circa 1985 and 1990 and Non-Methane Volatile Organic Compounds (NMVOCs) for circa 1990 have been compiled by this project. Work on the inventories has been carried out under the umbrella of the Global Emissions Inventory Activity (GEIA) of the International Global Atmospheric Chemistry (IGAC) Program. The 1985 NO{sub x} inventory was compiled using default data sets of global emissions that were refined via the use of more detailed regional data sets; this inventory is being distributed to the scientific community at large as the GEIA Version 1A inventory. Global emissions of NO{sub x} for 1985 are estimated to be 21 Tg N y{sup -1}, with approximately 84% originating in the Northern Hemisphere. The 1990 inventories of NO{sub x} and NMVOCs were compiled using unified methodologies and data sets in collaboration with the Netherlands National Institute of Public Health and Environmental Protection (Rijksinstituut Voor Volksgezondheid en Milieuhygiene, RIVM) and the Division of Technology for Society of the Netherlands Organization for Applied Scientific Research, (IMW-TNO); these emissions will be used as the default estimates to be updated with more accurate regional data. The NMVOC inventory was gridded and speciated into 23 chemical categories.

  4. Dry deposition of NO2 over China inferred from OMI columnar NO2 and atmospheric chemistry transport model

    Science.gov (United States)

    Zhang, X. Y.; Lu, X. H.; Liu, L.; Chen, D. M.; Zhang, X. M.; Liu, X. J.; Zhang, Y.

    2017-11-01

    The NO2 dry deposition over China was estimated based on an inferential model, in which the surface NO2 concentrations and deposition velocities were derived from OMI columnar NO2 and the simulation results from atmospheric chemistry transport models. Nationally, the annual NO2 dry deposition fluxes ranged from 0.0005 to 8.54 kg N ha-1, with an average of 0.48 kg N ha-1. The total NO2 dry deposition over China was 0.46 Tg N yr-1, mainly contributed by northern and southeast China. Due to contrary seasonal trends of the NO2 concentrations (high in cold months) and deposition velocities (high in warm months), the estimated NO2 dry depositions did not show strong seasonal pattern, instead showing relatively high values from August to October and low ones in February. The annual NO2 dry deposition has an increasing trend from 2007 to 2014, with the highest deposition level achieved in 2011. This research conducts a thorough validation between estimated NO2 dry depositions with ground measurements of NO2 concentrations and provides an objective spatial perspective and insight on the existing NO2 dry deposition maps in China.

  5. Spatial heterogeneity in geothermally-influenced lakes derived from atmospherically corrected Landsat thermal imagery and three-dimensional hydrodynamic modelling

    DEFF Research Database (Denmark)

    Allan, Mathew G; Hamilton, David P.; Trolle, Dennis

    2016-01-01

    Atmospheric correction of Landsat 7 thermal data was carried out for the purpose of retrieval of lake skin water temperature in Rotorua lakes, and Lake Taupo, North Island, New Zealand. The effect of the atmosphere was modelled using four sources of atmospheric profile data as input to the MODera...

  6. Radical budget and ozone chemistry during autumn in the atmosphere of an urban site in central China

    Science.gov (United States)

    Lu, Xingcheng; Chen, Nan; Wang, Yuhang; Cao, Wenxiang; Zhu, Bo; Yao, Teng; Fung, Jimmy C. H.; Lau, Alexis K. H.

    2017-03-01

    The ROx (=OH + HO2 + RO2) budget and O3 production at an urban site in central China (Wuhan) during autumn were simulated and analyzed for the first time using a UW Chemical Model 0-D box model constrained by in situ observational data. The daytime average OH, HO2, and RO2 concentrations were 2.2 × 106, 1.0 × 108, and 5.2 × 107 molecules cm-3, respectively. The average daytime O3 production rate was 8.8 ppbv h-1, and alkenes were the most important VOC species for O3 formation (contributing 45%) at this site. Our sensitivity test indicated that the atmospheric environment in Wuhan during autumn belongs to the VOC-limited regime. The daily average HONO concentration at this site during the study period reached 1.1 ppbv and played an important role in the oxidative capacity of the atmosphere. Without the source of excess HONO, the average daytime OH, HO2, RO2, and O3 production rates decreased by 36%, 26%, 27%, and 31% respectively. A correlation between the HONO to NO2 heterogeneous conversion efficiency and PM2.5 × SWR was found at this site; based on this relationship, if the PM2.5 concentration met the World Health Organization air quality standard (25 µg m-3), the O3 production rate in this city would decrease by 19% during late autumn. The burning of agricultural biomass severely affected the air quality in Wuhan during summer and autumn. Agricultural burning was found to account for 18% of the O3 formation during the study period. Our results suggest that VOC control and a ban on agricultural biomass burning should be considered as high-priority measures for improving the air quality in this region.

  7. Does Everyone's Motivational Beliefs about Physical Science Decline in Secondary School?: Heterogeneity of Adolescents' Achievement Motivation Trajectories in Physics and Chemistry.

    Science.gov (United States)

    Wang, Ming-Te; Chow, Angela; Degol, Jessica Lauren; Eccles, Jacquelynne Sue

    2017-08-01

    Students' motivational beliefs about learning physical science are critical for achieving positive educational outcomes. In this study, we incorporated expectancy-value theory to capture the heterogeneity of adolescents' motivational trajectories in physics and chemistry from seventh to twelfth grade and linked these trajectories to science-related outcomes. We used a cross-sequential design based on three different cohorts of adolescents (N = 699; 51.5 % female; 95 % European American; M ages for youngest, middle, and oldest cohorts at the first wave = 13.2, 14.1, and 15.3 years) coming from ten public secondary schools. Although many studies claim that physical science motivation declines on average over time, we identified seven differential motivational trajectories of ability self-concept and task values, and found associations of these trajectories with science achievement, advanced science course taking, and science career aspirations. Adolescents' ability self-concept and task values in physics and chemistry were also positively related and interlinked over time. Examining how students' motivational beliefs about physical science develop in secondary school offers insight into the capacity of different groups of students to successfully adapt to their changing educational environments.

  8. Atmospheric methane and carbon dioxide from SCIAMACHY satellite data: initial comparison with chemistry and transport models

    Directory of Open Access Journals (Sweden)

    M. Buchwitz

    2005-01-01

    Full Text Available The remote sensing of the atmospheric greenhouse gases methane (CH4 and carbon dioxide (CO2 in the troposphere from instrumentation aboard satellites is a new area of research. In this manuscript, results obtained from observations of the up-welling radiation in the near-infrared by SCIAMACHY on board ENVISAT are presented. Vertical columns of CH4, CO2 and oxygen (O2 have been retrieved and the (air or O2-normalised CH4 and CO2 column amounts, the dry air column averaged mixing ratios XCH4 and XCO2 derived. In this manuscript the first results, obtained by using the version 0.4 of the Weighting Function Modified (WFM DOAS retrieval algorithm applied to SCIAMACHY data, are described and compared with global models. For the set of individual cloud free measurements over land the standard deviation of the difference with respect to the models is in the range ~100–200 ppbv (5–10% for XCH4 and ~14–32 ppmv (4–9% for XCO2. The inter-hemispheric difference of the methane mixing ratio, as determined from single day data, is in the range 30–110 ppbv and in reasonable agreement with the corresponding model data (48–71 ppbv. The weak inter-hemispheric difference of the CO2 mixing ratio can also be detected with single day data. The spatiotemporal pattern of the measured and the modelled XCO2 are in reasonable agreement. However, the amplitude of the difference between the maximum and the minimum for SCIAMACHY XCO2 is about ±20 ppmv which is about a factor of four larger than the variability of the model data which is about ±5 ppmv. More studies are needed to explain the observed differences. The XCO2 model field shows low CO2 concentrations beginning of January 2003 over a spatially extended CO2 sink region located in southern tropical/sub-tropical Africa. The SCIAMACHY data also show low CO2 mixing ratios over this area. According to the model the sink region becomes a source region about six months later and exhibits higher mixing ratios

  9. Organic chemistry in Titan's upper atmosphere and its astrobiological consequences: I. Views towards Cassini plasma spectrometer (CAPS) and ion neutral mass spectrometer (INMS) experiments in space

    Science.gov (United States)

    Ali, A.; Sittler, E. C.; Chornay, D.; Rowe, B. R.; Puzzarini, C.

    2015-05-01

    The discovery of carbocations and carbanions by Ion Neutral Mass Spectrometer (INMS) and the Cassini Plasma Spectrometer (CAPS) instruments onboard the Cassini spacecraft in Titan's upper atmosphere is truly amazing for astrochemists and astrobiologists. In this paper we identify the reaction mechanisms for the growth of the complex macromolecules observed by the CAPS Ion Beam Spectrometer (IBS) and Electron Spectrometer (ELS). This identification is based on a recently published paper (Ali et al., 2013. Planet. Space Sci. 87, 96) which emphasizes the role of Olah's nonclassical carbonium ion chemistry in the synthesis of the organic molecules observed in Titan's thermosphere and ionosphere by INMS. The main conclusion of that work was the demonstration of the presence of the cyclopropenyl cation - the simplest Huckel's aromatic molecule - and its cyclic methyl derivatives in Titan's atmosphere at high altitudes. In this study, we present the transition from simple aromatic molecules to the complex ortho-bridged bi- and tri-cyclic hydrocarbons, e.g., CH2+ mono-substituted naphthalene and phenanthrene, as well as the ortho- and peri-bridged tri-cyclic aromatic ring, e.g., perinaphthenyl cation. These rings could further grow into tetra-cyclic and the higher order ring polymers in Titan's upper atmosphere. Contrary to the pre-Cassini observations, the nitrogen chemistry of Titan's upper atmosphere is found to be extremely rich. A variety of N-containing hydrocarbons including the N-heterocycles where a CH group in the polycyclic rings mentioned above is replaced by an N atom, e.g., CH2+ substituted derivative of quinoline (benzopyridine), are found to be dominant in Titan's upper atmosphere. The mechanisms for the formation of complex molecular anions are discussed as well. It is proposed that many closed-shell complex carbocations after their formation first, in Titan's upper atmosphere, undergo the kinetics of electron recombination to form open-shell neutral

  10. Heterogeneous OH oxidation of organic aerosols

    Science.gov (United States)

    Smith, J.; Kroll, J.; Cappa, C.; Che, D.; Ahmed, M.; Leone, S.; Worsnop, D.; Wilson, K.

    2008-12-01

    The hydroxyl radical (OH) is the most important reactive species in both clean and polluted atmospheres, and therefore gas-phase OH chemistry has been extensively studied for decades. Due to this enormous effort the rates and mechanism of OH reactions with gas phase organics are relatively well understood. However, it unclear whether these well established gas-phase chemical mechanisms apply to the more complex heterogeneous reactions of OH radicals with organic aerosols (OA). Although recent studies have begun to examine OH oxidation of OA, numerous outstanding questions still remain regarding both the rate and chemical mechanism of these reactions. Here we present an in depth investigation of the heterogeneous oxidation of organic squalane particles by OH radicals. By combining a photochemical aerosol flow reactor with a high-resolution aerosol mass spectrometer (AMS), with both electron impact and vacuum ultraviolet photoionization, we investigate OH heterogeneous chemistry in unprecedented detail. Employing elemental composition measurements with detailed kinetics we have arrived at a simple oxidation model which accurately accounts for the evolution of squalane and its" oxidation products. In addition, by exploring a large range of OH concentrations we are able to directly measure the role of secondary particle-phase chain chemistry which can significantly accelerate the oxidation of OA in the atmosphere. Based on these measurements we have arrived at an explicit chemical mechanism for heterogeneous OH oxidation of OA which accurately accounts for our observations over a wide range of reaction conditions.

  11. Validation of HNO3, ClONO2, and N2O5 from the Atmospheric Chemistry Experiment Fourier Transform Spectrometer (ACE-FTS)

    OpenAIRE

    M. A. Wolff; Kerzenmacher, T.; Strong, K.; Walker, K. A.; Toohey, M.; Dupuy, E.; Bernath, P. F.; Boone, C. D.; Brohede, S.; Catoire, V.; Clarmann, T.; Coffey, M.; Daffer, W.H.; De Mazière, M.; Duchatelet, P.

    2008-01-01

    The Atmospheric Chemistry Experiment (ACE) satellite was launched on 12 August 2003. Its two instruments measure vertical profiles of over 30 atmospheric trace gases by analyzing solar occultation spectra in the ultraviolet/visible and infrared wavelength regions. The reservoir gases HNO3, ClONO2, and N2O5 are three of the key species provided by the primary instrument, the ACE Fourier Transform Spectrometer (ACE-FTS). This paper describes the ACE-FTS version 2.2 data products, ...

  12. The interplay between acid-base and free radical chemistry in the heterogeneous oxidation and fragmentation of citric acid in aqueous aerosol by OH radicals

    Science.gov (United States)

    Liu, M.; Wiegel, A. A.; Wilson, K. R.; Houle, F. A.

    2016-12-01

    A key uncertainty in the oxidation of organic compounds such as carboxylic acids in aqueous phase aerosol is how β-scission of alkoxy radicals is altered by acid-base chemistry. In particular, the differences between the unimolecular fragmentation rates of radical anions and their neutral forms may impact the partitioning of organic carbon between the gas and aqueous phase. To investigate the fragmentation reactions that occur during the oxidation of highly oxygenated organic aqueous aerosol, a kinetics model is developed for the OH initiated oxidation of citric acid aerosol at high relative humidities. The reaction scheme includes both free radical and acid-base reactions, uses physically validated rate coefficients, and thus accurately predicts the experimentally observed molecular composition, particle size, and average elemental composition of the aerosol upon oxidation. Free radical reactions functionalize the carbon skeleton while carboxylate groups from acid-base chemistry activate the carbon-carbon bond fragmentation of alkoxy radicals, leading to the formation of low molecular weight, highly oxidized products such as oxaloacetic and mesoxalic acid. Subsequent hydration of carbonyl groups in the oxidized products increases the aerosol hygroscopicity and causes the substantial water uptake and volume growth observed to accompany oxidation. These results highlight the significant role of water in controlling not only changes in physical properties but also the mechanisms of oxidation and fragmentation of aerosol in the atmosphere.

  13. Multi-model simulations of the impact of international shipping on Atmospheric Chemistry and Climate in 2000 and 2030

    Science.gov (United States)

    Eyring, V.; Stevenson, D. S.; Lauer, A.; Dentener, F. J.; Butler, T.; Collins, W. J.; Ellingsen, K.; Gauss, M.; Hauglustaine, D. A.; Isaksen, I. S. A.; Lawrence, M. G.; Richter, A.; Rodriguez, J. M.; Sanderson, M.; Strahan, S. E.; Sudo, K.; Szopa, S.; van Noije, T. P. C.; Wild, O.

    2007-02-01

    The global impact of shipping on atmospheric chemistry and radiative forcing, as well as the associated uncertainties, have been quantified using an ensemble of ten state-of-the-art atmospheric chemistry models and a pre-defined set of emission data. The analysis is performed for present-day conditions (year 2000) and for two future ship emission scenarios. In one scenario ship emissions stabilize at 2000 levels; in the other ship emissions increase with a constant annual growth rate of 2.2% up to 2030 (termed the "Constant Growth Scenario" (CGS)). Most other anthropogenic emissions follow the IPCC (Intergovernmental Panel on Climate Change) SRES (Special Report on Emission Scenarios) A2 scenario, while biomass burning and natural emissions remain at year 2000 levels. An intercomparison of the model results with observations over the Northern Hemisphere (25°-60° N) oceanic regions in the lower troposphere showed that the models are capable to reproduce ozone (O3) and nitrogen oxides (NOx=NO+NO2) reasonably well, whereas sulphur dioxide (SO2) in the marine boundary layer is significantly underestimated. The most pronounced changes in annual mean tropospheric NO2 and sulphate columns are simulated over the Baltic and North Seas. Other significant changes occur over the North Atlantic, the Gulf of Mexico and along the main shipping lane from Europe to Asia, across the Red and Arabian Seas. Maximum contributions from shipping to annual mean near-surface O3 are found over the North Atlantic (5-6 ppbv in 2000; up to 8 ppbv in 2030). Ship contributions to tropospheric O3 columns over the North Atlantic and Indian Oceans reach 1 DU in 2000 and up to 1.8 DU in 2030. Tropospheric O3 forcings due to shipping are 9.8±2.0 mW/m2 in 2000 and 13.6±2.3 mW/m2 in 2030. Whilst increasing O3, ship NOx simultaneously enhances hydroxyl radicals over the remote ocean, reducing the global methane lifetime by 0.13 yr in 2000, and by up to 0.17 yr in 2030, introducing a negative

  14. Multi-model simulations of the impact of international shipping on Atmospheric Chemistry and Climate in 2000 and 2030

    Directory of Open Access Journals (Sweden)

    V. Eyring

    2007-01-01

    Full Text Available The global impact of shipping on atmospheric chemistry and radiative forcing, as well as the associated uncertainties, have been quantified using an ensemble of ten state-of-the-art atmospheric chemistry models and a pre-defined set of emission data. The analysis is performed for present-day conditions (year 2000 and for two future ship emission scenarios. In one scenario ship emissions stabilize at 2000 levels; in the other ship emissions increase with a constant annual growth rate of 2.2% up to 2030 (termed the "Constant Growth Scenario" (CGS. Most other anthropogenic emissions follow the IPCC (Intergovernmental Panel on Climate Change SRES (Special Report on Emission Scenarios A2 scenario, while biomass burning and natural emissions remain at year 2000 levels. An intercomparison of the model results with observations over the Northern Hemisphere (25°–60° N oceanic regions in the lower troposphere showed that the models are capable to reproduce ozone (O3 and nitrogen oxides (NOx=NO+NO2 reasonably well, whereas sulphur dioxide (SO2 in the marine boundary layer is significantly underestimated. The most pronounced changes in annual mean tropospheric NO2 and sulphate columns are simulated over the Baltic and North Seas. Other significant changes occur over the North Atlantic, the Gulf of Mexico and along the main shipping lane from Europe to Asia, across the Red and Arabian Seas. Maximum contributions from shipping to annual mean near-surface O3 are found over the North Atlantic (5–6 ppbv in 2000; up to 8 ppbv in 2030. Ship contributions to tropospheric O3 columns over the North Atlantic and Indian Oceans reach 1 DU in 2000 and up to 1.8 DU in 2030. Tropospheric O3 forcings due to shipping are 9.8±2.0 mW/m2 in 2000 and 13.6±2.3 mW/m2 in 2030. Whilst increasing O3, ship NOx simultaneously enhances hydroxyl radicals over the remote ocean, reducing the global methane lifetime by 0.13 yr in 2000, and by up to 0.17 yr in 2030, introducing a

  15. The Atmospheric Chemistry Suite (ACS) of Three Spectrometers for the ExoMars 2016 Trace Gas Orbiter

    Science.gov (United States)

    Korablev, O.; Montmessin, F.; Trokhimovskiy, A.; Fedorova, A. A.; Shakun, A. V.; Grigoriev, A. V.; Moshkin, B. E.; Ignatiev, N. I.; Forget, F.; Lefèvre, F.; Anufreychik, K.; Dzuban, I.; Ivanov, Y. S.; Kalinnikov, Y. K.; Kozlova, T. O.; Kungurov, A.; Makarov, V.; Martynovich, F.; Maslov, I.; Merzlyakov, D.; Moiseev, P. P.; Nikolskiy, Y.; Patrakeev, A.; Patsaev, D.; Santos-Skripko, A.; Sazonov, O.; Semena, N.; Semenov, A.; Shashkin, V.; Sidorov, A.; Stepanov, A. V.; Stupin, I.; Timonin, D.; Titov, A. Y.; Viktorov, A.; Zharkov, A.; Altieri, F.; Arnold, G.; Belyaev, D. A.; Bertaux, J. L.; Betsis, D. S.; Duxbury, N.; Encrenaz, T.; Fouchet, T.; Gérard, J.-C.; Grassi, D.; Guerlet, S.; Hartogh, P.; Kasaba, Y.; Khatuntsev, I.; Krasnopolsky, V. A.; Kuzmin, R. O.; Lellouch, E.; Lopez-Valverde, M. A.; Luginin, M.; Määttänen, A.; Marcq, E.; Martin Torres, J.; Medvedev, A. S.; Millour, E.; Olsen, K. S.; Patel, M. R.; Quantin-Nataf, C.; Rodin, A. V.; Shematovich, V. I.; Thomas, I.; Thomas, N.; Vazquez, L.; Vincendon, M.; Wilquet, V.; Wilson, C. F.; Zasova, L. V.; Zelenyi, L. M.; Zorzano, M. P.

    2018-02-01

    The Atmospheric Chemistry Suite (ACS) package is an element of the Russian contribution to the ESA-Roscosmos ExoMars 2016 Trace Gas Orbiter (TGO) mission. ACS consists of three separate infrared spectrometers, sharing common mechanical, electrical, and thermal interfaces. This ensemble of spectrometers has been designed and developed in response to the Trace Gas Orbiter mission objectives that specifically address the requirement of high sensitivity instruments to enable the unambiguous detection of trace gases of potential geophysical or biological interest. For this reason, ACS embarks a set of instruments achieving simultaneously very high accuracy (ppt level), very high resolving power (>10,000) and large spectral coverage (0.7 to 17 μm—the visible to thermal infrared range). The near-infrared (NIR) channel is a versatile spectrometer covering the 0.7-1.6 μm spectral range with a resolving power of ˜20,000. NIR employs the combination of an echelle grating with an AOTF (Acousto-Optical Tunable Filter) as diffraction order selector. This channel will be mainly operated in solar occultation and nadir, and can also perform limb observations. The scientific goals of NIR are the measurements of water vapor, aerosols, and dayside or night side airglows. The mid-infrared (MIR) channel is a cross-dispersion echelle instrument dedicated to solar occultation measurements in the 2.2-4.4 μm range. MIR achieves a resolving power of >50,000. It has been designed to accomplish the most sensitive measurements ever of the trace gases present in the Martian atmosphere. The thermal-infrared channel (TIRVIM) is a 2-inch double pendulum Fourier-transform spectrometer encompassing the spectral range of 1.7-17 μm with apodized resolution varying from 0.2 to 1.3 cm-1. TIRVIM is primarily dedicated to profiling temperature from the surface up to ˜60 km and to monitor aerosol abundance in nadir. TIRVIM also has a limb and solar occultation capability. The technical concept of

  16. Research in physical chemistry and chemical education: Part A: Water Mediated Chemistry of Oxidized Atmospheric Compounds Part B: The Development of Surveying Tools to Determine How Effective Laboratory Experiments Contribute to Student Conceptual Understanding

    Science.gov (United States)

    Maron, Marta Katarzyna

    This dissertation is a combination of two research areas, experimental physical chemistry, Chapters I to V, and chemical education, Chapters VI to VII. Chapters I to V describe research on the water-mediated chemistry of oxidized atmospheric molecules and the impact that water has on the spectra of these environmental systems. The role of water in the Earth's atmosphere has been of considerable interest due to its ability to impact chemistry and climate. Oxidized atmospheric molecules in the presence of water have the ability to form hydrogen bonded water complexes. The spectroscopic investigation of nitric acid-water complexes, outlined in Chapter III, was undertaken to characterize intermolecular hydrogen bonds in a water-restricted environment at ambient temperatures. Additionally, this characterization of nitric acid-water complexes allowed for the comparison of calculated overtone OH-stretching vibrational band frequencies, intensities, and anharmonicities of intermolecular hydrogen-bonded water complexes with experimental observations. Oxidized organic molecules, such as aldehydes and ketones, in addition to forming hydrogen-bonded water complexes can undergo a hydration reaction of the carbonyl group and form germinal diols in the presence of water. This chemistry has been studied extensively in bulk aqueous media, however little is known about this process in the gas-phase at low water concentrations. The focus of the studies outlined in Chapters IV and V is motivated by the ability of pyruvic acid and formaldehyde to form germinal diols and water complexes in water-restricted environment. This water-mediated chemistry changes the physical and chemical properties of these organic molecules, therefore, impacting the partitioning between gas and particle phase, as well as the chemistry and photochemistry of oxidized organic molecules in the Earth's atmosphere. The results presented in this dissertation may help resolve the significant discrepancy between

  17. A new 2D climate model with chemistry and self consistent eddy-parameterization. The impact of airplane NO{sub x} on the chemistry of the atmosphere

    Energy Technology Data Exchange (ETDEWEB)

    Gepraegs, R.; Schmitz, G.; Peters, D. [Institut fuer Atmosphaerenphysik, Kuehlungsborn (Germany)

    1997-12-31

    A 2D version of the ECHAM T21 climate model has been developed. The new model includes an efficient spectral transport scheme with implicit diffusion. Furthermore, photodissociation and chemistry of the NCAR 2D model have been incorporated. A self consistent parametrization scheme is used for eddy heat- and momentum flux in the troposphere. It is based on the heat flux parametrization of Branscome and mixing-length formulation for quasi-geostrophic vorticity. Above 150 hPa the mixing-coefficient K{sub yy} is prescribed. Some of the model results are discussed, concerning especially the impact of aircraft NO{sub x} emission on the model chemistry. (author) 6 refs.

