WorldWideScience

Sample records for combined atmospheric photochemistry

  1. Photochemistry in Outer Solar System Atmospheres

    Science.gov (United States)

    Strobel, Darrell F.

    2005-01-01

    The photochemistries of the H2-He atmospheres of the gas giants Jupiter, Saturn and ice giants Uranus and Neptune and Titan’s mildly reducing N2 atmosphere are reviewed in terms of general chemical and physical principles. The thermochemical furnace regions in the deep atmospheres and the photochemical regions of the giant planets are coupled by vertical mixing to ensure efficient recyling of photochemical products. On Titan,mass loss of hydrogen ensures photochemical evolution of methane into less saturated hydrocarbons. A summary discussion of major dissociation paths and essential chemical reactions is given. The chapter ends with a overview of vertical transport processes in planetary atmospheres.

  2. Photochemistry of planetary atmospheres. [Mars atmospheric composition

    Science.gov (United States)

    Stief, L. J.

    1973-01-01

    The atmospheric composition of Mars is presented, and the applicability of laboratory data on CO2 absorption cross sections and quantum yields of dissociation is discussed. A summary and critical evaluation are presented on the various mechanisms proposed for converting the photodissociation products CO and O2 back to CO2.

  3. Sunlight-Initiated Photochemistry: Excited Vibrational States of Atmospheric Chromophores

    Directory of Open Access Journals (Sweden)

    Veronica Vaida

    2008-01-01

    Full Text Available Atmospheric chemical reactions are often initiated by ultraviolet (UV solar radiation since absorption in that wavelength range coincides to typical chemical bond energies. In this review, we present an alternative process by which chemical reactions occur with the excitation of vibrational levels in the ground electronic state by red solar photons. We focus on the O–H vibrational manifold which can be an atmospheric chromophore for driving vibrationally mediated overtone-induced chemical reactions. Experimental and theoretical O–H intensities of several carboxylic acids, alcohols, and peroxides are presented. The importance of combination bands in spectra at chemically relevant energies is examined in the context of atmospheric photochemistry. Candidate systems for overtone-initiated chemistry are provided, and their lowest energy barrier for reaction and the minimum quanta of O–H stretch required for reaction are calculated. We conclude with a discussion of the major pathways available for overtone-induced reactions in the atmosphere.

  4. VUV photochemistry simulation of planetary upper atmosphere using synchrotron radiation.

    Science.gov (United States)

    Carrasco, Nathalie; Giuliani, Alexandre; Correia, Jean Jacques; Cernogora, Guy

    2013-07-01

    The coupling of a gas reactor, named APSIS, with a vacuum-ultraviolet (VUV) beamline at the SOLEIL synchrotron radiation facility, for a photochemistry study of gas mixtures, is reported. The reactor may be irradiated windowless with gas pressures up to hundreds of millibar, and thus allows the effect of energetic photons below 100 nm wavelength to be studied on possibly dense media. This set-up is perfectly suited to atmospheric photochemistry investigations, as illustrated by a preliminary report of a simulation of the upper atmospheric photochemistry of Titan, the largest satellite of Saturn. Titan's atmosphere is mainly composed of molecular nitrogen and methane. Solar VUV irradiation with wavelengths no longer than 100 nm on the top of the atmosphere enables the dissociation and ionization of nitrogen, involving a nitrogen chemistry specific to nitrogen-rich upper atmospheres.

  5. Photochemistry in terrestrial exoplanet atmospheres. III. Photochemistry and thermochemistry in thick atmospheres on super Earths and mini Neptunes

    Energy Technology Data Exchange (ETDEWEB)

    Hu, Renyu; Seager, Sara, E-mail: hury@caltech.edu [Department of Earth, Atmospheric and Planetary Sciences, Massachusetts Institute of Technology, Cambridge, MA 02139 (United States)

    2014-03-20

    Some super Earths and mini Neptunes will likely have thick atmospheres that are not H{sub 2}-dominated. We have developed a photochemistry-thermochemistry kinetic-transport model for exploring the compositions of thick atmospheres on super Earths and mini Neptunes, applicable for both H{sub 2}-dominated atmospheres and non-H{sub 2}-dominated atmospheres. Using this model to study thick atmospheres for wide ranges of temperatures and elemental abundances, we classify them into hydrogen-rich atmospheres, water-rich atmospheres, oxygen-rich atmospheres, and hydrocarbon-rich atmospheres. We find that carbon has to be in the form of CO{sub 2} rather than CH{sub 4} or CO in a H{sub 2}-depleted water-dominated thick atmosphere and that the preferred loss of light elements from an oxygen-poor carbon-rich atmosphere leads to the formation of unsaturated hydrocarbons (C{sub 2}H{sub 2} and C{sub 2}H{sub 4}). We apply our self-consistent atmosphere models to compute spectra and diagnostic features for known transiting low-mass exoplanets GJ 1214 b, HD 97658 b, and 55 Cnc e. For GJ 1214 b, we find that (1) C{sub 2}H{sub 2} features at 1.0 and 1.5 μm in transmission and C{sub 2}H{sub 2} and C{sub 2}H{sub 4} features at 9-14 μm in thermal emission are diagnostic for hydrocarbon-rich atmospheres; (2) a detection of water-vapor features and a confirmation of the nonexistence of methane features would provide sufficient evidence for a water-dominated atmosphere. In general, our simulations show that chemical stability has to be taken into account when interpreting the spectrum of a super Earth/mini Neptune. Water-dominated atmospheres only exist for carbon to oxygen ratios much lower than the solar ratio, suggesting that this kind of atmospheres could be rare.

  6. Photochemistry in Saturn’s Ring-Shadowed Atmosphere: Photochemistry and Haze Observations

    Science.gov (United States)

    Edgington, Scott G.; Atreya, Sushil K.; Baines, Kevin H.; West, Robert A.; Bjoraker, Gordon L.; Fletcher, Leigh; Momary, Thomas W.; Wilson, Eric; CIRS, ISS, UVIS, VIMS

    2017-10-01

    After 13 years of observing Saturn, Cassini would have ended nearly a half Saturnian year. During this epoch, the ring shadow has moved from covering much of the northern hemisphere to covering a large swath southern hemisphere. The net effect is that the intensity of both ultraviolet and visible sunlight penetrating through the rings to any particular latitude will vary depending on both Saturn’s axis relative to the Sun and the optical thickness of each ring system. In essence, the rings act like semi-transparent venetian blinds. This effect magnifies the effect due to axial tilt alone and acts to turn off photochemistry and haze generation. This effect is seen in both the presence of a bluish Rayleigh-scattering atmosphere in 2004 in the northern hemisphere and color change to blue in the northern hemisphere.Previous work examined the variation of the solar flux as a function of solar inclination, i.e. for each 7.25-year season at Saturn. We report on the impact of the oscillating ring shadow, in addition to variation due to axial tilt, on photolysis and production rates of hydrocarbons and phosphine in Saturn’s stratosphere and upper troposphere. The impact of these production and loss rates on the abundance of long-lived photochemical products leading to haze formation are explored. We assess their impact on a disequilibrium species whose presence in the upper troposphere can be used as a tracer of convective processes in the deeper atmosphere.We will also present our ongoing analysis of Cassini’s CIRS, UVIS, and VIMS datasets that provide an estimate of the evolving haze content. In particular, we will examine how the region inside Saturn’s famous hexagonal jet stream changes over time from a relatively clear atmosphere to a hazy one. We also explore how the hexagon acts like a barrier to transport, isolating Saturn’s north polar region from outside influences of photochemically-generated molecules and haze.The research described in this paper was

  7. Sunlight-Initiated Photochemistry: Excited Vibrational States of Atmospheric Chromophores

    OpenAIRE

    Veronica Vaida; Karl J. Feierabend; Nabilah Rontu; Kaito Takahashi

    2008-01-01

    Atmospheric chemical reactions are often initiated by ultraviolet (UV) solar radiation since absorption in that wavelength range coincides to typical chemical bond energies. In this review, we present an alternative process by which chemical reactions occur with the excitation of vibrational levels in the ground electronic state by red solar photons. We focus on the O–H vibrational manifold which can be an atmospheric chromophore for driving vibrationally mediated overtone-induced chemical re...

  8. On the relationship between the greenhouse effect, atmospheric photochemistry, and species distribution

    Science.gov (United States)

    Callis, L. B.; Boughner, R. E.; Natarajan, M.

    1983-01-01

    The coupling that exists between infrared opacity changes and tropospheric (and to a lesser extent stratospheric) chemistry is explored in considerable detail, and the effects arising from various perturbations are examined. The studies are carried out with a fully coupled one-dimensional radiative-convective-photochemical model (RCP) that extends from the surface to 53.5 km and has the capability of calculating surface temperature changes due to both chemical and radiative perturbations. The model encompasses contemporary atmospheric chemistry and photochemistry involving the O(x), HO(x), NO(x), and Cl(x) species.

  9. A combined continuous microflow photochemistry and asymmetric organocatalysis approach for the enantioselective synthesis of tetrahydroquinolines

    OpenAIRE

    Erli Sugiono; Magnus Rueping

    2013-01-01

    Summary A continuous-flow asymmetric organocatalytic photocyclization?transfer hydrogenation cascade reaction has been developed. The new protocol allows the synthesis of tetrahydroquinolines from readily available 2-aminochalcones using a combination of photochemistry and asymmetric Br?nsted acid catalysis. The photocylization and subsequent reduction was performed with catalytic amount of chiral BINOL derived phosphoric acid diester and Hantzsch dihydropyridine as hydrogen source providing ...

  10. A combined continuous microflow photochemistry and asymmetric organocatalysis approach for the enantioselective synthesis of tetrahydroquinolines.

    Science.gov (United States)

    Sugiono, Erli; Rueping, Magnus

    2013-01-01

    A continuous-flow asymmetric organocatalytic photocyclization-transfer hydrogenation cascade reaction has been developed. The new protocol allows the synthesis of tetrahydroquinolines from readily available 2-aminochalcones using a combination of photochemistry and asymmetric Brønsted acid catalysis. The photocylization and subsequent reduction was performed with catalytic amount of chiral BINOL derived phosphoric acid diester and Hantzsch dihydropyridine as hydrogen source providing the desired products in good yields and with excellent enantioselectivities.

  11. A combined continuous microflow photochemistry and asymmetric organocatalysis approach for the enantioselective synthesis of tetrahydroquinolines

    Directory of Open Access Journals (Sweden)

    Erli Sugiono

    2013-11-01

    Full Text Available A continuous-flow asymmetric organocatalytic photocyclization–transfer hydrogenation cascade reaction has been developed. The new protocol allows the synthesis of tetrahydroquinolines from readily available 2-aminochalcones using a combination of photochemistry and asymmetric Brønsted acid catalysis. The photocylization and subsequent reduction was performed with catalytic amount of chiral BINOL derived phosphoric acid diester and Hantzsch dihydropyridine as hydrogen source providing the desired products in good yields and with excellent enantioselectivities.

  12. A Microwave Plasma Discharge in Rare Gases as a VUV Source for Planetary Atmospheric Photochemistry

    OpenAIRE

    Tigrine, Sarah; Carrasco, Nathalie; Vettier, Ludovic; Cernogora, Guy

    2016-01-01

    International audience; The aim of this work is to show that micro-wave discharges in rare gases, can be an efficient windowless VUV photon source for planetaryatmospheric photochemistry experiments. In this context, we perform a microwave discharge (surfatron) in a neon gas flow. We characterizethe VUV photon flux emitted in different conditions, when working in the mbar pressure range, and compare it to synchrotron VUV fluxes alsoused for similar applications.

  13. Sources and photochemistry of volatile organic compounds in the remote atmosphere of western China: results from the Mt. Waliguan Observatory

    Directory of Open Access Journals (Sweden)

    L. K. Xue

    2013-09-01

    Full Text Available The chemistry of the natural atmosphere and the influence by long-range transport of air pollution are key issues in the atmospheric sciences. Here we present two intensive field measurements of volatile organic compounds (VOCs in late spring and summer of 2003 at Mt. Waliguan (WLG, 36.28° N, 100.90° E, 3816 m a.s.l., a baseline station in the northeast part of the Qinghai-Tibetan Plateau. Most VOC species exhibited higher concentrations in late spring than in summer. A typical diurnal variation was observed with higher nighttime levels, in contrast to results from other mountainous sites. Five different air masses were identified from backward trajectory analysis showing distinct VOC speciation. Air masses originating from the central Eurasian continent contained the lowest VOC levels compared to the others that were impacted by anthropogenic emissions from China and the Indian subcontinent. A photochemical box model based on the Master Chemical Mechanism (version 3.2 and constrained by a full suite of measurements was developed to probe the photochemistry of atmosphere at WLG. Our results show net ozone production from in situ photochemistry during both late spring and summer. Oxidation of nitric oxide (NO by the hydroperoxyl radical (HO2 dominates the ozone production relative to the oxidation by the organic peroxy radicals (RO2, and the ozone is primarily destroyed by photolysis and reactions with the HOx (HOx = OH + HO2 radicals. Ozone photolysis is the predominant primary source of radicals (ROx = OH + HO2 + RO2, followed by the photolysis of secondary oxygenated VOCs and hydrogen peroxides. The radical losses are governed by the self and cross reactions among the radicals. Overall, the findings of the present study provide insights into the background chemistry and the impacts of pollution transport on the pristine atmosphere over the Eurasian continent.

  14. ROLE OF CANOPY-SCALE PHOTOCHEMISTRY IN MODIFYING BIOGENIC-ATMOSPHERE EXCHANGE OF REACTIVE TERPENE SPECIES: RESULTS FROM THE CELTIC FIELD STUDY

    Science.gov (United States)

    A one-dimensional canopy model was used to quantify the impact of photochemistry in modifying biosphere-atmosphere exchange of trace gases. Canopy escape efficiencies, defined as the fraction of emission that escapes into the well-mixed boundary layer, were calculated for reactiv...

  15. Modeling the Effects of Aircraft Emissions on Atmospheric Photochemistry Using Layered Plume Dynamics

    Science.gov (United States)

    Cameron, M. A.; Jacobson, M. Z.; Naiman, A. D.; Lele, S. K.

    2012-12-01

    Aviation is an expanding industry, experiencing continued growth and playing an increasingly noticed role in upper tropospheric/lower stratospheric composition. Nitrogen oxides and other gas-phase emissions from aircraft react to affect ozone photochemistry. This research investigates the effects of treating aircraft gas-phase chemistry within an expanding layered plume versus at the grid scale. SMVGEAR II, a sparse-matrix, vectorized Gear-type solver for ordinary differential equations, is used to solve chemical equations at both the grid scale and subgrid scale. A Subgrid Plume Model (SPM) is used to advance the expanding plume, accounting for wind shear and diffusion. Simulations suggest that using a layered plume approach results in noticeably different final NOx concentrations, demonstrating the importance of these plume dynamics in predicting the effects of aircraft on ozone concentrations. Results showing the effects of a layered plume, single plume, and no plume on ozone after several hours will be presented.

  16. Chiral photochemistry

    CERN Document Server

    Inoue, Yoshihisa

    2004-01-01

    Direct Asymmetric Photochemistry with Circularly Polarized Light, H. RauCoherent Laser Control of the Handedness of Chiral Molecules, P. Brumer and M. ShapiroMagnetochiral Anisotropy in Asymmetric Photochemistry, G.L.J.A.RikkenEnantiodifferentiating Photosensitized Reactions, Y. InoueDiastereodifferentiating Photoreactions, N. Hoffmann and J.-P. PeteChirality in Photochromism, Y. Yokoyama and M. SaitoChiral Photochemistry with Transition Metal Complexes, S. Sakaki and T. HamadaTemplate-Induced Enantioselective Photochemical Reactions in S

  17. Atmospheric degradation of 2-chloroethyl vinyl ether, allyl ether and allyl ethyl ether: Kinetics with OH radicals and UV photochemistry.

    Science.gov (United States)

    Antiñolo, M; Ocaña, A J; Aranguren, J P; Lane, S I; Albaladejo, J; Jiménez, E

    2017-08-01

    Unsaturated ethers are oxygenated volatile organic compounds (OVOCs) emitted by anthropogenic sources. Potential removal processes in the troposphere are initiated by hydroxyl (OH) radicals and photochemistry. In this work, we report for the first time the rate coefficients of the gas-phase reaction with OH radicals (k OH ) of 2-chloroethyl vinyl ether (2ClEVE), allyl ether (AE), and allyl ethyl ether (AEE) as a function of temperature in the 263-358 K range, measured by the pulsed laser photolysis-laser induced fluorescence technique. No pressure dependence of k OH was observed in the 50-500 Torr range in He as bath gas, while a slightly negative T-dependence was observed. The temperature dependent expressions for the rate coefficients determined in this work are: The estimated atmospheric lifetimes (τ OH ) assuming k OH at 288 K were 3, 2, and 4 h for 2ClEVE, AE and AEE, respectively. The kinetic results are discussed in terms of the chemical structure of the unsaturated ethers by comparison with similar compounds. We also report ultraviolet (UV) and infrared (IR) absorption cross sections (σ λ and σ(ν˜), respectively). We estimate the photolysis rate coefficients in the solar UV actinic region to be less than 10 -7 s -1 , implying that these compounds are not removed from the atmosphere by this process. In addition, from σ(ν˜) and τ OH , the global warming potential of each unsaturated ether was calculated to be almost zero. A discussion on the atmospheric implications of the titled compounds is presented. Copyright © 2017 Elsevier Ltd. All rights reserved.

  18. Forest-atmosphere exchange of ozone: sensitivity to very reactive biogenic VOC emissions and implications for in-canopy photochemistry

    Directory of Open Access Journals (Sweden)

    G. M. Wolfe

    2011-08-01

    Full Text Available Understanding the fate of ozone within and above forested environments is vital to assessing the anthropogenic impact on ecosystems and air quality at the urban-rural interface. Observed forest-atmosphere exchange of ozone is often much faster than explicable by stomatal uptake alone, suggesting the presence of additional ozone sinks within the canopy. Using the Chemistry of Atmosphere-Forest Exchange (CAFE model in conjunction with summer noontime observations from the 2007 Biosphere Effects on Aerosols and Photochemistry Experiment (BEARPEX-2007, we explore the viability and implications of the hypothesis that ozonolysis of very reactive but yet unidentified biogenic volatile organic compounds (BVOC can influence the forest-atmosphere exchange of ozone. Non-stomatal processes typically generate 67 % of the observed ozone flux, but reactions of ozone with measured BVOC, including monoterpenes and sesquiterpenes, can account for only 2 % of this flux during the selected timeframe. By incorporating additional emissions and chemistry of a proxy for very reactive VOC (VRVOC that undergo rapid ozonolysis, we demonstrate that an in-canopy chemical ozone sink of ~2 × 108 molec cm−3 s−1 can close the ozone flux budget. Even in such a case, the 65 min chemical lifetime of ozone is much longer than the canopy residence time of ~2 min, highlighting that chemistry can influence reactive trace gas exchange even when it is "slow" relative to vertical mixing. This level of VRVOC ozonolysis could enhance OH and RO2 production by as much as 1 pptv s−1 and substantially alter their respective vertical profiles depending on the actual product yields. Reaction products would also contribute significantly to the oxidized VOC budget and, by extension, secondary organic aerosol mass. Given the potentially significant ramifications of a chemical ozone flux for both in-canopy chemistry and estimates of ozone

  19. Response of atmospheric biomarkers to NO(x)-induced photochemistry generated by stellar cosmic rays for earth-like planets in the habitable zone of M dwarf stars.