  18. Química organometálica de superfície aplicada à preparação de catalisadores heterogêneos bem definidos Surface organometallic chemistry applied to the preparation of well defined heterogeneous catalysts

    Directory of Open Access Journals (Sweden)

    Silvana I. Wolke

    2002-11-01

    Full Text Available The study of the reactions of organometallic complexes with the surfaces of inorganic oxides, zeolites and metals constitutes the basis of Surface Organometallic Chemistry (SOMC. The basic rules of organometallic chemistry are often valid when applied to surfaces and well-defined surface organometallic complexes can be obtained. These complexes can be used as heterogeneous catalysts or, by controlled reactions, can be transformed in other species useful for a given catalytic reaction. In some cases, these catalysts exhibit higher activity and/or selectivity than their analogous molecular complexes.

  19. Impacts of climate warming on atmospheric phase transition mechanisms

    Science.gov (United States)

    Varotsos, Costas A.; Ghosh, Satyajit

    2017-11-01

    Nowadays, climate change is a fact, and its impacts on heterogeneous chemistry mechanisms that take place in various atmospheric layers are of great interest. As an example, the uptake of atmospheric species on solid and liquid surfaces induces qualitative and quantitative changes from climatic alterations of the atmospheric thermal regime. We hereby present the experience gained on this subject by analysing real measurements of various atmospheric species and parameters conducted in Athens, Greece, exploring the atmospheric height region from the Earth's surface up to the lower stratosphere.

  20. Spatial Heterogeneity and Inter-annual Variation in Ecosystem-Atmosphere CO2/H2O Exchange in the Southern Great Plains

    Science.gov (United States)

    Fischer, M. L.; Billesbach, D. P.; Riley, W. J.; Berry, J. A.; Torn, M. S.

    2002-12-01

    Spatial heterogeneity in mass and energy fluxes in the Southern Great Plains are controlled by a combination of driving variables (e.g. climate, topography and soil, vegetation, and land use and management). Accurate estimation of landscape-averaged ecosystem-atmosphere exchange hence suggests the need for predictive models tested with extensive ground based measurements and/or a measurement method with regional coverage. This is particularly true for estimation of regional responses of carbon and water cycles to changing climate, land use, or management because of the potentially strong interactions among the driving variables. We report measurements of the spatial heterogeneity in land surface-atmosphere exchanges of carbon dioxide, water, and energy observed in three winter wheat fields and two mixed annual- perennial pastures during the spring 2002 growing season. Eddy covariance measurements of net ecosystem carbon exchange (NEE) and heat fluxes were made in fields surrounding the US-DOE Atmospheric Radiation Measurement Program central facility near Lamont, Oklahoma (36.605 N, 97.485 W). Additional measurements included soil microclimate; leaf area index; changes in plant biomass; and plant and soil carbon and nitrogen. The differences in time integrated NEE are approximately consistent with measured differences in accumulated above ground biomass. Initial consideration suggests that the differences in carbon uptake result from differing management practices because the fields are closely spaced and have very similar underlying soil properties and experienced similar micro-climate. A distinct inter-annual climate variation was also observed in which an large increase in early to mid summer precipitation and lower air temperatures (2002 vs. 2001) lengthened the summer growing season and increased pasture production.

  1. Observations of biogenic isoprene emissions and atmospheric chemistry components at the Savé super site in Benin, West Africa, during the DACCIWA field campaign.

    Science.gov (United States)

    Jambert, Corinne; Pacifico, Federica; Delon, Claire; Lohou, Fabienne; Reinares Martinez, Irene; Brilouet, Pierre-Etienne; Derrien, Solene; Dione, Cheikh; Brosse, Fabien; Gabella, Omar; Pedruzzo Bagazgoitia, Xavier; Durand, Pierre

    2017-04-01

    Tropospheric oxidation of VOCs (Volatile Organic Compounds), including isoprene, in the presence of NOx and sunlight leads to the formation of O3 and Secondary Organic Aerosols (SOA). Changes in NO or VOCs sources will consequently modify their atmospheric concentrations and thus, the rate of O3 production and SOA formation. NOx have also an impact on the abundance of the hydroxyl radical (OH) which determines the lifetime of some pollutants and greenhouse gases. Anthropogenic emissions of pollutants from mega cities located on the Guinean coast in South West Africa are likely to increase in the next decades due to a strong anthropogenic pressure and to land use changes at the regional or continental scale. The consequences on regional air quality and on pollutant deposition onto surfaces may have some harmful effects on human and ecosystem health. Furthermore, the regional climate and water cycle are affected by changes in atmospheric chemistry. When transported northward on the African continent, polluted air masses meet biogenic emissions from rural areas which contributes to increase ozone and SOA production, in high temperature and solar radiation conditions, highly favourable to enhanced photochemistry. During the Dynamics-aerosol-chemistry-cloud interactions in West Africa (DACCIWA) field campaign, we measured the atmospheric chemical composition and the exchanges of trace components in a hinterland area of Benin, at the Savé super-site (8°02'03" N, 2°29'11″ E). The observations, monitored in June and July 2016, in a rural mixed agricultural area, include near surface concentrations of ozone (O3), carbon monoxide (CO), nitrogen oxides (NOx) and isoprene, isoprene fluxes and meteorological parameters. We observed hourly average concentrations of O3 up to 50 ppb, low NOx concentrations (ca. 1 ppb and CO concentrations between 75 and 300 ppb. An 8 m tower was equipped with a Fast Isoprene Sensor and sonic anemometer to measure isoprene concentrations and

  2. Atmospheric chemistry and physics in the atmosphere of a developed megacity (London: an overview of the REPARTEE experiment and its conclusions

    Directory of Open Access Journals (Sweden)

    R. M. Harrison

    2012-03-01

    Full Text Available The REgents PARk and Tower Environmental Experiment (REPARTEE comprised two campaigns in London in October 2006 and October/November 2007. The experiment design involved measurements at a heavily trafficked roadside site, two urban background sites and an elevated site at 160–190 m above ground on the BT Tower, supplemented in the second campaign by Doppler lidar measurements of atmospheric vertical structure. A wide range of measurements of airborne particle physical metrics and chemical composition were made as well as measurements of a considerable range of gas phase species and the fluxes of both particulate and gas phase substances. Significant findings include (a demonstration of the evaporation of traffic-generated nanoparticles during both horizontal and vertical atmospheric transport; (b generation of a large base of information on the fluxes of nanoparticles, accumulation mode particles and specific chemical components of the aerosol and a range of gas phase species, as well as the elucidation of key processes and comparison with emissions inventories; (c quantification of vertical gradients in selected aerosol and trace gas species which has demonstrated the important role of regional transport in influencing concentrations of sulphate, nitrate and secondary organic compounds within the atmosphere of London; (d generation of new data on the atmospheric structure and turbulence above London, including the estimation of mixed layer depths; (e provision of new data on trace gas dispersion in the urban atmosphere through the release of purposeful tracers; (f the determination of spatial differences in aerosol particle size distributions and their interpretation in terms of sources and physico-chemical transformations; (g studies of the nocturnal oxidation of nitrogen oxides and of the diurnal behaviour of nitrate aerosol in the urban atmosphere, and (h new information on the chemical composition and source apportionment of particulate

  3. Atmospheric chemistry and physics in the atmosphere of a developed megacity (London): an overview of the REPARTEE experiment and its conclusions

    Science.gov (United States)

    Harrison, R. M.; Dall'Osto, M.; Beddows, D. C. S.; Thorpe, A. J.; Bloss, W. J.; Allan, J. D.; Coe, H.; Dorsey, J. R.; Gallagher, M.; Martin, C.; Whitehead, J.; Williams, P. I.; Jones, R. L.; Langridge, J. M.; Benton, A. K.; Ball, S. M.; Langford, B.; Hewitt, C. N.; Davison, B.; Martin, D.; Petersson, K. F.; Henshaw, S. J.; White, I. R.; Shallcross, D. E.; Barlow, J. F.; Dunbar, T.; Davies, F.; Nemitz, E.; Phillips, G. J.; Helfter, C.; Di Marco, C. F.; Smith, S.

    2012-03-01

    The REgents PARk and Tower Environmental Experiment (REPARTEE) comprised two campaigns in London in October 2006 and October/November 2007. The experiment design involved measurements at a heavily trafficked roadside site, two urban background sites and an elevated site at 160-190 m above ground on the BT Tower, supplemented in the second campaign by Doppler lidar measurements of atmospheric vertical structure. A wide range of measurements of airborne particle physical metrics and chemical composition were made as well as measurements of a considerable range of gas phase species and the fluxes of both particulate and gas phase substances. Significant findings include (a) demonstration of the evaporation of traffic-generated nanoparticles during both horizontal and vertical atmospheric transport; (b) generation of a large base of information on the fluxes of nanoparticles, accumulation mode particles and specific chemical components of the aerosol and a range of gas phase species, as well as the elucidation of key processes and comparison with emissions inventories; (c) quantification of vertical gradients in selected aerosol and trace gas species which has demonstrated the important role of regional transport in influencing concentrations of sulphate, nitrate and secondary organic compounds within the atmosphere of London; (d) generation of new data on the atmospheric structure and turbulence above London, including the estimation of mixed layer depths; (e) provision of new data on trace gas dispersion in the urban atmosphere through the release of purposeful tracers; (f) the determination of spatial differences in aerosol particle size distributions and their interpretation in terms of sources and physico-chemical transformations; (g) studies of the nocturnal oxidation of nitrogen oxides and of the diurnal behaviour of nitrate aerosol in the urban atmosphere, and (h) new information on the chemical composition and source apportionment of particulate matter size

  4. Radiance simulations of selected atmospheric species at different ...

    African Journals Online (AJOL)

    Continuous FTIR measurements in aerosol-polluted regions on the other hand can be a novel method for establishing more links between mineral aerosols and trace gas mixing ratios and or heterogeneous chemistry. Keywords: Trace gases, FTIR, spectroscopy, aerosols, and atmospheric pollution. Nigerian Journal of ...

  5. Elements of environmental chemistry

    National Research Council Canada - National Science Library

    Hites, R. A; Raff, Jonathan D

    2012-01-01

    ... more. Extensively revised, updated, and expanded, this second edition includes new chapters on atmospheric chemistry, climate change, and polychlorinated biphenyls and dioxins, and brominated flame retardants...

  6. Middle atmosphere response to different descriptions of the 11-yr solar cycle in spectral irradiance in a chemistry-climate model

    Directory of Open Access Journals (Sweden)

    W. H. Swartz

    2012-07-01

    Full Text Available The 11-yr solar cycle in solar spectral irradiance (SSI inferred from measurements by the SOlar Radiation & Climate Experiment (SORCE suggests a much larger variation in the ultraviolet than previously accepted. We present middle atmosphere ozone and temperature responses to the solar cycles in SORCE SSI and the ubiquitous Naval Research Laboratory (NRL SSI reconstruction using the Goddard Earth Observing System chemistry-climate model (GEOSCCM. The results are largely consistent with other recent modeling studies. The modeled ozone response is positive throughout the stratosphere and lower mesosphere using the NRL SSI, while the SORCE SSI produces a response that is larger in the lower stratosphere but out of phase with respect to total solar irradiance above 45 km. The modeled responses in total ozone are similar to those derived from satellite and ground-based measurements, 3–6 Dobson Units per 100 units of 10.7-cm radio flux (F10.7 in the tropics. The peak zonal mean tropical temperature response using the SORCE SSI is nearly 2 K per 100 units F10.7 – 3 times larger than the simulation using the NRL SSI. The GEOSCCM and the Goddard Space Flight Center (GSFC 2-D coupled model are used to examine how the SSI solar cycle affects the atmosphere through direct solar heating and photolysis processes individually. Middle atmosphere ozone is affected almost entirely through photolysis, whereas the solar cycle in temperature is caused both through direct heating and photolysis feedbacks, processes that are mostly linearly separable. This is important in that it means that chemistry-transport models should simulate the solar cycle in ozone well, while general circulation models without coupled chemistry will underestimate the temperature response to the solar cycle significantly in the middle atmosphere. Further, the net ozone response results from the balance of ozone production at wavelengths less than 242 nm

  7. A global model for prediction of the stratospheric ozone layer including climate feedback and heterogeneous chemistry. Final report; Globales Modell zur Vorhersage der Entwicklung der stratosphaerischen Ozonschicht mit Beruecksichtigung von Klimaeffekten und heterogener Chemie. Abschlussbericht

    Energy Technology Data Exchange (ETDEWEB)

    Bruehl, C.; Steil, B. [Max-Planck-Institut fuer Chemie (Otto-Hahn-Institut), Mainz (Germany). Abt. Luftchemie; Manzini, E. [Max-Planck-Institut fuer Meteorologie, Hamburg (Germany); Dameris, M.; Grewe, V. [DLR Deutsches Zentrum fuer Luft- und Raumfahrt e.V., Oberpfaffenhofen (Germany)

    2000-08-01

    The circulation model with interactive chemistry MA-ECHAM-CHEM is able to simulate temperatures and trace gas distributions in the stratosphere in good agreement with satellite observations, including seasonal cycle and interannual variability, and also polar stratospheric clouds in Arctic and Antarctic, as well as filament-like structures in midlatitudes observed by CHRISTA. The model is stable and driftfree in the considered scenarios. The computed differences in temperature patterns, ozone and water vapor distributions between sixties and nineties agree well with observations, increasing confidence of the prediction capability of the model. For the conditions of 2030 the model predicts a partial recovery of the Antarctic ozone hole because of decreasing chlorine. In the Arctic spring the variability increases especially towards midlatitudes, in contradiction to other studies there is no tendency for stabilization of the polar vortex or a northern ozone hole. On average the effect of the chlorine decrease dominates. The greenhouse effect has, however, complex implications on dynamics in the middle atmosphere. (orig.) [German] Das Zirkulationsmodell mit interaktiver Chemie MA-ECHAM-CHEM ist in der Lage, Temperaturen und Spurenstoffverteilungen in der Stratosphaere einschliesslich von Jahresgang und Variabilitaet zwischen einzelnen Jahren in guter Uebereinstimmung mit Satellitenbeobachtungen zu simulieren. Dies schliesst polare Stratosphaerenwolken in Arktis und Antarktis sowie von CHRISTA beobachtete Filamenstrukturen in mittleren Breiten ein. Das Modell ist stabil und in der Lage, vorgegebene Szenarien driftfrei einzuhalten. Die berechneten Unterschiede in Temperaturmustern, Ozon- und Wasserdampfverteilungen zwischen den Sechzigern und den Neunzigern passen zu den Beobachtungen, was das Vertrauen in die Prognosefaehigkeit des Modells erhoeht. Fuer die Bedingungen des Jahres 2030 sagt das Modell eine teilweise Auffuellung des antarktischen Ozonlochs durch

  8. Atmospheric chemistry and physics in the atmosphere of a developed megacity (London): An overview of the REPARTEE experiment and its conclusions

    OpenAIRE

    Harrison, R. M.; Dall?Osto, M.; D. C. S. Beddows; Thorpe, A. J.; Bloss, W.J.; Allan, J. D.; Coe, H; J. R. Dorsey; Gallagher, M; Martin, C.; J. Whitehead; Williams, P. I.; Jones, R L; Langridge, J. M.; A. K. Benton

    2012-01-01

    The REgents PARk and Tower Environmental Experiment (REPARTEE) comprised two campaigns in London in October 2006 and October/November 2007. The experiment design involved measurements at a heavily trafficked roadside site, two urban background sites and an elevated site at 160–190 m above ground on the BT Tower, supplemented in the second campaign by Doppler lidar measurements of atmospheric vertica...

  9. Atmospheric Chemistry of Six Methyl-perfluoroheptene-ethers Used as Heat Transfer Fluid Replacement Compounds: Measured OH Radical Reaction Rate Coefficients, Atmospheric Lifetimes, and Global Warming Potentials

    Science.gov (United States)

    Jubb, A. M.; Gierczak, T.; Baasandorj, M.; Waterland, R. L.; Burkholder, J. B.

    2013-12-01

    Mixtures of methyl-perfluoroheptene-ethers (C7F13OCH3, MPHEs) are currently in use as a replacement for perfluorinated alkane (PFC) and polyether mixtures (both persistent greenhouse gases with atmospheric lifetimes >1000 years) used as heat transfer fluids. Currently, the atmospheric fate of the MPHE isomers are not well characterized, however, reaction with the OH radical is expected to be a dominant tropospheric loss process for these compounds. In order to assess the atmospheric lifetimes and environmental implications of MPHE use, rate coefficients for MPHE isomers' reaction with OH radicals are desired. In the work presented here, rate coefficients, k, for the gas-phase reaction of the OH radical with six MPHEs commonly used in commercial mixtures (isomers and stereoisomers) and their deuterated analogs (d3-MPHE) were determined at 296 K using a relative rate method with combined gas-chromatography/IR spectroscopy detection. A range of OH rate coefficient values was observed, up to a factor of 20× different, between the MPHE isomers with the (E)-stereoisomers exhibiting the greatest reactivity. The measured OH reaction rate coefficients for the d3-MPHE isomers were lower than the observed MPHE values although a large range of k values between isomers was still observed. The reduction in reactivity with deuteration signifies that the MPHE + OH reaction proceeds via both addition to the olefinic C=C bond and H-abstraction from the methyl ester group. OH addition to the C=C bond was determined to be the primary reaction channel. Atmospheric lifetimes with respect to the OH reaction for the six MPHE isomers were found to be in the range of days to months. The short lifetimes indicate that MPHE use will primarily impact tropospheric local and regional air quality. A MPHE atmospheric degradation mechanism will be presented. As part of this work, radiative efficiencies and global warming potentials (GWPs) for the MPHE isomers were estimated based on measured

  10. Impact of a future H2-based road transportation sector on the composition and chemistry of the atmosphere – Part 1: Tropospheric composition and air quality

    Directory of Open Access Journals (Sweden)

    D. Wang

    2013-07-01

    Full Text Available Vehicles burning fossil fuel emit a number of substances that change the composition and chemistry of the atmosphere, and contribute to global air and water pollution and climate change. For example, nitrogen oxides and volatile organic compounds (VOCs emitted as byproducts of fossil fuel combustion are key precursors to ground-level ozone and aerosol formation. In addition, on-road vehicles are major CO2 emitters. In order to tackle these problems, molecular hydrogen (H2 has been proposed as an energy carrier to substitute for fossil fuels in the future. However, before implementing any such strategy it is crucial to evaluate its potential impacts on air quality and climate. Here, we evaluate the impact of a future (2050 H2-based road transportation sector on tropospheric chemistry and air quality for several possible growth and technology adoption scenarios. The growth scenarios are based on the high and low emissions Intergovernmental Panel on Climate Change Special Report on Emissions Scenarios, A1FI and B1, respectively. The technological adoption scenarios include H2 fuel cell and H2 internal combustion engine options. The impacts are evaluated with the Community Atmospheric Model Chemistry global chemistry transport model (CAM-Chem. Higher resolution simulations focusing on the contiguous United States are also carried out with the Community Multiscale Air Quality Modeling System (CMAQ regional chemistry transport model. For all scenarios future air quality improves with the adoption of a H2-based road transportation sector; however, the magnitude and type of improvement depend on the scenario. Model results show that the adoption of H2 fuel cells would decrease tropospheric burdens of ozone (7%, CO (14%, NOx (16%, soot (17%, sulfate aerosol (4%, and ammonium nitrate aerosol (12% in the A1FI scenario, and would decrease those of ozone (5%, CO (4%, NOx (11%, soot (7%, sulfate aerosol (4%, and ammonium nitrate aerosol (9% in the B1 scenario

  11. Describing the direct and indirect radiative effects of atmospheric aerosols over Europe by using coupled meteorology-chemistry simulations: a contribution from the AQMEII-Phase II exercise

    Science.gov (United States)

    Jimenez-Guerrero, Pedro; Balzarini, Alessandra; Baró, Rocío; Curci, Gabriele; Forkel, Renate; Hirtl, Marcus; Honzak, Luka; Langer, Matthias; Pérez, Juan L.; Pirovano, Guido; San José, Roberto; Tuccella, Paolo; Werhahn, Johannes; Zabkar, Rahela

    2014-05-01

    The study of the response of the aerosol levels in the atmosphere to a changing climate and how this affects the radiative budget of the Earth (direct, semi-direct and indirect effects) is an essential topic to build confidence on climate science, since these feedbacks involve the largest uncertainties nowadays. Air quality-climate interactions (AQCI) are, therefore, a key, but uncertain contributor to the anthropogenic forcing that remains poorly understood. To build confidence in the AQCI studies, regional-scale integrated meteorology-atmospheric chemistry models (i.e., models with on-line chemistry) that include detailed treatment of aerosol life cycle and aerosol impacts on radiation (direct effects) and clouds (indirect effects) are in demand. In this context, the main objective of this contribution is the study and definition of the uncertainties in the climate-chemistry-aerosol-cloud-radiation system associated to the direct radiative forcing and the indirect effect caused by aerosols over Europe, using an ensemble of fully-coupled meteorology-chemistry model simulations with the WRF-Chem model run under the umbrella of AQMEII-Phase 2 international initiative. Simulations were performed for Europe for the entire year 2010. According to the common simulation strategy, the year was simulated as a sequence of 2-day time slices. For better comparability, the seven groups applied the same grid spacing of 23 km and shared common processing of initial and boundary conditions as well as anthropogenic and fire emissions. With exception of a simulation with different cloud microphysics, identical physics options were chosen while the chemistry options were varied. Two model set-ups will be considered here: one sub-ensemble of simulations not taking into account any aerosol feedbacks (the baseline case) and another sub-ensemble of simulations which differs from the former by the inclusion of aerosol-radiation feedback. The existing differences for meteorological

  12. Updated operational protocols for the U.S. Geological Survey Precipitation Chemistry Quality Assurance Project in support of the National Atmospheric Deposition Program

    Science.gov (United States)

    Wetherbee, Gregory A.; Martin, RoseAnn

    2017-02-06

    The U.S. Geological Survey Branch of Quality Systems operates the Precipitation Chemistry Quality Assurance Project (PCQA) for the National Atmospheric Deposition Program/National Trends Network (NADP/NTN) and National Atmospheric Deposition Program/Mercury Deposition Network (NADP/MDN). Since 1978, various programs have been implemented by the PCQA to estimate data variability and bias contributed by changing protocols, equipment, and sample submission schemes within NADP networks. These programs independently measure the field and laboratory components which contribute to the overall variability of NADP wet-deposition chemistry and precipitation depth measurements. The PCQA evaluates the quality of analyte-specific chemical analyses from the two, currently (2016) contracted NADP laboratories, Central Analytical Laboratory and Mercury Analytical Laboratory, by comparing laboratory performance among participating national and international laboratories. Sample contamination and stability are evaluated for NTN and MDN by using externally field-processed blank samples provided by the Branch of Quality Systems. A colocated sampler program evaluates the overall variability of NTN measurements and bias between dissimilar precipitation gages and sample collectors.This report documents historical PCQA operations and general procedures for each of the external quality-assurance programs from 2007 to 2016.

  13. Implementation of the chemistry module MECCA (v2.5 in the modal aerosol version of the Community Atmosphere Model component (v3.6.33 of the Community Earth System Model

    Directory of Open Access Journals (Sweden)

    M. S. Long

    2013-02-01

    Full Text Available A coupled atmospheric chemistry and climate system model was developed using the modal aerosol version of the National Center for Atmospheric Research Community Atmosphere Model (modal-CAM; v3.6.33 and the Max Planck Institute for Chemistry's Module Efficiently Calculating the Chemistry of the Atmosphere (MECCA; v2.5 to provide enhanced resolution of multiphase processes, particularly those involving inorganic halogens, and associated impacts on atmospheric composition and climate. Three Rosenbrock solvers (Ros-2, Ros-3, RODAS-3 were tested in conjunction with the basic load-balancing options available to modal-CAM (1 to establish an optimal configuration of the implicitly-solved multiphase chemistry module that maximizes both computational speed and repeatability of Ros-2 and RODAS-3 results versus Ros-3, and (2 to identify potential implementation strategies for future versions of this and similar coupled systems. RODAS-3 was faster than Ros-2 and Ros-3 with good reproduction of Ros-3 results, while Ros-2 was both slower and substantially less reproducible relative to Ros-3 results. Modal-CAM with MECCA chemistry was a factor of 15 slower than modal-CAM using standard chemistry. MECCA chemistry integration times demonstrated a systematic frequency distribution for all three solvers, and revealed that the change in run-time performance was due to a change in the frequency distribution of chemical integration times; the peak frequency was similar for all solvers. This suggests that efficient chemistry-focused load-balancing schemes can be developed that rely on the parameters of this frequency distribution.

  14. Oxidative capacity and radical chemistry in the polluted atmosphere of Hong Kong and Pearl River Delta region: analysis of a severe photochemical smog episode

    Science.gov (United States)

    Xue, Likun; Gu, Rongrong; Wang, Tao; Wang, Xinfeng; Saunders, Sandra; Blake, Donald; Louie, Peter K. K.; Luk, Connie W. Y.; Simpson, Isobel; Xu, Zheng; Wang, Zhe; Gao, Yuan; Lee, Shuncheng; Mellouki, Abdelwahid; Wang, Wenxing

    2016-08-01

    We analyze a photochemical smog episode to understand the oxidative capacity and radical chemistry of the polluted atmosphere in Hong Kong and the Pearl River Delta (PRD) region. A photochemical box model based on the Master Chemical Mechanism (MCM v3.2) is constrained by an intensive set of field observations to elucidate the budgets of ROx (ROx = OH+HO2+RO2) and NO3 radicals. Highly abundant radical precursors (i.e. O3, HONO and carbonyls), nitrogen oxides (NOx) and volatile organic compounds (VOCs) facilitate strong production and efficient recycling of ROx radicals. The OH reactivity is dominated by oxygenated VOCs (OVOCs), followed by aromatics, alkenes and alkanes. Photolysis of OVOCs (except for formaldehyde) is the dominant primary source of ROx with average daytime contributions of 34-47 %. HONO photolysis is the largest contributor to OH and the second-most significant source (19-22 %) of ROx. Other considerable ROx sources include O3 photolysis (11-20 %), formaldehyde photolysis (10-16 %), and ozonolysis reactions of unsaturated VOCs (3.9-6.2 %). In one case when solar irradiation was attenuated, possibly by the high aerosol loadings, NO3 became an important oxidant and the NO3-initiated VOC oxidation presented another significant ROx source (6.2 %) even during daytime. This study suggests the possible impacts of daytime NO3 chemistry in the polluted atmospheres under conditions with the co-existence of abundant O3, NO2, VOCs and aerosols, and also provides new insights into the radical chemistry that essentially drives the formation of photochemical smog in the high-NOx environment of Hong Kong and the PRD region.

  15. Oxidative capacity and radical chemistry in the polluted atmosphere of Hong Kong and Pearl River Delta region: analysis of a severe photochemical smog episode

    Directory of Open Access Journals (Sweden)

    L. Xue

    2016-08-01

    Full Text Available We analyze a photochemical smog episode to understand the oxidative capacity and radical chemistry of the polluted atmosphere in Hong Kong and the Pearl River Delta (PRD region. A photochemical box model based on the Master Chemical Mechanism (MCM v3.2 is constrained by an intensive set of field observations to elucidate the budgets of ROx (ROx =  OH+HO2+RO2 and NO3 radicals. Highly abundant radical precursors (i.e. O3, HONO and carbonyls, nitrogen oxides (NOx and volatile organic compounds (VOCs facilitate strong production and efficient recycling of ROx radicals. The OH reactivity is dominated by oxygenated VOCs (OVOCs, followed by aromatics, alkenes and alkanes. Photolysis of OVOCs (except for formaldehyde is the dominant primary source of ROx with average daytime contributions of 34–47 %. HONO photolysis is the largest contributor to OH and the second-most significant source (19–22 % of ROx. Other considerable ROx sources include O3 photolysis (11–20 %, formaldehyde photolysis (10–16 %, and ozonolysis reactions of unsaturated VOCs (3.9–6.2 %. In one case when solar irradiation was attenuated, possibly by the high aerosol loadings, NO3 became an important oxidant and the NO3-initiated VOC oxidation presented another significant ROx source (6.2 % even during daytime. This study suggests the possible impacts of daytime NO3 chemistry in the polluted atmospheres under conditions with the co-existence of abundant O3, NO2, VOCs and aerosols, and also provides new insights into the radical chemistry that essentially drives the formation of photochemical smog in the high-NOx environment of Hong Kong and the PRD region.

  16. Studies in Atmospheric Chemistry. I. Assessing Exposure to Environmental Tobacco Smoke. I. Sulfur Oxides Chemistry Related to PM(10) Formation and Visibility Degradation

    Science.gov (United States)

    Caka, Fern M.

    I. Data from four DC-10 flights and forty-eight DC-9 flights are used to evaluate a model which predicts concentrations of ETS onboard commercial aircraft. A first order rate of penetration (decay) is shown to predict concentrations well. II. Two studies were conducted in Utah Valley and the Grand Canyon region. Annular diffusion denuders, impingers and real-time instruments were used to collect and measure sulfur oxide and nitrogen oxide species, ammonia, particulate acidity, and various oxidants. The data provided information on the distribution between gas and particulate phase species as a function of time, location and meteorology. Trends in the data sets which shed light on the factors which may contribute to atmospheric particulate conversion and the effect on PM_{10} formation and visibility degradation are presented.

  17. A Lagrangian stochastic model to demonstrate multi-scale interactions between convection and land surface heterogeneity in the atmospheric boundary layer

    Science.gov (United States)

    Parsakhoo, Zahra; Shao, Yaping

    2017-04-01

    Near-surface turbulent mixing has considerable effect on surface fluxes, cloud formation and convection in the atmospheric boundary layer (ABL). Its quantifications is however a modeling and computational challenge since the small eddies are not fully resolved in Eulerian models directly. We have developed a Lagrangian stochastic model to demonstrate multi-scale interactions between convection and land surface heterogeneity in the atmospheric boundary layer based on the Ito Stochastic Differential Equation (SDE) for air parcels (particles). Due to the complexity of the mixing in the ABL, we find that linear Ito SDE cannot represent convections properly. Three strategies have been tested to solve the problem: 1) to make the deterministic term in the Ito equation non-linear; 2) to change the random term in the Ito equation fractional, and 3) to modify the Ito equation by including Levy flights. We focus on the third strategy and interpret mixing as interaction between at least two stochastic processes with different Lagrangian time scales. The model is in progress to include the collisions among the particles with different characteristic and to apply the 3D model for real cases. One application of the model is emphasized: some land surface patterns are generated and then coupled with the Large Eddy Simulation (LES).

  18. Implications of Future Water Use Efficiency for Ecohydrological Responses to Climate Change and Spatial Heterogeneity of Atmospheric CO2 in China

    Directory of Open Access Journals (Sweden)

    Zhen Zhang

    2013-01-01

    Full Text Available As the atmospheric carbon dioxide (CO2 increases substantially, the spatial distribution of atmospheric CO2 should be considered when estimating the effects of CO2 on the carbon and water cycle coupling of terrestrial ecosystems. To evaluate this effect on future ecohydrological processes, the spatial-temporal patterns of CO2 were established over 1951 - 2099 according to the IPCC emission scenarios SRES A2 and SRES B1. Thereafter, water use efficiency (WUE was used (i.e., Net Primary Production/Evaportranspiration as an indicator to quantify the effects of climate change and uneven CO2 fertilization in China. We carried out several simulated experiments to estimate WUE under different future scenarios using a land process model (Integrated Biosphere Simulator, IBIS. Results indicated that the geographical distributions of averaged WUE have considerable differences under a heterogeneous atmospheric CO2 condition. Under the SRES A2 scenario, WUE decreased slightly with a 5% value in most areas of the southeastern and northwestern China during the 2050s, while decreasing by approximately 15% in southeastern China during the 2090s. During the period of the 2050s under SRES B1 scenario, the change rate of WUE was similar with that under SRES A2 scenario, but the WUE has a more moderate decreasing trend than that under the SRES A2 scenario. In all, the ecosystems in median and low latitude areas had a weakened effect on resisting extreme climate event such as drought. Conversely, the vegetation in a boreal forest had an enhanced buffering capability to tolerate drought events.

  19. Fine root chemistry and decomposition in model communities of north-temperate tree species show little response to elevated atmospheric CO2 and varying soil resource availability.

    Science.gov (United States)

    King, J S; Pregitzer, K S; Zak, D R; Holmes, W E; Schmidt, K

    2005-12-01

    Rising atmospheric [CO2] has the potential to alter soil carbon (C) cycling by increasing the content of recalcitrant constituents in plant litter, thereby decreasing rates of decomposition. Because fine root turnover constitutes a large fraction of annual NPP, changes in fine root decomposition are especially important. These responses will likely be affected by soil resource availability and the life history characteristics of the dominant tree species. We evaluated the effects of elevated atmospheric [CO2] and soil resource availability on the production and chemistry, mycorrhizal colonization, and decomposition of fine roots in an early- and late-successional tree species that are economically and ecologically important in north temperate forests. Open-top chambers were used to expose young trembling aspen (Populus tremuloides) and sugar maple (Acer saccharum) trees to ambient (36 Pa) and elevated (56 Pa) atmospheric CO2. Soil resource availability was composed of two treatments that bracketed the range found in the Upper Lake States, USA. After 2.5 years of growth, sugar maple had greater fine root standing crop due to relatively greater allocation to fine roots (30% of total root biomass) relative to aspen (7% total root biomass). Relative to the low soil resources treatment, aspen fine root biomass increased 76% with increased soil resource availability, but only under elevated [CO2]. Sugar maple fine root biomass increased 26% with increased soil resource availability (relative to the low soil resources treatment), and showed little response to elevated [CO2]. Concentrations of N and soluble phenolics, and C/N ratio in roots were similar for the two species, but aspen had slightly higher lignin and lower condensed tannins contents compared to sugar maple. As predicted by source-sink models of carbon allocation, pooled constituents (C/N ratio, soluble phenolics) increased in response to increased relative carbon availability (elevated [CO2]/low soil resource

  20. High C/O Chemistry and Weak Thermal Inversion in the Extremely Irradiated Atmosphere of Exoplanet WASP-12b

    Science.gov (United States)

    Madhusudhan, Nikku; Harrington, Joseph; Nymeyer, Sarah; Campo, Christopher J.; Wheatley, Peter J.; Deming, Drake; Blecie, Jasmina; Hardy, Ryan A.; Lust, Nate B.; Anderson, David R.; hide

    2010-01-01

    The carbon-to-oxygen ratio (C/O) in a planet provides critical information about its primordial origins and subsequent evolution. A primordial C/O greater than 0.8 causes a carbide-dominated interior as opposed to the silicate-dominated composition as found on Earth; the solar C/O is 0.54. Theory, shows that high C/O leads to a diversity of carbon-rich planets that can have very different interiors and atmospheres from those in the solar system. Here we report the detection of C/O greater than or equal to 1 in a planetary atmosphere. The transiting hot Jupiter WASP-12b has a dayside atmosphere depleted in water vapour and enhanced in methane by over two orders of magnitude compared to a solar-abundance chemical equilibrium model at the expected temperatures. The observed concentrations of the prominent molecules CO, CH4, and H2O are consistent with theoretical expectations for an atmosphere with the observed C/O = 1. The C/O ratios are not known for giant planets in the solar system, although they are expected to equal the solar value. If high C/O ratios are common, then extrasolar planets are likely very different in interior composition, and formed very differently, from expectations based on solar composition, potentially explaining the large diversity in observed radii. We also find that the extremely irradiated atmosphere (greater than 2500 K) of WASP-12b lacks a prominent thermal inversion, or a stratosphere, and has very efficient day-night energy circulation. The absence of a strong thermal inversion is in stark contrast to theoretical predictions for the most highly irradiated hot-Jupiter atmospheres.

  1. On the relationship between total ozone and atmospheric dynamics and chemistry at mid-latitudes – Part 2: The effects of the El Niño/Southern Oscillation, volcanic eruptions and contributions of atmospheric dynamics and chemistry to long-term total ozone changes

    Directory of Open Access Journals (Sweden)

    H. E. Rieder

    2013-01-01

    Full Text Available We present the first spatial analysis of "fingerprints" of the El Niño/Southern Oscillation (ENSO and atmospheric aerosol load after major volcanic eruptions (El Chichón and Mt. Pinatubo in extreme low and high (termed ELOs and EHOs, respectively and mean values of total ozone for the northern and southern mid-latitudes (defined as the region between 30° and 60° north and south, respectively. Significant influence on ozone extremes was found for the warm ENSO phase in both hemispheres during spring, especially towards low latitudes, indicating the enhanced ozone transport from the tropics to the extra-tropics. Further, the results confirm findings of recent work on the connection between the ENSO phase and the strength and extent of the southern ozone "collar". For the volcanic eruptions the analysis confirms findings of earlier studies for the northern mid-latitudes and gives new insights for the Southern Hemisphere. The results provide evidence that the negative effect of the eruption of El Chichón might be partly compensated by a strong warm ENSO phase in 1982–1983 at southern mid-latitudes. The strong west-east gradient in the coefficient estimates for the Mt. Pinatubo eruption and the analysis of the relationship between the AAO and ENSO phase, the extent and the position of the southern ozone "collar" and the polar vortex structure provide clear evidence for a dynamical "masking" of the volcanic signal at southern mid-latitudes. The paper also analyses the contribution of atmospheric dynamics and chemistry to long-term total ozone changes. Here, quite heterogeneous results have been found on spatial scales. In general the results show that EESC and the 11-yr solar cycle can be identified as major contributors to long-term ozone changes. However, a strong contribution of dynamical features (El Niño/Southern Oscillation (ENSO, North Atlantic Oscillation (NAO, Antarctic Oscillation (AAO, Quasi-Biennial Oscillation (QBO to ozone

  2. Chemistry and decomposition of litter from Populus tremuloides Michaux grown at elevated atmospheric CO2and varying N availability

    Science.gov (United States)

    John S. King; Kurt S. Pregitzer; Donald R. Zak; Mark E. Kubiske; Jennifer A. Ashby; William E. Holmes

    2001-01-01

    It has been hypothesized that greater production of total nonstructural carbohydrates (TNC) in foliage grown under elevated atmospheric carbon dioxide (CO2) will result in higher concentrations of defensive compounds in tree leaf litter, possibly leading to reduced rates of decomposition and nutrient cycling in forest ecosystems of the future....

  3. Pathways of PFOA to the Arctic: variabilities and contributions of oceanic currents and atmospheric transport and chemistry sources

    Directory of Open Access Journals (Sweden)

    I. Stemmler

    2010-10-01

    Full Text Available Perfluorooctanoic acid (PFOA and other perfluorinated compounds are industrial chemicals in use for decades which resist degradation in the environment and seem to accumulate in polar regions. Transport of PFOA was modeled using a spatially resolved global multicompartment model including fully coupled three-dimensional ocean and atmosphere general circulation models, and two-dimensional top soil, vegetation surfaces, and sea ice compartments. In addition to primary emissions, the formation of PFOA in the atmosphere from degradation of 8:2 fluorotelomer alcohol was included as a PFOA source. Oceanic transport, delivered 14.8±5.0 (8–23 t a−1 to the Arctic, strongly influenced by changes in water transport, which determined its interannual variability. This pathway constituted the dominant source of PFOA to the Arctic. Formation of PFOA in the atmosphere led to episodic transport events (timescale of days into the Arctic with small spatial extent. Deposition in the polar region was found to be dominated by wet deposition over land, and shows maxima in boreal winter. The total atmospheric deposition of PFOA in the Arctic in the 1990s was ≈1 t a−1, much higher than previously estimated, and is dominated by primary emissions rather than secondary formation.

  4. PREP-CHEM-SRC – 1.0: a preprocessor of trace gas and aerosol emission fields for regional and global atmospheric chemistry models

    Directory of Open Access Journals (Sweden)

    S. R. Freitas

    2011-05-01

    Full Text Available The preprocessor PREP-CHEM-SRC presented in the paper is a comprehensive tool aiming at preparing emission fields of trace gases and aerosols for use in atmospheric-chemistry transport models. The considered emissions are from the most recent databases of urban/industrial, biogenic, biomass burning, volcanic, biofuel use and burning from agricultural waste sources. For biomass burning, emissions can be also estimated directly from satellite fire detections using a fire emission model included in the tool. The preprocessor provides emission fields interpolated onto the transport model grid. Several map projections can be chosen. The inclusion of these emissions in transport models is also presented. The preprocessor is coded using Fortran90 and C and is driven by a namelist allowing the user to choose the type of emissions and the databases.

  5. Atmospheric chemistry of dimethyl sulfide. Kinetics of the CH3SCH2O2 + NO2 reaction in the gas phase at 296 K

    DEFF Research Database (Denmark)

    Nielsen, O.J.; Sehested, J.; Wallington, T.J.

    1995-01-01

    The pulse radiolysis of SF6/CH3SCH3/O-2/NO2 gas mixtures was used to generate CH3SCH2O2 radicals in the presence of NO2. By monitoring the rate of NO2 decay using its absorption at 400 nm, rate constants for the reaction of CH3SCH2O2 radicals with NO2 were measured to be (9.2 +/- 0.9) x 10(-12) a......(-12) and (7.1 +/- 0.9) X 10(-12) cm(3) molecule(-1) s(-1) at room temperature in 1000 and 300 mbar of SF6 diluent, respectively. Results are discussed with respect to the atmospheric chemistry of dimethyl sulfide....

  6. Middle Atmosphere Response to Different Descriptions of the 11-Year Solar Cycle in Spectral Irradiance in a Chemistry-Climate Model

    Science.gov (United States)

    Swartz, W. H.; Stolarski, R. S.; Oman, L. D.; Fleming, E. L.; Jackman, C. H.

    2012-01-01

    The 11-year solar cycle in solar spectral irradiance (SSI) inferred from measurements by the SOlar Radiation & Climate Experiment (SORCE) suggests a much larger variation in the ultraviolet than previously accepted. We present middle atmosphere ozone and temperature responses to the solar cycles in SORCE SSI and the ubiquitous Naval Research Laboratory (NRL) SSI reconstruction using the Goddard Earth Observing System chemistry-climate model (GEOS CCM). The results are largely consistent with other recent modeling studies. The modeled ozone response is positive throughout the stratosphere and lower mesosphere using the NRL SSI, while the SORCE SSI produces a response that is larger in the lower stratosphere but out of phase with respect to total solar irradiance above 45 km. The modeled responses in total ozone are similar to those derived from satellite and ground-based measurements, 3-6 Dobson Units per 100 units of 10.7-cm radio flux (F10.7) in the tropics. The peak zonal mean tropical temperature response 50 using the SORCE SSI is nearly 2 K per 100 units 3 times larger than the simulation using the NRL SSI. The GEOS CCM and the Goddard Space Flight Center (GSFC) 2-D coupled model are used to examine how the SSI solar cycle affects the atmosphere through direct solar heating and photolysis processes individually. Middle atmosphere ozone is affected almost entirely through photolysis, whereas the solar cycle in temperature is caused both through direct heating and photolysis feedbacks, processes that are mostly linearly separable. Further, the net ozone response results from the balance of ozone production at wavelengths less than 242 nm and destruction at longer wavelengths, coincidentally corresponding to the wavelength regimes of the SOLar STellar Irradiance Comparison Experiment (SOLSTICE) and Spectral Irradiance Monitor (SIM) on SORCE, respectively. A higher wavelength-resolution analysis of the spectral response could allow for a better prediction of the

  7. Absolutely calibrated mass spectrometry measurement of reactive and stable plasma chemistry products in the effluent of a He/H2O atmospheric plasma

    Science.gov (United States)

    Willems, Gert; Benedikt, Jan; von Keudell, Achim

    2017-08-01

    Mass spectrometry has been used to analyse the effluent of a micro-scaled atmospheric plasma jet operated in helium with a controlled concentration of water vapour. Absolute densities of H2O2 and OH have been measured as function of water vapour concentration and distance from the jet nozzle. The trend for both species densities are correlated and after an initial increase, the densities of H2O2 and OH saturate around 5000 ppm to 6000 ppm of water admixture. The largest densities for H2O2 (2.37× 1014 cm-3 ) and OH (1.96× 1014 cm-3 ) were measured at 7980 ppm water admixture and 2 mm distance from the jet. Densities of HO2 (1× 1014 cm-3 ) and O2 (4× 1014 cm-3 ) have been measured as well, although no trend could be observed. The direct electron impact ionisation cross-section of H2O2 at 70 eV electron energy was experimentally determined to be 1.02 × 10-16 cm2 . The measured densities and profiles have been compared to a 2D axially symmetric fluid model of species transport and recombination reactions. The effluent reaction chemistry is dominated by the hydroxyl radical, where the hydrogen atoms seem to play an important role as well. The analysis of neutral plasma chemistry products have been complemented by measurements of qualitative ion signals.

  8. Reactions of substituted benzene anions with N and O atoms: Chemistry in Titan’s upper atmosphere and the interstellar medium

    Energy Technology Data Exchange (ETDEWEB)

    Wang, Zhe-Chen; Bierbaum, Veronica M. [Department of Chemistry and Biochemistry, University of Colorado, Boulder, Colorado 80309 (United States)

    2016-06-07

    The likely existence of aromatic anions in many important extraterrestrial environments, from the atmosphere of Titan to the interstellar medium (ISM), is attracting increasing attention. Nitrogen and oxygen atoms are also widely observed in the ISM and in the ionospheres of planets and moons. In the current work, we extend previous studies to explore the reactivity of prototypical aromatic anions (deprotonated toluene, aniline, and phenol) with N and O atoms both experimentally and computationally. The benzyl and anilinide anions both exhibit slow associative electron detachment (AED) processes with N atom, and moderate reactivity with O atom in which AED dominates but ionic products are also formed. The reactivity of phenoxide is dramatically different; there is no measurable reaction with N atom, and the moderate reactivity with O atom produces almost exclusively ionic products. The reaction mechanisms are studied theoretically by employing density functional theory calculations, and spin conversion is found to be critical for understanding some product distributions. This work provides insight into the rich gas-phase chemistry of aromatic ion-atom reactions and their relevance to ionospheric and interstellar chemistry.

  9. The 1-way on-line coupled atmospheric chemistry model system MECO(n) - Part 3: Meteorological evaluation of the on-line coupled system

    Science.gov (United States)

    Hofmann, C.; Kerkweg, A.; Wernli, H.; Jöckel, P.

    2012-01-01

    Three detailed meteorological case studies are conducted with the global and regional atmospheric chemistry model system ECHAM5/MESSy(→COSMO/MESSy)n, shortly named MECO(n). The aim of this article is to assess the general performance of the on-line coupling of the regional model COSMO to the global model ECHAM5. The cases are characterised by intense weather systems in Central Europe: a cold front passage in March 2010, a convective frontal event in July 2007, and the high impact winter storm "Kyrill" in January 2007. Simulations are performed with the new on-line-coupled model system and compared to classical, off-line COSMO hindcast simulations driven by ECMWF analyses. Precipitation observations from rain gauges and ECMWF analysis fields are used as reference, and both qualitative and quantitative measures are used to characterise the quality of the various simulations. It is shown that, not surprisingly, simulations with a shorter lead time generally produce more accurate simulations. Irrespective of lead time, the accuracy of the on-line and off-line COSMO simulations are comparable for the three cases. This result indicates that the new global and regional model system MECO(n) is able to simulate key mid-latitude weather systems, including cyclones, fronts, and convective precipitation, as accurately as present-day state-of-the-art regional weather prediction models in standard off-line configuration. Therefore, MECO(n) will be applied to simulate atmospheric chemistry exploring the model's full capabilities during meteorologically challenging conditions.