    Science.gov (United States)

    Grenfell, John Lee; Grießmeier, Jean-Mathias; von Paris, Philip; Patzer, A Beate C; Lammer, Helmut; Stracke, Barbara; Gebauer, Stefanie; Schreier, Franz; Rauer, Heike

    2012-12-01

    Understanding whether M dwarf stars may host habitable planets with Earth-like atmospheres and biospheres is a major goal in exoplanet research. If such planets exist, the question remains as to whether they could be identified via spectral signatures of biomarkers. Such planets may be exposed to extreme intensities of cosmic rays that could perturb their atmospheric photochemistry. Here, we consider stellar activity of M dwarfs ranging from quiet up to strong flaring conditions and investigate one particular effect upon biomarkers, namely, the ability of secondary electrons caused by stellar cosmic rays to break up atmospheric molecular nitrogen (N(2)), which leads to production of nitrogen oxides (NO(x)) in the planetary atmosphere, hence affecting biomarkers such as ozone (O(3)). We apply a stationary model, that is, without a time dependence; hence we are calculating the limiting case where the atmospheric chemistry response time of the biomarkers is assumed to be slow and remains constant compared with rapid forcing by the impinging stellar flares. This point should be further explored in future work with time-dependent models. We estimate the NO(x) production using an air shower approach and evaluate the implications using a climate-chemical model of the planetary atmosphere. O(3) formation proceeds via the reaction O+O(2)+M→O(3)+M. At high NO(x) abundances, the O atoms arise mainly from NO(2) photolysis, whereas on Earth this occurs via the photolysis of molecular oxygen (O(2)). For the flaring case, O(3) is mainly destroyed via direct titration, NO+O(3)→NO(2)+O(2), and not via the familiar catalytic cycle photochemistry, which occurs on Earth. For scenarios with low O(3), Rayleigh scattering by the main atmospheric gases (O(2), N(2), and CO(2)) became more important for shielding the planetary surface from UV radiation. A major result of this work is that the biomarker O(3) survived all the stellar-activity scenarios considered except for the strong

  20. Lifetimes of organic photovoltaics: photochemistry, atmosphere effects and barrier layers in ITO-MEHPPV:PCBM-aluminium devices

    DEFF Research Database (Denmark)

    Krebs, Frederik C; Carlé, Jon Eggert; Cruys-Bagger, N.

    2005-01-01

    Large area polymer photovoltaic cells based on poly[(2-methoxy-5-ethylhexyloxy)-1, 4-phenylenevinylene] (MEH-PPV) and [6,6]-phenyl-C-61-butyric acid methyl ester (PCBM) were prepared. The lifetimes of the photovoltaic cells were studied in terms of the atmosphere, handling, electrode treatment, m...

  1. THE APSIS EXPERIMENT: SIMULATING TITAN'S UPPER ATMOSPHERE AND ITS PHOTOCHEMISTRY IN THE VACUUM ULTRA-VIOLET (VUV)

    OpenAIRE

    Tigrine, Sarah; Carrasco, Nathalie; Vettier, Ludovic; Nahon, Laurent

    2015-01-01

    International audience; Titan, the largest moon of Saturn, has a dense atmosphere whose upper layers are mainly composed of methane (CH4) and molecular nitrogen (N2). The Cassini mission revealed that the interaction between those molecules and the solar VUV photons, as well as the electrons from Saturn’s magnetosphere, leads to a complex chemistry.Moreover, this naturally ionized environment contains heavy organic molecules like benzene (C6H6) even at altitudes higher than 900 km.The presenc...

  2. Sensitivity and uncertainty analysis of atmospheric ozone photochemistry models. Final report, September 30, 1993--December 31, 1998

    Energy Technology Data Exchange (ETDEWEB)

    Smith, G.P.

    1999-03-01

    The author has examined the kinetic reliability of ozone model predictions by computing direct first-order sensitivities of model species concentrations to input parameters: S{sub ij} = [dC{sub i}/C{sub i}]/[dk{sub j}/k{sub j}], where C{sub i} is the abundance of species i (e.g., ozone) and k{sub j} is the rate constant of step j (reaction, photolysis, or transport), for localized boxes from the LLNL 2-D diurnally averaged atmospheric model. An ozone sensitivity survey of boxes at altitudes of 10--55 km, 2--62N latitude, for spring, equinox, and winter is presented. Ozone sensitivities are used to evaluate the response of model predictions of ozone to input rate coefficient changes, to propagate laboratory rate uncertainties through the model, and to select processes and regions suited to more precise measurements. By including the local chemical feedbacks, the sensitivities quantify the important roles of oxygen and ozone photolysis, transport from the tropics, and the relation of key catalytic steps and cycles in regulating stratospheric ozone as a function of altitude, latitude, and season. A sensitivity-uncertainty analysis uses the sensitivity coefficients to propagate laboratory error bars in input photochemical parameters and estimate the net model uncertainties of predicted ozone in isolated boxes; it was applied to potential problems in the upper stratospheric ozone budget, and also highlights superior regions for model validation.

  3. Photochemistry of Flavonoids

    Directory of Open Access Journals (Sweden)

    Jan H. Van der Westhuizen

    2010-08-01

    Full Text Available Flavonoids and their photochemical transformations play an important role in biological processes in nature. Synthetic photochemistry allows access to molecules that cannot be obtained via more conventional methods. This review covers all published synthetic photochemical transformations of the different classes of flavonoids. It is first comprehensive review on the photochemistry of flavonoids.

  4. Photochemistry on solid surfaces

    CERN Document Server

    Matsuura, T

    1989-01-01

    The latest developments in photochemistry on solid surfaces, i.e. photochemistry in heterogeneous systems, including liquid crystallines, are brought together for the first time in a single volume. Distinguished photochemists from various fields have contributed to the book which covers a number of important applications: molecular photo-devices for super-memory, photochemical vapor deposition to produce thin-layered electronic semiconducting materials, sensitive optical media, the control of photochemical reactions pathways, etc. Photochemistry on solid surfaces is now a major field and this

  5. Photochemistry research at NREL

    Energy Technology Data Exchange (ETDEWEB)

    Lyons, C.E.; Carlson, C.E. [National Renewable Energy Laboratory, Golden, CO (United States)

    1996-09-01

    Photochemistry research team at NREL conducts research and development work in all R&D areas, basic, applied, demonstration and transfer to commercialization. Basic research includes core PCO R&D and catalysts work as well as conducting research into new photochemistry areas such as photoinduced adsorption and high temperature solar PCO. Applied research work consists of remediation of chloroethylenes in gas phase, gas phase solar photoreactor development, and application research including indoor air quality, hybrid biological/PCO processes and more. We are demonstrating the PCO treatment technology in the gas phase with SEMATECH through CRADA work and remediation of organics in aqueous phase through the Solarchem Environmental Systems. We are working with IT through a CRADA to transfer the PCO gas phase remediation technology to IT to commercialize this promising -technology. Photochemistry research conducted at NREL spans the R&D spectrum from basic research through technology demonstration with the goal of technology commercialization.

  6. Photochemistry of materials in the stratosphere

    Energy Technology Data Exchange (ETDEWEB)

    Johnston, H.S. [Lawrence Berkeley Laboratories, CA (United States)

    1993-12-01

    This research is concerned with global change in the atmosphere, including photochemical modeling and, in the past, experimental gas-phase photochemistry involving molecular dynamics and laboratory study of atmospheric chemical reactions. The experimental work on this project concluded in August 1991, but there is a back-log of several journal articles to be written and submitted for publication. The theoretical work involves photochemical modeling in collaboration with Lawrence Livermore National Laboratory (LLNL) and advising the Upper Atmosphere Research Program on Atmospheric Effects of Stratospheric Aircraft, National Aeronautics and Space Administration (NASA).

  7. 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.

  8. Recent Advances in Photochemistry

    Indian Academy of Sciences (India)

    Unknown

    The formation of the Asian and Oceanic Photochemistry Association (APA) was for- mally announced during the APC-2002. This international society will catalyse R&D activities and bring together researchers in various institutions and the industry in differ- ent Asian countries. We take this opportunity to thank the Board of ...

  9. Atmospheric propagation and combining of high-power lasers.

    Science.gov (United States)

    Nelson, W; Sprangle, P; Davis, C C

    2016-03-01

    In this paper, we analyze beam combining and atmospheric propagation of high-power lasers for directed-energy (DE) applications. The large linewidths inherent in high-power fiber and slab lasers cause random phase and intensity fluctuations that occur on subnanosecond time scales. Coherently combining these high-power lasers would involve instruments capable of precise phase control and operation at rates greater than ∼10  GHz. To the best of our knowledge, this technology does not currently exist. This presents a challenging problem when attempting to phase lock high-power lasers that is not encountered when phase locking low-power lasers, for example, at milliwatt power levels. Regardless, we demonstrate that even if instruments are developed that can precisely control the phase of high-power lasers, coherent combining is problematic for DE applications. The dephasing effects of atmospheric turbulence typically encountered in DE applications will degrade the coherent properties of the beam before it reaches the target. Through simulations, we find that coherent beam combining in moderate turbulence and over multikilometer propagation distances has little advantage over incoherent combining. Additionally, in cases of strong turbulence and multikilometer propagation ranges, we find nearly indistinguishable intensity profiles and virtually no difference in the energy on the target between coherently and incoherently combined laser beams. Consequently, we find that coherent beam combining at the transmitter plane is ineffective under typical atmospheric conditions.

  10. Supramolecular photochemistry and solar cells

    Directory of Open Access Journals (Sweden)

    IHA NEYDE YUKIE MURAKAMI

    2000-01-01

    Full Text Available Supramolecular photochemistry as well as solar cells are fascinating topics of current interest in Inorganic Photochemistry and very active research fields which have attracted wide attention in last two decades. A brief outline of the investigations in these fields carried out in our Laboratory of Inorganic Photochemistry and Energy Conversion is given here with no attempt of an exhaustive coverage of the literature. The emphasis is placed on recent work and information on the above mentioned subjects. Three types of supramolecular systems have been the focus of this work: (i cage-type coordination compounds; (ii second-sphere coordination compounds, exemplified by ion-pair photochemistry of cobalt complexes and (iii covalently-linked systems. In the latter, modulation of the photoluminescence and photochemistry of some rhenium complexes are discussed. Solar energy conversion and development of thin-layer photoelectrochemical solar cells based on sensitization of nanocrystalline semiconductor films by some ruthenium polypyridyl complexes are presented as an important application that resulted from specifically engineered artificial assemblies.

  11. Active molecular iodine photochemistry in the Arctic

    Science.gov (United States)

    Raso, Angela R. W.; Custard, Kyle D.; May, Nathaniel W.; Tanner, David; Newburn, Matt K.; Walker, Lawrence; Moore, Ronald J.; Huey, L. G.; Alexander, Liz; Shepson, Paul B.; Pratt, Kerri A.

    2017-09-01

    During springtime, the Arctic atmospheric boundary layer undergoes frequent rapid depletions in ozone and gaseous elemental mercury due to reactions with halogen atoms, influencing atmospheric composition and pollutant fate. Although bromine chemistry has been shown to initiate ozone depletion events, and it has long been hypothesized that iodine chemistry may contribute, no previous measurements of molecular iodine (I2) have been reported in the Arctic. Iodine chemistry also contributes to atmospheric new particle formation and therefore cloud properties and radiative forcing. Here we present Arctic atmospheric I2 and snowpack iodide (I-) measurements, which were conducted near Utqiaġvik, AK, in February 2014. Using chemical ionization mass spectrometry, I2 was observed in the atmosphere at mole ratios of 0.3-1.0 ppt, and in the snowpack interstitial air at mole ratios up to 22 ppt under natural sunlit conditions and up to 35 ppt when the snowpack surface was artificially irradiated, suggesting a photochemical production mechanism. Further, snow meltwater I- measurements showed enrichments of up to ˜1,900 times above the seawater ratio of I-/Na+, consistent with iodine activation and recycling. Modeling shows that observed I2 levels are able to significantly increase ozone depletion rates, while also producing iodine monoxide (IO) at levels recently observed in the Arctic. These results emphasize the significance of iodine chemistry and the role of snowpack photochemistry in Arctic atmospheric composition, and imply that I2 is likely a dominant source of iodine atoms in the Arctic.

  12. Active molecular iodine photochemistry in the Arctic.

    Science.gov (United States)

    Raso, Angela R W; Custard, Kyle D; May, Nathaniel W; Tanner, David; Newburn, Matt K; Walker, Lawrence; Moore, Ronald J; Huey, L G; Alexander, Liz; Shepson, Paul B; Pratt, Kerri A

    2017-09-19

    During springtime, the Arctic atmospheric boundary layer undergoes frequent rapid depletions in ozone and gaseous elemental mercury due to reactions with halogen atoms, influencing atmospheric composition and pollutant fate. Although bromine chemistry has been shown to initiate ozone depletion events, and it has long been hypothesized that iodine chemistry may contribute, no previous measurements of molecular iodine (I2) have been reported in the Arctic. Iodine chemistry also contributes to atmospheric new particle formation and therefore cloud properties and radiative forcing. Here we present Arctic atmospheric I2 and snowpack iodide (I(-)) measurements, which were conducted near Utqiaġvik, AK, in February 2014. Using chemical ionization mass spectrometry, I2 was observed in the atmosphere at mole ratios of 0.3-1.0 ppt, and in the snowpack interstitial air at mole ratios up to 22 ppt under natural sunlit conditions and up to 35 ppt when the snowpack surface was artificially irradiated, suggesting a photochemical production mechanism. Further, snow meltwater I(-) measurements showed enrichments of up to ∼1,900 times above the seawater ratio of I(-)/Na(+), consistent with iodine activation and recycling. Modeling shows that observed I2 levels are able to significantly increase ozone depletion rates, while also producing iodine monoxide (IO) at levels recently observed in the Arctic. These results emphasize the significance of iodine chemistry and the role of snowpack photochemistry in Arctic atmospheric composition, and imply that I2 is likely a dominant source of iodine atoms in the Arctic.

  13. Photochemistry on Pluto - I. Hydrocarbons and aerosols

    Science.gov (United States)

    Luspay-Kuti, Adrienn; Mandt, Kathleen; Jessup, Kandis-Lea; Kammer, Joshua; Hue, Vincent; Hamel, Mark; Filwett, Rachael

    2017-11-01

    In light of the recent New Horizons flyby measurements, we present a coupled ion-neutral-photochemistry model developed for simulating the atmosphere of Pluto. Our model results closely match the observed density profiles of CH4, N2 and the C2 hydrocarbons in the altitude range where available New Horizons measurements are most accurate (above ∼100-200 km). We found a high eddy coefficient of 106 cm2 s-1 from the surface to an altitude of 150 km, and 3 × 106 cm2 s-1 above 150 km for Pluto's atmosphere. Our results demonstrate that C2 hydrocarbons must stick to and be removed by aerosol particles in order to reproduce the C2 profiles observed by New Horizons. Incorporation into aerosols in Pluto's atmosphere is a significantly more effective process than condensation, and we found that condensation alone cannot account for the observed shape of the vertical profiles. We empirically determined the sticking efficiency of C2 hydrocarbons to aerosol particles as a function of altitude, and found that the sticking efficiency of C2 hydrocarbons is inversely related to the aerosol surface area. Aerosols must harden and become less sticky as they age in Pluto's atmosphere. Such hardening with ageing is both necessary and sufficient to explain the vertical profiles of C2 hydrocarbons in Pluto's atmosphere. This result is in agreement with the fundamental idea of aerosols hardening as they age, as proposed for Titan's aerosols.

  14. NUCAPS: NOAA Unique Combined Atmospheric Processing System Cloud-Cleared Radiances (CCR)

    Data.gov (United States)

    National Oceanic and Atmospheric Administration, Department of Commerce — This dataset consists of Cloud-Cleared Radiances (CCRs) from the NOAA Unique Combined Atmospheric Processing System (NUCAPS). NUCAPS was developed by the NOAA/NESDIS...

  15. NUCAPS: NOAA Unique Combined Atmospheric Processing System Outgoing Longwave Radiation (OLR)

    Data.gov (United States)

    National Oceanic and Atmospheric Administration, Department of Commerce — This data set consists of Outgoing Longwave Radiation (OLR) from the NOAA Unique Combined Atmospheric Processing System (NUCAPS). NUCAPS was developed by the...

  16. Active molecular iodine photochemistry in the Arctic

    Energy Technology Data Exchange (ETDEWEB)

    Raso, Angela R.; Custard, Kyle D.; May, Nathaniel W.; Tanner, David; Newburn, Matthew K.; Walker, Lawrence R.; Moore, Ronald J.; Huey, L. G.; Alexander, Lizabeth; Shepson, Paul B.; Pratt, Kerri A.

    2017-09-05

    During springtime, the Arctic atmospheric boundary layer undergoes frequent rapid depletions in ozone and gaseous elemental mercury due to reactions with halogen atoms, influencing atmospheric composition and pollutant fate. Although bromine chemistry has been shown to initiate ozone depletion events, and it has long been hypothesized that iodine chemistry may contribute, no previous measurements of molecular iodine (I2) have been reported in the Arctic. Iodine chemistry also contributes to atmospheric new particle formation and therefore cloud properties and radiative forcing. Here we present Arctic atmospheric I2 and snowpack iodide (I-) measurements, which were conducted near Utqiagvik, AK, in February 2014. Using chemical ionization mass spectrometry, I2 was observed in the atmosphere at mole ratios of 0.3–1.0 ppt, and in the snowpack interstitial air at mole ratios up to 22 ppt under natural sunlit conditions and up to 35 ppt when the snowpack surface was artificially irradiated, suggesting a photochemical production mechanism. Further, snow meltwater I-measurements showed enrichments of up to ~1,900 times above the seawater ratio of I-/Na+, consistent with iodine activation and recycling. Modeling shows that observed I2 levels are able to significantly increase ozone depletion rates, while also producing iodine monoxide (IO) at levels recently observed in the Arctic. These results emphasize the significance of iodine chemistry and the role of snowpack photochemistry in Arctic atmospheric composition, and imply that I2 is likely a dominant source of iodine atoms in the Arctic.

  17. Ultraviolet photochemistry of cyanoacetylene: Application to Titan. [Abstract only

    Science.gov (United States)

    Clarke, D. W.; Ferris, J. P.

    1994-01-01

    Cyanoacetylene is believed to have had a central role in the formation of the pyrimidines essential for RNA synthesis leading to the origin of life on Earth. Cyanoacetylene has also been detected on Titan, Saturn's largest moon, and the only moon in the solar system that possesses a dense atmosphere. It is generally accepted that photochemistry plays a major role in the formation of the complex organic molecules and aerosols found in Titan's atmosphere. Because of its long wavelength absorption and low dissociation threshold it is expected that cyanoacetylene is an important part of these photochemical processes. Since cyanoacetylene would also have been subject to ultraviolet light in the atmosphere of early Earth, an investigation of cyanoacetylene photochemistry on Titan might lead to a better understanding of both the photochemical reactions occurring on primitive earth and the processes of chemical evolution as they occur in planetary atmospheres. The effects of irradiation wavelength, mixing with Titan's atmospheric gases, reducing the temperature and lowering cyanoacetylene partial pressures on product formation and polymer composition have been determined with the ultimate goal of understanding the chemical transformations taking place in Titan's atmosphere.

  18. Hydrocarbon photochemistry and Lyman alpha albedo of Jupiter

    OpenAIRE

    Yung, Yuk L.; Strobel, Darrell F.

    1980-01-01

    A combined study of hydrocarbon and atomic hydrogen photochemistry is made to calculate self-consistently the Lɑ albedo of Jupiter. It is shown that the Lɑ emissions observed by Voyagers I and II can be explained by resonance scattering of sunlight. Precipitation-of energetic particles from the magnetosphere can provide the large required source of atomic hydrogen, although the contribution of direct particle excitation to the disk-averaged brightness is insignificant. The variability of t...