  10. The 1-way on-line coupled atmospheric chemistry model system MECO(n – Part 3: Meteorological evaluation of the on-line coupled system

    Directory of Open Access Journals (Sweden)

    C. Hofmann

    2012-01-01

    Full Text Available Three detailed meteorological case studies are conducted with the global and regional atmospheric chemistry model system ECHAM5/MESSy(→COSMO/MESSyn, shortly named MECO(n. The aim of this article is to assess the general performance of the on-line coupling of the regional model COSMO to the global model ECHAM5. The cases are characterised by intense weather systems in Central Europe: a cold front passage in March 2010, a convective frontal event in July 2007, and the high impact winter storm "Kyrill" in January 2007. Simulations are performed with the new on-line-coupled model system and compared to classical, off-line COSMO hindcast simulations driven by ECMWF analyses. Precipitation observations from rain gauges and ECMWF analysis fields are used as reference, and both qualitative and quantitative measures are used to characterise the quality of the various simulations. It is shown that, not surprisingly, simulations with a shorter lead time generally produce more accurate simulations. Irrespective of lead time, the accuracy of the on-line and off-line COSMO simulations are comparable for the three cases. This result indicates that the new global and regional model system MECO(n is able to simulate key mid-latitude weather systems, including cyclones, fronts, and convective precipitation, as accurately as present-day state-of-the-art regional weather prediction models in standard off-line configuration. Therefore, MECO(n will be applied to simulate atmospheric chemistry exploring the model's full capabilities during meteorologically challenging conditions.

  11. Multi-model Mean Nitrogen and Sulfur Deposition from the Atmospheric Chemistry and Climate Model Intercomparison Project (ACCMIP): Evaluation Historical and Projected Changes

    Science.gov (United States)

    Lamarque, J.-F.; Dentener, F.; McConnell, J.; Ro, C.-U.; Shaw, M.; Vet, R.; Bergmann, D.; Cameron-Smith, P.; Doherty, R.; Faluvegi, G.; hide

    2013-01-01

    We present multi-model global datasets of nitrogen and sulfate deposition covering time periods from 1850 to 2100, calculated within the Atmospheric Chemistry and Climate Model Intercomparison Project (ACCMIP). The computed deposition fluxes are compared to surface wet deposition and ice-core measurements. We use a new dataset of wet deposition for 2000-2002 based on critical assessment of the quality of existing regional network data. We show that for present-day (year 2000 ACCMIP time-slice), the ACCMIP results perform similarly to previously published multi-model assessments. For this time slice, we find a multi-model mean deposition of 50 Tg(N) yr1 from nitrogen oxide emissions, 60 Tg(N) yr1 from ammonia emissions, and 83 Tg(S) yr1 from sulfur emissions. The analysis of changes between 1980 and 2000 indicates significant differences between model and measurements over the United States but less so over Europe. This difference points towards misrepresentation of 1980 NH3 emissions over North America. Based on ice-core records, the 1850 deposition fluxes agree well with Greenland ice cores but the change between 1850 and 2000 seems to be overestimated in the Northern Hemisphere for both nitrogen and sulfur species. Using the Representative Concentration Pathways to define the projected climate and atmospheric chemistry related emissions and concentrations, we find large regional nitrogen deposition increases in 2100 in Latin America, Africa and parts of Asia under some of the scenarios considered. Increases in South Asia are especially large, and are seen in all scenarios, with 2100 values more than double 2000 in some scenarios and reaching 1300 mg(N) m2 yr1 averaged over regional to continental scale regions in RCP 2.6 and 8.5, 3050 larger than the values in any region currently (2000). The new ACCMIP deposition dataset provides novel, consistent and evaluated global gridded deposition fields for use in a wide range of climate and ecological studies.

  12. A computer model for one-dimensional mass and energy transport in and around chemically reacting particles, including complex gas-phase chemistry, multicomponent molecular diffusion, surface evaporation, and heterogeneous reaction

    Science.gov (United States)

    Cho, S. Y.; Yetter, R. A.; Dryer, F. L.

    1992-01-01

    Various chemically reacting flow problems highlighting chemical and physical fundamentals rather than flow geometry are presently investigated by means of a comprehensive mathematical model that incorporates multicomponent molecular diffusion, complex chemistry, and heterogeneous processes, in the interest of obtaining sensitivity-related information. The sensitivity equations were decoupled from those of the model, and then integrated one time-step behind the integration of the model equations, and analytical Jacobian matrices were applied to improve the accuracy of sensitivity coefficients that are calculated together with model solutions.

  13. Study of the atmospheric chemistry of radon progeny in laboratory and real indoor atmospheres. Progress report, May 1, 1993--January 31, 1994

    Energy Technology Data Exchange (ETDEWEB)

    Hopke, P.K.

    1993-01-01

    Progress is reported on the chemical and physical behavior of the {sup 218}Po atom immediately following its formation by the alpha decay of radon. Two areas of radon progeny behavior are being pursued; laboratory studies under controlled conditions to better understand the fundamental physical and chemical processes that affect the progeny`s atmospheric behavior and studies in actual indoor environments to develop a better assessment of the exposure of the occupants of that space to the size and concentration of the indoor radioactive aerosol. The specific tasks addressed were to determine the formation rates of {center_dot}OH radicals formed by the radiolysis of air following radon decay, to examine the formation of particles by the radiolytic oxidation of substances like SO{sub 2}, ethylene, and H{sub 2}S to lower vapor pressure compounds and determine the role of gas phase additives such as H{sub 2}O and NH{sub 3} in determining the particle size, to measure the rate of ion-induced nucleation using a thermal diffusion cloud chamber, and to measure the neutralization rate of {sup 218}PoO{sub x}{sup +} in O{sub 2} at low radon concentrations. Initial measurements were conducted of the activity size distributions in actual homes with occupants present so that the variability of the indoor activity size distributions can be assessed with respect to indoor aerosol sources and general lifestyle variations of the occupants. A prospective study of the utility of measurement of deposited {sup 210}Pb embedded in glass surfaces as a measure of the long-term, integrated exposure of the population to radon are described. Methodology was developed to determine the hygroscopicity of the indoor aerosol so that the changes in deposition efficiency of the radioactive indoor aerosol with hygroscopic growth in the respiratory tract can be assessed.

  14. Decadal to multi-decadal scale variability of Indian summer monsoon rainfall in the coupled ocean-atmosphere-chemistry climate model SOCOL-MPIOM

    Science.gov (United States)

    Malik, Abdul; Brönnimann, Stefan; Stickler, Alexander; Raible, Christoph C.; Muthers, Stefan; Anet, Julien; Rozanov, Eugene; Schmutz, Werner

    2017-01-01

    The present study is an effort to deepen the understanding of Indian summer monsoon rainfall (ISMR) on decadal to multi-decadal timescales. We use ensemble simulations for the period AD 1600-2000 carried out by the coupled Atmosphere-Ocean-Chemistry-Climate Model (AOCCM) SOCOL-MPIOM. Firstly, the SOCOL-MPIOM is evaluated using observational and reanalyses datasets. The model is able to realistically simulate the ISMR as well as relevant patterns of sea surface temperature and atmospheric circulation. Further, the influence of Atlantic Multi-decadal Oscillation (AMO), Pacific Decadal Oscillation (PDO), and El Niño Southern Oscillation (ENSO) variability on ISMR is realistically simulated. Secondly, we investigate the impact of internal climate variability and external climate forcings on ISMR on decadal to multi-decadal timescales over the past 400 years. The results show that AMO, PDO, and Total Solar Irradiance (TSI) play a considerable role in controlling the wet and dry decades of ISMR. Resembling observational findings most of the dry decades of ISMR occur during a negative phase of AMO and a simultaneous positive phase of PDO. The observational and simulated datasets reveal that on decadal to multi-decadal timescales the ISMR has consistent negative correlation with PDO whereas its correlation with AMO and TSI is not stationary over time.

  15. Decadal to multi-decadal scale variability of Indian summer monsoon rainfall in the coupled ocean-atmosphere-chemistry climate model SOCOL-MPIOM

    Science.gov (United States)

    Malik, Abdul; Brönnimann, Stefan; Stickler, Alexander; Raible, Christoph C.; Muthers, Stefan; Anet, Julien; Rozanov, Eugene; Schmutz, Werner

    2017-11-01

    The present study is an effort to deepen the understanding of Indian summer monsoon rainfall (ISMR) on decadal to multi-decadal timescales. We use ensemble simulations for the period AD 1600-2000 carried out by the coupled Atmosphere-Ocean-Chemistry-Climate Model (AOCCM) SOCOL-MPIOM. Firstly, the SOCOL-MPIOM is evaluated using observational and reanalyses datasets. The model is able to realistically simulate the ISMR as well as relevant patterns of sea surface temperature and atmospheric circulation. Further, the influence of Atlantic Multi-decadal Oscillation (AMO), Pacific Decadal Oscillation (PDO), and El Niño Southern Oscillation (ENSO) variability on ISMR is realistically simulated. Secondly, we investigate the impact of internal climate variability and external climate forcings on ISMR on decadal to multi-decadal timescales over the past 400 years. The results show that AMO, PDO, and Total Solar Irradiance (TSI) play a considerable role in controlling the wet and dry decades of ISMR. Resembling observational findings most of the dry decades of ISMR occur during a negative phase of AMO and a simultaneous positive phase of PDO. The observational and simulated datasets reveal that on decadal to multi-decadal timescales the ISMR has consistent negative correlation with PDO whereas its correlation with AMO and TSI is not stationary over time.

  16. Atmospheric chemistry of mercury in Antarctica and the role of cryptogams to assess deposition patterns in coastal ice-free areas.

    Science.gov (United States)

    Bargagli, R

    2016-11-01

    Mercury in the Antarctic troposphere has a distinct chemistry and challenging long-term measurements are needed for a better understanding of the atmospheric Hg reactions with oxidants and the exchanges of the various mercury forms among air-snow-sea and biota. Antarctic mosses and lichens are reliable biomonitors of airborne metals and in short time they can give useful information about Hg deposition patterns. Data summarized in this review show that although atmospheric Hg concentrations in the Southern Hemisphere are lower than those in the Northern Hemisphere, Antarctic cryptogams accumulate Hg at levels in the same range or higher than those observed for related cryptogam species in the Arctic, suggesting an enhanced deposition of bioavailable Hg in Antarctic coastal ice-free areas. In agreement with the newest findings in the literature, the Hg bioaccumulation in mosses and lichens from a nunatak particularly exposed to strong katabatic winds can be taken as evidence for a Hg contribution to coastal ecosystems by air masses from the Antarctic plateau. Human activities on the continent are mostly concentrated in coastal ice-free areas, and the deposition in these areas of Hg from the marine environment, the plateau and anthropogenic sources raises concern. The use of Antarctic cryptogams as biomonitors will be very useful to map Hg deposition patterns in costal ice-free areas and will contribute to a better understanding of Hg cycling in Antarctica and its environmental fate in terrestrial ecosystems. Copyright © 2016 Elsevier Ltd. All rights reserved.

  17. Zeppelin NT - Measurement Platform for the Exploration of Atmospheric Chemistry and Dynamics in the Planetary Boundary Layer

    Science.gov (United States)

    Hofzumahaus, Andreas; Holland, Frank; Oebel, Andreas; Rohrer, Franz; Mentel, Thomas; Kiendler-Scharr, Astrid; Wahner, Andreas; Brauchle, Artur; Steinlein, Klaus; Gritzbach, Robert

    2014-05-01

    The planetary boundary layer (PBL) is the chemically most active and complex part of the atmosphere where freshly emitted reactive trace gases, tropospheric radicals, atmospheric oxidation products and aerosols exhibit a large variability and spatial gradients. In order to investigate the chemical degradation of trace gases and the formation of secondary pollutants in the PBL, a commercial Zeppelin NT was modified to be used as an airborne measurement platform for chemical and physical observations with high spatial resolution. The Zeppelin NT was developed by Zeppelin Luftschifftechnik (ZLT) and is operated by Deutsche Zeppelin Reederei (DZR) in Friedrichshafen, Germany. The modification was performed in cooperation between Forschungszentrum Jülich and ZLT. The airship has a length of 75 m, can lift about 1 ton of scientific payload and can be manoeuvered with high precision by propeller engines. The modified Zeppelin can carry measurement instruments mounted on a platform on top of the Zeppelin, or inside the gondola beneath the airship. Three different instrument packages were developed to investigate a. gas-phase oxidation processes involving free radicals (OH, HO2) b. formation of secondary organic aerosols (SOA) c. new particle formation (nucleation) The presentation will describe the modified airship and provide an overview of its technical performance. Examples of its application during the recent PEGASOS flight campaigns in Europe will be given.

  18. The effects of lightning-produced NOx and its vertical distribution on atmospheric chemistry: sensitivity simulations with MATCH-MPIC

    Directory of Open Access Journals (Sweden)

    L. J. Labrador

    2005-01-01

    Full Text Available The impact of different assumptions concerning the source magnitude as well as the vertical placement of lightning-produced nitrogen oxides is studied using the global chemistry transport model MATCH-MPIC. The responses of NOx, O3, OH, HNO3 and peroxyacetyl-nitrate (PAN are investigated. A marked sensitivity to both parameters is found. NOx burdens globally can be enhanced by up to 100% depending on the vertical placement and source magnitude strength. In all cases, the largest enhancements occur in the tropical upper troposphere, where lifetimes of most trace gases are longer and where they thus become more susceptible to long-range transport by large-scale circulation patterns. Comparison with observations indicate that 0 and 20 Tg(N/yr production rates of NOx from lightning are too low and too high, respectively. However, no single intermediate production rate or vertical distribution can be singled out as best fitting the observations, due to the large scatter in the datasets. This underscores the need for further measurement campaigns in key regions, such as the tropical continents.

  19. Sources and atmospheric chemistry of oxy- and nitro-PAHs in the ambient air of Grenoble (France)

    Science.gov (United States)

    Tomaz, Sophie; Jaffrezo, Jean-Luc; Favez, Olivier; Perraudin, Emilie; Villenave, Eric; Albinet, Alexandre

    2017-07-01

    Total individual concentrations (in both gaseous and particulate phases) of 80 polycyclic aromatic compounds (PACs) including 32 nitro-PAHs, 27 oxy-PAHs (polycyclic aromatic hydrocarbons) and 21 parent PAHs have been investigated over a year in the ambient air of Grenoble (France) together with an extended aerosol chemical characterization. The results indicated that their concentrations were strongly affected by primary emissions in cold period, especially from residential heating (i.e. biomass burning). Besides, secondary processes occurred in summer but also in cold period under specific conditions such as during long thermal inversion layer periods and severe PM pollution events. Different secondary processes were involved during both PM pollution events observed in March-April and in December 2013. During the first one, long range transport of air masses, nitrate chemistry and secondary nitro-PAH formation seemed linked. During the second one, the accumulation of primary pollutants over several consecutive days enhanced secondary chemical processes notably highlighted by the dramatic increase of oxy-PAH concentrations. The study of the time trends of ratios of individual nitro- or oxy-PAHs to parent PAHs, in combination with key primary or secondary aerosol species and literature data, allowed the identification of potential molecular markers of PAH oxidation. Finally, 6H-dibenzo[b,d]pyran-6-one, biphenyl-2,2'-dicarboxaldehyde and 3-nitrophenanthrene have been selected to be the best candidates as markers of PAH oxidation processes in ambient air.

  20. Applications of theoretical methods in atmospheric science

    DEFF Research Database (Denmark)

    Johnson, Matthew Stanley; Goodsite, Michael E.

    2008-01-01

    in addressing an issue of primary concern: understanding photochemical reaction rates at the various conditions found in the atmosphere. Atmospheric science includes both atmospheric chemistry and atmospheric physics, meteorology, climatology and the study of extraterrestrial atmospheres....

  1. Halogen Chemistry in the CMAQ Model

    Science.gov (United States)

    Halogens (iodine and bromine) emitted from oceans alter atmospheric chemistry and influence atmospheric ozone mixing ratio. We previously incorporated a representation of detailed halogen chemistry and emissions of organic and inorganic halogen species into the hemispheric Commun...

  2. Chemistry in the Troposphere.

    Science.gov (United States)

    Chameides, William L.; Davis, Douglas D.

    1982-01-01

    Topics addressed in this review of chemistry in the troposphere (layer of atmosphere extending from earth's surface to altitude of 10-16km) include: solar radiation/winds; earth/atmosphere interface; kinetic studies of atmospheric reactions; tropospheric free-radical photochemistry; instruments for nitric oxide detection; sampling…

  3. Southwest Pacific deep water carbonate chemistry linked to high southern latitude climate and atmospheric CO2 during the Last Glacial Termination

    Science.gov (United States)

    Allen, Katherine A.; Sikes, Elisabeth L.; Hönisch, Bärbel; Elmore, Aurora C.; Guilderson, Thomas P.; Rosenthal, Yair; Anderson, Robert F.

    2015-08-01

    A greater amount of CO2 was stored in the deep sea during glacial periods, likely via greater efficiency of the biologic pump and increased uptake by a more alkaline ocean. Reconstructing past variations in seawater carbonate ion concentration (a major component of alkalinity) enables quantification of the relative roles of different oceanic CO2 storage mechanisms and also places constraints on the timing, magnitude, and location of subsequent deep ocean ventilation. Here, we present a record of deep-water inorganic carbon chemistry since the Last Glacial Maximum (LGM; ∼19-23 ka BP), derived from sediment core RR0503-83 raised from 1627 m in New Zealand's Bay of Plenty. The core site lies within the upper limit of southern-sourced Circumpolar Deep Water (CDW), just below the lower boundary of Antarctic Intermediate Water (AAIW). We reconstruct past changes in bottom water inorganic carbon chemistry from the trace element and stable isotopic composition of calcite shells of the epibenthic foraminifer Cibicidoides wuellerstorfi. A record of ΔCO32-(ΔCO32- = [COCO32-] in situ - [CO32-] saturation) derived from the foraminiferal boron to calcium ratio (B/Ca) provides evidence for greater ice-age storage of respired CO2 and reveals abrupt deglacial shifts in [CO32-] in situ of up to 30 μmol/kg (5 times larger than the difference between average LGM and Holocene values). The rapidity of these changes suggests the influence of changing water mass structure and atmospheric circulation in addition to a decrease in CO2 content of interior waters.

  4. Real-Time Characterization of Aerosol Particle Composition above the Urban Canopy in Beijing: Insights into the Interactions between the Atmospheric Boundary Layer and Aerosol Chemistry.

    Science.gov (United States)

    Sun, Yele; Du, Wei; Wang, Qingqing; Zhang, Qi; Chen, Chen; Chen, Yong; Chen, Zhenyi; Fu, Pingqing; Wang, Zifa; Gao, Zhiqiu; Worsnop, Douglas R

    2015-10-06

    Despite extensive efforts into the characterization of air pollution during the past decade, real-time characterization of aerosol particle composition above the urban canopy in the megacity Beijing has never been performed to date. Here we conducted the first simultaneous real-time measurements of aerosol composition at two different heights at the same location in urban Beijing from December 19, 2013 to January 2, 2014. The nonrefractory submicron aerosol (NR-PM1) species were measured in situ by a high-resolution aerosol mass spectrometer at near-ground level and an aerosol chemical speciation monitor at 260 m on a 325 m meteorological tower in Beijing. Secondary aerosol showed similar temporal variations between ground level and 260 m, whereas much weaker correlations were found for the primary aerosol. The diurnal evolution of the ratios and correlations of aerosol species between 260 m and the ground level further illustrated a complex interaction between vertical mixing processes and local source emissions on aerosol chemistry in the atmospheric boundary layer. As a result, the aerosol compositions at the two heights were substantially different. Organic aerosol (OA), mainly composed of primary OA (62%), at the ground level showed a higher contribution to NR-PM1 (65%) than at 260 m (54%), whereas a higher concentration and contribution (15%) of nitrate was observed at 260 m, probably due to the favorable gas-particle partitioning under lower temperature conditions. In addition, two different boundary layer structures were observed, each interacting differently with the evolution processes of aerosol chemistry.

  5. Contrasting atmospheric boundary layer chemistry of methylhydroperoxide (CH3OOH and hydrogen peroxide (H2O2 above polar snow

    Directory of Open Access Journals (Sweden)

    D. K. Friel

    2009-05-01

    Full Text Available Atmospheric hydroperoxides (ROOH were measured at Summit, Greenland (72.97° N, 38.77° W in summer 2003 (SUM03 and spring 2004 (SUM04 and South Pole in December 2003 (SP03. The two dominant hydroperoxides were H2O2 and CH3OOH (from here on MHP with average (±1σ mixing ratios of 1448 (±688 pptv, 204 (±162 and 278 (±67 for H2O2 and 578 (±377 pptv, 139 (±101 pptv and 138 (±89 pptv for MHP, respectively. In early spring, MHP dominated the ROOH budget and showed night time maxima and daytime minima, out of phase with the diurnal cycle of H2O2, suggesting that the organic peroxide is controlled by photochemistry, while H2O2 is largely influenced by temperature driven exchange between the atmosphere and snow. Highly constrained photochemical box model runs yielded median ratios between modeled and observed MHP of 52%, 148% and 3% for SUM03, SUM04 and SP03, respectively. At Summit firn air measurements and model calculations suggest a daytime sink of MHP in the upper snow pack, which decreases in strength through the spring season into the summer. Up to 50% of the estimated sink rates of 1–5×1011 molecules m−3 s−1 equivalent to 24–96 pptv h−1 can be explained by photolysis and reaction with the OH radical in firn air and in the quasi-liquid layer on snow grains. Rapid processing of MHP in surface snow is expected to contribute significantly to a photochemical snow pack source of formaldehyde (CH2O. Conversely, summer levels of MHP at South Pole are inconsistent with the prevailing high NO concentrations, and cannot be explained currently by known photochemical precursors or transport, thus suggesting a missing source. Simultaneous measurements of H2O2, MHP and CH2O allow to constrain the NO background today and potentially also in the past using ice cores, although it seems less likely that MHP is preserved in firn and ice.

  6. Does Land-Surface Heterogeneity Affect the Evolution of Hurricanes after their Landfall in the Eastern US - A Numerical Study with the Ocean-Land-Atmosphere Model (OLAM)

    Science.gov (United States)

    Avissar, R.; Walko, R. L.

    2006-12-01

    The Ocean-Land-Atmosphere Model (OLAM) has been developed to extend the capabilities of the Regional Atmospheric Modeling System (RAMS) to a global modeling framework. OLAM is a new model with regard to its dynamic core, grid configuration, memory structure, and numerical solution technique. Instead of the Boussinesq approximation used in RAMS, OLAM solves the full compressible Navier-Stokes equations in conservation form using finite-volume numerical operators that conserve mass, momentum, and energy to machine precision. In place of RAMS' structured multiple nested grids and hexahedral grid cells on a polar stereographic projection, OLAM uses a single unstructured grid and pentahedral (prism) grid cells (with a triangular footprint) which conform to the sphere without a coordinate transformation. OLAM's grid topology enables local mesh refinement to any degree without the need for special grid nesting algorithms; all communication between regions of different resolution is accomplished seamlessly by flux-conservative advective and diffusive transport. OLAM represents topography using a form of the volume-fraction or shaved grid cell method in which model levels are strictly horizontal, rather than terrain-following, and therefore intersect topography. Grid cell face areas, which explicitly appear in the finite volume equations and are pre- computed and stored, are reduced in proportion to any blockage by topography, thereby correctly regulating inter-cell transport and preventing advective flux normal to the ground surface. Apart from its dynamic core and grid configuration, OLAM bears a strong resemblance to RAMS. Both models share the same physical parameterizations for microphysics, land and vegetation water and energy balances, radiative transfer, and sub-grid cumulus convection. Model coding structure, I/O file formats, and methods of compiling, initializing, and executing the models are very similar or identical. OLAM is particularly well designed to

  7. A kinetic study of Ca-containing ions reacting with O, O2, CO2 and H2O: implications for calcium ion chemistry in the upper atmosphere.

    Science.gov (United States)

    Broadley, Sarah; Vondrak, Tomas; Wright, Timothy G; Plane, John M C

    2008-09-14

    A series of gas-phase reactions involving molecular Ca-containing ions was studied by the pulsed laser ablation of a calcite target to produce Ca+ in a fast flow of He, followed by the addition of reagents downstream and detection of ions by quadrupole mass spectrometry. Most of the reactions that were studied are important for describing the chemistry of meteor-ablated calcium in the earth's upper atmosphere. The following rate coefficients were measured: k(CaO+ + O --> Ca+ + O2) = (4.2 +/- 2.8) x 10(-11) at 197 K and (6.3 +/- 3.0) x 10(-11) at 294 K; k(CaO+ + CO --> Ca+ + CO2, 294 K) = (2.8 +/- 1.5) x 10(-10); k(Ca+.CO2 + O2 --> CaO2+ + CO2, 294 K) = (1.2 +/- 0.5) x10(-10); k(Ca+.CO2 + H2O --> Ca+.H2O + CO2) = (13.0 +/- 4.0) x 10(-10); and k(Ca+.H2O + O2 --> CaO2+ + H2O, 294 K) = (4.0 +/- 2.5) x 10(-10) cm3 molecule(-1) s(-1). The quoted uncertainties are a combination of the 1 sigma standard errors in the kinetic data and the systematic errors in the models used to extract the rate coefficients. Rate coefficients were also obtained for the following recombination (also termed association) reactions in He bath gas: k(Ca+.CO2 + CO2 --> Ca+.(CO2)2, 294 K) = (2.6 +/- 1.0) x 10(-29); k(Ca+.H2O + H2O --> Ca+.(H2O)2) = (1.6 +/- 1.1) x 10(-27); and k(CaO2+ + O2 --> CaO2+.O2) high level quantum chemistry calculations and RRKM theory using an inverse Laplace transform solution of the master equation. The surprisingly slow reaction between CaO+ and O was explained using quantum chemistry calculations on the lowest 2A', 2A'' and 4A'' potential energy surfaces. These calculations indicate that reaction mostly occurs on the 2A' surface, leading to production of Ca+ (2S) + O2(1 Delta g). The importance of this reaction for controlling the lifetime of Ca+ in the upper mesosphere and lower thermosphere is then discussed.

  8. Prebiotic Atmospheric Chemistry on Titan: Formation Kinetics via Ab Initio Calculations for Potential Energy Surface (PES) Mapping

    Science.gov (United States)

    Gonzalez, Dayana; Mebel, Alexander

    2016-03-01

    It has been recently shown that Titan provides a unique perspective in our solar system: its atmosphere is comparable to a model of prebiotic Earth's. Provided the organic cationic and anionic molecular species identified by the Cassini spacecraft, this research characterizes reaction pathways for the reactions of methyl derivatives of the cyclopropenyl cation, the methyl cation with methyl- and dimethyl-acetylene, and reactions of resonance structures of protonated acrylonitrile with CH2NH. Isomerization and dissociation reactions involving methyl-cyclopropenyl cations, the perinaphthenyl cation and anion, and cations of pyrimidine and purine precursors of nucleobases will be examined to locate reaction pathways, intermediates, transition states, and products of the reactions. Gaussian '09 software is used for ab initio calculations to map out the PES. Geometry optimizations and vibrational frequency computations are preformed via the double-hybrid density functional B2PLYP-D3. Single-point energies are refined by use of the explicitly-correlated coupled-cluster CCSD(T)-F12 method. Rate constants are calculated using microcanonical RRKM theory, and pressure effects evaluated used the Master Equation approach; these allow for prediction of absolute rate constants and product branching ratios at different pressures and temperatures.

  9. O3 variability in the troposphere as observed by IASI over 2008-2016: Contribution of atmospheric chemistry and dynamics

    Science.gov (United States)

    Wespes, C.; Hurtmans, D.; Clerbaux, C.; Coheur, P.-F.

    2017-02-01

    We analyze the ozone (O3) variability in the troposphere (from ground to 300 hPa) using 8 years (January 2008 to March 2016) of O3 profile measurements provided by the Infrared Atmospheric Sounding Interferometer (IASI) on board the MetOp satellite. The capability of IASI to monitor the year-to-year variability in that layer is examined first in terms of vertical sensitivity, a priori contribution, and correlations in the deseasonalized anomalies with the upper layers. We present global patterns of the main geophysical drivers (e.g., solar flux, Quasi-biennal Oscillation—QBO, North Atlantic Oscillation—NAO, and El Niño-Southern Oscillation—ENSO) of IASI O3 variations, obtained by applying appropriate annual and seasonal multivariate regression models on time series of spatially gridded averaged O3. The results show that the models are able to explain most of the O3 variability captured by IASI. Large O3 changes in the North Arctic/Euro-Atlantic sector and over the equatorial band are attributed to the NAO and the QBO effects, respectively. ENSO is modeled as the main contributor to the O3 variations in the tropical band where direct effects of warm and cool ENSO phases are highlighted with a clear tropical-extratropical gradient. A strong west-east gradient in the tropics is also found and likely reflects an indirect effect related to ENSO dry conditions. Finally, we also show that the ENSO perturbs the O3 variability far from the tropics into middle and high latitudes where a significant 4-month time-lag in the response of O3 to ENSO is identified for the first time.

  10. Chemistry of atmospheric precipitation in the north-central united states: Influence of sulfate, nitrate, ammonia and calcareous soil particulates

    Science.gov (United States)

    Munger, James William

    The supply of alkaline soil dust and gaseous NH 3 available to neutralize anthropogenic acids in the atmosphere controls the acidity of precipitation in the north-central United States. Major ions and trace metals were determined in precipitation-event and snow-core samples from sites along a 600 km transect from the North Dakota prairie to the forests of northeastern Minnesota, collected during the period April 1978-June 1979. Acidity increased 4-fold from west to east as the effect of alkaline dust and NH 3 decreased with increasing distance from the cultivated prairie; calcium and Mg 2+ decreased 2 to 3-fold across the transect. However, minimum concentrations of NH 4+ and SO 42- were observed at Itasca, the central site. Natural emissions of these elements were important in the west, while anthropogenic emissions were responsible for the higher concentrations in the east. Wet deposition of H + decreased 8-fold and deposition of NO 3- and SO 42- decreased 1.5 to 2-fold from Hovland in the east to Tewaukon in the west. Wet deposition of the metal cations increased from Hovland to Tewaukon. Dry deposition followed a similar trend. Winter snow cover and freezing temperatures, which decreased airborne soil dust and the evolution of NH 3 from the prairie soils, led to an increase in precipitation acidity at all sites. The acid increase was accompanied by a decrease in alkaline metal cations, especially Ca 2+, and in NH 4+. At Hovland SO 42- and NO 3- also increased during the winter. The occurrence of snow events at Tewaukon that were appreciably more acid than the snowpack accumulated there indicates that snow was neutralized after it fell by alkaline dust entrained in resuspended snow, or deposited separately. Winter inputs of acid are especially important because they are released during a short period in the spring. Over half of the acid input at Hovland occurred during the winter. Precipitation inputs of P and N probably benefit nutrient-poor ecosystems in the

  11. Validation of the Atmospheric Chemistry Experiment (ACE version 2.2 temperature using ground-based and space-borne measurements

    Directory of Open Access Journals (Sweden)

    R. J. Sica

    2008-01-01

    Full Text Available An ensemble of space-borne and ground-based instruments has been used to evaluate the quality of the version 2.2 temperature retrievals from the Atmospheric Chemistry Experiment Fourier Transform Spectrometer (ACE-FTS. The agreement of ACE-FTS temperatures with other sensors is typically better than 2 K in the stratosphere and upper troposphere and 5 K in the lower mesosphere. There is evidence of a systematic high bias (roughly 3–6 K in the ACE-FTS temperatures in the mesosphere, and a possible systematic low bias (roughly 2 K in ACE-FTS temperatures near 23 km. Some ACE-FTS temperature profiles exhibit unphysical oscillations, a problem fixed in preliminary comparisons with temperatures derived using the next version of the ACE-FTS retrieval software. Though these relatively large oscillations in temperature can be on the order of 10 K in the mesosphere, retrieved volume mixing ratio profiles typically vary by less than a percent or so. Statistical comparisons suggest these oscillations occur in about 10% of the retrieved profiles. Analysis from a set of coincident lidar measurements suggests that the random error in ACE-FTS version 2.2 temperatures has a lower limit of about ±2 K.

  12. Do author-suggested reviewers rate submissions more favorably than editor-suggested reviewers? A study on atmospheric chemistry and physics.

    Directory of Open Access Journals (Sweden)

    Lutz Bornmann

    Full Text Available BACKGROUND: Ratings in journal peer review can be affected by sources of bias. The bias variable investigated here was the information on whether authors had suggested a possible reviewer for their manuscript, and whether the editor had taken up that suggestion or had chosen a reviewer that had not been suggested by the authors. Studies have shown that author-suggested reviewers rate manuscripts more favorably than editor-suggested reviewers do. METHODOLOGY/PRINCIPAL FINDINGS: Reviewers' ratings on three evaluation criteria and the reviewers' final publication recommendations were available for 552 manuscripts (in total 1145 reviews that were submitted to Atmospheric Chemistry and Physics, an interactive open access journal using public peer review (authors' and reviewers' comments are publicly exchanged. Public peer review is supposed to bring a new openness to the reviewing process that will enhance its objectivity. In the statistical analysis the quality of a manuscript was controlled for to prevent favorable reviewers' ratings from being attributable to quality instead of to the bias variable. CONCLUSIONS/SIGNIFICANCE: Our results agree with those from other studies that editor-suggested reviewers rated manuscripts between 30% and 42% less favorably than author-suggested reviewers. Against this backdrop journal editors should consider either doing without the use of author-suggested reviewers or, if they are used, bringing in more than one editor-suggested reviewer for the review process (so that the review by author-suggested reviewers can be put in perspective.

  13. Do author-suggested reviewers rate submissions more favorably than editor-suggested reviewers? A study on atmospheric chemistry and physics.

    Science.gov (United States)

    Bornmann, Lutz; Daniel, Hans-Dieter

    2010-10-14

    Ratings in journal peer review can be affected by sources of bias. The bias variable investigated here was the information on whether authors had suggested a possible reviewer for their manuscript, and whether the editor had taken up that suggestion or had chosen a reviewer that had not been suggested by the authors. Studies have shown that author-suggested reviewers rate manuscripts more favorably than editor-suggested reviewers do. Reviewers' ratings on three evaluation criteria and the reviewers' final publication recommendations were available for 552 manuscripts (in total 1145 reviews) that were submitted to Atmospheric Chemistry and Physics, an interactive open access journal using public peer review (authors' and reviewers' comments are publicly exchanged). Public peer review is supposed to bring a new openness to the reviewing process that will enhance its objectivity. In the statistical analysis the quality of a manuscript was controlled for to prevent favorable reviewers' ratings from being attributable to quality instead of to the bias variable. Our results agree with those from other studies that editor-suggested reviewers rated manuscripts between 30% and 42% less favorably than author-suggested reviewers. Against this backdrop journal editors should consider either doing without the use of author-suggested reviewers or, if they are used, bringing in more than one editor-suggested reviewer for the review process (so that the review by author-suggested reviewers can be put in perspective).

  14. Compendium of NASA data base for the global tropospheric experiment's Transport and Atmospheric Chemistry Near the Equator-Atlantic (TRACE-A)

    Science.gov (United States)

    Gregory, Gerald L.; Scott, A. Donald, Jr.

    1995-01-01

    This compendium describes aircraft data that are available from NASA's Transport and Atmospheric Chemistry near the Equator - Atlantic (TRACE-A) conducted in September/October 1992. The broad objectives of TRACE-A were to study chemical processes and long-range transport associated with South American and African continental outflow during periods of widespread vegetation burning, and to understand the ozone enhancements observed from satellite data measured over the southern tropical Atlantic Ocean during the September/October time period. Flight experiments were conducted from Brazil, South Africa, Namibia, and the Ascension Island. This document provides a representation of aircraft data that are available from NASA Langley's Distributed Active Archive Center (DAAC). The data format of time series and altitude profile plots is not intended to support original analyses, but to assist the reader in identifying data that are of interest. This compendium is for only the NASA aircraft data. The DAAC data base includes numerous supporting data-meteorological products, results from surface studies, satellite observations, and data from sonde releases.

  15. Atmospheric Deposition and Surface-Water Chemistry in Mount Rainier and North Cascades National Parks, U.S.A., Water Years 2000 and 2005-2006

    Science.gov (United States)

    Clow, David W.; Campbell, Donald H.

    2008-01-01

    High-elevation aquatic ecosystems in Mount Rainier and North Cascades National Parks are highly sensitive to atmospheric deposition of nitrogen and sulfur. Thin, rocky soils promote fast hydrologic flushing rates during snowmelt and rain events, limiting the ability of basins to neutralize acidity and assimilate nitrogen deposited from the atmosphere. Potential effects of nitrogen and sulfur deposition include episodic or chronic acidification of terrestrial and aquatic ecosystems. In addition, nitrogen deposition can cause eutrophication of water bodies and changes in species composition in lakes and streams. This report documents results of a study performed by the U.S. Geological Survey, in cooperation with the National Park Service, of the effects of atmospheric deposition of nitrogen and sulfur on surface-water chemistry in Mount Rainier and North Cascades National Parks. Inorganic nitrogen in wet deposition was highest in the vicinity of North Cascades National Park, perhaps due to emissions from human sources and activities in the Puget Sound area. Sulfur in wet deposition was highest near the Pacific coast, reflecting the influence of marine aerosols. Dry deposition generally accounted for less than 30 percent of wet plus dry inorganic nitrogen and sulfur deposition, but occult deposition (primarily fog) represents a potentially substantial unmeasured component of total deposition. Trend analyses indicate inorganic nitrogen in wet deposition was relatively stable during 1986-2005, but sulfur in wet deposition declined substantially during that time, particularly after 2001, when emissions controls were added to a large powerplant in western Washington. Surface-water sulfate concentrations at the study site nearest the powerplant showed a statistically significant decrease between 2000 and 2005-06, but there was no statistically significant change in alkalinity, indicating a delayed response in surface-water alkalinity. Seasonal patterns in surface

  16. Comparisons between SCIAMACHY atmospheric CO2 retrieved using (FSI WFM-DOAS to ground based FTIR data and the TM3 chemistry transport model

    Directory of Open Access Journals (Sweden)

    M. P. Barkley

    2006-01-01

    Full Text Available Atmospheric CO2 concentrations, retrieved from spectral measurements made in the near infrared (NIR by the SCIAMACHY instrument, using Full Spectral Initiation Weighting Function Modified Differential Optical Absorption Spectroscopy (FSI WFM-DOAS, are compared to ground based Fourier Transform Infrared (FTIR data and to the output from a global chemistry-transport model. Analysis of the FSI WFM-DOAS retrievals with respect to the ground based FTIR instrument, located at Egbert, Canada, show good agreement with an average negative bias of approximately −4.0% with a standard deviation of  3.0%. This bias which exhibits an apparent seasonal trend, is of unknown origin, though slight differences between the averaging kernels of the instruments and the limited temporal coverage of the FTIR data may be the cause. The relative scatter of the retrieved vertical column densities is larger than the spread of the FTIR measurements. Normalizing the CO2 columns using the surface pressure does not affect the magnitude of this bias although it slightly decreases the scatter of the FSI data. Comparisons of the FSI retrievals to the TM3 global chemistry-transport model, performed over four selected Northern Hemisphere scenes show reasonable agreement. The correlation, between the time series of the SCIAMACHY and model monthly scene averages, are  0.7 or greater, demonstrating the ability of SCIAMACHY to detect seasonal changes in the CO2 distribution. The amplitude of the seasonal cycle, peak to peak, observed by SCIAMACHY however, is larger by a factor of 2–3 with respect to the model, which cannot be explained. The yearly means detected by SCIAMACHY are within 2% of those of the model with the mean difference between the CO2 distributions also approximately 2.0%. Additionally, analysis of the retrieved CO2 distributions reveals structure not evident in the model fields which correlates well with land classification type. From these comparisons, it is

  17. Atmospheric chemistry of CF3C(O)O2 radicals. Kinetics of their reaction with NO2 and kinetics of the thermal decomposition of the product CF3C(O)O2NO2

    DEFF Research Database (Denmark)

    Wallington, T.J.; Sehested, J.; Nielsen, O.J.

    1994-01-01

    decomposition CF3C(O)O2NO2. The rate of decomposition of CF3C(O)O2NO2 was independent of the total pressure of N2 diluent over the range 100-700 Torr and was fit by the expression k-1 = (1.9(-1.5)+7.6) x 10(16) exp[(-14000 +/- 480)/T] s-1. Implications for the atmospheric chemistry of CFC replacements...

  18. Atmospheric chemistry of (CF3)2C=CH2: OH radicals, Cl atoms and O3 rate coefficients, oxidation end-products and IR spectra.

    Science.gov (United States)

    Papadimitriou, Vassileios C; Spitieri, Christina S; Papagiannakopoulos, Panos; Cazaunau, Mathieu; Lendar, Maria; Daële, Véronique; Mellouki, Abdelwahid

    2015-10-14

    The rate coefficients for the gas phase reactions of OH radicals, k1, Cl atoms, k2, and O3, k3, with 3,3,3-trifluoro-2(trifluoromethyl)-1-propene ((CF3)2C=CH2, hexafluoroisobutylene, HFIB) were determined at room temperature and atmospheric pressure employing the relative rate method and using two atmospheric simulation chambers and a static photochemical reactor. OH and Cl rate coefficients obtained by both techniques were indistinguishable, within experimental precision, and the average values were k1 = (7.82 ± 0.55) × 10(-13) cm(3) molecule(-1) s(-1) and k2 = (3.45 ± 0.24) × 10(-11) cm(3) molecule(-1) s(-1), respectively. The quoted uncertainties are at 95% level of confidence and include the estimated systematic uncertainties. An upper limit for the O3 rate coefficient was determined to be k3 < 9.0 × 10(-22) cm(3) molecule(-1) s(-1). In global warming potential (GWP) calculations, radiative efficiency (RE) was determined from the measured IR absorption cross-sections and treating HFIB both as long (LLC) and short (SLC) lived compounds, including estimated lifetime dependent factors in the SLC case. The HFIB lifetime was estimated from kinetic measurements considering merely the OH reaction, τOH = 14.8 days and including both OH and Cl chemistry, τeff = 10.3 days. Therefore, GWP(HFIB,OH) and GWP(HFIB,eff) were estimated to be 4.1 (LLC) and 0.6 (SLC), as well as 2.8 (LLC) and 0.3 (SLC) for a hundred year time horizon. Moreover, the estimated photochemical ozone creation potential (ε(POCP)) of HFIB was calculated to be 4.60. Finally, HCHO and (CF3)2C(O) were identified as final oxidation products in both OH- and Cl-initiated oxidation, while HC(O)Cl was additionally observed in the Cl-initiated oxidation.

  19. Organic composition of PM 2.5 and size-segregated aerosols and their sources during the 2002 Bay Regional Atmospheric Chemistry Experiment (BRACE), Florida, USA

    Science.gov (United States)

    Tremblay, Raphaël T.; Riemer, Daniel D.; Zika, Rod G.

    PM 2.5 and size-segregated aerosols were collected in May 2002 as part of the Bay Regional Atmospheric Chemistry Experiment (BRACE), Florida, USA. Aerosol organic composition was used to estimate sources of a series of alkanes and polycyclic aromatic hydrocarbons (PAHs) using chemical indices, hierarchical cluster analysis (HCA) and a chemical mass balance receptor model (CMB). Aerosols were collected on quartz fiber filters (QFF) using a PM 2.5 high volume sampler and on aluminum foil discs using a Micro-Orifice Uniform Deposit Impactor (MOUDI, 50% aerodynamic cut diameters were 18, 10, 5.6, 3.2, 1.8, 1.0, 0.56, 0.315 and 0.171 μm). Target compounds included alkanes and PAHs and were solvent extracted using a mixture of dichloromethane, acetone and hexane, concentrated and then analyzed using a gas chromatograph/mass spectrometer (GC/MS). The target compounds in PM 2.5 were dominated by six sources during the study period: mobile sources (39±5%), coal burning (33±5%), biogenic primary emission (20±2%), oil combustion (5±2%), biomass burning (1.0±0.3%) and an unidentified source (3±2%). Results obtained from the chemical indices, HCA and CMB were in very good agreement with each other. PAH size distributions are presented for days dominated by a same source. Seventy-five percent and 50% of the PAH were found below 1.8 and 0.56 μm, respectively (monthly PAH geometric diameters averaged 0.43 μm). Coarse size PAHs were observed on 1 day (15 May) and were correlated with nitrate and sodium size distribution. It is hypothesized that the PAHs, sodium and nitrate were internally mixed and that the PAHs deposited onto a pre-existing marine aerosol. This transfer process has significant implications for PAH deposition and lifetime and warrants further study.

  20. The effect of a strong stellar flare on the atmospheric chemistry of an earth-like planet orbiting an M dwarf.

    Science.gov (United States)

    Segura, Antígona; Walkowicz, Lucianne M; Meadows, Victoria; Kasting, James; Hawley, Suzanne

    2010-09-01

    Main sequence M stars pose an interesting problem for astrobiology: their abundance in our galaxy makes them likely targets in the hunt for habitable planets, but their strong chromospheric activity produces high-energy radiation and charged particles that may be detrimental to life. We studied the impact of the 1985 April 12 flare from the M dwarf AD Leonis (AD Leo), simulating the effects from both UV radiation and protons on the atmospheric chemistry of a hypothetical, Earth-like planet located within its habitable zone. Based on observations of solar proton events and the Neupert effect, we estimated a proton flux associated with the flare of 5.9 × 10⁸ protons cm⁻² sr⁻¹ s⁻¹ for particles with energies >10 MeV. Then we calculated the abundance of nitrogen oxides produced by the flare by scaling the production of these compounds during a large solar proton event called the Carrington event. The simulations were performed with a 1-D photochemical model coupled to a 1-D radiative/convective model. Our results indicate that the UV radiation emitted during the flare does not produce a significant change in the ozone column depth of the planet. When the action of protons is included, the ozone depletion reaches a maximum of 94% two years after the flare for a planet with no magnetic field. At the peak of the flare, the calculated UV fluxes that reach the surface, in the wavelength ranges that are damaging for life, exceed those received on Earth during less than 100 s. Therefore, flares may not present a direct hazard for life on the surface of an orbiting habitable planet. Given that AD Leo is one of the most magnetically active M dwarfs known, this conclusion should apply to planets around other M dwarfs with lower levels of chromospheric activity.

  1. Extreme events in total ozone over Arosa – Part 2: Fingerprints of atmospheric dynamics and chemistry and effects on mean values and long-term changes

    Directory of Open Access Journals (Sweden)

    H. E. Rieder

    2010-10-01

    Full Text Available In this study the frequency of days with extreme low (termed ELOs and extreme high (termed EHOs total ozone values and their influence on mean values and trends are analyzed for the world's longest total ozone record (Arosa, Switzerland. The results show (i an increase in ELOs and (ii a decrease in EHOs during the last decades and (iii that the overall trend during the 1970s and 1980s in total ozone is strongly dominated by changes in these extreme events. After removing the extremes, the time series shows a strongly reduced trend (reduction by a factor of 2.5 for trend in annual mean. Excursions in the frequency of extreme events reveal "fingerprints" of dynamical factors such as ENSO or NAO, and chemical factors, such as cold Arctic vortex ozone losses, as well as major volcanic eruptions of the 20th century (Gunung Agung, El Chichón, Mt. Pinatubo. Furthermore, atmospheric loading of ozone depleting substances leads to a continuous modification of column ozone in the Northern Hemisphere also with respect to extreme values (partly again in connection with polar vortex contributions. Application of extreme value theory allows the identification of many more such "fingerprints" than conventional time series analysis of annual and seasonal mean values. The analysis shows in particular the strong influence of dynamics, revealing that even moderate ENSO and NAO events have a discernible effect on total ozone. Overall the approach to extremal modelling provides new information on time series properties, variability, trends and the influence of dynamics and chemistry, complementing earlier analyses focusing only on monthly (or annual mean values.