  19. Determination of O2(a1 delta g) and O2(b1 sigma+ g) yields in the reaction O + ClO --> Cl + O2: implications for photochemistry in the atmosphere of Venus

    Science.gov (United States)

    Leu, M. T.; Yung, Y. L.

    1987-01-01

    A discharge flow apparatus with chemiluminescence detector has been used to study the reaction O + ClO --> Cl + O2, where O2 = O2(a1 delta g) or O2(b1 sigma+ g). The measured quantum yields for producing O2(a1 delta g) and O2(b1 sigma+ g) in the above reaction are less than 2.5 x 10(-2) and equal to (4.4 +/- 1.1) x 10(-4), respectively. The observed O2(a1 delta g) airglow of Venus cannot be explained in the context of standard photochemistry using our experimental results and those reported in recent literature. The possibility of an alternative source of O atoms derived from SO2 photolysis in the mesosphere of Venus is suggested.

  20. CHEM2D-OPP: A new linearized gas-phase ozone photochemistry parameterization for high-altitude NWP and climate models

    Directory of Open Access Journals (Sweden)

    J. P. McCormack

    2006-01-01

    Full Text Available The new CHEM2D-Ozone Photochemistry Parameterization (CHEM2D-OPP for high-altitude numerical weather prediction (NWP systems and climate models specifies the net ozone photochemical tendency and its sensitivity to changes in ozone mixing ratio, temperature and overhead ozone column based on calculations from the CHEM2D interactive middle atmospheric photochemical transport model. We evaluate CHEM2D-OPP performance using both short-term (6-day and long-term (1-year stratospheric ozone simulations with the prototype high-altitude NOGAPS-ALPHA forecast model. An inter-comparison of NOGAPS-ALPHA 6-day ozone hindcasts for 7 February 2005 with ozone photochemistry parameterizations currently used in operational NWP systems shows that CHEM2D-OPP yields the best overall agreement with both individual Aura Microwave Limb Sounder ozone profile measurements and independent hemispheric (10°–90° N ozone analysis fields. A 1-year free-running NOGAPS-ALPHA simulation using CHEM2D-OPP produces a realistic seasonal cycle in zonal mean ozone throughout the stratosphere. We find that the combination of a model cold temperature bias at high latitudes in winter and a warm bias in the CHEM2D-OPP temperature climatology can degrade the performance of the linearized ozone photochemistry parameterization over seasonal time scales despite the fact that the parameterized temperature dependence is weak in these regions.

  1. Isoprene photochemistry over the Amazon rainforest

    Science.gov (United States)

    Liu, Yingjun; Brito, Joel; Dorris, Matthew R.; Rivera-Rios, Jean C.; Seco, Roger; Bates, Kelvin H.; Artaxo, Paulo; Duvoisin, Sergio; Keutsch, Frank N.; Kim, Saewung; Goldstein, Allen H.; Guenther, Alex B.; Manzi, Antonio O.; Souza, Rodrigo A. F.; Springston, Stephen R.; Watson, Thomas B.; McKinney, Karena A.; Martin, Scot T.

    2016-05-01

    Isoprene photooxidation is a major driver of atmospheric chemistry over forested regions. Isoprene reacts with hydroxyl radicals (OH) and molecular oxygen to produce isoprene peroxy radicals (ISOPOO). These radicals can react with hydroperoxyl radicals (HO2) to dominantly produce hydroxyhydroperoxides (ISOPOOH). They can also react with nitric oxide (NO) to largely produce methyl vinyl ketone (MVK) and methacrolein (MACR). Unimolecular isomerization and bimolecular reactions with organic peroxy radicals are also possible. There is uncertainty about the relative importance of each of these pathways in the atmosphere and possible changes because of anthropogenic pollution. Herein, measurements of ISOPOOH and MVK + MACR concentrations are reported over the central region of the Amazon basin during the wet season. The research site, downwind of an urban region, intercepted both background and polluted air masses during the GoAmazon2014/5 Experiment. Under background conditions, the confidence interval for the ratio of the ISOPOOH concentration to that of MVK + MACR spanned 0.4-0.6. This result implies a ratio of the reaction rate of ISOPOO with HO2 to that with NO of approximately unity. A value of unity is significantly smaller than simulated at present by global chemical transport models for this important, nominally low-NO, forested region of Earth. Under polluted conditions, when the concentrations of reactive nitrogen compounds were high (>1 ppb), ISOPOOH concentrations dropped below the instrumental detection limit (<60 ppt). This abrupt shift in isoprene photooxidation, sparked by human activities, speaks to ongoing and possible future changes in the photochemistry active over the Amazon rainforest.

  2. Hydrocarbon photochemistry and Lyman alpha albedo of Jupiter

    Science.gov (United States)

    Yung, Y. L.; Strobel, D. F.

    1980-01-01

    A combined study of hydrocarbon and atomic hydrogen photochemistry is made to calculate self-consistently the L alpha albedo of Jupiter. It is shown that the L alpha emissions observed by Voyagers I and II can be explained by resonance scattering of sunlight. Precipitation of energetic particles from the magnetosphere can provide the large required source of atomic hydrogen, although the contribution of direct particle excitation to the disk-averaged brightness is insignificant. The variability of the L alpha brightness inferred from many observations in recent years is examined. The large difference in the brightness of the He 584 A resonance line observed by Pioneer and Voyager is briefly discussed. Driving the photochemistry by solar ultraviolet radiation alone yields a maximum mixing ratio of C2H6 + C2H2 at 0.01 atm of about 4 x 10 to the -6th. The possibility of additional CH4 dissociation from precipitation of magnetospheric particles is discussed. The photochemistry of C2H2 and C2H3 is sufficiently uncertain not to permit accurate calculations of their densities and the ratio C2H6/C2H2.

  3. Perfect Strangers: Inorganic Photochemistry and Nucleic Acids

    Science.gov (United States)

    Carter, Pamela J.; Ciftan, Suzanne A.; Sistare, Mark F.; Holden Thorp, H.

    1997-06-01

    The applications of inorganic photochemistry to nucleic acid chemistry are discussed. A brief review of nucleic acid structure is given. Methods for probing DNA using emissive inorganic complexes are discussed. Photoreactions that damage DNA by hydrogen atom transfer from sugar or electron abstraction from guanine are presented. The method of photochemical footprinting using a diplatinum photocatalyst is described. The final section discusses advances in combinatorial selection experiments that increase the urgency for rapid screening methods such as those derived from inorganic photochemistry.

  4. Photochemistry and photophysics of coordination compounds

    Energy Technology Data Exchange (ETDEWEB)

    Yersin, H.; Volger, A. (ed.)

    1987-01-01

    This softbound volume of typescript papers is the result of a symposium held in Bavaria in 1987. The many papers in it are grouped as follows: Metal-centered Excited States; Photophysics and Photochemistry of Cr(III) Complexes; Excited State Properties of Tris-2,2'-Bipyridine Ruthenium(II) and Related Complexes; Photoredox Processes; Organometallic Photochemistry; and Methods, Applications, and Other Aspects.

  5. Do Photochemical Hazes Cloud the Atmosphere of 51 Eri b?

    Science.gov (United States)

    Marley, Mark; Zahnle, Kevin; Moses, Julianne; Morley, Caroline

    2015-12-01

    The first young giant planet to be discovered by the Gemini Planet Imager was the ~ 2MJ planet 51 Eri b. This ~20 Myr old young Jupiter is the first directly imaged planet to show unmistakable methane in H band. To constrain the planet’s mass, atmospheric temperature, and composition, the GPI J and H band spectra as well as some limited photometric points were compared to the predictions of substellar atmosphere models. The best fitting models reported in the discovery paper (Macintosh et al. 2015) relied upon a combination of clear and cloudy atmospheric columns to reproduce the data. In the atmosphere of an object as cool as 700 K the global silicate and iron clouds would be expected to be found well below the photosphere, although strong vertical mixing in the low gravity atmosphere is a possibility. Instead, clouds of Na2S, as have been detected in brown dwarf atmospheres, are a likely source of particle opacity. As a third explanation we have explored whether atmospheric photochemistry, driven by the UV flux from the primary star, may yield hazes that also influence the observed spectrum of the planet. To explore this possibility we have modeled the atmospheric photochemistry of 51 Eri b using two state-of-the-art photochemical models, both capable of predicting yields of complex hydrocarbons under various atmospheric conditions. We also have explored whether photochemical products can alter the equilibrium temperature profile of the atmosphere. In our presentation we will summarize the modeling approach employed to characterize 51 Eri b, explaining constraints on the planet’s effective temperature, gravity, and atmospheric composition and also present results of our studies of atmospheric photochemistry. We will discuss whether photochemical hazes could indeed be responsible for the particulate opacity that apparently sculpts the spectrum of the planet.

  6. Model for Atmospheric Propagation of Spatially Combined Laser Beams

    Science.gov (United States)

    2016-09-01

    are various types of SSL structures but only fiber and slab SSLs have been used as DE weapons. 2.4.2.1 Slab Solid-State Lasers In a slab SSL, the gain...Demonstration (MLD) that leveraged slab SSL technology. In 2010, the MLD project group coherently combined seven 15 kW slab SSLs to create a 1.064 µm laser with...an output power of 105 kW [1]. During field testing, the MLD successfully tracked and engaged small boats in a marine environment. In May 2011, a

  7. Photochemistry of iron citrates initiated by UV-VIS light

    Science.gov (United States)

    Corral Arroyo, Pablo; Dou, Jing; Alpert, Peter; Krieger, Ulrich; Ammann, Markus

    2017-04-01

    Aerosol aging refers to the multitude of physical and chemical transformation atmospheric particles undergo, which play an important role in the impact of aerosols on climate, air quality and health. Aging processes may be started by chromophores, which act as photocatalysts that induce the oxidation of non-absorbing molecules [1]. Iron (Fe(III)) carboxylate complexes absorb light below about 500 nm, which is followed by ligand to metal charge transfer (LMCT) resulting in the reduction of iron to Fe(II) and oxidation of the carboxylate ligands, a process that represents an important sink of organic acids in the troposphere [2]. Our goal is to investigate how these photochemical processes contribute to the change of chemical and physical properties of the aerosol particles. To achieve this scope, we carry out coated wall flow tube experiments, exposing films with iron citrate to UV light, which will give information about the radical and LVOC production (connecting the CWFT to a Chemiluminescent Detector or PTR-TOF-MS respectively). From extracting and analyzing the films after irradiation with UV light, we obtain a profile of low-volatility products evolving from the photochemistry of iron citrates. By Scanning Transmission X-Ray Microspectroscopy (STXM) we analyze changes in the C K-edge and Fe L-edge in particles loaded with iron citrate upon exposure to light and follow their chemical and structural evolution upon photochemical oxidation in situ to investigate the degradation kinetics under varying environmental conditions. [1] George G., Ammann M., D'Anna B., Donaldson D. J., Nizkorodov S. A., Heterogeneous photochemistry in the Atmosphere, Chem. Rev., 2015, 115 (10), pp 4218-4258 [2] Weller, C., Horn, S., and Herrmann, H.: Photolysis of Fe(III) carboxylate complexes: Fe(II) quantum yields and reaction mechanisms, Photochemistry and Photobiology A: Chemistry, 268, 24-36, 2013.

  8. Atmospheric nitrogen uptake by soyabean cultivars in combination with Bradyrhizobium japonicum strains

    Directory of Open Access Journals (Sweden)

    A. D. P Botha

    1997-07-01

    Full Text Available A pot experiment was conducted, using three soyabean (Giycinc max (L. Merrill cultivars (Forrest, Prima and A5409 inoculated at planting, with no (0 and two Bradyrhizobium japonicum strains (WB1 and WB74. The objectives were to investigate the effect of cultivar-rhizobial strain combinations on biomass and N derived from the atmosphere (Ndfa and to compare the atmospheric N uptake determined by the isolope technique, with the conventional method.

  9. LOW POWER UPCONVERSION FOR SOLAR FUELS PHOTOCHEMISTRY

    Energy Technology Data Exchange (ETDEWEB)

    Castellano, Felix N. [Bowling Green State University

    2013-08-05

    Earth abundant copper(I) diimine complexes represent a renewable and economically feasible alternative to commonly used heavy metal containing chromophores. In the metal-to-ligand charge transfer (MLCT) excited state, copper(I) diimine complexes typically undergo a significant structural rearrangement, leading to molecules with large Stokes shifts and very short excited state lifetimes, thereby limiting their usefulness as sensitizers in bimolecular electron and triplet energy transfer reactions. Strategically placed bulky substituents on the coordinating phenanthroline ligands have proven useful in restricting the transiently produced excited state Jahn-Teller distortion, leading to longer-lived excited states. By combining bulky sec-butyl groups in the 2- and 9- positions with methyl groups in the 3-,4-, 7-, and 8- positions, a remarkably long-lived (2.8 μs in DCM) copper(I) bis-phenanthroline complex, [Cu(dsbtmp)2]+, has been synthesized and characterized. Unlike other copper(I) diimine complexes, [Cu(dsbtmp)2]+ also retains a μs lifetime in coordinating solvents such as acetonitrile and water as a result of the cooperative sterics inherent in the molecular design. Preliminary results on the use of this complex in hydrogen-forming homogeneous photocatalysis is presented. Photon upconversion based on sensitized triplet-triplet annihilation (TTA) represents a photochemical means to generate high-energy photons (or high-energy chemical products) from low-energy excitation, having potential applications in solar energy conversion and solar fuels producing devices. For the first time, synthetically facile and earth abundant Cu(I) MLCT sensitizers have been successfully incorporated into two distinct photochemical upconversion schemes, affording both red-to-green and orange-to-blue wavelength conversions. Preliminary results on aqueous-based photochemical upconversion as well as intramolecular Sn(IV) porphyrins containing axially coordinated aromatic hydrocarbon

  10. Fifteenth DOE solar photochemistry research conference

    Energy Technology Data Exchange (ETDEWEB)

    1991-01-01

    This is a compilation of abstracts from the Fifteenth DOE Solar Photochemistry Research Conference hosted by the Solar Energy Research Institute which took place June 2--6, 1991. A large variety of topics pertinent to solar energy conversion are covered, including photoinduced electron transfer, photochemical energy conversion, and photosynthetic energy conversion. (GHH)

  11. Quinone Photoreactivity: An Undergraduate Experiment in Photochemistry

    Science.gov (United States)

    Vaughan, Pamela P.; Cochran, Michael; Haubrich, Nicole

    2010-01-01

    An experiment exploring the photochemical properties of quinones was developed. Their unique photochemistry and highly reactive nature make them an ideal class of compounds for examining structure-activity relationships. For several substituted quinones, photochemical reactivity was related to structure and ultimately to the Gibbs energy for…

  12. Combined Effects of Atmospheric and Seafloor Iron Fluxes to the Glacial Ocean

    Science.gov (United States)

    Muglia, Juan; Somes, Christopher J.; Nickelsen, Levin; Schmittner, Andreas

    2017-11-01

    Changes in the ocean iron cycle could help explain the low atmospheric CO2 during the Last Glacial Maximum (LGM). Previous modeling studies have mostly considered changes in aeolian iron fluxes, although it is known that sedimentary and hydrothermal fluxes are important iron sources for today's ocean. Here we explore effects of preindustrial-to-LGM changes in atmospheric dust, sedimentary, and hydrothermal fluxes on the ocean's iron and carbon cycles in a global coupled biogeochemical-circulation model. Considering variable atmospheric iron solubility decreases LGM surface soluble iron fluxes compared with assuming constant solubility. This limits potential increases in productivity and export production due to surface iron fertilization, lowering atmospheric CO2 by only 4 ppm. The effect is countered by a decrease in sedimentary flux due to lower sea level, which increases CO2 by 15 ppm. Assuming a 10 times higher iron dust solubility in the Southern Ocean, combined with changes in sedimentary flux, we obtain an atmospheric CO2 reduction of 13 ppm. The high uncertainty in the iron fluxes does not allow us to determine the net direction and magnitude of variations in atmospheric CO2 due to changes in the iron cycle. Our model does not account for changes to iron-binding ligand concentrations that could modify the results. We conclude that when evaluating glacial-interglacial changes in the ocean iron cycle, not only surface but also seafloor fluxes must be taken into account.

  13. A Framework to Combine Low- and High-resolution Spectroscopy for the Atmospheres of Transiting Exoplanets

    Science.gov (United States)

    Brogi, M.; Line, M.; Bean, J.; Désert, J.-M.; Schwarz, H.

    2017-04-01

    Current observations of the atmospheres of close-in exoplanets are predominantly obtained with two techniques: low-resolution spectroscopy with space telescopes and high-resolution spectroscopy from the ground. Although the observables delivered by the two methods are in principle highly complementary, no attempt has ever been made to combine them, perhaps due to the different modeling approaches that are typically used in their interpretation. Here, we present the first combined analysis of previously published dayside spectra of the exoplanet HD 209458 b obtained at low resolution with HST/Wide Field Camera 3 (WFC3) and Spitzer/IRAC and at high resolution with VLT/CRIRES. By utilizing a novel retrieval algorithm capable of computing the joint probability distribution of low- and high-resolution spectra, we obtain tight constraints on the chemical composition of the planet’s atmosphere. In contrast to the WFC3 data, we do not confidently detect H2O at high spectral resolution. The retrieved water abundance from the combined analysis deviates by 1.9σ from the expectations for a solar-composition atmosphere in chemical equilibrium. Measured relative molecular abundances of CO and H2O strongly favor an oxygen-rich atmosphere (C/O exoplanet surveys between the flagship ground- and space-based facilities, which ultimately will be crucial for characterizing potentially habitable planets.

  14. Photochemistry on Pluto: part II HCN and nitrogen isotope fractionation

    Science.gov (United States)

    Mandt, Kathleen; Luspay-Kuti, Adrienn; Hamel, Mark; Jessup, Kandis-Lea; Hue, Vincent; Kammer, Josh; Filwett, Rachael

    2017-11-01

    We have converted our Titan one-dimensional photochemical model to simulate the photochemistry of Pluto's atmosphere and include condensation and aerosol trapping in the model. We find that condensation and aerosol trapping are important processes in producing the HCN altitude profile observed by the Atacama Large Millimeter Array (ALMA). The nitrogen isotope chemistry in Pluto's atmosphere does not appear to significantly fractionate the isotope ratio between N2 and HCN as occurs at Titan. However, our simulations only cover a brief period of time in a Pluto year, and thus only a brief portion of the solar forcing conditions that Pluto's atmosphere experiences. More work is needed to evaluate photochemical fractionation over a Pluto year. Condensation and aerosol trapping appear to have a major impact on the altitude profile of the isotope ratio in HCN. Since ALMA did not detect HC15N in Pluto's atmosphere, we conclude that condensation and aerosol trapping must be much more efficient for HC15N compared to HC14N. The large uncertainty in photochemical fractionation makes it difficult to use any potential current measurement of 14N/15N in N2 to determine the origin of Pluto's nitrogen. More work is needed to understand photochemical fractionation and to evaluate how condensation, sublimation and aerosol trapping will fractionate N2 and HCN.

  15. Modelling photochemistry in alpine valleys

    Directory of Open Access Journals (Sweden)

    G. Brulfert

    2005-01-01

    Full Text Available Road traffic is a serious problem in the Chamonix Valley, France: traffic, noise and above all air pollution worry the inhabitants. The big fire in the Mont-Blanc tunnel made it possible, in the framework of the POVA project (POllution in Alpine Valleys, to undertake measurement campaigns with and without heavy-vehicle traffic through the Chamonix and Maurienne valleys, towards Italy (before and after the tunnel re-opening. Modelling is one of the aspects of POVA and should make it possible to explain the processes leading to episodes of atmospheric pollution, both in summer and in winter. Atmospheric prediction model ARPS 4.5.2 (Advanced Regional Prediction System, developed at the CAPS (Center for Analysis and Prediction of Storms of the University of Oklahoma, enables to resolve the dynamics above a complex terrain. This model is coupled to the TAPOM 1.5.2 atmospheric chemistry (Transport and Air POllution Model code developed at the Air and Soil Pollution Laboratory of the Ecole Polytechnique Fédérale de Lausanne. The numerical codes MM5 and CHIMERE are used to compute large scale boundary forcing. This paper focuses on modelling Chamonix valley using 300-m grid cells to calculate the dynamics and the reactive chemistry which makes possible to accurately represent the dynamics in the Chamonix valley (slope and valley winds and to process chemistry at fine scale. The summer 2003 intensive campaign was used to validate the model and to study chemistry. NOy according to O3 reduction demonstrates a VOC controlled regime, different from the NOx controlled regime expected and observed in the nearby city of Grenoble.

  16. 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.

  17. Photochemistry of cyclohexane on Cu(111).

    Science.gov (United States)

    Yamaguchi, Dai; Matsumoto, Taketoshi; Watanabe, Kazuya; Takagi, Noriaki; Matsumoto, Yoshiyasu

    2006-01-07

    The photochemistry of cyclohexane on Cu(111) and its excitation mechanism have been studied by temperature-programmed desorption, ultraviolet and X-ray photoelectron spectroscopy. Cyclohexane weakly adsorbed on Cu(111) has been known to show a broadened and redshifted CH stretching band, i.e., CH vibrational mode softening. Although no dehydrogenation takes place thermally on this surface and by the irradiation of photons at 5.0 eV, adsorbed cyclohexane is dissociated to cyclohexyl and hydrogen by the irradiation of photons at 6.4 eV. This is a marked contrast to cyclohexane in the gas phase where the onset of absorption is located at 7 eV. When the surface irradiated by 6.4-eV photons is further annealed, cyclohexyl is dehydrogenated to form cylcohexene that desorbs at 230 K. The systematic measurements of photochemical cross sections at 6.4 eV with linearly polarized light as a function of incident angle indicate that the electronic transition from the highest occupied band of cyclohexane to a partially occupied hybridized band near the Fermi level is responsible for the photochemistry. The hybridized band is formed by the interactions between the electronic states of cyclohexane and the metal substrate. The role of the hybridized band in the photochemistry and the CH vibrational mode softening is discussed.

  18. Experimental and Theoretical Study on the OH-Reaction Kinetics and Photochemistry of Acetyl Fluoride (CH3C(O)F), an Atmospheric Degradation Intermediate of HFC-161 (C2H5F).

    Science.gov (United States)

    Song, Xinli; Zügner, Gábor L; Farkas, Mária; Illés, Ádám; Sarzyński, Dariusz; Rozgonyi, Tamás; Wang, Baoshan; Dóbé, Sándor

    2015-07-16

    photochemical processes, C-C bond cleavage is by far dominating compared with CO-elimination. The absorption spectrum of AcF has also been determined by displaying a strong blue shift compared with the spectra of aliphatic carbonyls. Consequences of the results on atmospheric chemistry have been discussed.

  19. Dust ablation on the giant planets: Consequences for stratospheric photochemistry

    Science.gov (United States)

    Moses, Julianne I.; Poppe, Andrew R.

    2017-11-01

    Ablation of interplanetary dust supplies oxygen to the upper atmospheres of Jupiter, Saturn, Uranus, and Neptune. Using recent dynamical model predictions for the dust influx rates to the giant planets (Poppe et al., 2016), we calculate the ablation profiles and investigate the subsequent coupled oxygen-hydrocarbon neutral photochemistry in the stratospheres of these planets. We find that dust grains from the Edgeworth-Kuiper Belt, Jupiter-family comets, and Oort-cloud comets supply an effective oxygen influx rate of 1.0-0.7+2.2 ×107 O atoms cm-2 s-1 to Jupiter, 7.4-5.1+16 ×104 cm-2 s-1 to Saturn, 8.9-6.1+19 ×104 cm-2 s-1 to Uranus, and 7.5-5.1+16 ×105 cm-2 s-1 to Neptune. The fate of the ablated oxygen depends in part on the molecular/atomic form of the initially delivered products, and on the altitude at which it was deposited. The dominant stratospheric products are CO, H2O, and CO2, which are relatively stable photochemically. Model-data comparisons suggest that interplanetary dust grains deliver an important component of the external oxygen to Jupiter and Uranus but fall far short of the amount needed to explain the CO abundance currently seen in the middle stratospheres of Saturn and Neptune. Our results are consistent with the theory that all of the giant planets have experienced large cometary impacts within the last few hundred years. Our results also suggest that the low background H2O abundance in Jupiter's stratosphere is indicative of effective conversion of meteoric oxygen to CO during or immediately after the ablation process - photochemistry alone cannot efficiently convert the H2O into CO on the giant planets.

  20. Combined effects of iron and copper from atmospheric dry deposition on ocean productivity

    Science.gov (United States)

    Wang, F. J.; Chen, Y.; Guo, Z. G.; Gao, H. W.; Mackey, K. R.; Yao, X. H.; Zhuang, G. S.; Paytan, A.

    2017-03-01

    Atmospheric deposition can provide nutrients and potential toxicants to marine ecosystem, hence affecting ocean net primary productivity (NPP). Nonetheless, the interactive effects of mixed aerosol components on phytoplankton have rarely been reported. Here we explored the combined effects of iron (Fe) and copper (Cu) on NPP over the East China Sea. In aerosol addition mesocosm experiments, phytoplankton growth was suppressed under high aerosol Cu but was increased when high Cu was accompanied by high Fe in aerosols. A time series of soluble aerosol Fe and Cu deposition was obtained and compared to regional chlorophyll a (Chl a) abundances from Moderate Resolution Imaging Spectroradiometer/Aqua. Strong positive correlations were observed between the dry flux ratios of soluble Fe/Cu and Chl a abundances in the large offshore area, whereas these variables were uncoupled in coastal regions where riverine input and upwelling dominated the biogeochemistry. Current work provides insight into the complex linkage between atmospheric deposition and marine productivity.

  1. 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.

  2. Understanding the Atmosphere of 51 Eri b: Do Photochemical Hazes Cloud the Planets Spectrum?

    Science.gov (United States)

    Marley, Mark Scott; Zahnle, Kevin; Moses, J.; Morley, C.

    2015-01-01

    The first young giant planet to be discovered by the Gemini Planet Imager was the (is) approximately 2MJ planet 51 Eri b. This approximately 20 Myr old young Jupiter is the first directly imaged planet to show unmistakable methane in H band. To constrain the planet's mass, atmospheric temperature, and composition, the GPI J and H band spectra as well as some limited photometric points were compared to the predictions of substellar atmosphere models. The best fitting models reported in the discovery paper (Macintosh et al. 2015) relied upon a combination of clear and cloudy atmospheric columns to reproduce the data. However for an object as cool as 700 K, the origin of the cloud coverage is somewhat puzzling, as the global silicate and iron clouds would be expected to have sunk well below the photosphere by this effective temperature. While strong vertical mixing in these low gravity atmospheres remains a plausible explanation, we have explored whether atmospheric photochemistry, driven by the UV flux from the primary star, may yield hazes that also influence the observed spectrum of the planet. To explore this possibility we have modeled the atmospheric photochemistry of 51 Eri b using two state-of-the-art photochemical models, both capable of predicting yields of complex hydrocarbons under various atmospheric conditions. In our presentation we will summarize the modeling approach employed to characterize 51 Eri b, explaining constraints on the planet's effective temperature, gravity, and atmospheric composition and also present results of our studies of atmospheric photochemistry. We will discuss whether photochemical hazes could indeed be responsible for the particulate opacity that apparently sculpts the spectrum of the planet.

  3. 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.

  4. Photochemistry and photophysics concepts, research, applications

    CERN Document Server

    Balzani , Vincenzo; Juris, Alberto

    2014-01-01

    This textbook covers the spectrum from basic concepts of photochemistry and photophysics to selected examples of current applications and research.Clearly structured, the first part of the text discusses the formation, properties and reactivity of excited states of inorganic and organic molecules and supramolecular species, as well as experimental techniques. The second part focuses on the photochemical and photophysical processes in nature and artificial systems, using a wealth of examples taken from applications in nature, industry and current research fields, ranging from natural photosynth

  5. Efficient photochemistry of coronene:water complexes

    Science.gov (United States)

    Noble, J. A.; Jouvet, C.; Aupetit, C.; Moudens, A.; Mascetti, J.

    2017-03-01

    The photochemistry of ices with polycyclic aromatic hydrocarbons (PAHs) has been extensively studied, but to date no investigation has been made of PAHs in interaction with low numbers (nPAH photoproducts, and we postulate a reaction mechanism via a charge transfer Rydberg state. This result suggests that oxygenated PAHs should be widely observed in regions of the ISM with sufficiently high water abundances, for example near the edges of molecular clouds where water molecules begin to form, but before icy layers are observed, that is at AVPAHs, additional destruction routes must be invoked.

  6. Proceedings of the Nineteenth DOE Solar Photochemistry Research Conference

    Energy Technology Data Exchange (ETDEWEB)

    NONE

    1995-07-01

    This document is a compilation of reports presented at the Nineteenth DOE Solar Photochemistry Research Conference. Sessions included photophysical properties of transition metal complexes, cage effects on photochemistry, charge transfer, photo-induced charge separation in biomimetic molecules, photosynthesis, and electron transfer.

  7. Tautomer selective photochemistry in 1-(tetrazol-5-yl)ethanol.

    Science.gov (United States)

    Ismael, A; Cristiano, M L S; Fausto, R; Gómez-Zavaglia, A

    2010-12-23

    A combined matrix isolation FTIR and theoretical DFT/B3LYP/6-311++G(d,p) study of the molecular structure and photochemistry of 1-(tetrazol-5-yl)ethanol [1-TE] was performed. The potential energy surface landscapes of the 1H and 2H tautomers of the compound were investigated and the theoretical results were used to help characterize the conformational mixture existing in equilibrium in the gas phase prior to deposition of the matrices, as well as the conformers trapped in the latter. In the gas phase, at room temperature, the compound exists as a mixture of 12 conformers (five of the 1H tautomer and seven of the 2H tautomer). Upon deposition of the compound in an argon matrix at 10 K, only three main forms survive, because the low barriers for conformational isomerization allow extensive conformational cooling during deposition. Deposition of the matrix at 30 K led to further simplification of the conformational mixture with only one conformer of each tautomer of 1-TE surviving. These conformers correspond to the most stable forms of each tautomer, which bear different types of intramolecular H-bonds: 1H-I has an NH···O hydrogen bond, whereas 2H-I has an OH···N hydrogen bond. Upon irradiating with UV light (λ > 200 nm), a matrix containing both 1H-I and 2H-I forms, an unprecedented tautomer selective photochemistry was observed, with the 2H tautomeric form undergoing unimolecular decomposition to azide + hydroxypropanenitrile and the 1H-tautomer being photostable.

  8. Solar photochemistry - twenty years of progress, what`s been accomplished, and where does it lead?

    Energy Technology Data Exchange (ETDEWEB)

    Blake, D M

    1995-01-01

    It has been more than 20 years since the first oil embargo. That event created an awareness of the need for alternative sources of energy and renewed interest in combining sunlight and chemistry to produce the chemicals and materials required by industry. This paper will review approaches that have been taken, progress that has been made, and give some projections for the near and longer term prospects for commercialization of solar photochemistry.

  9. Combined atmospheric oxidant capacity and increased levels of exhaled nitric oxide

    Science.gov (United States)

    Yang, Changyuan; Li, Huichu; Chen, Renjie; Xu, Wenxi; Wang, Cuicui; Tse, Lap Ah; Zhao, Zhuohui; Kan, Haidong

    2016-07-01

    Nitrogen dioxide and ozone are two interrelated oxidative pollutants in the atmosphere. Few studies have evaluated the health effects of combined oxidant capacity (O x ). We investigated the short-term effects of O x on fractional exhaled nitric oxide (FeNO), a well-established biomarker for airway inflammation, in a group of chronic obstructive pulmonary disease patients. Real-time concentrations of O x were obtained by calculating directly the sum of nitrogen dioxide and ozone. Linear mixed-effect models were applied to explore the acute effects of O x on FeNO levels. Short-term exposure to Ox was significantly associated with elevated FeNO. This effect was strongest in the first 24 h after exposure, and was robust to the adjustment of PM2.5. A 10 μg m-3 increase in 24 h average concentrations of O x was associated with 4.28% (95% confidence interval: 1.19%, 7.37%) increase in FeNO. The effect estimates were statistically significant only among males, elders, and those with body mass index ≥24 kg m-2, a comorbidity, higher educational attainment, or moderate airflow limitation. This analysis demonstrated an independent effect of O x on respiratory inflammation, and suggested that a single metric O x might serve as a preferable indicator of atmospheric oxidative capacity in further air pollution epidemiological studies.

  10. Combined Atmospheric and Ocean Profiling from an Airborne High Spectral Resolution Lidar

    Directory of Open Access Journals (Sweden)

    Hair Johnathan

    2016-01-01

    Full Text Available First of its kind combined atmospheric and ocean profile data were collected by the recently upgraded NASA Langley Research Center’s (LaRC High Spectral Resolution Lidar (HSRL-1 during the 17 July – 7 August 2014 Ship-Aircraft Bio-Optical Research Experiment (SABOR. This mission sampled over a region that covered the Gulf of Maine, open-ocean near Bermuda, and coastal waters from Virginia to Rhode Island. The HSRL-1 and the Research Scanning Polarimeter from NASA Goddard Institute for Space Studies collected data onboard the NASA LaRC King Air aircraft and flight operations were closely coordinated with the Research Vessel Endeavor that made in situ ocean optical measurements. The lidar measurements provided profiles of atmospheric backscatter and particulate depolarization at 532nm, 1064nm, and extinction (532nm from approximately 9km altitude. In addition, for the first time HSRL seawater backscatter, depolarization, and diffuse attenuation data at 532nm were collected and compared to both the ship measurements and the Moderate Resolution Imaging Spectrometer (NASA MODIS-Aqua satellite ocean retrievals.

  11. Scintillation reduction for combined Gaussian-vortex beam propagating through turbulent atmosphere

    Energy Technology Data Exchange (ETDEWEB)

    Berman, Gennady P [Los Alamos National Laboratory; Gorshkov, V. N. [NATL' TECH. UNIV. OF UA; Torous, S. V. [NATL' TECH. UNIV. OF UA

    2010-12-14

    We numerically examine the spatial evolution of the structure of coherent and partially coherent laser beams (PCBs), including the optical vortices, propagating in turbulent atmospheres, The influence of beam fragmentation and wandering relative to the axis of propagation (z-axis) on the value of the scintillation index (SI) of the signal at the detector is analyzed. A method for significantly reducing the SI, by averaging the signal at the detector over a set of PCBs, is described, This novel method is to generate the PCBs by combining two laser beams - Gaussian and vortex beams, with different frequencies (the difference between these two frequencies being significantly smaller than the frequencies themselves). In this case, the SI is effectively suppressed without any high-frequency modulators.

  12. Search for HBr and bromine photochemistry on Venus

    Science.gov (United States)

    Krasnopolsky, Vladimir A.; Belyaev, Denis A.

    2017-09-01

    HBr (1-0) R2 2605.8/6.2 cm-1, the strongest line of the strongest band of HBr, was observed when searching for this species on Venus. The observation was conducted using the NASA IRTF and a high-resolution long-slit spectrograph CSHELL with resolving power of 4 × 104. 101 spectra of Venus were analyzed, and the retrieved HBr abundances varied from -8 to + 5 ppb. Their mean value is -1.2 ppb, standard deviation is 2.5 ppb, and uncertainty of the mean is 0.25 ppb. The negative value presumes a systematic error, and the estimated upper limit of the HBr mixing ratio at the cloud tops of Venus is ∼1 ppb. From the simultaneously retrieved CO2 abundances, this corresponds to an altitude of 78 km for the uniform distribution of HBr. A simplified version of the bromine photochemistry is included into the photochemical model (Krasnopolsky 2012, Icarus 218, 230-246). Photolysis of HBr and its reactions with O and H deplete the HBr mixing ratio at 70-80 km relative to that below 60 km by a factor of ≈300. Reanalysis of the observational data with the calculated profile of HBr gives an upper limit of 20-70 ppb for HBr below 60 km and the aerosol optical depth of 0.7 at 70 km and 3.84 μm. The bromine chemistry may be effective on Venus even under the observed upper limit. However, if a Cl/Br ratio in the Venus atmosphere is similar to that in the Solar System, then HBr is ≈1 ppb in the lower atmosphere and the bromine chemistry is insignificant. Thermodynamic calculations based on the chemical kinetic model (Krasnopolsky 2013, Icarus 225, 570-580) predict HBr as a major bromine species in the lower atmosphere.

  13. Enhanced surface photochemistry in chloride-nitrate ion mixtures.

    Science.gov (United States)

    Wingen, Lisa M; Moskun, Amy C; Johnson, Stanley N; Thomas, Jennie L; Roeselová, Martina; Tobias, Douglas J; Kleinman, Michael T; Finlayson-Pitts, Barbara J

    2008-10-01

    Heterogeneous reactions of sea salt aerosol with various oxides of nitrogen lead to replacement of chloride ion by nitrate ion. Studies of the photochemistry of a model system were carried out using deliquesced mixtures of NaCl and NaNO3 on a Teflon substrate. Varying molar ratios of NaCl to NaNO3 (1 : 9 Cl- : NO3-, 1 : 1 Cl- : NO3-, 3 : 1 Cl- : NO3-, 9 : 1 Cl- : NO3-) and NaNO3 at the same total concentration were irradiated in air at 299 +/- 3 K and at a relative humidity of 75 +/- 8% using broadband UVB light (270-380 nm). Gaseous NO2 production was measured as a function of time using a chemiluminescence NO(y) detector. Surprisingly, an enhanced yield of NO2 was observed as the chloride to nitrate ratio increased. Molecular dynamics (MD) simulations show that as the Cl- : NO3- ratio increases, the nitrate ions are drawn closer to the interface due to the existence of a double layer of interfacial Cl- and subsurface Na+. This leads to a decreased solvent cage effect when the nitrate ion photodissociates to NO2+O*-, increasing the effective quantum yield and hence the production of gaseous NO2. The implications of enhanced NO2 and likely OH production as sea salt aerosols become processed in the atmosphere are discussed.

  14. Performance analysis of decode-and-forward dual-hop optical spatial modulation with diversity combiner over atmospheric turbulence

    Science.gov (United States)

    Odeyemi, Kehinde O.; Owolawi, Pius A.; Srivastava, Viranjay M.

    2017-11-01

    Dual-hops transmission is a growing interest technique that can be used to mitigate against atmospheric turbulence along the Free Space Optical (FSO) communication links. This paper analyzes the performance of Decode-and-Forward (DF) dual-hops FSO systems in-conjunction with spatial modulation and diversity combiners over a Gamma-Gamma atmospheric turbulence channel using heterodyne detection. Maximum Ratio Combiner (MRC), Equal Gain Combiner (EGC) and Selection Combiner (SC) are considered at the relay and destination as mitigation tools to improve the system error performance. Power series expansion of modified Bessel function is used to derive the closed form expression for the end-to-end Average Pairwise Error Probability (APEP) expressions for each of the combiners under study and a tight upper bound on the Average Bit Error Rate (ABER) per hop is given. Thus, the overall end-to-end ABER for the dual-hops FSO system is then evaluated. The numerical results depicted that dual-hops transmission systems outperformed the direct link systems. Moreover, the impact of having the same and different combiners at the relay and destination are also presented. The results also confirm that the combination of dual hops transmission with spatial modulation and diversity combiner significantly improves the systems error rate with the MRC combiner offering an optimal performance with respect to variation in atmospheric turbulence, change in links average received SNR and link range of the system.