  2. Ozone uptake on glassy, semi-solid and liquid organic matter and the role of reactive oxygen intermediates in atmospheric aerosol chemistry.

    Science.gov (United States)

    Berkemeier, Thomas; Steimer, Sarah S; Krieger, Ulrich K; Peter, Thomas; Pöschl, Ulrich; Ammann, Markus; Shiraiwa, Manabu

    2016-05-14

    Heterogeneous and multiphase reactions of ozone are important pathways for chemical ageing of atmospheric organic aerosols. To demonstrate and quantify how moisture-induced phase changes can affect the gas uptake and chemical transformation of organic matter, we apply a kinetic multi-layer model to a comprehensive experimental data set of ozone uptake by shikimic acid. The bulk diffusion coefficients were determined to be 10(-12) cm(2) s(-1) for ozone and 10(-20) cm(2) s(-1) for shikimic acid under dry conditions, increasing by several orders of magnitude with increasing relative humidity (RH) due to phase changes from amorphous solid over semisolid to liquid. Consequently, the reactive uptake of ozone progresses through different kinetic regimes characterised by specific limiting processes and parameters. At high RH, ozone uptake is driven by reaction throughout the particle bulk; at low RH it is restricted to reaction near the particle surface and kinetically limited by slow diffusion and replenishment of unreacted organic molecules. Our results suggest that the chemical reaction mechanism involves long-lived reactive oxygen intermediates, likely primary ozonides or O atoms, which may provide a pathway for self-reaction and catalytic destruction of ozone at the surface. Slow diffusion and ozone destruction can effectively shield reactive organic molecules in the particle bulk from degradation. We discuss the potential non-orthogonality of kinetic parameters, and show how this problem can be solved by using comprehensive experimental data sets to constrain the kinetic model, providing mechanistic insights into the coupling of transport, phase changes, and chemical reactions of multiple species in complex systems.

  3. Heterogeneous chemistry related to Antarctic ozone depletion: Reaction of ClONO2 and N2O5 on ice surfaces

    Science.gov (United States)

    Tolbert, Margaret A.; Rossi, Michel J.; Golden, David M.

    1988-01-01

    Laboratory studies of heterogeneous reactions of possible importance for Antarctic ozone depletion were performed. In particular, the reactions of chlorine nitrate (ClONO2) and dinitrogen pentoxide (N2O5) were investigated on ice and HCl/ice surfaces. These reactions occur on the surfaces of polar stratospheric clouds (PSCs) over Antarctica. One reaction transforms the stable chlorine reservoir species (ClONO2 and HCl) into photochemically active chlorine in the form of HOCl and Cl2. Condensation of HNO3 in the reactions removes odd nitrogen from the stratosphere, a requirement in nearly all models of Antarctic ozone depletion. Other reactions may also be important for Antarctic ozone depletion. Like the reactions of chlorine nitrate, these reactions deplete odd nitrogen through HNO3 condensation. In addition, one reaction converts a stable chlorine reservior species (HCl) into photochemically active chlorine (ClNO2). These reactions were studied with a modified version of a Knudsen cell flow reactor.

  4. Impact of surface chemistry

    Science.gov (United States)

    Somorjai, Gabor A.; Li, Yimin

    2011-01-01

    The applications of molecular surface chemistry in heterogeneous catalyst technology, semiconductor-based technology, medical technology, anticorrosion and lubricant technology, and nanotechnology are highlighted in this perspective. The evolution of surface chemistry at the molecular level is reviewed, and the key roles of surface instrumentation developments for in situ studies of the gas–solid, liquid–solid, and solid–solid interfaces under reaction conditions are emphasized. PMID:20880833

  5. NASA Data Evaluation (2015): Chemical Kinetics and Photochemical Data for Use in Atmospheric Studies

    Science.gov (United States)

    Burkholder, J. B.; Sander, S. P.; Abbatt, J.; Barker, J. R.; Huie, R. E.; Kolb, C. E., Jr.; Kurylo, M. J., III; Orkin, V. L.; Wilmouth, D. M.; Wine, P. H.

    2015-12-01

    Atmospheric chemistry models must include a large number of processes to accurately describe the temporal and spatial behavior of atmospheric composition. They require a wide range of chemical and physical data (parameters) that describe elementary gas-phase and heterogeneous processes. The review and evaluation of chemical and physical data has, therefore, played an important role in the development of chemical models and in their use in environmental assessment activities. The NASA data panel evaluation has a broad atmospheric focus that includes Ox, O(1D), singlet O2, HOx, NOx, Organic, FOx, ClOx, BrOx, IOx, SOx, and Na reactions, three-body reactions, equilibrium constants, photochemistry, Henry's Law coefficients, aqueous chemistry, heterogeneous chemistry and processes, and thermodynamic parameters. The 2015 evaluation includes critical coverage of ~700 bimolecular reactions, 86 three-body reactions, 33 equilibrium constants, ~220 photochemical species, ~360 aqueous and heterogeneous processes, and thermodynamic parameters for ~800 species with over 5000 literature citations reviewed. Each evaluation includes (1) recommended values (e.g. rate coefficients, absorption cross sections, solubilities, and uptake coefficients) with estimated uncertainty factors and (2) a note describing the available experimental and theoretical data and an explanation for the recommendation. This presentation highlights some of the recent additions to the evaluation that include: (1) expansion of thermochemical parameters, including Hg species, (2) CH2OO (Criegee) chemistry, (3) Isoprene and its major degradation product chemistry, (4) halocarbon chemistry, (5) Henry's law solubility data, and (6) uptake coefficients. In addition, a listing of complete references with the evaluation notes has been implemented. Users of the data evaluation are encouraged to suggest potential improvements and ways that the evaluation can better serve the atmospheric chemistry community.

  6. Air Composition and Chemistry

    Science.gov (United States)

    Brimblecombe, Peter

    1996-01-01

    This book is about the atmosphere and humanity's influence on it. For this new edition, Brimblecombe has rewritten and updated much of the book. In the early chapters, he discusses the geochemical, biological and maritime sources of the trace gases. Next, he examines the chemistry of atmospheric gases, suspended particles, and rainfall. After dealing with the natural atmosphere, he examines the sources of air pollution and its effects, with all scenarios updated from the last edition. Scenarios include decline in health, damage to plants and animals, indoor pollution, and acid rain. The final chapters, also revised, are concerned with the chemistry and evolution of the atmospheres of the planets of the solar system. Students with an interest in chemistry and the environmental sciences will find this book highly valuable.

  7. Preindustrial to Present-Day Changes in Tropospheric Hydroxyl Radical and Methane Lifetime from the Atmospheric Chemistry and Climate Model Intercomparison Project (ACCMIP)

    Science.gov (United States)

    Naik, V.; Voulgarakis, A.; Fiore, A. M.; Horowitz, L. W.; Lamarque, J.-F.; Lin, M.; Prather, M. J.; Young, P. J.; Bergmann, D.; Cameron-Smith, P. J.; hide

    2013-01-01

    We have analysed time-slice simulations from 17 global models, participating in the Atmospheric Chemistry and Climate Model Intercomparison Project (ACCMIP), to explore changes in present-day (2000) hydroxyl radical (OH) concentration and methane (CH4) lifetime relative to preindustrial times (1850) and to 1980. A comparison of modeled and observation-derived methane and methyl chloroform lifetimes suggests that the present-day global multi-model mean OH concentration is overestimated by 5 to 10% but is within the range of uncertainties. The models consistently simulate higher OH concentrations in the Northern Hemisphere (NH) compared with the Southern Hemisphere (SH) for the present-day (2000; inter-hemispheric ratios of 1.13 to 1.42), in contrast to observation-based approaches which generally indicate higher OH in the SH although uncertainties are large. Evaluation of simulated carbon monoxide (CO) concentrations, the primary sink for OH, against ground-based and satellite observations suggests low biases in the NH that may contribute to the high north–south OH asymmetry in the models. The models vary widely in their regional distribution of present-day OH concentrations (up to 34%). Despite large regional changes, the multi-model global mean (mass-weighted) OH concentration changes little over the past 150 yr, due to concurrent increases in factors that enhance OH (humidity, tropospheric ozone, nitrogen oxide (NOx) emissions, and UV radiation due to decreases in stratospheric ozone), compensated by increases in OH sinks (methane abundance, carbon monoxide and non-methane volatile organic carbon (NMVOC) emissions). The large inter-model diversity in the sign and magnitude of preindustrial to present-day OH changes (ranging from a decrease of 12.7% to an increase of 14.6%) indicate that uncertainty remains in our understanding of the long-term trends in OH and methane lifetime. We show that this diversity is largely explained by the different ratio of the

  8. Preindustrial to present-day changes in tropospheric hydroxyl radical and methane lifetime from the Atmospheric Chemistry and Climate Model Intercomparison Project (ACCMIP

    Directory of Open Access Journals (Sweden)

    V. Naik

    2013-05-01

    Full Text Available We have analysed time-slice simulations from 17 global models, participating in the Atmospheric Chemistry and Climate Model Intercomparison Project (ACCMIP, to explore changes in present-day (2000 hydroxyl radical (OH concentration and methane (CH4 lifetime relative to preindustrial times (1850 and to 1980. A comparison of modeled and observation-derived methane and methyl chloroform lifetimes suggests that the present-day global multi-model mean OH concentration is overestimated by 5 to 10% but is within the range of uncertainties. The models consistently simulate higher OH concentrations in the Northern Hemisphere (NH compared with the Southern Hemisphere (SH for the present-day (2000; inter-hemispheric ratios of 1.13 to 1.42, in contrast to observation-based approaches which generally indicate higher OH in the SH although uncertainties are large. Evaluation of simulated carbon monoxide (CO concentrations, the primary sink for OH, against ground-based and satellite observations suggests low biases in the NH that may contribute to the high north–south OH asymmetry in the models. The models vary widely in their regional distribution of present-day OH concentrations (up to 34%. Despite large regional changes, the multi-model global mean (mass-weighted OH concentration changes little over the past 150 yr, due to concurrent increases in factors that enhance OH (humidity, tropospheric ozone, nitrogen oxide (NOx emissions, and UV radiation due to decreases in stratospheric ozone, compensated by increases in OH sinks (methane abundance, carbon monoxide and non-methane volatile organic carbon (NMVOC emissions. The large inter-model diversity in the sign and magnitude of preindustrial to present-day OH changes (ranging from a decrease of 12.7% to an increase of 14.6% indicate that uncertainty remains in our understanding of the long-term trends in OH and methane lifetime. We show that this diversity is largely explained by the different ratio of the

  9. Isoprene and monoterpene fluxes from Central Amazonian rainforest inferred from tower-based and airborne measurements, and implications on the atmospheric chemistry and the local carbon budget

    Directory of Open Access Journals (Sweden)

    U. Kuhn

    2007-06-01

    Full Text Available We estimated the isoprene and monoterpene source strengths of a pristine tropical forest north of Manaus in the central Amazon Basin using three different micrometeorological flux measurement approaches. During the early dry season campaign of the Cooperative LBA Airborne Regional Experiment (LBA-CLAIRE-2001, a tower-based surface layer gradient (SLG technique was applied simultaneously with a relaxed eddy accumulation (REA system. Airborne measurements of vertical profiles within and above the convective boundary layer (CBL were used to estimate fluxes on a landscape scale by application of the mixed layer gradient (MLG technique. The mean daytime fluxes of organic carbon measured by REA were 2.1 mg C m−2 h−1 for isoprene, 0.20 mg C m−2 h−1 for α-pinene, and 0.39 mg C m−2 h−1 for the sum of monoterpenes. These values are in reasonable agreement with fluxes determined with the SLG approach, which exhibited a higher scatter, as expected for the complex terrain investigated. The observed VOC fluxes are in good agreement with simulations using a single-column chemistry and climate model (SCM.

    In contrast, the model-derived mixing ratios of VOCs were by far higher than observed, indicating that chemical processes may not be adequately represented in the model. The observed vertical gradients of isoprene and its primary degradation products methyl vinyl ketone (MVK and methacrolein (MACR suggest that the oxidation capacity in the tropical CBL is much higher than previously assumed. A simple chemical kinetics model was used to infer OH radical concentrations from the vertical gradients of (MVK+MACR/isoprene. The estimated range of OH concentrations during the daytime was 3–8×106 molecules cm−3, i.e., an order of magnitude higher than is estimated for the tropical CBL by current state-of-the-art atmospheric chemistry and transport models

  10. Taming Prebiotic Chemistry: The Role of Heterogeneous and Interfacial Catalysis in the Emergence of a Prebiotic Catalytic/Information Polymer System.

    Science.gov (United States)

    Monnard, Pierre-Alain

    2016-11-04

    Cellular life is based on interacting polymer networks that serve as catalysts, genetic information and structural molecules. The complexity of the DNA, RNA and protein biochemistry suggests that it must have been preceded by simpler systems. The RNA world hypothesis proposes RNA as the prime candidate for such a primal system. Even though this proposition has gained currency, its investigations have highlighted several challenges with respect to bulk aqueous media: (1) the synthesis of RNA monomers is difficult; (2) efficient pathways for monomer polymerization into functional RNAs and their subsequent, sequence-specific replication remain elusive; and (3) the evolution of the RNA function towards cellular metabolism in isolation is questionable in view of the chemical mixtures expected on the early Earth. This review will address the question of the possible roles of heterogeneous media and catalysis as drivers for the emergence of RNA-based polymer networks. We will show that this approach to non-enzymatic polymerizations of RNA from monomers and RNA evolution cannot only solve some issues encountered during reactions in bulk aqueous solutions, but may also explain the co-emergence of the various polymers indispensable for life in complex mixtures and their organization into primitive networks.

  11. Pre-industrial to End 21st Century Projections of Tropospheric Ozone from the Atmospheric Chemistry and Climate Model Intercomparison Project (ACCMIP)

    Science.gov (United States)

    Young, P. J.; Archibald, A. T.; Bowman, K. W.; Lamarque, J.-F.; Naik, V.; Stevenson, D. S.; Tilmes, S.; Voulgarakis, A.; Wild, O.; Bergmann, D.; hide

    2013-01-01

    Present day tropospheric ozone and its changes between 1850 and 2100 are considered, analysing 15 global models that participated in the Atmospheric Chemistry and Climate Model Intercomparison Project (ACCMIP). The ensemble mean compares well against present day observations. The seasonal cycle correlates well, except for some locations in the tropical upper troposphere. Most (75 %) of the models are encompassed with a range of global mean tropospheric ozone column estimates from satellite data, but there is a suggestion of a high bias in the Northern Hemisphere and a low bias in the Southern Hemisphere, which could indicate deficiencies with the ozone precursor emissions. Compared to the present day ensemble mean tropospheric ozone burden of 337+/-23 Tg, the ensemble mean burden for 1850 time slice is approx. 30% lower. Future changes were modelled using emissions and climate projections from four Representative Concentration Pathways (RCPs). Compared to 2000, the relative changes in the ensemble mean tropospheric ozone burden in 2030 (2100) for the different RCPs are: -4% (-16 %) for RCP2.6, 2% (-7%) for RCP4.5, 1% (-9%) for RCP6.0, and 7% (18 %) for RCP8.5. Model agreement on the magnitude of the change is greatest for larger changes. Reductions in most precursor emissions are common across the RCPs and drive ozone decreases in all but RCP8.5, where doubled methane and a 40-150% greater stratospheric influx (estimated from a subset of models) increase ozone. While models with a high ozone burden for the present day also have high ozone burdens for the other time slices, no model consistently predicts large or small ozone changes; i.e. the magnitudes of the burdens and burden changes do not appear to be related simply, and the models are sensitive to emissions and climate changes in different ways. Spatial patterns of ozone changes are well correlated across most models, but are notably different for models without time evolving stratospheric ozone concentrations

  12. Validation of HNO3, ClONO2, and N2O5 from the Atmospheric Chemistry Experiment Fourier Transform Spectrometer (ACE-FTS

    Directory of Open Access Journals (Sweden)

    P. Raspollini

    2008-07-01

    Full Text Available The Atmospheric Chemistry Experiment (ACE satellite was launched on 12 August 2003. Its two instruments measure vertical profiles of over 30 atmospheric trace gases by analyzing solar occultation spectra in the ultraviolet/visible and infrared wavelength regions. The reservoir gases HNO3, ClONO2, and N2O5 are three of the key species provided by the primary instrument, the ACE Fourier Transform Spectrometer (ACE-FTS. This paper describes the ACE-FTS version 2.2 data products, including the N2O5 update, for the three species and presents validation comparisons with available observations. We have compared volume mixing ratio (VMR profiles of HNO3, ClONO2, and N2O5 with measurements by other satellite instruments (SMR, MLS, MIPAS, aircraft measurements (ASUR, and single balloon-flights (SPIRALE, FIRS-2. Partial columns of HNO3 and ClONO2 were also compared with measurements by ground-based Fourier Transform Infrared (FTIR spectrometers. Overall the quality of the ACE-FTS v2.2 HNO3 VMR profiles is good from 18 to 35 km. For the statistical satellite comparisons, the mean absolute differences are generally within ±1 ppbv ±20% from 18 to 35 km. For MIPAS and MLS comparisons only, mean relative differences lie within±10% between 10 and 36 km. ACE-FTS HNO3 partial columns (~15–30 km show a slight negative bias of −1.3% relative to the ground-based FTIRs at latitudes ranging from 77.8° S–76.5° N. Good agreement between ACE-FTS ClONO2 and MIPAS, using the Institut für Meteorologie und Klimaforschung and Instituto de Astrofísica de Andalucía (IMK-IAA data processor is seen. Mean absolute differences are typically within ±0.01 ppbv between 16 and 27 km and less than +0.09 ppbv between 27 and 34 km. The ClONO2 partial column comparisons show varying degrees of agreement, depending on the location and the quality of the FTIR measurements. Good agreement was found for the comparisons with the midlatitude Jungfraujoch partial columns for which

  13. Tropospheric Halogen Chemistry

    Science.gov (United States)

    von Glasow, R.; Crutzen, P. J.

    2003-12-01

    processes. Early work by Cauer (1951) had shown that Cl/Na and Cl/Mg ratios were lower in air than in seawater, indicating loss of chlorine by "acid displacement" from sea salt by the strong acids, H2SO4 (Eriksson (1959a, b) and HNO3 (Robbins et al., 1959). Already the first measurements of bromine in aerosols by Duce et al. (1963) showed that bromine, like chlorine, was lost from the sea salt particles, whereas iodine was strongly enriched ( Duce et al., 1965). Research since the early 1980s has shown that photochemical processes are actively involved.Interest in the chemistry of atmospheric halogens took a steep upward surge after it was postulated that the release of industrially produced halocarbons, in particular the chlorofluorocarbons (CFCs), CFCl3, and CF2Cl2, could cause severe depletions in stratospheric ozone (Molina and Rowland, 1974) by the reactions involving the CFC photolytic product radicals, Cl and ClO, as catalysts. The first stratospheric measurements of ClO did indeed show its presence in significant quantities in the stratosphere so that by the end of the 1970s USA, Canada, and the Scandinavian countries issued laws against the use of CFC gases as propellants in spray cans. In the mid-1980s the springtime stratospheric ozone hole over Antarctica was discovered by Farman et al. (1985), involving heterogeneous reactions on polar stratospheric clouds that lead to chlorine activation ( Solomon et al., 1986). Ten years later, in 1996, a complete phaseout ofthe production of the CFCs and a number of other chlorine- or bromine-containing chemicals came into effect for all nations in the developed world. In this contribution we will, however, concentrate on the impact of reactive chlorine, bromine, and iodine on tropospheric ozone chemistry.Halogens have the potential to be important in many facets of tropospheric chemistry. A multitude of gas phase reactions and gas-particle interactions occur that include coupling with the sulfur cycle and reactions with

  14. Laser-pulsed Plasma Chemistry: Laser-initiated Plasma Oxidation Of Niobium

    OpenAIRE

    Marks R.F.; Pollak R.A.; Avouris Ph.; Lin C.T.; Thefaine Y.J.

    1983-01-01

    We report the first observation of the chemical modification of a solid surface exposed to an ambient gas plasma initiated by the interaction of laser radiation with the same surface. A new technique, which we designate laser-pulsed plasma chemistry (LPPC), is proposed for activating heterogeneous chemical reactions at solid surfaces in a gaseous ambient by means of a plasma initiated by laser radiation. Results for niobium metal in one atmosphere oxygen demonstrate single-pulse, self-limitin...

  15. Dimethylsulfide Chemistry: Annual, Seasonal, and Spatial Impacts on Sulfate

    Science.gov (United States)

    We incorporated oceanic emissions and atmospheric chemistry of dimethylsulfide (DMS) into the hemispheric Community Multiscale Air Quality model and performed annual model simulations without and with DMS chemistry. The model without DMS chemistry predicts higher concentrations o...

  16. Evaluation of preindustrial to present-day black carbon and its albedo forcing from Atmospheric Chemistry and Climate Model Intercomparison Project (ACCMIP

    Directory of Open Access Journals (Sweden)

    Y. H. Lee

    2013-03-01

    Full Text Available As part of the Atmospheric Chemistry and Climate Model Intercomparison Project (ACCMIP, we evaluate the historical black carbon (BC aerosols simulated by 8 ACCMIP models against observations including 12 ice core records, long-term surface mass concentrations, and recent Arctic BC snowpack measurements. We also estimate BC albedo forcing by performing additional simulations using offline models with prescribed meteorology from 1996–2000. We evaluate the vertical profile of BC snow concentrations from these offline simulations using the recent BC snowpack measurements. Despite using the same BC emissions, the global BC burden differs by approximately a factor of 3 among models due to differences in aerosol removal parameterizations and simulated meteorology: 34 Gg to 103 Gg in 1850 and 82 Gg to 315 Gg in 2000. However, the global BC burden from preindustrial to present-day increases by 2.5–3 times with little variation among models, roughly matching the 2.5-fold increase in total BC emissions during the same period. We find a large divergence among models at both Northern Hemisphere (NH and Southern Hemisphere (SH high latitude regions for BC burden and at SH high latitude regions for deposition fluxes. The ACCMIP simulations match the observed BC surface mass concentrations well in Europe and North America except at Ispra. However, the models fail to predict the Arctic BC seasonality due to severe underestimations during winter and spring. The simulated vertically resolved BC snow concentrations are, on average, within a factor of 2–3 of the BC snowpack measurements except for Greenland and the Arctic Ocean. For the ice core evaluation, models tend to adequately capture both the observed temporal trends and the magnitudes at Greenland sites. However, models fail to predict the decreasing trend of BC depositions/ice core concentrations from the 1950s to the 1970s in most Tibetan Plateau ice cores. The distinct temporal trend at the Tibetan

  17. Evaluation of preindustrial to present-day black carbon and its albedo forcing from Atmospheric Chemistry and Climate Model Intercomparison Project (ACCMIP)

    Science.gov (United States)

    Lee, Y. H.; Lamarque, J.-F.; Flanner, M. G.; Jiao, C.; Shindell, D. T.; Bernsten, T.; Bisiaux, M. M.; Cao, J.; Collins, W. J.; Curran, M.; hide

    2013-01-01

    As part of the Atmospheric Chemistry and Climate Model Intercomparison Project (ACCMIP), we evaluate the historical black carbon (BC) aerosols simulated by 8 ACCMIP models against observations including 12 ice core records, long-term surface mass concentrations, and recent Arctic BC snowpack measurements. We also estimate BC albedo forcing by performing additional simulations using offline models with prescribed meteorology from 1996-2000. We evaluate the vertical profile of BC snow concentrations from these offline simulations using the recent BC snowpack measurements. Despite using the same BC emissions, the global BC burden differs by approximately a factor of 3 among models due to differences in aerosol removal parameterizations and simulated meteorology: 34 Gg to 103 Gg in 1850 and 82 Gg to 315 Gg in 2000. However, the global BC burden from preindustrial to present-day increases by 2.5-3 times with little variation among models, roughly matching the 2.5-fold increase in total BC emissions during the same period.We find a large divergence among models at both Northern Hemisphere (NH) and Southern Hemisphere (SH) high latitude regions for BC burden and at SH high latitude regions for deposition fluxes. The ACCMIP simulations match the observed BC surface mass concentrations well in Europe and North America except at Ispra. However, the models fail to predict the Arctic BC seasonality due to severe underestimations during winter and spring. The simulated vertically resolved BC snow concentrations are, on average, within a factor of 2-3 of the BC snowpack measurements except for Greenland and the Arctic Ocean. For the ice core evaluation, models tend to adequately capture both the observed temporal trends and the magnitudes at Greenland sites. However, models fail to predict the decreasing trend of BC depositions/ice core concentrations from the 1950s to the 1970s in most Tibetan Plateau ice cores. The distinct temporal trend at the Tibetan Plateau ice cores

  18. Bad chemistry

    OpenAIRE

    Petsko, Gregory A

    2004-01-01

    General chemistry courses haven't changed significantly in forty years. Because most basic chemistry students are premedical students, medical schools have enormous influence and could help us start all over again to create undergraduate chemistry education that works.