  15. Proceedings of the Fourteenth DOE solar photochemistry research conference

    Energy Technology Data Exchange (ETDEWEB)

    1989-01-01

    The central themes of this year's Solar Photochemistry Research Conference encompassed initial charge separation in photosynthesis, photoinduced charge separation in other organized assemblies, electron transfer, organic and inorganic photochemistry, and photoelectrochemistry. This volume contains a copy of the program the abstracts of 29 formal presentations and 47 posters, a record of the discussion following each presentation, and an address list for the 96 attendees. Individual projects are processed separately for the databases. .

  16. Instability of combined gravity-inertial-Rossby waves in atmospheres and oceans

    Directory of Open Access Journals (Sweden)

    J. F. McKenzie

    2011-06-01

    Full Text Available The properties of the instability of combined gravity-inertial-Rossby waves on a β-plane are investigated. The wave-energy exchange equation shows that there is an exchange of energy with the background stratified medium. The energy source driving the instability lies in the background enthalpy released by the gravitational buoyancy force.

    It is shown that if the phase speed of the westward propagating low frequency-long wavelength Rossby wave exceeds the Poincaré-Kelvin (or "equivalent" shallow water wave speed, instability arises from the merging of Rossby and Poincaré modes. There are two key parameters in this instability condition; namely, the equatorial/rotational Mach (or Froude number M and the latitude θ0 of the β-plane. In general waves equatorward of a critical latitude for given M can be driven unstable, with corresponding growth rates of the order of a day or so. Although these conclusions may only be safely drawn for short wavelengths corresponding to a JWKB wave packet propagating internally and located far from boundaries, nevertheless such a local instability may play a significant role in atmosphere-ocean dynamics.

  17. Combined influence of the impurities and radial electric field on dielectric barrier discharges in atmospheric helium

    Science.gov (United States)

    Huang, Zhiming; Hao, Yanpeng; Han, Yuying; Yang, Lin; Tang, Li; Liao, Yifan; Li, Licheng

    2017-11-01

    The combined influence of nitrogen impurities and radial electric field on dielectric barrier discharges in atmospheric helium is investigated using a two-dimensional (2D) fluid simulation. Discharge current waveforms, 2D electron densities, distributions of surface charge, and radial and axial components of the electric field at the electrode edge are calculated for different impurity levels varying from 0 to 30 ppm. It is observed that the discharge presents the characteristic of a column in pure helium, and it gradually becomes a relatively uniform glow discharge as the impurity level is increased to 20 ppm; for the higher impurity level of 30 ppm, the discharge adopts a concentric-ring pattern discharge. Our result shows that the radial electric field at the electrode edge is approximately 0.6-1.2 kV/cm during the discharge. This radial electric field has an effect that leads to a non-uniform discharge. After doping a low level of impurities, the Penning ionizations caused by the impurities can inhibit this effect and lead to a uniform discharge. However, for a higher impurity level (30 ppm), the effect of the radial electric field again becomes dominant, which easily leads to a non-uniform discharge. These results provide a new perspective on obtaining a uniform glow discharge when both influences of the impurity and radial electric field are taken into account.

  18. Control of Salmonella enterica Typhimurium in chicken breast meat by irradiation combined with modified atmosphere packaging.

    Science.gov (United States)

    Kudra, L L; Sebranek, J G; Dickson, J S; Mendonca, A F; Zhang, Q; Jackson-Davis, A; Prusa, K J

    2011-11-01

    Salmonella is one of the leading causes of human foodborne illnesses originating from meat and poultry products. Cross-contamination of Salmonella from raw to cooked products continues to be problematic in the food industry. Therefore, new intervention strategies are needed for meat and poultry products. Vacuum or modified atmosphere packaging (MAP) are common packaging techniques used to extend the shelf life of meat products. Irradiation has been well established as an antibacterial treatment to reduce pathogens on meat and poultry. Combining irradiation with high-CO(2)+CO MAP was investigated in this study for improving the control of Salmonella enterica Typhimurium on chicken breast meat. The radiation sensitivities (D10-values) of this pathogen in chicken breast meat were found to be similar in vacuum and in high-CO(2)+CO MAP (0.55 ± 0.03 kGy and 0.54 ± 0.03 kGy, respectively). Irradiation at 1.5 kGy reduced the Salmonella population by an average of 3 log. Some Salmonella cells survived in both vacuum and high-CO(2) + CO MAP through 6 weeks of refrigerated storage following irradiation. This pathogen also grew in both vacuum and MAP when the product was held at 25°C. This study demonstrated that irradiation is an effective means of reducing Salmonella on meat or poultry, but packaging in either vacuum or MAP had little impact during subsequent refrigerated storage.

  19. Instability of combined gravity-inertial-Rossby waves in atmospheres and oceans

    Directory of Open Access Journals (Sweden)

    J. F. McKenzie

    2011-06-01

    Full Text Available The properties of the instability of combined gravity-inertial-Rossby waves on a β-plane are investigated. The wave-energy exchange equation shows that there is an exchange of energy with the background stratified medium. The energy source driving the instability lies in the background enthalpy released by the gravitational buoyancy force. It is shown that if the phase speed of the westward propagating low frequency-long wavelength Rossby wave exceeds the Poincaré-Kelvin (or "equivalent" shallow water wave speed, instability arises from the merging of Rossby and Poincaré modes. There are two key parameters in this instability condition; namely, the equatorial/rotational Mach (or Froude number M and the latitude θ0 of the β-plane. In general waves equatorward of a critical latitude for given M can be driven unstable, with corresponding growth rates of the order of a day or so. Although these conclusions may only be safely drawn for short wavelengths corresponding to a JWKB wave packet propagating internally and located far from boundaries, nevertheless such a local instability may play a significant role in atmosphere-ocean dynamics.

  20. Antimicrobial effects of vapor phase thymol, modified atmosphere and their combination against Salmonella spp. on raw shrimp

    Science.gov (United States)

    Salmonella contamination of raw shrimp is a food safety concern in the U.S. and other countries. This research evaluated the effects of vapor phase thymol, modified atmosphere (MA) and their combination against Salmonella spp. on raw shrimp. Growth profiles of a Salmonella spp. cocktail (6 strains),...

  1. Performance analysis of free space optical system with spatial modulation and diversity combiners over the Gamma Gamma atmospheric turbulence

    Science.gov (United States)

    Odeyemi, Kehinde O.; Owolawi, Pius A.; Srivastava, Viranjay M.

    2017-01-01

    Atmospheric turbulence is a major impairment that degrades the performance of free space optical (FSO) communication systems. Spatial modulation (SM) with receive spatial diversity is considered as a powerful technique to mitigate the fading effect induced by atmospheric turbulence. In this paper, the performance of free space optical spatial modulation (FSO-SM) system under Gamma-Gamma atmospheric turbulence is presented. We studied the Average Bit Error Rate (ABER) for the system by employing spatial diversity combiners such Maximum Ratio Combining (MRC) and Equal Gain Combining (EGC) at the receiving end. In particular, we provide a theoretical framework for the system error by deriving Average Pairwise Error Probability (APEP) expression using a generalized infinite power series expansion approach and union bounding technique is applied to obtain the ABER for each combiner. Based on this study, it was found that spatial diversity combiner significantly improved the system error rate where MRC outperforms the EGC. The performance of this system is also compared with other well established diversity combiner systems. The proposed system performance is further improved by convolutional coding technique and our analysis confirmed that the system performance of MRC coded system is enhanced by approximately 20 dB while EGC falls within 17 dB.

  2. Combined wind measurements by two different lidar instruments in the Arctic middle atmosphere

    Directory of Open Access Journals (Sweden)

    J. Hildebrand

    2012-10-01

    Full Text Available During a joint campaign in January 2009, the Rayleigh/Mie/Raman (RMR lidar and the sodium lidar at the ALOMAR Observatory (69° N, 16° E in Northern Norway were operated simultaneously for more than 40 h, collecting data for wind measurements in the middle atmosphere from 30 up to 110 km altitude. As both lidars share the same receiving telescopes, the upper altitude range of the RMR lidar and the lower altitude range of the sodium lidar overlap in the altitude region of ≈80–85 km. For this overlap region we are thus able to present the first simultaneous wind measurements derived from two different lidar instruments. The comparison of winds derived by RMR and sodium lidar is excellent for long integration times of 10 h as well as shorter ones of 1 h. Combination of data from both lidars allows identifying wavy structures between 30 and 110 km altitude, whose amplitudes increase with height. We have also performed vertical wind measurements and measurements of the same horizontal wind component using two independent lasers and telescopes of the RMR lidar and show how to use this data to calibrate and validate the wind retrieval. For the latter configuration we found a good agreement of the results but also identified inhomogeneities in the horizontal wind at about 55 km altitude of up to 20 ms−1 for an integration time of nearly 4 h. Such small-scale inhomogeneities in the horizontal wind field are an essential challenge when comparing data from different instruments.

  3. Combined Tree-Ring Carbon and Nitrogen Isotopes to infer past atmospheric deposition in Northeastern Alberta

    Science.gov (United States)

    Savard, M. M.; Bégin, C.; Marion, J.

    2013-12-01

    Monitoring atmospheric emissions from industrial centers in North America is significantly younger than the emitting activities themselves. Attention should be placed on SOx and NOx emissions as they have been increasing over the last 15 years in western Canada. In Northeastern Alberta in particular, two distinct diffuse pollution contexts deserve attention: the Lower Athabasca Oil Sands (OS) district (north of Fort McMurray), and the coal fired power plant (CFPP) area (west of Edmonton). The NOx and SO2 emissions started in 1967 and 1956, but the direct air quality monitoring has been initiated in 1997 and 1985, in these respective contexts. In an attempt to address the gap in emission and deposition monitoring, we explored the δ13C and δ15N patterns of spruce trees (Picea glauca and Picea mariana) growing in four stands in the OS district and one stand, in the CFPP area. Tree-ring series collected from these five sites all covering the 1880-2010 period were analyzed and their δ13C and δ15N values examined along with the climatic parameters and SOx and NOx emission proxies. For two stands in the OS district where soil drainage was poor δ15N series did not vary significantly, but the intermediate and long-term δ13C and δ15N trends inversely correlate in the three other studied stands. For these three sites statistical analyses for the pre-operation calibration periods (1910-1961 and 1900-1951) allowed developing transfer functions and predicting the natural δ13C and δ15N responses to climatic conditions for the operation periods. The measured series all depart from the modeled natural trends, depicting anomalies. Interestingly, the anomalies in the two regions can be nicely reproduced by multiple-regression models combining local climatic parameters with acidifying emissions. Notwithstanding the significant inverse correlations between the δ13C and δ15N series for the three well drained sites and their link to acidifying emissions, it is too early to

  4. NUCAPS: NOAA Unique Combined Atmospheric Processing System Environmental Data Record (EDR) Products

    Data.gov (United States)

    National Oceanic and Atmospheric Administration, Department of Commerce — This dataset consists of numerous retrieved estimates of hydrological variables and trace gases as Environmental Data Record (EDR) products from the NOAA Unique...

  5. Near-infrared photochemistry at interfaces based on upconverting nanoparticles.

    Science.gov (United States)

    Wu, Si; Butt, Hans-Jürgen

    2017-09-13

    Near-infrared (NIR) light is better suited than ultraviolet (UV) light for biomedical applications because it penetrates deeper into tissue and causes less photodamage to biological systems. The use of NIR light to control biointerfaces has attracted increasing interest. Here, we review NIR photoreactions at interfaces based on upconverting nanoparticles (UCNPs). UCNPs can convert NIR light to UV or visible light, which can then induce photoreactions of photosensitive compounds. This process is referred to as UCNP-assisted photochemistry. Recently, we and others demonstrated UCNP-assisted photochemistry at interfaces to control interfacial properties of nano-carriers, implants, emulsions, and cells. We introduce the fundamentals of UCNP-assisted photochemistry at interfaces, highlight its potential applications, and discuss remaining challenges.

  6. Proceedings of the 15th DOE Solar Photochemistry Research Conference

    Science.gov (United States)

    The annual Solar Photochemistry Research Conference brings together contractors and grantees of the Division of Chemical Sciences engaged in fundamental research on solar photochemical energy conversion to exchange information on recently completed studies, research in progress, and future plans. The meeting also provided an opportunity for interested representatives of government and industry to assess the current status of the field. The program encompassed the themes of photoelectrochemistry, organic and inorganic photochemistry, supramolecular assemblies, solvent effects on electron transfer, and photosynthesis. This year, in an effort to provide an overview on solar photochemical energy conversion to new participants and to foster a cohesive approach in problem solving, a panel discussion was added, in which the panelists addressed the current status of the field and identified propitious pathways in solar photochemistry.

  7. Modeling of a severe dust event and its impacts on ozone photochemistry over the downstream Nanjing megacity of eastern China

    Science.gov (United States)

    Li, Mengmeng; Wang, Tijian; Han, Yong; Xie, Min; Li, Shu; Zhuang, Bingliang; Chen, Pulong

    2017-07-01

    Dust aerosols could affect tropospheric photochemistry by interacting with solar radiation or providing reactive surfaces for heterogeneous reactions. This study examines the effects of a typical springtime dust storm (16-18 March, 2014) on ozone photochemistry over the downstream Nanjing megacity in eastern China. The on-line coupled Weather Research and Forecasting-Chemistry (WRF-Chem) model is used, with the inclusion of eight heterogeneous reactions on dust surfaces. Comparisons with satellite data and visibility record indicate that the model is capable of reproducing the onset time and downstream transport of this dust event. Dust particles act as a sink for all these trace gases examined here. The net decreases of O3, NO2, NO3, N2O5, HNO3, rad OH, HO2rad and H2O2 in the atmosphere are estimated as -6.1%, -16.0%, -37.4%, -13.9%, -47.7%, -6.0%, -9.2% and -29.7%, of which more than 80% can be explained by heterogeneous chemistry on dust surfaces. The decreases in ground photolysis rate and rad OH concentration, along with changes in other weather variables induced by dust aerosols (i.e., radiation and temperature) lead to lower photochemical activity and a small decrease of O3 mixing ratio by roughly 0.5%. This study highlights the importance of dust interaction with ozone photochemistry, and also sets the stage for further investigation of the complicated dust impacts on tropospheric aerosol chemistry.

  8. Some results of an experimental study of the atmospheric aerosol in Tomsk: A combined approach

    Energy Technology Data Exchange (ETDEWEB)

    Zuev, V.V. [Institute of Atmospheric Optics, Tomsk (Russian Federation)

    1996-04-01

    As widely accepted, aerosols strongly contribute to the formation of the earth`s radiation balance through the absorption and scattering of solar radiation. In addition, aerosols, being active condensation nuclei, also have a role in the cloud formation process. In this paper, results are presented of aerosol studies undertaken at the field measurement sites of the Institute of Atmospheric Optics in Tomsk and the Tomsk region.

  9. Combination of Cold Atmospheric Plasma and Vitamin C Effectively Disrupts Bacterial Biofilms

    DEFF Research Database (Denmark)

    Pandit, Santosh; Mokkapati, Venkata R. S. S.; Helgadóttir, Saga Huld

    2017-01-01

    Cold atmospheric plasma (CAP) is increasingly used in medical applications for eradication of bacterial and tumor cells. CAP treatment devices, known as plasma jet pens, produce reactive oxygen and nitrogen species at atmospheric pressure and room temperature. The produced reactive species are co...... that a pre-treatment with vitamin C could have on CAP applications in medicine. Specifically, we argue that vitamin C could enhance the effectiveness of CAP treatments against both the bacterial biofilms and some selected tumors....... are concentrated in a small and precisely defined area, allowing for high precision medical treatments. CAP has been demonstrated as very effective against planktonic bacterial cells. Unfortunately, bacterial cells in biofilms are typically aggregated and protected by dense exopolymeric matrix, synthesized...... and secreted by the bacterial community. The main limitation in using CAP against bacterial biofilms is the thick protective matrix of extracellular polymers that shields bacterial cells within this complex architecture. CAP has also been shown to effectively eradicate tumor cells, but the main current...

  10. Combined effects of gamma-irradiation and modified atmosphere packaging on quality of some spices.

    Science.gov (United States)

    Kirkin, Celale; Mitrevski, Blagoj; Gunes, Gurbuz; Marriott, Philip J

    2014-07-01

    Thyme (Thymus vidgaris L.), rosemary (Rosmarinus officinalis L.), black pepper (Piper nigrum L.) and cumin (Cuminum cyminum L.) in ground form were packaged in either air or 100% N2 and γ-irradiated at 3 different irradiation levels (7kGy, 12kGy, 17kGy). Total viable bacterial count, yeast and mould count, colour, essential oil yield and essential oil composition were determined. Microbial load was not detectable after 12kGy irradiation of all samples. Irradiation resulted in significant changes in colour values of rosemary and black pepper. The discolouration of the irradiated black pepper was lower in modified atmosphere packaging (MAP) compared to air packaging. Essential oil yield of irradiated black pepper and cumin was lower in air packaging compared to MAP. Gamma-irradiation generally decreased monoterpenes and increased oxygenated compounds, but the effect was lower in MAP. Overall, spices should be irradiated under an O2-free atmosphere to minimise quality deterioration. Copyright © 2014 Elsevier Ltd. All rights reserved.

  11. Combined effect of natural essential oils, modified atmosphere packaging, and gamma radiation on the microbial growth on ground beef.

    Science.gov (United States)

    Turgis, M; Han, J; Borsa, J; Lacroix, M

    2008-06-01

    Selected Chinese cinnamon, Spanish oregano, and mustard essential oils (EOs) were used in combination with irradiation to evaluate their ability to eliminate pathogenic bacteria and extend the shelf life of medium-fat-content ground beef (23% fat). Shelf life was defined as the time when the total bacterial count reached 10(7) CFU/g. The shelf life of ground beef was determined for 28 days at 4 degrees C after treatment with EOs. The concentrations of EOs were predetermined such that sensory properties of cooked meat were maintained: 0.025% Spanish oregano, 0.025% Chinese cinnamon, and 0.075% mustard. Ground beef samples containing EOs were then packaged under air or a modified atmosphere and irradiated at 1.5 kGy. Ground beef samples (10 g) were taken during the storage period for enumeration of total mesophilic aerobic bacteria, Escherichia coli, Salmonella, total coliforms, lactic acid bacteria, and Pseudomonas. Mustard EO was the most efficient for reducing the total mesophilic aerobic bacteria and eliminating pathogenic bacteria. Irradiation alone completely inhibited the growth of total mesophilic aerobic and pathogenic bacteria. The combination of irradiation and EOs was better for reducing lactic acid bacteria (mustard and cinnamon EOs) and Pseudomonas (oregano and mustard EOs). The best combined treatment for extending the shelf life of ground beef for up to 28 days was EO plus irradiation (1.5 kGy) and modified atmosphere packaging.

  12. Solar eclipse demonstrating the importance of photochemistry in new particle formation

    Science.gov (United States)

    Jokinen, Tuija; Kontkanen, Jenni; Lehtipalo, Katrianne; Manninen, Hanna E.; Aalto, Juho; Porcar-Castell, Albert; Garmash, Olga; Nieminen, Tuomo; Ehn, Mikael; Kangasluoma, Juha; Junninen, Heikki; Levula, Janne; Duplissy, Jonathan; Ahonen, Lauri R.; Rantala, Pekka; Heikkinen, Liine; Yan, Chao; Sipilä, Mikko; Worsnop, Douglas R.; Bäck, Jaana; Petäjä, Tuukka; Kerminen, Veli-Matti; Kulmala, Markku

    2017-01-01

    Solar eclipses provide unique possibilities to investigate atmospheric processes, such as new particle formation (NPF), important to the global aerosol load and radiative balance. The temporary absence of solar radiation gives particular insight into different oxidation and clustering processes leading to NPF. This is crucial because our mechanistic understanding on how NPF is related to photochemistry is still rather limited. During a partial solar eclipse over Finland in 2015, we found that this phenomenon had prominent effects on atmospheric on-going NPF. During the eclipse, the sources of aerosol precursor gases, such as sulphuric acid and nitrogen- containing highly oxidised organic compounds, decreased considerably, which was followed by a reduced formation of small clusters and nanoparticles and thus termination of NPF. After the eclipse, aerosol precursor molecule concentrations recovered and re-initiated NPF. Our results provide direct evidence on the key role of the photochemical production of sulphuric acid and highly oxidized organic compounds in maintaining atmospheric NPF. Our results also explain the rare occurrence of this phenomenon under dark conditions, as well as its seemingly weak connection with atmospheric ions. PMID:28374761

  13. Investigation and validation of wake model combinations for large wind farm modelling in neutral atmospheric boundary layers

    Science.gov (United States)

    Tromeur, E.; Puygrenier, S.; Sanquer, S.

    2016-09-01

    This study is focused on assessing the ability of two refined large wind farm models to describe the disturbance of the neutral atmospheric flow caused by large offshore wind farms. Sensitivity studies of internal boundary layer parameters are carried out. An optimum large wind farm correction is then proposed and combined with two different standard single wake models, the Park and EVM models. The large wind farm wake effect is evaluated and validated against measurements of two offshore wind farms at Horns Rev and Nysted and four standard wake models by computing velocity deficit and normalized power. All large wind farm models proposed were able to capture wake width to some degree and the decrease of power output moving through the wind farm. Despite some uncertainties, this very promising model combinations allows us to take into account the slowdown in large wind farms.

  14. Oxidation photochemistry in the Southern Atlantic boundary layer: unexpected deviations of photochemical steady state

    Directory of Open Access Journals (Sweden)

    Z. Hosaynali Beygi

    2011-08-01

    Full Text Available Ozone (O3 is a photochemical oxidant, an air pollutant and a greenhouse gas. As the main precursor of the hydroxyl radical (OH it strongly affects the oxidation power of the atmosphere. The remote marine boundary layer (MBL is considered an important region in terms of chemical O3 loss; however surface-based atmospheric observations are sparse and the photochemical processes are not well understood. To investigate the photochemistry under the clean background conditions of the Southern Atlantic Ocean, ship measurements of NO, NO2, O3, JNO2, J(O1D, HO2, OH, ROx and a range of meteorological parameters were carried out. The concentrations of NO and NO2 measured on board the French research vessel Marion-Dufresne (28° S–57° S, 46° W–34° E in March 2007, are among the lowest yet observed.

    The data is evaluated for consistency with photochemical steady state (PSS conditions, and the calculations indicate substantial deviations from PSS (Φ>1. The deviations observed under low NOx conditions (5–25 pptv demonstrate a remarkable upward tendency in the Leighton ratio (used to characterize PSS with increasing NOx mixing ratio and JNO2 intensity.

    It is a paradigm in atmospheric chemistry that OH largely controls the oxidation efficiency of the atmosphere. However, evidence is growing that for unpolluted low-NOx (NO + NO2 conditions the atmospheric oxidant budget is poorly understood. Nevertheless, for the very cleanest conditions, typical for the remote marine boundary layer, good model agreement with measured OH and HO2 radicals has been interpreted as accurate understanding of baseline photochemistry. Here we show that such agreement can be deceptive and that a yet unidentified oxidant is needed to explain the photochemical

  15. Conformational landscape, photochemistry, and infrared spectra of sulfanilamide.

    Science.gov (United States)

    Borba, Ana; Gómez-Zavaglia, Andrea; Fausto, Rui

    2013-01-31

    A combined matrix isolation FTIR and theoretical DFT(B3LYP)/6-311++G(3df,3pd) study of sulfanilamide (SA) was performed. The full conformational search on the potential energy surface of the compound allowed the identification of four different minima, all of them bearing the sulfamide nitrogen atom placed in the perpendicular orientation relatively to the aromatic ring and differing from each other in the orientation of the hydrogen atoms connected to the two nitrogen atoms of the molecule. All conformers were predicted to be significantly populated in the gas phase (at 100 °C, their relative populations were estimated as being 1:0.9:0.3:0.2). However, in agreement with the theoretically calculated low-energy barriers for conformational isomerization, in the low-temperature matrices, only the most stable conformer could be observed, with the remaining forms being converted into this form during matrix deposition (conformational cooling). The unimolecular photochemistry of matrix-isolated SA (in both argon and xenon) was also investigated. Upon broadband UV irradiation (λ > 215 nm), two photofragmentation pathways were observed: the prevalent pathway (A), leading to extrusion of sulfur dioxide and simultaneous formation of benzene-1,4-diamine, which then converts to 2,5-cyclohexadiene-1,4-diimine, and the minor pathway (B), conducting an γ-cleavage plus [1,3] H-atom migration from the sulfamide group to the aromatic ring, which leads to formation of iminosulfane dioxide and aniline, the latter undergoing subsequent phototransformation into cyclohexa-2,5-dien-1-imine. Finally, the crystalline polymorph of SA resulting from warming (265 K) the amorphous solid obtained from fast cooling of the vapor of the compound onto the cold (13 K) substrate of the cryostat was identified spectroscopically, and found to be the γ-crystalline phase, the one exhibiting in average longer H-bonds and an infrared spectrum resembling more that of the low temperature SA glass. Full

  16. Computational mechanistic photochemistry: The central role of conical intersections

    OpenAIRE

    Boggio-Pasqua, Martial

    2015-01-01

    In this thesis, I review my own contributions in the field of computational photochemistry. This manuscript is written as an introduction to this field of research. It is not intended to be a textbook, as more emphasis has been made on illustrations rather than on methodologies and technical guidelines. In this way, I hope that it will be accessible to a large audience, from undergraduate students to more experienced scientists who would be interested in learning about this fascinating and re...

  17. Analysing and combining atmospheric general circulation model simulations forced by prescribed SST: northern extratropical response

    Directory of Open Access Journals (Sweden)

    K. Maynard

    2001-06-01

    Full Text Available The ECHAM 3.2 (T21, ECHAM 4 (T30 and LMD (version 6, grid-point resolution with 96 longitudes × 72 latitudes atmospheric general circulation models were integrated through the period 1961 to 1993 forced with the same observed Sea Surface Temperatures (SSTs as compiled at the Hadley Centre. Three runs were made for each model starting from different initial conditions. The mid-latitude circulation pattern which maximises the covariance between the simulation and the observations, i.e. the most skilful mode, and the one which maximises the covariance amongst the runs, i.e. the most reproducible mode, is calculated as the leading mode of a Singular Value Decomposition (SVD analysis of observed and simulated Sea Level Pressure (SLP and geopotential height at 500 hPa (Z500 seasonal anomalies. A common response amongst the different models, having different resolution and parametrization should be considered as a more robust atmospheric response to SST than the same response obtained with only one model. A robust skilful mode is found mainly in December-February (DJF, and in June-August (JJA. In DJF, this mode is close to the SST-forced pattern found by Straus and Shukla (2000 over the North Pacific and North America with a wavy out-of-phase between the NE Pacific and the SE US on the one hand and the NE North America on the other. This pattern evolves in a NAO-like pattern over the North Atlantic and Europe (SLP and in a more N-S tripole on the Atlantic and European sector with an out-of-phase between the middle Europe on the one hand and the northern and southern parts on the other (Z500. There are almost no spatial shifts between either field around North America (just a slight eastward shift of the highest absolute heterogeneous correlations for SLP relative to the Z500 ones. The time evolution of the SST-forced mode is moderatly to strongly related to the ENSO/LNSO events but the spread amongst the ensemble of runs is not systematically related

  18. Simultaneous Observations of Atmospheric Tides from Combined in Situ and Remote Observations at Mars from the MAVEN Spacecraft

    Science.gov (United States)

    England, Scott L.; Liu, Guiping; Withers, Paul; Yigit, Erdal; Lo, Daniel; Jain, Sonal; Schneider, Nicholas M. (Inventor); Deighan, Justin; McClintock, William E.; Mahaffy, Paul R.; hide

    2016-01-01

    We report the observations of longitudinal variations in the Martian thermosphere associated with nonmigrating tides. Using the Neutral Gas Ion Mass Spectrometer (NGIMS) and the Imaging Ultraviolet Spectrograph (IUVS) on NASA's Mars Atmosphere and Volatile EvolutioN Mission (MAVEN) spacecraft, this study presents the first combined analysis of in situ and remote observations of atmospheric tides at Mars for overlapping volumes, local times, and overlapping date ranges. From the IUVS observations, we determine the altitude and latitudinal variation of the amplitude of the nonmigrating tidal signatures, which is combined with the NGIMS, providing information on the compositional impact of these waves. Both the observations of airglow from IUVS and the CO2 density observations from NGIMS reveal a strong wave number 2 signature in a fixed local time frame. The IUVS observations reveal a strong latitudinal dependence in the amplitude of the wave number 2 signature. Combining this with the accurate CO2 density observations from NGIMS, this would suggest that the CO2 density variation is as high as 27% at 0-10 deg latitude. The IUVS observations reveal little altitudinal dependence in the amplitude of the wave number 2 signature, varying by only 20% from 160 to 200 km. Observations of five different species with NGIMS show that the amplitude of the wave number 2 signature varies in proportion to the inverse of the species scale height, giving rise to variation in composition as a function of longitude. The analysis and discussion here provide a roadmap for further analysis as additional coincident data from these two instruments become available.

  19. Combining microscopy with spectroscopic and chemical methods for tracing the origin of atmospheric fallouts from mining sites

    Energy Technology Data Exchange (ETDEWEB)

    Navel, Aline; Uzu, Gaëlle; Spadini, Lorenzo [University Grenoble Alpes — LTHE UMR 5564–CNRS-INSU/UGA/INPG/IRD, 1025 rue de la Piscine, DU BP53 - 38041 Grenoble CEDEX 9 (France); Sobanska, Sophie [LASIR, (UMR CNRS 8516), Université de Lille 1, Bât. C5, 59655 Villeneuve d' Ascq CEDEX (France); Martins, Jean M.F., E-mail: jean.martins@yujf-grenoble.fr [University Grenoble Alpes — LTHE UMR 5564–CNRS-INSU/UGA/INPG/IRD, 1025 rue de la Piscine, DU BP53 - 38041 Grenoble CEDEX 9 (France)

    2015-12-30

    Highlights: • Numerous ancient mines are left over without specific care for contaminated wastes. • Sources similarity makes the tracing of the origin of metallic fallouts challenging. • Physico-chemical fingerprints of all metal-source sites and fallouts were established. • Combining physical/chemical methods allowed discriminating polluted fallouts origin. • A Hierarchical cluster analysis permitted to identify the dominant particles source. - Abstract: Populations living close to mining sites are often exposed to important heavy metal concentrations, especially through atmospheric fallouts. Identifying the main sources of metal-rich particles remains a challenge because of the similarity of the particle signatures from the polluted sites. This work provides an original combination of physical and chemical methods to determine the main sources of airborne particles impacting inhabited zones. Raman microspectrometry (RMS), X-ray diffraction (DRX), morphology analyses by microscopy and chemical composition were assessed. Geochemical analysis allowed the identification of target and source areas; XRD and RMS analysis identified the main mineral phases in association with their metal content and speciation. The characterization of the dominant minerals was combined with particle morphology analysis to identify fallout sources. The complete description of dust morphologies permitted the successful determination of a fingerprint of each source site. The analysis of these chemical and morphological fingerprints allowed identification of the mine area as the main contributor of metal-rich particles impacting the inhabited zone. In addition to the identification of the main sources of airborne particles, this study will also permit to better define the extent of polluted zones requiring remediation or protection from eolian erosion inducing metal-rich atmospheric fallouts.

  20. Proceedings of the twenty-first DOE solar photochemistry research conference

    Energy Technology Data Exchange (ETDEWEB)

    NONE

    1997-06-01

    The Solar Photochemistry Research Conference brings together grantees and contractors of the Division of Chemical Sciences who are engaged in fundamental research on solar photochemical energy conversion. The annual conference provides a focus for the program by allowing for the exchange of new information and ideas, identification of needs and opportunities, and fostering of collaborations among investigators of disparate chemistry backgrounds. The synergy that has been achieved is a major strength of the program. The research provides the foundations for future solar technologies, in which light-induced charge separation processes will be applied to conversion of light energy to chemical energy, e.g., production of alcohols from carbon dioxide, hydrogen from water, ammonia from atmospheric nitrogen, or other needed chemicals at lower cost of by using sunlight as the energy source. The program includes topical sessions on semiconductor nanoparticles, nanocrystalline films, and photoinduced charge separation at the semiconductor/liquid interface; photochemistry and photophysics of transition metal complexes; photoinduced charge separation in zeolites and lamellar assemblies; intramolecular charge separation and electron transfer; dynamics of solvation and solution interfaces; and photoconversion via porphyrins and biomimetic constructs. The special guest plenary lecturer is Professor Moungi Bawendi of the Massachusetts Institute of Technology, who spoke on semiconductor nanocrystallites (quantum dots). As an added feature, Tom Surek, the Photovoltaics Technology program manager at NREL, presented a status report on one of the most promising and heavily supported programs in solar energy conversion technology, solid state photovoltaics. This volume contains the agenda for the meeting, abstracts of the 31 formal presentations and 55 posters, as well as an address list for the 111 participants.

  1. Combining Satellite Microwave Radiometer and Radar Observations to Estimate Atmospheric Latent Heating Profiles

    Science.gov (United States)

    Grecu, Mircea; Olson, William S.; Shie, Chung-Lin; L'Ecuyer, Tristan S.; Tao, Wei-Kuo

    2009-01-01

    In this study, satellite passive microwave sensor observations from the TRMM Microwave Imager (TMI) are utilized to make estimates of latent + eddy sensible heating rates (Q1-QR) in regions of precipitation. The TMI heating algorithm (TRAIN) is calibrated, or "trained" using relatively accurate estimates of heating based upon spaceborne Precipitation Radar (PR) observations collocated with the TMI observations over a one-month period. The heating estimation technique is based upon a previously described Bayesian methodology, but with improvements in supporting cloud-resolving model simulations, an adjustment of precipitation echo tops to compensate for model biases, and a separate scaling of convective and stratiform heating components that leads to an approximate balance between estimated vertically-integrated condensation and surface precipitation. Estimates of Q1-QR from TMI compare favorably with the PR training estimates and show only modest sensitivity to the cloud-resolving model simulations of heating used to construct the training data. Moreover, the net condensation in the corresponding annual mean satellite latent heating profile is within a few percent of the annual mean surface precipitation rate over the tropical and subtropical oceans where the algorithm is applied. Comparisons of Q1 produced by combining TMI Q1-QR with independently derived estimates of QR show reasonable agreement with rawinsonde-based analyses of Q1 from two field campaigns, although the satellite estimates exhibit heating profile structure with sharper and more intense heating peaks than the rawinsonde estimates. 2

  2. Combined application of modified atmosphere packaging and superchilled storage to extend the shelf life of fresh cod (Gadus morhua) loins.

    Science.gov (United States)

    Wang, T; Sveinsdóttir, K; Magnússon, H; Martinsdóttir, E

    2008-01-01

    Development of new technologies and preservation methods to offer conveniently packed fish with sufficient keeping quality is important to meet increasing demand for value-added fresh fish products on the market. The aim of this study was to investigate the effect of combined application of modified atmosphere packaging (MAP) and superchilled storage on the shelf life of fresh cod loins. Fresh cod loins were packed in polystyrene boxes and in MA (CO(2)/N(2)/O(2): 50%/45%/5%) on day 3 postcatch and stored at chilled (1.5 degrees C) and superchilled (-0.9 degrees C) temperatures. Quantitative descriptive analysis (QDA) and physical, chemical, and microbial analyses were carried out during the 21 d of storage. Superchilled storage alone compared with traditional chilled storage in polystyrene boxes increased the total shelf life (days from catch) of cod loins from 9 to 16 or 17 d. Chilled MA packaging increased the shelf life from 9 to 14 d and when MAP and superchilled storage were combined, a synergistic effect was observed and the shelf life was further extended to at least 21 d. It is noteworthy that the characteristic fresh and sweet taste can be maintained longer under such conditions. This could contribute to enhanced eating quality of fresh cod fillets for consumers in distant markets. However, MAP combined with superchilled storage resulted in different textural properties. Superchilled MA packed cod loins had more meaty texture compared to other sample groups after 7-d storage.

  3. Three-dimensional vapor intrusion modeling approach that combines wind and stack effects on indoor, atmospheric, and subsurface domains.

    Science.gov (United States)

    Shirazi, Elham; Pennell, Kelly G

    2017-12-13

    Vapor intrusion (IV) exposure risks are difficult to characterize due to the role of atmospheric, building and subsurface processes. This study presents a three-dimensional VI model that extends the common subsurface fate and transport equations to incorporate wind and stack effects on indoor air pressure, building air exchange rate (AER) and indoor contaminant concentration to improve VI exposure risk estimates. The model incorporates three modeling programs: (1) COMSOL Multiphysics to model subsurface fate and transport processes, (2) CFD0 to model atmospheric air flow around the building, and (3) CONTAM to model indoor air quality. The combined VI model predicts AER values, zonal indoor air pressures and zonal indoor air contaminant concentrations as a function of wind speed, wind direction and outdoor and indoor temperature. Steady state modeling results for a single-story building with a basement demonstrate that wind speed, wind direction and opening locations in a building play important roles in changing the AER, indoor air pressure, and indoor air contaminant concentration. Calculated indoor air pressures ranged from approximately -10 Pa to +4 Pa depending on weather conditions and building characteristics. AER values, mass entry rates and indoor air concentrations vary depending on weather conditions and building characteristics. The presented modeling approach can be used to investigate the relationship between building features, AER, building pressures, soil gas concentrations, indoor air concentrations and VI exposure risks.

  4. Global atmospheric response to specific linear combinations of the main SST modes. Part I: numerical experiments and preliminary results

    Directory of Open Access Journals (Sweden)

    S. Trzaska

    1996-10-01

    Full Text Available This article investigates through numerical experiments the controversial question of the impact of El Niño-Southern Oscillation (ENSO phenomena on climate according to large-scale and regional-scale interhemispheric thermal contrast. Eight experiments (two considering only inversed Atlantic thermal anomalies and six combining ENSO warm phase with large-scale interhemispheric contrast and Atlantic anomaly patterns were performed with the Météo-France atmospheric general circulation model. The definition of boundary conditions from observed composites and principal components is presented and preliminary results concerning the month of August, especially over West Africa and the equatorial Atlantic are discussed. Results are coherent with observations and show that interhemispheric and regional scale sea-surface-temperature anomaly (SST patterns could significantly modulate the impact of ENSO phenomena: the impact of warm-phase ENSO, relative to the atmospheric model intercomparison project (AMIP climatology, seems stronger when embedded in global and regional SSTA patterns representative of the post-1970 conditions [i.e. with temperatures warmer (colder than the long-term mean in the southern hemisphere (northern hemisphere]. Atlantic SSTAs may also play a significant role.