  19. Gas phase ion chemistry

    CERN Document Server

    Bowers, Michael T

    1979-01-01

    Gas Phase Ion Chemistry, Volume 1 covers papers on the advances of gas phase ion chemistry. The book discusses the advances in flow tubes and the measurement of ion-molecule rate coefficients and product distributions; the ion chemistry of the earth's atmosphere; and the classical ion-molecule collision theory. The text also describes statistical methods in reaction dynamics; the state selection by photoion-photoelectron coincidence; and the effects of temperature and pressure in the kinetics of ion-molecule reactions. The energy distribution in the unimolecular decomposition of ions, as well

  20. Coupling between the JULES land-surface scheme and the CCATT-BRAMS atmospheric chemistry model (JULES-CCATT-BRAMS1.0: applications to numerical weather forecasting and the CO2 budget in South America

    Directory of Open Access Journals (Sweden)

    D. S. Moreira

    2013-08-01

    Full Text Available This article presents the coupling of the JULES surface model to the CCATT-BRAMS atmospheric chemistry model. This new numerical system is denominated JULES-CCATT-BRAMS. We demonstrate the performance of this new model system in relation to several meteorological variables and the CO2 mixing ratio over a large part of South America, focusing on the Amazon basin. The evaluation was conducted for two time periods, the wet (March and dry (September seasons of 2010. The model errors were calculated in relation to meteorological observations at conventional stations in airports and automatic stations. In addition, CO2 mixing ratios in the first model level were compared with meteorological tower measurements and vertical CO2 profiles were compared with observations obtained with airborne instruments. The results of this study show that the JULES-CCATT-BRAMS modeling system provided a significant gain in performance for the considered atmospheric fields relative to those simulated by the LEAF (version 3 surface model originally employed by CCATT-BRAMS. In addition, the new system significantly increases the ability to simulate processes involving air–surface interactions, due to the ability of JULES to simulate photosynthesis, respiration and dynamic vegetation, among other processes. We also discuss a wide range of numerical studies involving coupled atmospheric, land surface and chemistry processes that could be done with the system introduced here. Thus, this work presents to the scientific community a free modeling tool, with good performance in comparison with observational data and reanalysis model data, at least for the region and time period discussed here. Therefore, in principle, this model is able to produce atmospheric hindcast/forecast simulations at different spatial resolutions for any time period and any region of the globe.

  1. Differential effects of high atmospheric N and S deposition on bog plant/lichen tissue and porewater chemistry across the Athabasca Oil Sands Region

    Science.gov (United States)

    R. Kelman Wieder; Melanie A. Vile; Kimberli D. Scott; Cara M. Albright; Kelly J. McMillen; Dale H. Vitt; Mark E. Fenn

    2016-01-01

    Oil extraction and development activities in the Athabasca Oil Sands Region of northern Alberta, Canada, release NOx, SOx, and NHy to the atmosphere, ultimately resulting in increasing N and S inputs to surrounding ecosystems through atmospheric deposition. Peatlands are a major feature of the northern Alberta landscape, with bogs covering 6-10% of the land area, and...

  2. The influence of chemistry, production and community composition under elevated atmospheric CO2 and tropospheric O3 in a northern hardwood ecosystem

    Science.gov (United States)

    Lingli Liu; John S. King; Christian P. Giardina; Fitzgerald L. Booker

    2009-01-01

    We examined the effects of elevated CO2 and O3 and their interaction on leaf litter chemistry and decomposition in pure stands of aspen (Populus tremuloides) and mixed stands of birch (Betula papyrifera) and aspen at the Aspen Free Air CO2 Enrichment (FACE) experiment. A 935-day in situ incubation...

  3. Heterogeneous Ozonolysis of Surface Adsorbed Lignin Pyrolysis Products

    Science.gov (United States)

    Hinrichs, R. Z.

    2012-12-01

    Biomass combustion releases semi-volatile organic compounds into the troposphere, including many phenols and methoxyphenols as the result of lignin pyrolysis. Given their relatively low vapor pressures, these compounds readily adsorb on inorganic and organic aerosol substrates where they may alter aerosol properties and undergo heterogeneous chemistry. We use infrared spectroscopy (DRIFTS and ATR-FTIR) to monitor the adsorption and subsequent heterogeneous ozonolysis of model lignin pyrolysis products, including catechol, eugenol, and 4-propylguaiacol. Ozonolysis reaction kinetics were compared on various inorganic substrates - such as Al2O3 and NaCl, which serve as mineral and sea salt aerosol substrates, respectively - and as a function of ozone concentration and relative humidity. Following in situ FTIR analysis, the adsorbed organics were extracted and analyzed using gas chromatography-mass spectroscopy to identify reaction products and quantify product branching ratios. Ozonolysis of catechol and 4-propylguaiacol readily resulted in ring cleavage forming dicarboxylic acids (e.g., muconic acid). Eugenol ozonolysis proceeded rapidly at the alkene side chain producing homovanillic acid and homovanillin in an approximate 2:1 branching ratio at 0% RH; ring cleavage was also observed. For all lignin pyrolysis products, heterogeneous ozonolysis was faster on NaCl versus Al2O3. Implications for the atmospheric chemistry of semi-volatile methoxylphenols adsorbed on aerosol substrates will be discussed.

  4. EPA Contribution to Manuscript "Evaluation and Error Apportionment of an Ensemble of Atmospheric Chemistry Transport Modelling Systems: Multi-variable Temporal and Spatial Breakdown"

    Data.gov (United States)

    U.S. Environmental Protection Agency — This dataset contains the data contributed by EPA/ORD/NERL/CED researchers to the manuscript "Evaluation and Error Apportionment of an Ensemble of Atmospheric...

  5. The potential importance of non-local, deep transport on the energetics, momentum, chemistry, and aerosol distributions in the atmospheres of Earth, Mars, and Titan

    Science.gov (United States)

    Rafkin, Scot C. R.

    2012-01-01

    A review of non-local, deep transport mechanisms in the atmosphere of Earth provides a good foundation for examining whether similar mechanisms are operating in the atmospheres of Mars and Titan. On Earth, deep convective clouds in the tropics constitute the upward branch of the Hadley Cell and provide a conduit through which energy, moisture, momentum, aerosols, and chemical species are moved from the boundary layer to the upper troposphere and lower stratosphere. This transport produces mid-tropospheric minima in quantities such as water vapor and moist static energy and maxima where the clouds detrain. Analogs to this terrestrial transport are found in the strong and deep thermal circulations associated with topography on Mars and with Mars dust storms. Observations of elevated dust layers on Mars further support the notion that non-local deep transport is an important mechanism in the atmosphere of Mars. On Titan, the presence of deep convective clouds almost assures that non-local, deep transport is occurring and these clouds may play a role in global cycling of energy, momentum, and methane. Based on the potential importance of non-local deep transport in Earth's atmosphere and supported by evidence for such transport in the atmospheres of Mars and Titan, greater attention to this mechanism in extraterrestrial atmospheres is warranted.

  6. Organic chemistry on Titan

    Science.gov (United States)

    Chang, S.; Scattergood, T.; Aronowitz, S.; Flores, J.

    1979-01-01

    Features taken from various models of Titan's atmosphere are combined in a working composite model that provides environmental constraints within which different pathways for organic chemical synthesis are determined. Experimental results and theoretical modeling suggest that the organic chemistry of the satellite is dominated by two processes: photochemistry and energetic particle bombardment. Photochemical reactions of CH4 in the upper atmosphere can account for the presence of C2 hydrocarbons. Reactions initiated at various levels of the atmosphere by cosmic rays, Saturn 'wind', and solar wind particle bombardment of a CH4-N2 atmospheric mixture can account for the UV-visible absorbing stratospheric haze, the reddish appearance of the satellite, and some of the C2 hydrocarbons. In the lower atmosphere photochemical processes will be important if surface temperatures are sufficiently high for gaseous NH3 to exist. It is concluded that the surface of Titan may contain ancient or recent organic matter (or both) produced in the atmosphere.

  7. Atmospheric thermodynamics

    CERN Document Server

    Iribarne, J V

    1973-01-01

    The thermodynamics of the atmosphere is the subject of several chapters in most textbooks on dynamic meteorology, but there is no work in English to give the subject a specific and more extensive treatment. In writing the present textbook, we have tried to fill this rather remarkable gap in the literature related to atmospheric sciences. Our aim has been to provide students of meteorology with a book that can playa role similar to the textbooks on chemical thermodynamics for the chemists. This implies a previous knowledge of general thermodynamics, such as students acquire in general physics courses; therefore, although the basic principles are reviewed (in the first four chapters), they are only briefly discussed, and emphasis is laid on those topics that will be useful in later chapters, through their application to atmospheric problems. No attempt has been made to introduce the thermodynamics of irreversible processes; on the other hand, consideration of heterogeneous and open homogeneous systems permits a...

  8. Molecular Mechanism of Heterogeneous Catalysis

    Indian Academy of Sciences (India)

    Home; Journals; Resonance – Journal of Science Education; Volume 13; Issue 6. Molecular Mechanism of Heterogeneous Catalysis - The 2007 Nobel Prize in Chemistry. R S Swathi K L Sebastian. General Article Volume 13 Issue 6 June 2008 pp 548-560 ...

  9. Colour chemistry in water

    OpenAIRE

    Cardona, Maria

    2015-01-01

    Atmospheric carbon dioxide (CO2) levels have increased dramatically in the last few decades. Famous for causing global warming, CO2 is also resulting in the acidification of seas and oceans. http://www.um.edu.mt/think/colour-chemistry-in-water/

  10. Chemistry in aircraft plumes

    Energy Technology Data Exchange (ETDEWEB)

    Kraabol, A.G.; Stordal, F.; Knudsen, S. [Norwegian Inst. for Air Research, Kjeller (Norway); Konopka, P. [Deutsche Forschungsanstalt fuer Luft- und Raumfahrt e.V. (DLR), Wessling (Germany). Inst. fuer Physik der Atmosphaere

    1997-12-31

    An expanding plume model with chemistry has been used to study the chemical conversion of NO{sub x} to reservoir species in aircraft plumes. The heterogeneous conversion of N{sub 2}O{sub 5} to HNO{sub 3}(s) has been investigated when the emissions take place during night-time. The plume from an B747 has been simulated. During a ten-hour calculation the most important reservoir species was HNO{sub 3} for emissions at noon. The heterogeneous reactions had little impact on the chemical loss of NO{sub x} to reservoir species for emissions at night. (author) 4 refs.

  11. Impact of Gobi desert dust on aerosol chemistry of Xi'an, inland China during spring 2009: differences in composition and size distribution between the urban ground surface and the mountain atmosphere

    Directory of Open Access Journals (Sweden)

    G. H. Wang

    2013-01-01

    Full Text Available Composition and size distribution of atmospheric aerosols from Xi'an city (~400 m, altitude in inland China during the spring of 2009 including a massive dust event on 24 April were measured and compared with a parallel measurement at the summit (2060 m, altitude of Mt. Hua, an alpine site nearby Xi'an. EC (elemental carbon, OC (organic carbon and major ions in the city were 2–22 times higher than those on the mountaintop during the whole sampling period. Compared to that in the non-dust period a sharp increase in OC was observed at both sites during the dust period, which was mainly caused by an input of biogenic organics from the Gobi desert. However, adsorption/heterogeneous reaction of gaseous organics with dust was another important source of OC in the urban, contributing 22% of OC in the dust event. In contrast to the mountain atmosphere where fine particles were less acidic when dust was present, the urban fine particles became more acidic in the dust event than in the non-dust event, mainly due to enhanced heterogeneous formation of nitrate and diluted NH3. Cl and NO3 in the urban air during the dust event significantly shifted toward coarse particles. Such redistributions were further pronounced on the mountaintop when dust was present, resulting in both ions almost entirely staying in coarse particles. On the contrary, no significant spatial difference in size distribution of SO42− was found between the urban ground surface and the mountain atmosphere, which dominated in the fine mode (<2.1 μm during the nonevent and comparably distributed in the fine (<2.1 μm and coarse (>2.1 μm modes during the dust event.

  12. Chemistry-nuclear chemistry division. Progress report, October 1979-September 1980

    Energy Technology Data Exchange (ETDEWEB)

    Ryan, R.R. (comp.)

    1981-05-01

    This report presents the research and development programs pursued by the Chemistry-Nuclear Chemistry Division of the Los Alamos National Laboratory. Topics covered include advanced analytical methods, atmospheric chemistry and transport, biochemistry, biomedical research, element migration and fixation, inorganic chemistry, isotope separation and analysis, atomic and molecular collisions, molecular spectroscopy, muonic x rays, nuclear cosmochemistry, nuclear structure and reactions, radiochemical separations, theoretical chemistry, and unclassified weapons research.

  13. Atmospheric chemistry of short-chain haloolefins: photochemical ozone creation potentials (POCPs), global warming potentials (GWPs), and ozone depletion potentials (ODPs).

    Science.gov (United States)

    Wallington, T J; Sulbaek Andersen, M P; Nielsen, O J

    2015-06-01

    Short-chain haloolefins are being introduced as replacements for saturated halocarbons. The unifying chemical feature of haloolefins is the presence of a CC double bond which causes the atmospheric lifetimes to be significantly shorter than for the analogous saturated compounds. We discuss the atmospheric lifetimes, photochemical ozone creation potentials (POCPs), global warming potentials (GWPs), and ozone depletion potentials (ODPs) of haloolefins. The commercially relevant short-chain haloolefins CF3CFCH2 (1234yf), trans-CF3CHCHF (1234ze(Z)), CF3CFCF2 (1216), cis-CF3CHCHCl (1233zd(Z)), and trans-CF3CHCHCl (1233zd(E)) have short atmospheric lifetimes (days to weeks), negligible POCPs, negligible GWPs, and ODPs which do not differ materially from zero. In the concentrations expected in the environment their atmospheric degradation products will have a negligible impact on ecosystems. CF3CFCH2 (1234yf), trans-CF3CHCHF (1234ze(Z)), CF3CFCF2 (1216), cis-CF3CHCHCl (1233zd(Z)), and trans-CF3CHCHCl (1233zd(E)) are environmentally acceptable. Copyright © 2015 Elsevier Ltd. All rights reserved.

  14. Atmospheric chemistry of CF3CFHCF2OCF3 and CF3CFHCF2OCF2H: Reaction with Cl atoms and OH radicals, degradation mechanism, and global warming potentials

    DEFF Research Database (Denmark)

    Wallington, TJ; Hurley, MD; Nielsen, OJ

    2004-01-01

    Fourier transform infrared (FTIR) smog chamber techniques were used to measure k(Cl + CF3CFHCF2OCF3) = (4.09 +/- 0.42) x 10(-17), k(OH + CF3CFHCF2OCF3) = (1.43 +/- 0.28) x 10(-15), k(Cl + CF3CFHCF2OCF2H) = (6.89 +/- 1.29) x 10(-17), and k(OH + CF3CFHCF2OCF2H) = (1.79 +/- 0.34) x 10(-15) cm(3) mol...... respectively. The 100-year time horizon global warming potentials of CF3CFHCF2OCF3 and CF3CFHCF2OCF2H relative to CO2 are 4530 and 4340. Results are discussed with respect to the atmospheric chemistry of hydrofluoroethers....

  15. Brazil-USA Collaborative Research: Modifications by Anthropogenic Pollution of the Natural Atmospheric Chemistry and Particle Microphysics of the Tropical Rain Forest During the GoAmazon Intensive Operating Periods (IOPs)

    Energy Technology Data Exchange (ETDEWEB)

    Kim, Saewung [Univ. of California, Irvine, CA (United States)

    2017-08-01

    Manaus, a city of nearly two million people, represents an isolated urban area having a distinct urban pollution plume within the otherwise pristine Amazon Basin. The plume has high concentrations of oxides of nitrogen and sulfur, carbon monoxide, particle concentrations, and soot, among other pollutants. Critically, the distinct plume in the setting of the surrounding tropical rain forest serves as a natural laboratory to allow direct comparisons between periods of pollution influence to those of pristine conditions. The funded activity of this report is related to the Brazil-USA collaborative project during the two Intensive Operating Periods (wet season, 1 Feb - 31 Mar 2014; dry season, 15 Aug - 15 Oct 2014) of GoAmazon2014/5. The project addresses key science questions regarding the modification of the natural atmospheric chemistry and particle microphysics of the forest by present and future anthropogenic pollution.

  16. Atmospheric chemistry of CH3O(CF2CF2O)(n)CH3 (n=1-3): Kinetics and mechanism of oxidation initiated by Cl atoms and OH radicals, IR spectra, and global warmin potentials

    DEFF Research Database (Denmark)

    Andersen, Mads Peter Sulbæk; Hurley, MD; Wallington, TJ

    2004-01-01

    Smog chambers equipped with FTIR spectrometers were used to study the Cl atom and OH radical initiated oxidation of CH3O(CF2CF2O)(n)CH3 (n = 1-3) in 720 +/- 20 Torr of air at 296 +/- 3 K. Relative rate techniques were used to measure k(Cl + CH3O(CF2CF2O)(n)CH3) (3.7 +/- 10.7) x 10(-13) and k(OH +...... of 0.051, 0.058, and 0.055 (100 year time horizon, relative to CFC-11) for CH3OCF2CF2OCH3, CH3O(CF2CF2O)(2)CH3, and CH3O(CF2CF2O)(3)CH3, respectively. Results are discussed with respect to the atmospheric chemistry of hydrofluoropolyethers (HFPEs)....

  17. Chemistry Dashboard

    Science.gov (United States)

    The Chemistry Dashboard is part of a suite of dashboards developed by EPA to help evaluate the safety of chemicals. The Chemistry Dashboard provides access to a variety of information on over 700,000 chemicals currently in use.

  18. Organic nitrate chemistry and its implications for nitrogen budgets in an isoprene- and monoterpene-rich atmosphere: constraints from aircraft (SEAC4RS) and ground-based (SOAS) observations in the Southeast US

    Science.gov (United States)

    Fisher, Jenny A.; Jacob, Daniel J.; Travis, Katherine R.; Kim, Patrick S.; Marais, Eloise A.; Miller, Christopher Chan; Yu, Karen; Zhu, Lei; Yantosca, Robert M.; Sulprizio, Melissa P.; Mao, Jingqiu; Wennberg, Paul O.; Crounse, John D.; Teng, Alex P.; Nguyen, Tran B.; St. Clair, Jason M.; Cohen, Ronald C.; Romer, Paul; Nault, Benjamin A.; Wooldridge, Paul J.; Jimenez, Jose L.; Campuzano-Jost, Pedro; Day, Douglas A.; Hu, Weiwei; Shepson, Paul B.; Xiong, Fulizi; Blake, Donald R.; Goldstein, Allen H.; Misztal, Pawel K.; Hanisco, Thomas F.; Wolfe, Glenn M.; Ryerson, Thomas B.; Wisthaler, Armin; Mikoviny, Tomas

    2016-05-01

    Formation of organic nitrates (RONO2) during oxidation of biogenic volatile organic compounds (BVOCs: isoprene, monoterpenes) is a significant loss pathway for atmospheric nitrogen oxide radicals (NOx), but the chemistry of RONO2 formation and degradation remains uncertain. Here we implement a new BVOC oxidation mechanism (including updated isoprene chemistry, new monoterpene chemistry, and particle uptake of RONO2) in the GEOS-Chem global chemical transport model with ~ 25 x 25 km2 resolution over North America. We evaluate the model using aircraft (SEAC4RS) and ground-based (SOAS) observations of NOx, BVOCs, and RONO2 from the Southeast US in summer 2013. The updated simulation successfully reproduces the concentrations of individual gas- and particle-phase RONO2 species measured during the campaigns. Gas-phase isoprene nitrates account for 25-50 % of observed RONO2 in surface air, and we find that another 10 % is contributed by gas-phase monoterpene nitrates. Observations in the free troposphere show an important contribution from long-lived nitrates derived from anthropogenic VOCs. During both campaigns, at least 10 % of observed boundary layer RONO2 were in the particle phase. We find that aerosol uptake followed by hydrolysis to HNO3 accounts for 60 % of simulated gas-phase RONO2 loss in the boundary layer. Other losses are 20 % by photolysis to recycle NOx and 15 % by dry deposition. RONO2 production accounts for 20 % of the net regional NOx sink in the Southeast US in summer, limited by the spatial segregation between BVOC and NOx emissions. This segregation implies that RONO2 production will remain a minor sink for NOx in the Southeast US in the future even as NOx emissions continue to decline.

  19. Organic nitrate chemistry and its implications for nitrogen budgets in an isoprene- and monoterpene-rich atmosphere: constraints from aircraft (SEAC4RS and ground-based (SOAS observations in the Southeast US

    Directory of Open Access Journals (Sweden)

    J. A. Fisher

    2016-05-01

    Full Text Available Formation of organic nitrates (RONO2 during oxidation of biogenic volatile organic compounds (BVOCs: isoprene, monoterpenes is a significant loss pathway for atmospheric nitrogen oxide radicals (NOx, but the chemistry of RONO2 formation and degradation remains uncertain. Here we implement a new BVOC oxidation mechanism (including updated isoprene chemistry, new monoterpene chemistry, and particle uptake of RONO2 in the GEOS-Chem global chemical transport model with  ∼  25  ×  25 km2 resolution over North America. We evaluate the model using aircraft (SEAC4RS and ground-based (SOAS observations of NOx, BVOCs, and RONO2 from the Southeast US in summer 2013. The updated simulation successfully reproduces the concentrations of individual gas- and particle-phase RONO2 species measured during the campaigns. Gas-phase isoprene nitrates account for 25–50 % of observed RONO2 in surface air, and we find that another 10 % is contributed by gas-phase monoterpene nitrates. Observations in the free troposphere show an important contribution from long-lived nitrates derived from anthropogenic VOCs. During both campaigns, at least 10 % of observed boundary layer RONO2 were in the particle phase. We find that aerosol uptake followed by hydrolysis to HNO3 accounts for 60 % of simulated gas-phase RONO2 loss in the boundary layer. Other losses are 20 % by photolysis to recycle NOx and 15 % by dry deposition. RONO2 production accounts for 20 % of the net regional NOx sink in the Southeast US in summer, limited by the spatial segregation between BVOC and NOx emissions. This segregation implies that RONO2 production will remain a minor sink for NOx in the Southeast US in the future even as NOx emissions continue to decline.