  5. Photochemistry of the α-Al2O3-PETN Interface

    Directory of Open Access Journals (Sweden)

    Roman V. Tsyshevsky

    2016-02-01

    Full Text Available Optical absorption measurements are combined with electronic structure calculations to explore photochemistry of an α-Al2O3-PETN interface formed by a nitroester (pentaerythritol tetranitrate, PETN, C5H8N4O12 and a wide band gap aluminum oxide (α-Al2O3 substrate. The first principles modeling is used to deconstruct and interpret the α-Al2O3-PETN absorption spectrum that has distinct peaks attributed to surface F0-centers and surface—PETN transitions. We predict the low energy α-Al2O3 F0-center—PETN transition, producing the excited triplet state, and α-Al2O3 F0-center—PETN charge transfer, generating the PETN anion radical. This implies that irradiation by commonly used lasers can easily initiate photodecomposition of both excited and charged PETN at the interface. The feasible mechanism of the photodecomposition is proposed.

  6. Mechanism for the Coupled Photochemistry of Ammonia and Acetylene: Implications for Giant Planets, Comets and Interstellar Organic Synthesis

    Science.gov (United States)

    Keane, Thomas C.

    2017-09-01

    Laboratory studies provide a fundamental understanding of photochemical processes in planetary atmospheres. Photochemical reactions taking place on giant planets like Jupiter and possibly comets and the interstellar medium are the subject of this research. Reaction pathways are proposed for the coupled photochemistry of NH3 (ammonia) and C2H2 (acetylene) within the context Jupiter's atmosphere. We then extend the discussion to the Great Red Spot, Extra-Solar Giant Planets, Comets and Interstellar Organic Synthesis. Reaction rates in the form of quantum yields were measured for the decomposition of reactants and the formation of products and stable intermediates: HCN (hydrogen cyanide), CH3CN (acetonitrile), CH3CH = N-N = CHCH3 (acetaldazine), CH3CH = N-NH2 (acetaldehyde hydrazone), C2H5NH2 (ethylamine), CH3NH2 (methylamine) and C2H4 (ethene) in the photolysis of NH3/C2H2 mixtures. Some of these compounds, formed in our investigation of pathways for HCN synthesis, were not encountered previously in observational, theoretical or laboratory photochemical studies. The quantum yields obtained allowed for the formulation of a reaction mechanism that attempts to explain the observed results under varying experimental conditions. In general, the results of this work are consistent with the initial observations of Ferris and Ishikawa (1988). However, their proposed reaction pathway which centers on the photolysis of CH3CH = N-N = CHCH3 does not explain all of the results obtained in this study. The formation of CH3CH = N-N = CHCH3 by a radical combination reaction of CH3CH = N• was shown in this work to be inconsistent with other experiments where the CH3CH = N• radical is thought to form but where no CH3CH = N-N = CHCH3 was detected. The importance of the role of H atom abstraction reactions was demonstrated and an alternative pathway for CH3CH = N-N = CHCH3 formation involving nucleophilic reaction between N2H4 and CH3CH = NH is advanced.

  7. Mechanism for the Coupled Photochemistry of Ammonia and Acetylene: Implications for Giant Planets, Comets and Interstellar Organic Synthesis.

    Science.gov (United States)

    Keane, Thomas C

    2017-09-01

    Laboratory studies provide a fundamental understanding of photochemical processes in planetary atmospheres. Photochemical reactions taking place on giant planets like Jupiter and possibly comets and the interstellar medium are the subject of this research. Reaction pathways are proposed for the coupled photochemistry of NH3 (ammonia) and C2H2 (acetylene) within the context Jupiter's atmosphere. We then extend the discussion to the Great Red Spot, Extra-Solar Giant Planets, Comets and Interstellar Organic Synthesis. Reaction rates in the form of quantum yields were measured for the decomposition of reactants and the formation of products and stable intermediates: HCN (hydrogen cyanide), CH3CN (acetonitrile), CH3CH = N-N = CHCH3 (acetaldazine), CH3CH = N-NH2 (acetaldehyde hydrazone), C2H5NH2 (ethylamine), CH3NH2 (methylamine) and C2H4 (ethene) in the photolysis of NH3/C2H2 mixtures. Some of these compounds, formed in our investigation of pathways for HCN synthesis, were not encountered previously in observational, theoretical or laboratory photochemical studies. The quantum yields obtained allowed for the formulation of a reaction mechanism that attempts to explain the observed results under varying experimental conditions. In general, the results of this work are consistent with the initial observations of Ferris and Ishikawa (1988). However, their proposed reaction pathway which centers on the photolysis of CH3CH = N-N = CHCH3 does not explain all of the results obtained in this study. The formation of CH3CH = N-N = CHCH3 by a radical combination reaction of CH3CH = N• was shown in this work to be inconsistent with other experiments where the CH3CH = N• radical is thought to form but where no CH3CH = N-N = CHCH3 was detected. The importance of the role of H atom abstraction reactions was demonstrated and an alternative pathway for CH3CH = N-N = CHCH3 formation involving nucleophilic reaction between N2H4 and CH3CH = NH is advanced.

  8. Combination of 1-methylcyclopropene treatment and controlled atmosphere storage retains overall fruit quality and bioactive compounds in mango.

    Science.gov (United States)

    Sivakumar, Dharini; Van Deventer, Francois; Terry, Leon Alexander; Polenta, Gustavo Alberto; Korsten, Lise

    2012-03-15

    Postharvest application of fungicide prochloraz and hot-water dip are commercially practiced to control postharvest diseases in mangoes. Owing to the increasing consumer demand for organically produced fruit, the search for natural environmentally friendly alternative products and processes has become important for the fruit industry. This study evaluated the combined effect of 1-methylcyclopropene (1-MCP) (500 nL L⁻¹) and controlled atmosphere storage conditions (CA-1, 5% O₂ + 5% CO₂ or CA-2, 3% O₂ + 8% CO₂) on the maintenance of fruit quality and bioactive compounds on hot-water treated mangoes (cv. Kent) during postharvest storage. In comparison to the 1-MCP + CA-1 treatment, 1-MCP + CA-2 reduced the incidence of anthracnose, weight and firmness loss; delayed the skin and flesh colour development; prevented the increase of soluble solids concentration/titratable acidity ratio, ethanol and acetaldehyde content; and maintained the ascorbic acid, carotenoid, total phenolic and flavonoid contents, and antioxidant scavenging activity in hot-water treated mangoes. The untrained panel preferred 1-MCP + CA-2 treated fruit to the fruit subjected to other postharvest treatments adopted in this investigation. Our investigation suggests that the combined effect of 1-MCP and CA-2 storage can be recommended as an alternative treatment to replace prochloraz application for hot-water treated mangoes and can be adopted commercially for organic export markets. Copyright © 2011 Society of Chemical Industry.

  9. Combined effect of active coating and modified atmosphere packaging on prolonging the shelf life of low-moisture Mozzarella cheese.

    Science.gov (United States)

    Mastromatteo, Marianna; Conte, Amalia; Faccia, Michele; Del Nobile, Matteo Alessandro; Zambrini, Angelo Vittorio

    2014-01-01

    In this work, the effect of active coating on the shelf life of low-moisture Mozzarella cheese packaged in air and modified atmosphere (MAP) was studied. The active coating was based on sodium alginate (2%, wt/vol) and potassium sorbate (1%, wt/vol). The MAP was made up of 75% CO₂ and 25% N₂ (MAP1), 25% CO₂ and 75% N₂ (MAP2), or 50% CO₂ and 50% N₂ (MAP3). The product quality decay was assessed by monitoring microbiological and sensory changes during storage at 4, 8, and 14°C. Results showed that the combination of active coating and MAP was able to improve the preservation of low-moisture Mozzarella cheese. Specifically, the shelf life increased up to 160 d for samples stored at 4°C, and 40 and 11 d for those at 8 and 14°C, respectively. A faster quality decay for untreated samples packaged in air was observed. In particular, the Pseudomonas spp. growth and the appearance of molds were responsible for product unacceptability. The combination of active coating and MAP represents a strategic solution to prolong the shelf life of low-moisture Mozzarella cheese and to ensure the safety of the product under thermal abuse conditions. Copyright © 2014 American Dairy Science Association. Published by Elsevier Inc. All rights reserved.

  10. Combined effect of aqueous chlorine dioxide and modified atmosphere packaging on inhibiting Salmonella Typhimurium and Listeria monocytogenes in mungbean sprouts.

    Science.gov (United States)

    Jin, H-H; Lee, S-Y

    2007-11-01

    This study was conducted to investigate the effect of chlorine dioxide (ClO2) combined with modified atmosphere packaging (MAP) on inhibiting total mesophilic microorganisms, Salmonella Typhimurium, and Listeria monocytogenes in mungbean sprouts during refrigerated storage. Mungbean sprouts were packaged using 4 different methods (air, vacuum, CO2 gas, and N2 gas) following treatment with water or 100 ppm ClO2 for 5 min and stored at 5 +/- 2 degrees C. The population of total mesophilic microorganisms in mungbean sprouts was about 8.4-log(10) CFU/g and this level was not significantly reduced by treatment with water or ClO2 (P > 0.05). However, when samples were packaged under vacuum, N2 gas, or CO2 gas following treatment with ClO2, the populations of total mesophilic microorganisms were significantly reduced during storage (P packaging conditions (air, vacuum, N2 gas, and CO2 gas) had no significant effect on population reduction (P > 0.05). However, treatment with ClO2 significantly reduced populations of S. Typhimurium and L. monocytogenes by 3.0- and 1.5-log CFU/g, respectively (P packaged under vacuum or in N2 or CO2 gas during storage. These results suggest that the combination of ClO2 treatment and MAP such as CO2 gas packaging may be useful for inhibiting microbial contamination and maintaining quality in mungbean sprouts during storage.

  11. 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.

  12. Recent advances in urocanic acid photochemistry, photobiology and photoimmunology.

    Science.gov (United States)

    Gibbs, Neil K; Tye, Joanne; Norval, Mary

    2008-06-01

    Urocanic acid (UCA), produced in the upper layers of mammalian skin, is a major absorber of ultraviolet radiation (UVR). Originally thought to be a 'natural sunscreen', studies conducted a quarter of a century ago proposed that UCA may be a chromophore for the immunosuppression that follows exposure to UVR. With its intriguing photochemistry, its role in immunosuppression and skin cancer development, and skin barrier function, UCA continues to be the subject of intense research effort. This review summarises the photochemical, photobiological and photoimmunological findings regarding UCA, published since 1998.

  13. Global atmospheric response to specific linear combinations of the main SST modes.. Part I: numerical experiments and preliminary results

    Science.gov (United States)

    Trzaska, S.; Moron, V.; Fontaine, B.

    1996-10-01

    This article investigates through numerical experiments the controversial question of the impact of El Niño-Southern Oscillation (ENSO) phenomena on climate according to large-scale and regional-scale interhemispheric thermal contrast. Eight experiments (two considering only inversed Atlantic thermal anomalies and six combining ENSO warm phase with large-scale interhemispheric contrast and Atlantic anomaly patterns) were performed with the Météo-France atmospheric general circulation model. The definition of boundary conditions from observed composites and principal components is presented and preliminary results concerning the month of August, especially over West Africa and the equatorial Atlantic are discussed. Results are coherent with observations and show that interhemispheric and regional scale sea-surface-temperature anomaly (SST) patterns could significantly modulate the impact of ENSO phenomena: the impact of warm-phase ENSO, relative to the atmospheric model intercomparison project (AMIP) climatology, seems stronger when embedded in global and regional SSTA patterns representative of the post-1970 conditions [i.e. with temperatures warmer (colder) than the long-term mean in the southern hemisphere (northern hemisphere)]. Atlantic SSTAs may also play a significant role. Acknowledgements. We gratefully appreciate the on-line DMSP database facility at APL (Newell et al., 1991) from which this study has benefited greatly. We wish to thank E. Friis-Christensen for his encouragement and useful discussions. A. Y. would like to thank the Danish Meteorological Institute, where this work was done, for its hospitality during his stay there and the Nordic Baltic Scholarship Scheme for its financial support of this stay. Topical Editor K.-H. Glassmeier thanks M. J. Engebretson and H. Lühr for their help in evaluating this paper.--> Correspondence to: A. Yahnin-->

  14. Control of Campylobacter jejuni in chicken breast meat by irradiation combined with modified atmosphere packaging including carbon monoxide.

    Science.gov (United States)

    Kudra, Li L; Sebranek, Joseph G; Dickson, James S; Mendonca, Aubrey F; Zhang, Q; Jackson-Davis, Armitra; Prusa, Kenneth J

    2012-10-01

    Campylobacter is one of the leading causes of human foodborne illnesses originating from meat and poultry products. Cross-contamination of this organism occurs in many poultry processing plants, and can occur in the kitchens and refrigerators of consumers. Therefore, new intervention strategies are needed for meat and poultry products to better protect consumers from this pathogen. Vacuum or modified atmosphere packaging is a common packaging technique used by the meat and poultry industry to extend the shelf life of meat products. In addition, irradiation has been well established as an antibacterial treatment to reduce pathogens on meat and poultry products. Irradiation in combination with high-CO(2) + CO modified atmosphere packaging (MAP) was investigated in this study for the control of Campylobacter jejuni in chicken breast meat. The radiation sensitivity (D(10)-value) of this foodborne pathogen in chicken breast meat was similar in vacuum or high-O(2) MAP (0.31 ± 0.01 kGy in vacuum packaging and 0.29 ± 0.03 kGy in MAP). C. jejuni survived in both vacuum and high-CO(2) MAP through 6 weeks of refrigerated storage. Irradiation was effective for eliminating C. jejuni from meat or poultry packaged in vacuum or MAP, and should reduce the chance of cross-contamination in retail stores or home kitchens. However, irradiated off-odor and sour aroma were observed for raw, irradiated chicken breast packaged with either vacuum or MAP. Therefore, additional means to mitigate quality changes appear necessary for these products.

  15. Effect of chemical sanitizer combined with modified atmosphere packaging on inhibiting Escherichia coli O157:H7 in commercial spinach.

    Science.gov (United States)

    Lee, Sun-Young; Baek, Seung-Youb

    2008-06-01

    Escherichia coli O157:H7 contaminated spinach has recently caused several outbreaks of human illness in the USA and Canada. However, to date, there has been no study demonstrating an effective way to eliminate E. coli O157:H7 in spinach. Therefore, this study was conducted to investigate the effect of chemical sanitizers alone or in combination with packaging methods such as vacuum and modified atmosphere packaging (MAP) on inactivating E. coli O157:H7 in spinach during storage time. Spinach inoculated with E. coli O157:H7 was packaged in four different methods (air, vacuum, N(2) gas, and CO(2) gas packaging) following treatment with water, 100 ppm chlorine dioxide, or 100 ppm sodium hypochlorite for 5 min at room temperature and stored at 7+/-2 degrees C. Treatment with water did not significantly reduce levels of E. coli O157:H7 in spinach. However, treatment with chlorine dioxide and sodium hypochlorite significantly decreased levels of E. coli O157:H7 by 2.6 and 1.1 log(10)CFU/g, respectively. Levels of E. coli O157:H7 in samples packaged in air following treatments grew during storage time, whereas levels were maintained in samples packaged in other packaging methods (vacuum, N(2) gas, and CO(2) gas packaging). Therefore there were significant differences (about 3-4 log) of E. coli O157:H7 populations between samples packed in air and other packaging methods following treatment with chemical sanitizers after 7 days storage. These results suggest that the combination of treatment with chlorine dioxide and packaging methods such as vacuum and MAP may be useful for improving the microbial safety of spinach against E. coli O157:H7 during storage.

  16. Confirmation and efficacy tests against codling moth and oriental fruit moth in apples using combination heat and controlled atmosphere treatments.

    Science.gov (United States)

    Neven, Lisa G; Rehfield-Ray, Linda

    2006-10-01

    Codling moth, Cydia pomonella (L.), and oriental fruit moth, Grapholita molesta (Busck), are serious pests of apples (Malus spp.) grown in the United States and other countries. In countries where these species are not found, there are strict quarantine restrictions in place to prevent their accidental introduction. The treatment used in this study consisted of hot, forced, moist air with a linear heating rate of 12 degrees C/h to a final chamber temperature of 46 degrees C under a 1% oxygen and 15% carbon dioxide environment. We found that the fourth instar of both species was the most tolerant to the treatment, with equal tolerance between the species. Efficacy tests against the fourth instar of both oriental fruit moth and codling moth by using a commercial controlled atmosphere temperature treatment system chamber resulted in > 5,000 individuals of each species being controlled using the combination treatment. Confirmation tests against codling moth resulted in mortality of > 30,000 fourth instars. These treatments may be used to meet quarantine restrictions for organic apples where fumigation with methyl bromide is not desirable.

  17. Combined chitosan-thyme treatments with modified atmosphere packaging on a ready-to-cook poultry product.

    Science.gov (United States)

    Giatrakou, V; Ntzimani, A; Savvaidis, I N

    2010-04-01

    In the present study, natural antimicrobials chitosan and thyme, and their combination, were evaluated for their effect on the shelf life of a ready-to-cook (RTC) chicken-pepper kebab (skewer) stored under modified atmosphere packaging (MAP) conditions at 4 +/- 0.5 degrees C for 14 days. The following treatments were examined: control samples stored under aerobic packaging (A), samples stored under MAP (M), samples treated with 1.5% chitosan (vol/wt) and stored under MAP (M-CH), samples treated with 0.2% thyme essential oil (vol/wt) (M-T), and samples treated with 1.5% chitosan (vol/wt) and 0.2% thyme essential oil (vol/wt) and stored under MAP (M-CH-T). Treatment M-CH-T significantly affected aerobic plate counts and counts of lactic acid bacteria, Pseudomonas spp., Brochothrix thermosphacta, Enterobacteriaceae, and yeasts and molds during the entire storage period. Similarly, lipid oxidation of the RTC product was retarded (M-CH-T treatment) during storage, whereas redness was maintained in M-T, M-CH, and M-CH-T samples. Based primarily on sensory data (taste attribute), M-CH and M-T treatments extended RTC product shelf life by 6 days, whereas M-CH-T treatment resulted in a product with a shelf life of 14 days that maintained acceptable sensory characteristics (shelf life of the control was 6 days).

  18. Secondary Organic Aerosol Formation from Acetylene (C2H2: seed effect on SOA yields due to organic photochemistry in the aerosol aqueous phase

    Directory of Open Access Journals (Sweden)

    P. J. Ziemann

    2009-03-01

    Full Text Available The lightest Non Methane HydroCarbon (NMHC, i.e., acetylene (C2H2 is found to form secondary organic aerosol (SOA. Contrary to current belief, the number of carbon atoms, n, for a NMHC to act as SOA precursor is lowered to n=2 here. The OH-radical initiated oxidation of C2H2 forms glyoxal (CHOCHO as the highest yield product, and >99% of the SOA from C2H2 is attributed to CHOCHO. SOA formation from C2H2 and CHOCHO was studied in a photochemical and a dark simulation chamber. Further, the experimental conditions were varied with respect to the chemical composition of the seed aerosols, mild acidification with sulphuric acid (SA, 3photochemistry in the liquid water associated with internally mixed inorganic/WSOC seed aerosols is found responsible for this seed effect. WSOC photochemistry enhances the SOA source from CHOCHO, while seeds containing amino acids (AA and/or SA showed among the lowest of all YSOA values, and largely suppress the photochemical enhancement on the rate of CHOCHO uptake. Our results give first evidence for the importance of heterogeneous photochemistry of CHOCHO in SOA formation, and identify a potential bias in the currently available YSOA data for other SOA precursor NMHCs. We demonstrate that SOA formation via the aqueous phase is not limited to cloud droplets, but proceeds also in the absence of clouds, i.e., does not stop once a cloud droplet evaporates. Atmospheric models need to be expanded to include SOA formation from WSOC photochemistry of CHOCHO, and possibly other α-dicarbonyls, in aqueous aerosols.