  20. Application of MAGIC to Lake Redó (Central Pyrenees: an assessment of the effects of possible climate driven changes in atmospheric precipitation, base cation deposition, and weathering rates on lake water chemistry

    Directory of Open Access Journals (Sweden)

    Marc VENTURA

    2004-02-01

    Full Text Available The process-oriented catchment-scale model MAGIC was used to simulate water chemistry at Lake Redó, a high mountain lake in the Central Pyrenees, Spain. Data on lakewater and atmospheric deposition chemistry for the period 1984-1998 were used to calibrate the model, which was then used to reconstruct past and to provide forecasts for three hypothetical future scenarios of deposition. Forecast scenarios considered several combinations of changes in S and N deposition due to abatement strategies, and in base cation deposition due to climate-induced changes in air-mass trajectories from northern Africa. Scenario 1 assumed constant deposition of base cations at the present level plus the expected decrease in S and N deposition resulting from reduced emissions; scenario 2 (best case assumed an increase in base cation deposition plus the same decrease in S and N deposition as in scenario 1; scenario 3 (worst case assumed a decrease in base cation deposition plus no decrease in S and N deposition. The hindcast indicated that during the past 140-year period changes in lake water chemistry have been significant for a remote mountain catchment, although no substantial acidification has occurred. In this regard Lake Redó can be described as a "non-sensitive lake" maintaining a reference condition. The forecasts indicated changes that do not affect this status, but the trends, even if slight, were different between scenarios. A slight decline in the surface water ANC is predicted by Scenario 3. The N budget indicates an unusually low retention in the catchment, which may result in enhanced sensitivity to further increased N deposition. Some of the discrepancy between modelled and measured Ca2+ in lake water during 1984-98 could be explained by changes in rainfall amounts and by increased weathering rates due to increases in air temperature.

  1. Combinatorial chemistry

    DEFF Research Database (Denmark)

    Nielsen, John

    1994-01-01

    An overview of combinatorial chemistry is presented. Combinatorial chemistry, sometimes referred to as `irrational drug design,' involves the generation of molecular diversity. The resulting chemical library is then screened for biologically active compounds.......An overview of combinatorial chemistry is presented. Combinatorial chemistry, sometimes referred to as `irrational drug design,' involves the generation of molecular diversity. The resulting chemical library is then screened for biologically active compounds....

  2. Atmospheric Chemistry of 1-Methoxy 2-Propyl Acetate: UV Absorption Cross Sections, Rate Coefficients, and Products of Its Reactions with OH Radicals and Cl Atoms.

    Science.gov (United States)

    Zogka, Antonia G; Mellouki, Abdelwahid; Romanias, Manolis N; Bedjanian, Yuri; Idir, Mahmoud; Grosselin, Benoit; Daële, Véronique

    2016-11-17

    The rate coefficients for the reactions of OH and Cl with 1-methoxy 2-propyl acetate (MPA) in the gas phase were measured using absolute and relative methods. The kinetic study on the OH reaction was conducted in the temperature (263-373) K and pressure (1-760) Torr ranges using the pulsed laser photolysis-laser-induced fluorescence technique, a low pressure fast flow tube reactor-quadrupole mass spectrometer, and an atmospheric simulation chamber/GC-FID. The derived Arrhenius expression is k MPA+OH (T) = (2.01 ± 0.02) × 10 -12 exp[(588 ± 123/T)] cm 3 molecule -1 s -1 . The absolute and relative rate coefficients for the reaction of Cl with MPA were measured at room temperature in the flow reactor and the atmospheric simulation chamber, which led to k (Cl+MPA) = (1.98 ± 0.31) × 10 -10 cm 3 molecule -1 s -1 . GC-FID, GC-MS, and FT-IR techniques were used to investigate the reaction mechanism in the presence of NO. The products formed from the reaction of MPA with OH and their yields were methyl formate (80 ± 7.3%), acetic acid (50 ± 4.8%), and acetic anhydride (22 ± 2.4%), while for Cl reaction, the obtained yields were 60 ± 5.4, 41 ± 3.8, and 11 ± 1.2%, respectively, for the same products. The UV absorption cross section spectrum of MPA was determined in the wavelength range 210-370 nm. The study has shown no photolysis of MPA under atmospheric conditions. The obtained results are used to derive the atmospheric implication.

  3. Light changes the atmospheric reactivity of soot

    Science.gov (United States)

    D'Anna, Barbara; Monge, Maria-Eugenia; George, Christian; Ammann, Markus; Donaldson, D. Jamie

    2010-05-01

    Soot particles formed by incomplete combustion processes comprise a significant portion of the fine aerosol loading (below 1micron). These particles affect the radiative forcing contributing to global warming and have increased toxicity relative to larger particles because they may settle and persist in the deeper respiratory tract, and can even cross biological barriers. In addition, they are often coated with polycyclic aromatic hydrocarbons (PAHs). Soot particles exhibit a large specific surface area, approx. 100 m2 g-1, which suggests a potential for heterogeneous interactions with atmospheric trace gases. Consequently, soot was suggested to be an important sink for some atmospheric oxidants such as O3 or NOx and its heterogeneous chemistry has been largely investigated in the past years. However, its atmospheric impact was suggested to be negligible due to a rapid soot surface deactivation under atmospheric conditions. As previous studies were done under dark conditions, we decided to investigate the effect of light on the heterogeneous reaction of NO2 on various soot samples. As well, we studied the effect of O3 and light exposure on the aging of soot samples. The heterogeneous reaction between soot particles and NO2 was studied by means of a coated flow tube equipped with near-UV emitting lamps (300-420 nm). The effect of O3 and light on the wettability of soot was studied by contact angle measurements. The characterization of the soot particles was performed by TEM, ESEM and AMS. Different combustion conditions were used to produce the soot samples, which were generated with a mini-CAST soot generator using propane as fuel. We determined the uptake coefficients for different gas phase NO2 concentrations (15-120 ppbv) under near UV irradiation. The results showed that the heterogeneous reaction of NO2 and soot under irradiation leads to NO and HONO production with different yields according to the combustion conditions of the generated soot particles. The

  4. Nobel Prize in Chemistry 1995 "for their work in atmospheric chemistry, particularly concerning the formation and decomposition of ozone" : Paul J Crutzen, Mario J Molina and F Sherwood Rowland

    CERN Multimedia

    1997-01-01

    Prof. Paul J Crutzen presents "The stratospheric ozone hole : a man-caused chemical instability".The discovery of the spring time stratospheric ozone hole by scientists of the British Antarctic Survey, led by Joe Farman, was one of the greatest surprises in the history of the atmospheric sciences and global change studies. After intensive research efforts by many international scientific teams it has clearly been demonstrated that the observed rapid ozone depletions are due to catalytic reactions involving CIO radicals, more than 80571130f which are produced by the photochemical breakdown of the industrial chlorofluorocarbon (CFC) gases. In this lecture I will present the course of events leading to the rapid ozone depletions. International agreements have been reached to forbid the production of the CFC gases. However, despite these measures, it will take almost 50 years before the ozone hole will have disappeared. I will also show that mankind has indeed been very lucky and that things could have been far w...

  5. Organic Nitrate Chemistry and Its Implications for Nitrogen Budgets in an Isoprene- and Monoterpene-Rich Atmosphere: Constraints From Aircraft (SEAC4RS) and Ground-Based (SOAS) Observations in the Southeast US

    Science.gov (United States)

    Fisher, Jenny; Jacob, D. J.; Travis, K. R.; Kim, P. S.; Marais, E. A.; Miller, C. Chan; Yu, K.; Zhu, L.; Yantosca, R. M.; Sulprizio, M. P.; hide

    2016-01-01

    Formation of organic nitrates (RONO2) during oxidation of biogenic volatile organic compounds (BVOCs: isoprene, monoterpenes) is a significant loss pathway for atmospheric nitrogen oxide radicals (NOx), but the chemistry of RONO2 formation and degradation remains uncertain. Here we implement a new BVOC oxidation mechanism (including updated isoprene chemistry, new monoterpene chemistry, and particle uptake of RONO2) in the GEOS-Chem global chemical transport model with approximately 25 times 25 km(exp 2) resolution over North America. We evaluate the model using aircraft (SEAC4RS) and ground-based (SOAS) observations of NOx, BVOCs, and RONO2 from the Southeast US in summer 2013. The updated simulation successfully reproduces the concentrations of individual gas- and particle-phase RONO2 species measured during the campaigns. Gas-phase isoprene nitrates account for 2550 of observed RONO2 in surface air, and we find that another 10 is contributed by gas-phase monoterpene nitrates. Observations in the free troposphere show an important contribution from long-lived nitrates derived from anthropogenic VOCs. During both campaigns, at least 10 of observed boundary layer RONO2 were in the particle phase. We find that aerosol uptake followed by hydrolysis to HNO3 accounts for 60 of simulated gas-phase RONO2 loss in the boundary layer. Other losses are 20 by photolysis to recycle NOx and 15 by dry deposition. RONO2 production accounts for 20 of the net regional NOx sink in the Southeast US in summer, limited by the spatial segregation between BVOC and NOx emissions. This segregation implies that RONO2 production will remain a minor sink for NOx in the Southeast US in the future even as NOx emissions continue to decline. XXXX We have used airborne and ground-based observations from two summer 2013 campaigns in the Southeast US (SEAC4RS, SOAS) to better understand the chemistry and impacts of alkyl and multi-functional organic nitrates (RONO2). We used the observations, along

  6. Simulation of the urban atmosphere chemistry polluted by alcohol fueled automobiles; Simulacao da quimica da atmosfera poluida por automoveis movidos a alcool

    Energy Technology Data Exchange (ETDEWEB)

    Pimentel, A.S.; Arbilla, G. [Universidade Federal, Rio de Janeiro, RJ (Brazil). Inst. de Quimica

    1997-05-01

    Numerical modeling studies of urban atmosphere were performed with a photochemical box sub model which incorporates primary emission rates, temperature and solar irradiance rate coefficients. Actinic flux calculation were made for an appropriate latitude for Rio de Janeiro city - Southeast Brazil - and initial concentrations and emissions rates were taken from experimental data. The relative importance of individual reactions is discussed as well as the effect of enhanced aldehyde emission from vehicles using ethanol; and ethanol-containing fuels. (author). 35 refs., 12 figs., 3 tabs.

  7. Advances in electron transfer chemistry

    CERN Document Server

    Mariano, Patrick S

    1993-01-01

    Advances in Electron Transfer Chemistry, Volume 3 presents studies that discuss findings in the various aspects of electron chemistry. The book is comprised of four chapters; each chapter reviews a work that tackles an issue in electron transfer chemistry. Chapter 1 discusses the photoinduced electron transfer in flexible biaryl donor-acceptor molecules. Chapter 2 tackles light-induced electron transfer in inorganic systems in homogeneous and heterogeneous phases. The book also covers internal geometry relaxation effects on electron transfer rates of amino-centered systems. The sequential elec

  8. Resolving Heterogeneity

    DEFF Research Database (Denmark)

    Hölzenspies, Jurriaan; Dela Cruz, Gelo Victoriano; M Brickman, Joshua

    2016-01-01

    sets of pluripotency and differentiation markers. It has become increasingly apparent that this transcriptional heterogeneity is an important characteristic of ESC culture. By sorting for specific populations of ESCs it is possible to enrich for cells with a capacity to colonize the embryo proper...

  9. Exploring the atmospheric chemistry of O2SO3- and assessing the maximum turnover number of ion-catalysed H2SO4 formation

    DEFF Research Database (Denmark)

    Bork, Nicolai Christian; Kurtén, T.; Vehkamäki, H.

    2013-01-01

    It has recently been demonstrated that the O2SO3- ion forms in the atmosphere as a natural consequence of ionizing radiation. Here, we present a density functional theory-based study of the reactions of O2SO3- with O-3. The most important reactions are (a) oxidation to O3SO3- and (b) cluster...... the two major sinks for O2SO3- is assessed, thereby providing a measure of the maximum turnover number of ion-catalysed SO2 oxidation, i.e. how many SO2 can be oxidized per free electron. The rate ratio between reactions (a) and (b) is significantly altered by the presence or absence of a single water...

  10. Exploring the atmospheric chemistry of O2SO3− and assessing the maximum turnover number of ion-catalysed H2SO4 formation

    Directory of Open Access Journals (Sweden)

    N. Bork

    2013-04-01

    Full Text Available It has recently been demonstrated that the O2SO3− ion forms in the atmosphere as a natural consequence of ionizing radiation. Here, we present a density functional theory-based study of the reactions of O2SO3− with O3. The most important reactions are (a oxidation to O2SO3− and (b cluster decomposition into SO3, O2 and O3−. The former reaction is highly exothermic, and the nascent O2SO3− will rapidly decompose into SO4− and O2. If the origin of O2SO3− is SO2 oxidation by O3−, the latter reaction closes a catalytic cycle wherein SO2 is oxidized to SO3. The relative rate between the two major sinks for O2SO3− is assessed, thereby providing a measure of the maximum turnover number of ion-catalysed SO2 oxidation, i.e. how many SO2 can be oxidized per free electron. The rate ratio between reactions (a and (b is significantly altered by the presence or absence of a single water molecule, but reaction (b is in general much more probable. Although we are unable to assess the overall importance of this cycle in the real atmosphere due to the unknown influence of CO2 and NOx, we roughly estimate that ion-induced catalysis may contribute with several percent of H2SO4 levels in typical CO2-free and low NOx reaction chambers, e.g. the CLOUD chamber at CERN.

  11. Analytical chemistry in space

    CERN Document Server

    Wainerdi, Richard E

    1970-01-01

    Analytical Chemistry in Space presents an analysis of the chemical constitution of space, particularly the particles in the solar wind, of the planetary atmospheres, and the surfaces of the moon and planets. Topics range from space engineering considerations to solar system atmospheres and recovered extraterrestrial materials. Mass spectroscopy in space exploration is also discussed, along with lunar and planetary surface analysis using neutron inelastic scattering. This book is comprised of seven chapters and opens with a discussion on the possibilities for exploration of the solar system by

  12. Chemistry Technology

    Data.gov (United States)

    Federal Laboratory Consortium — Chemistry technology experts at NCATS engage in a variety of innovative translational research activities, including:Design of bioactive small molecules.Development...

  13. Designing global climate and atmospheric chemistry simulations for 1 and 10 km diameter asteroid impacts using the properties of ejecta from the K-Pg impact

    Science.gov (United States)

    Toon, Owen B.; Bardeen, Charles; Garcia, Rolando

    2016-10-01

    About 66 million years ago, an asteroid about 10 km in diameter struck the Yucatan Peninsula creating the Chicxulub crater. The crater has been dated and found to be coincident with the Cretaceous-Paleogene (K-Pg) mass extinction event, one of six great mass extinctions in the last 600 million years. This event precipitated one of the largest episodes of rapid climate change in Earth's history, yet no modern three-dimensional climate calculations have simulated the event. Similarly, while there is an ongoing effort to detect asteroids that might hit Earth and to develop methods to stop them, there have been no modern calculations of the sizes of asteroids whose impacts on land would cause devastating effects on Earth. Here, we provide the information needed to initialize such calculations for the K-Pg impactor and for a 1 km diameter impactor. There is considerable controversy about the details of the events that followed the Chicxulub impact. We proceed through the data record in the order of confidence that a climatically important material was present in the atmosphere. The climatic importance is roughly proportional to the optical depth of the material. Spherules with diameters of several hundred microns are found globally in an abundance that would have produced an atmospheric layer with an optical depth around 20, yet their large sizes would only allow them to stay airborne for a few days. They were likely important for triggering global wildfires. Soot, probably from global or near-global wildfires, is found globally in an abundance that would have produced an optical depth near 100, which would effectively prevent sunlight from reaching the surface. Nanometer-sized iron particles are also present globally. Theory suggests these particles might be remnants of the vaporized asteroid and target that initially remained as vapor rather than condensing on the hundred-micron spherules when they entered the atmosphere. If present in the greatest abundance allowed

  14. Designing global climate and atmospheric chemistry simulations for 1 and 10 km diameter asteroid impacts using the properties of ejecta from the K-Pg impact

    Directory of Open Access Journals (Sweden)

    O. B. Toon

    2016-10-01

    Full Text Available About 66 million years ago, an asteroid about 10 km in diameter struck the Yucatan Peninsula creating the Chicxulub crater. The crater has been dated and found to be coincident with the Cretaceous–Paleogene (K-Pg mass extinction event, one of six great mass extinctions in the last 600 million years. This event precipitated one of the largest episodes of rapid climate change in Earth's history, yet no modern three-dimensional climate calculations have simulated the event. Similarly, while there is an ongoing effort to detect asteroids that might hit Earth and to develop methods to stop them, there have been no modern calculations of the sizes of asteroids whose impacts on land would cause devastating effects on Earth. Here, we provide the information needed to initialize such calculations for the K-Pg impactor and for a 1 km diameter impactor. There is considerable controversy about the details of the events that followed the Chicxulub impact. We proceed through the data record in the order of confidence that a climatically important material was present in the atmosphere. The climatic importance is roughly proportional to the optical depth of the material. Spherules with diameters of several hundred microns are found globally in an abundance that would have produced an atmospheric layer with an optical depth around 20, yet their large sizes would only allow them to stay airborne for a few days. They were likely important for triggering global wildfires. Soot, probably from global or near-global wildfires, is found globally in an abundance that would have produced an optical depth near 100, which would effectively prevent sunlight from reaching the surface. Nanometer-sized iron particles are also present globally. Theory suggests these particles might be remnants of the vaporized asteroid and target that initially remained as vapor rather than condensing on the hundred-micron spherules when they entered the atmosphere. If present in the

  15. Multi-Year Application and Evaluation over U.S. using the Weather Research and Forecasting model with Chemistry and the Physics/Aerosol Packages from the Community Atmosphere Model version 5 (WRF-CAM5)

    Science.gov (United States)

    Jena, C. K.; Zhang, Y.; Campbell, P. C.

    2016-12-01

    Multiyear applications of an online-coupled meteorological and chemical transport model allow an assessment of the variation trends in simulated meteorology, air quality and their interactions over a period of time during which emissions and meteorology are changed. In this work, the Weather Research and Forecasting model with Chemistry and the physics/aerosol packages of the Community Atmosphere Model version 5 (WRF-CAM5) is applied for five full years of 2008 - 2012 over U.S. to evaluate the model's capability in reproducing the observations and to examine the changes in model predictions due to changes in meteorology and emissions. The model predictions of meteorological, radiative, and cloud variables, chemical concentrations, and column mass abundances are evaluated against satellite data and surface measurements across U.S. A comprehensive evaluation shows overall good performance for temperature and relative humidity at 2-m, precipitation against most datasets (except for NCDC), radiation variables, cloud fraction, cloud droplet number concentration, and precipitable water vapor in terms of domain average performance statistics, multi-year trends and inter-seasonal variability. Large biases exist in surface concentrations of sulfate, elemental carbon, PM2.5 against IMPROVE and PM10, column abundances of NO2 and O3, aerosol optical depth, cloud condensation nuclei, cloud liquid and ice water paths, cloud optical thickness. These biases indicate uncertainties in the model representations of boundary layer processes (e.g., surface roughness), cloud processes (e.g., microphysics and cumulus parameterization), emissions (e.g., biogenic and wildfire emissions), chemistry and aerosol treatment (e.g., winter photochemistry, aerosol thermodynamics). Overall, these results demonstrate promising skills of WRF-CAM5 for long-term simulations at a regional scale and suggest the above areas of potential improvements to further improve model skill and reduce uncertainties.

  16. Atmospheric Pressure Microwave Assisted Heterogeneous Catalytic Reactions

    Directory of Open Access Journals (Sweden)

    Ken Belmore

    2007-07-01

    Full Text Available The newly synthesized 5,10,15,20-tetra[3-(3-trifluoromethylphenoxy]porphyrin, TTFMPP, has been characterized using mass spectroscopy, 1H-, 13C- and 19F-NMR, MALDI-TOF mass spectrometry, UV-Vis and fluorescence spectrophotometry, andcyclic voltammetry. The NMR confirmed the structure of the compound and the massspectrum was in agreement with the proposed molecular formula. The UV-Vis absorptionspectrum of TTFMPP shows characteristic spectral patterns similar to those of tetraphenylporphryin, with a Soret band at 419 nm and four Q bands at 515, 550, 590, and 648 nm.Protonation of the porphyrin with TFA resulted in the expected red shift of the Soret band.Excitation at 419 nm gave an emission at 650 nm. The quantum yield of the porphyrin wasdetermined to be 0.08. Cyclic voltammetry was used to determine the oxidation andreduction potentials of the new porphyrin. Two quasi-reversible one-electron reductions at–1.00 and –1.32 V and a quasi-reversible oxidation at 1.20 V versus the silver/silverchloride reference electrode with tetrabutylammonium tetrafluoroborate as the supportingelectrolyte in methylene chloride were observed.

  17. Impact of a future H2-based road transportation sector on the composition and chemistry of the atmosphere - Part 2: Stratospheric ozone

    Science.gov (United States)

    Wang, D.; Jia, W.; Olsen, S. C.; Wuebbles, D. J.; Dubey, M. K.; Rockett, A. A.

    2013-07-01

    The prospective future adoption of molecular hydrogen (H2) to power the road transportation sector could greatly improve tropospheric air quality but also raises the question of whether the adoption would have adverse effects on the stratospheric ozone. The possibility of undesirable impacts must be fully evaluated to guide future policy decisions. Here we evaluate the possible impact of a future (2050) H2-based road transportation sector on stratospheric composition and chemistry, especially on the stratospheric ozone, with the MOZART (Model for OZone And Related chemical Tracers) model. Since future growth is highly uncertain, we evaluate the impact of two world evolution scenarios, one based on an IPCC (Intergovernmental Panel on Climate Change) high-emitting scenario (A1FI) and the other on an IPCC low-emitting scenario (B1), as well as two technological options: H2 fuel cells and H2 internal combustion engines. We assume a H2 leakage rate of 2.5% and a complete market penetration of H2 vehicles in 2050. The model simulations show that a H2-based road transportation sector would reduce stratospheric ozone concentrations as a result of perturbed catalytic ozone destruction cycles. The magnitude of the impact depends on which growth scenario evolves and which H2 technology option is applied. For the evolution growth scenario, stratospheric ozone decreases more in the H2 fuel cell scenarios than in the H2 internal combustion engine scenarios because of the NOx emissions in the latter case. If the same technological option is applied, the impact is larger in the A1FI emission scenario. The largest impact, a 0.54% decrease in annual average global mean stratospheric column ozone, is found with a H2 fuel cell type road transportation sector in the A1FI scenario; whereas the smallest impact, a 0.04% increase in stratospheric ozone, is found with applications of H2 internal combustion engine vehicles in the B1 scenario. The impacts of the other two scenarios fall

  18. The impact of a future H2-based road transportation sector on the composition and chemistry of the atmosphere - Part 2: Stratospheric ozone

    Science.gov (United States)

    Wang, D.; Jia, W.; Olsen, S. C.; Wuebbles, D. J.; Dubey, M. K.; Rockett, A. A.

    2012-08-01

    The prospective future adoption of hydrogen to power the road transportation sector could greatly improve tropospheric air quality but also raises the question whether the adoption would have adverse effects on stratospheric ozone. The possibility of these undesirable impacts must be fully evaluated to guide future policy decisions. Here we evaluate the possible impact of a future (2050) H2-based road transportation sector on stratospheric composition and chemistry, especially on stratospheric ozone, with the MOZART chemical transport model. Since future growth is highly uncertain we evaluate the impact for two world evolution scenarios, one based on a high emitting scenario (IPCC A1FI) and the other on a low emitting scenario (IPCC B1), as well as two technological options: H2 fuel cells and H2 internal combustion engines. We assume a H2 leakage rate of 2.5% and a complete market penetration of H2 vehicles in 2050. The model simulations show that a H2-based road transportation sector would reduce stratospheric ozone concentrations as a result of perturbed catalytic ozone destruction cycles. The magnitude of the impact depends on which growth scenario the world evolves and which H2 technology option is applied. For the same world evolution scenario, stratospheric ozone decreases more in the H2 fuel cell scenarios than in the H2 internal combustion engine scenarios because of the NOx emissions in the latter case. If the same technological option is applied, the impact is larger in the A1FI emission scenario. The largest impact, a 0.54% decrease in annual average global mean stratospheric column ozone, is found with a H2 fuel cell type road transportation sector in the A1FI scenario; whereas the smallest impact, a 0.04% increase in stratospheric ozone, is found with applications of H2 internal combustion engine vehicles in the B1 scenario. The impacts of the other two scenarios fall between the above two bounding scenarios. However, the magnitude of these changes is

  19. Impact of a future H2-based road transportation sector on the composition and chemistry of the atmosphere – Part 2: Stratospheric ozone

    Directory of Open Access Journals (Sweden)

    D. Wang

    2013-07-01

    Full Text Available The prospective future adoption of m