  19. Photochemistry of psoralen-DNA adducts, biological effects of psoralen-DNA adducts, applications of psoralen-DNA photochemistry

    Energy Technology Data Exchange (ETDEWEB)

    Shi, Yun-bo

    1988-03-01

    This thesis consists of three main parts and totally eight chapters. In Part I, The author will present studies on the photochemistry of psoralen-DNA adducts, specifically, the wavelength dependencies for the photoreversals of thymidine-HMT (4'-hydroxymethyl-4, 5', 8-trimenthylpsoralen) monoadducts and diadduct and the same adducts incorporated in DNA helices and the wavelength dependecies for the photocrossslinking of thymidine-HMT monoadducts in double-stranded helices. In Part II, The author will report some biological effects of psoralen-DNA adducts, i.e., the effects on double-stranded DNA stability, DNA structure, and transcription by E. coli and T7 RNA polymerases. Finally, The author will focus on the applications of psoralen-DNA photochemistry to investigation of protein-DNA interaction during transcription, which includes the interaction of E. coli and T7 RNA polymerases with DNA in elongation complexes arrested at specific psoralen-DNA adduct sites as revealed by DNase I footprinting experiments. 123 refs., 52 figs., 12 tabs.

  20. Combined Effect of an Atmospheric River and a Cut-off Low in Hiroshima Flooding Event on August 19, 2014

    Science.gov (United States)

    Takayabu, Y. N.; Hirota, N.; Kato, M.; Arakane, S.

    2015-12-01

    An extraordinary precipitation over 100 mmhr-1in Hiroshima on August 19, 2014, caused a flash flood which resulted in 74 fatalities and collapse of 330 houses. In order to examine the meteorological background of this flooding event, we carried out a detailed analysis utilizing rain gauge data, satellite precipitation dataset, and a meso scale and a global scale objective analyses provided from the Japan Meteorological Agency. Then, we performed numerical experiments using a nonhydrostatic compressible equation model called the Cloud-Resolving Storm Simulator (CReSS). As a result, a combined effect of an atmospheric river (AR) and a cut-off low (COL) in this flooding event was elucidated. During the event, a filamentary transport of moisture extending from the Indochina Peninsula to the Japanese Islands was observed along the southern side of the subtropical jet, forming an AR. This AR had a deep structure with an amount of free tropospheric moisture comparable to that of the boundary layer. Concurrently, there was a COL, detached from the Mid-Pacific Trough, moving northwestward toward the Japanese Archipelago. With various sensitivity experiments, we concluded that a mid-tropospheric instability associated with the cold core of the COL and a dynamical ascent induced in its foreside, collaboratively worked with the anomalous moisture in the free troposphere associated with the AR, to extraordinarily enhance the precipitation over Hiroshima region. An orographic effect to concentrate the precipitation in this region was also confirmed. An implication on a difference in effects of AR in this event with a climatologically moist boundary layer, from those in the US west coast with a very dry environment, was also obtained. Acknowledgment: This study is supported by the Environment Research and Technology Development Fund (2-1503) of the Ministry of the Environment, Japan, and by the Ministry of Education, Culture, Sports, Science and Technology, Japan.

  1. Model error analyses of photochemistry mechanisms using the BEATBOX/BOXMOX data assimilation toy model

    Science.gov (United States)

    Knote, C. J.; Eckl, M.; Barré, J.; Emmons, L. K.

    2016-12-01

    Simplified descriptions of photochemistry in the atmosphere ('photochemical mechanisms') necessary to reduce the computational burden of a model simulation contribute significantly to the overall uncertainty of an air quality model. Understanding how the photochemical mechanism contributes to observed model errors through examination of results of the complete model system is next to impossible due to cancellation and amplification effects amongst the tightly interconnected model components. Here we present BEATBOX, a novel method to evaluate photochemical mechanisms using the underlying chemistry box model BOXMOX. With BOXMOX we can rapidly initialize various mechanisms (e.g. MOZART, RACM, CBMZ, MCM) with homogenized observations (e.g. from field campaigns) and conduct idealized 'chemistry in a jar' simulations under controlled conditions. BEATBOX is a data assimilation toy model built upon BOXMOX which allows to simulate the effects of assimilating observations (e.g., CO, NO2, O3) into these simulations. In this presentation we show how we use the Master Chemical Mechanism (MCM, U Leeds) as benchmark for more simplified mechanisms like MOZART, use BEATBOX to homogenize the chemical environment and diagnose errors within the more simplified mechanisms. We present BEATBOX as a new, freely available tool that allows researchers to rapidly evaluate their chemistry mechanism against a range of others under varying chemical conditions.

  2. 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.

  3. Gas-phase experiments on Au(III) photochemistry.

    Science.gov (United States)

    Marcum, Jesse C; Kaufman, Sydney H; Weber, J Mathias

    2011-04-14

    Irradiation of AuCl(4)(-) and AuCl(2)(OH)(2)(-) in the gas-phase using ultraviolet light (220-415 nm) leads to their dissociation. Observed fragment ions for AuCl(4)(-) are AuCl(3)(-) and AuCl(2)(-) and for AuCl(2)(OH)(2)(-) are AuCl(2)(-) and AuClOH(-). All fragment channels correspond to photoreduction of the gold atom to either Au(II) or Au(I) depending on the number of neutral ligands lost. Fragment branching ratios of AuCl(4)(-) are observed to be highly energy dependent and can be explained by comparison of the experimental data to calculated threshold energies obtained using density functional theory. The main observed spectral features are attributed to ligand-to-metal charge transfer transitions. These results are discussed in the context of the molecular-level mechanisms of Au(III) photochemistry.

  4. 3D printing of natural organic materials by photochemistry

    Science.gov (United States)

    Da Silva Gonçalves, Joyce Laura; Valandro, Silvano Rodrigo; Wu, Hsiu-Fen; Lee, Yi-Hsiung; Mettra, Bastien; Monnereau, Cyrille; Schmitt Cavalheiro, Carla Cristina; Pawlicka, Agnieszka; Focsan, Monica; Lin, Chih-Lang; Baldeck, Patrice L.

    2016-03-01

    In previous works, we have used two-photon induced photochemistry to fabricate 3D microstructures based on proteins, anti-bodies, and enzymes for different types of bio-applications. Among them, we can cite collagen lines to guide the movement of living cells, peptide modified GFP biosensing pads to detect Gram positive bacteria, anti-body pads to determine the type of red blood cells, and trypsin columns in a microfluidic channel to obtain a real time biochemical micro-reactor. In this paper, we report for the first time on two-photon 3D microfabrication of DNA material. We also present our preliminary results on using a commercial 3D printer based on a video projector to polymerize slicing layers of gelatine-objects.

  5. Impact of atmospheric convection on south Tibet summer precipitation isotopologue composition using a combination of in situ measurements, satellite data, and atmospheric general circulation modeling

    Science.gov (United States)

    He, You; Risi, Camille; Gao, Jing; Masson-Delmotte, Valérie; Yao, Tandong; Lai, Chun-Ta; Ding, Yongjian; Worden, John; Frankenberg, Christian; Chepfer, Helene; Cesana, Gregory

    2015-05-01

    Precipitation isotopologues recorded in natural archives from the southern Tibetan Plateau may document past variations of Indian monsoon intensity. The exact processes controlling the variability of precipitation isotopologue composition must therefore first be deciphered and understood. This study investigates how atmospheric convection affects the summer variability of δ18O in precipitation (δ18Op) and δD in water vapor (δDv) at the daily scale. This is achieved using isotopic data from precipitation samples at Lhasa, isotopic measurements of water vapor retrieved from satellites (Tropospheric Emission Spectrometer (TES), GOSAT) and atmospheric general circulation modeling. We reveal that both δ18Op and δDv at Lhasa are well correlated with upstream convective activity, especially above northern India. First, during days of strong convection, northern India surface air contains large amounts of vapor with relatively low δDv. Second, when this low-δDv moisture is uplifted toward southern Tibet, this initial depletion in HDO is further amplified by Rayleigh distillation as the vapor moves over the Himalayan. The intraseasonal variability of the isotopologue composition of vapor and precipitation over the southern Tibetan Plateau results from these processes occurring during air mass transportation.

  6. Proceedings of the Seventeenth DOE Solar Photochemistry Research Conference

    Energy Technology Data Exchange (ETDEWEB)

    1993-12-31

    The Seventeenth DOE Solar Photochemistry Research Conference sponsored by the Division of Chemical Sciences, Office of Basic Energy Sciences, is being held June 6--10, 1993, at Cragun`s Lodge and Conference Center, Brainerd, Minnesota The meeting is hosted this year by the Ames Laboratory of Iowa State University. The purpose of the meeting is to foster cooperation, collaboration, and exchange of current research ideas among grantees and contractors of the DOE Division of Chemical Sciences engaged in fundamental research on solar photochemical energy conversion. This conference provides a special opportunity for interaction among investigators from diverse traditional chemistry disciplines who share the common good of providing the knowledge and concepts needed for production of low cost fuels and chemicals or electricity by photochemical conversion of solar energy. Our special guest plenary lecturer is Professor Graham Fleming, of the University of Chicago, who will speak on ultrafast spectroscopic studies of molecular dynamics in the condensed phase. The remaining presentations on Monday will feature further investigations of ultrafast phenomena in solvation, electron transfer, and charge separation at interfaces. These will lead into the topical sessions which follow on photosynthesis, molecular models, photoinduced charge transfer in homogeneous and heterogeneous solutions, inorganic photochemistry, and photoelectrochemistry. As an added feature, the photoelectrochemistry session will include six short introductory lectures for the benefit of nonspecialists on outstanding issues and problems in that field. In this volume may be found a copy of the program, the abstracts of 28 formal presentations and 59 posters, as well as an address listing of the 114 participants.

  7. The role of VUV radiation in the inactivation of bacteria with an atmospheric pressure plasma jet

    CERN Document Server

    Schneider, Simon; Ellerweg, Dirk; Denis, Benjamin; Narberhaus, Franz; Bandow, Julia E; Benedikt, Jan

    2011-01-01

    A modified version of a micro scale atmospheric pressure plasma jet (\\mu-APPJ) source, so-called X-Jet, is used to study the role of plasma generated VUV photons in the inactivation of E. coli bacteria. The plasma is operated in He gas or a He/O2 mixture and the X-Jet modification of the jet geometry allows effective separation of heavy reactive particles (such as O atoms or ozone molecules) from the plasma-generated photons. The measurements of the evolution of zone of inhibitions formed in monolayers of vegetative E. coli bacteria, of VUV emission intensity and of positive ion spectra show that photochemistry in the gas phase followed by photochemistry products impacting on bacteria can result in bacterial inactivation. Interestingly, this process is more effective than direct inactivation by VUV radiation damage. Mainly protonated water cluster ions are detected by mass spectrometry indicating that water impurity has to be carefully considered. The measurements indicate that the combination of the presence...

  8. The Atmospheric Neutral Density Experiment (ANDE) and Modulating Retroreflector in Space (MODRAS): Combined Flight Experiments for the Space Test Program

    National Research Council Canada - National Science Library

    Nicholas, A. C; Gilbreath, G. C; Thonnard, S. E; Kessel, R; Lucke, R; Sillman, C. P

    2003-01-01

    The Atmospheric Neutral Density Experiment (ANDE) is a low cost mission proposed by the Naval Research Laboratory to demonstrate a method to monitor the thermospheric neutral density at an altitude of 400 km...

  9. Combined model-data analysis during the recent stratospheric warming events: WACCM-X predictions and upper atmosphere data assimilation

    Science.gov (United States)

    Yudin, V.; Liu, H.; Goncharenko, L.

    2012-12-01

    The paper will present the initial investigations of predictability of the Mesosphere and Thermosphere (MT) region and examination of the physical mechanisms of variability in the community MT models governed and constrained by two important sources of information, (1) lower atmosphere weather patterns and (2) Middle Atmosphere (MA) observations. To relate explicitly Numerical Weather and Space Weather predictions, this study explores the novel framework for constraining the Whole Atmosphere Community Climate Model (WACCM) and its extension in the thermosphere and ionosphere, WACCM-X, by the meteorological analyses (MERRA and GEOS-5) of Global Modeling and Assimilation Office (GMAO). During the recent stratospheric warming events the research satellite data from NASA's TIMED (SABER and TIDI) and EOS-Aura (HIRDLS and MLS) instruments resolve the vertical structures of mean flow, waves and composition providing additional constraints for modeling of the lower-upper atmosphere coupling. Their sequential assimilation in the WACCM-X/MERRA will allow data constrained predictions of tides, planetary waves, and neutral-ion chemistry with the realistic weather in the lower atmosphere. For constraining the fast varying wave dynamics and composition novel aspects of the upper atmosphere data assimilation will be discussed including recreation of the fast diurnal variations in WACCM-X. The model and analysis results will be compared with independent ground-based and space-borne observations during stratospheric warming events.

  10. Vapor hydrogen and oxygen isotopes reflect water of combustion in the urban atmosphere.

    Science.gov (United States)

    Gorski, Galen; Strong, Courtenay; Good, Stephen P; Bares, Ryan; Ehleringer, James R; Bowen, Gabriel J

    2015-03-17

    Anthropogenic modification of the water cycle involves a diversity of processes, many of which have been studied intensively using models and observations. Effective tools for measuring the contribution and fate of combustion-derived water vapor in the atmosphere are lacking, however, and this flux has received relatively little attention. We provide theoretical estimates and a first set of measurements demonstrating that water of combustion is characterized by a distinctive combination of H and O isotope ratios. We show that during periods of relatively low humidity and/or atmospheric stagnation, this isotopic signature can be used to quantify the concentration of water of combustion in the atmospheric boundary layer over Salt Lake City. Combustion-derived vapor concentrations vary between periods of atmospheric stratification and mixing, both on multiday and diurnal timescales, and respond over periods of hours to variations in surface emissions. Our estimates suggest that up to 13% of the boundary layer vapor during the period of study was derived from combustion sources, and both the temporal pattern and magnitude of this contribution were closely reproduced by an independent atmospheric model forced with a fossil fuel emissions data product. Our findings suggest potential for water vapor isotope ratio measurements to be used in conjunction with other tracers to refine the apportionment of urban emissions, and imply that water vapor emissions associated with combustion may be a significant component of the water budget of the urban boundary layer, with potential implications for urban climate, ecohydrology, and photochemistry.

  11. Combined Effects of Long-Living Chemical Species during Microbial Inactivation Using Atmospheric Plasma-Treated Water▿

    OpenAIRE

    Naïtali, Murielle; Kamgang-Youbi, Georges; Herry, Jean-Marie; Bellon-Fontaine, Marie-Noëlle; Brisset, Jean-Louis

    2010-01-01

    Electrical discharges in humid air at atmospheric pressure (nonthermal quenched plasma) generate long-lived chemical species in water that are efficient for microbial decontamination. The major role of nitrites was evidenced together with a synergistic effect of nitrates and H2O2 and matching acidification. Other possible active compounds are considered, e.g., peroxynitrous acid.

  12. Combined Effects of Long-Living Chemical Species during Microbial Inactivation Using Atmospheric Plasma-Treated Water▿

    Science.gov (United States)

    Naïtali, Murielle; Kamgang-Youbi, Georges; Herry, Jean-Marie; Bellon-Fontaine, Marie-Noëlle; Brisset, Jean-Louis

    2010-01-01

    Electrical discharges in humid air at atmospheric pressure (nonthermal quenched plasma) generate long-lived chemical species in water that are efficient for microbial decontamination. The major role of nitrites was evidenced together with a synergistic effect of nitrates and H2O2 and matching acidification. Other possible active compounds are considered, e.g., peroxynitrous acid. PMID:20889799

  13. Detection of CO2 leaks from carbon capture and storage sites with combined atmospheric CO2 and O-2 measurements

    NARCIS (Netherlands)

    van Leeuwen, Charlotte; Meijer, Harro A. J.

    2015-01-01

    This paper presents a transportable instrument that simultaneously measures the CO2 and (relative) O-2 concentration of the atmosphere with the purpose to aid in the detection of CO2 leaks from CCS sites. CO2 and O-2 are coupled in most processes on earth (e.g., photosynthesis, respiration and

  14. Asian dust storm observed at a rural mountain site in southern China: chemical evolution and heterogeneous photochemistry

    Directory of Open Access Journals (Sweden)

    W. Nie

    2012-12-01

    Full Text Available Heterogeneous processes on dust particles are important for understanding the chemistry and radiative balance of the atmosphere. This paper investigates an intense Asian dust storm episode observed at Mount Heng (1269 m a.s.l. in southern China on 24–26 April 2009. A set of aerosol and trace gas data collected during the study was analyzed to investigate their chemical evolution and heterogeneous photochemistry as the dust traveled to southern China. Results show that the mineral dust arriving at Mt. Heng experienced significant modifications during transport, with large enrichments in secondary species (sulfate, nitrate, and ammonium compared with the dust composition collected at an upwind mountain top site (Mount Hua. A photochemical age "clock" (−Log10(NOx/NOy was employed to quantify the atmospheric processing time. The result indicates an obvious increase in the abundance of secondary water-soluble ions in dust particles with the air mass atmospheric processing time. Based on the observations, a 4-stage evolution process is proposed for carbonate-containing Asian dust, starting from fresh dust to particles coated with hydrophilic and acidic materials. Daytime-enhanced nitrite formation on the dust particles was also observed, which indicates the recent laboratory result of the TiO2 photocatalysis of NO2 as a potential source of nitrite and nitrous acid.

  15. Kinetics and Photochemistry of Ruthenium Bisbipyridine Diacetonitrile Complexes: An Interdisciplinary Inorganic and Physical Chemistry Laboratory Exercise.

    Science.gov (United States)

    Rapp, Teresa L; Phillips, Susan R; Dmochowski, Ivan J

    2016-12-13

    The study of ruthenium polypyridyl complexes can be widely applied across disciplines in the undergraduate curriculum. Ruthenium photochemistry has advanced many fields including dye-sensitized solar cells, photoredox catalysis, light-driven water oxidation, and biological electron transfer. Equally promising are ruthenium polypyridyl complexes that provide a sterically bulky, photolabile moiety for transiently "caging" biologically active molecules. Photouncaging involves the use of visible (1-photon) or near-IR (2-photon) light to break one or more bonds between ruthenium and coordinated ligand(s), which can occur on short time scales and in high quantum yields. In this work we demonstrate the use of a model "caged" acetonitrile complex, Ru(2,2'-bipyridine) 2 (acetonitrile) 2 , or RuMeCN in an advanced synthesis and physical chemistry laboratory. Students made RuMeCN in an advanced synthesis laboratory course and performed UV-vis spectroscopy and electrochemistry. The following semester students investigated RuMeCN photolysis kinetics in a physical chemistry laboratory. These two exercises may also be combined to create a 2-week module in an advanced undergraduate laboratory course.

  16. Photodynamic Efficiency: From Molecular Photochemistry to Cell Death

    Directory of Open Access Journals (Sweden)

    Isabel O. L. Bacellar

    2015-08-01

    Full Text Available Photodynamic therapy (PDT is a clinical modality used to treat cancer and infectious diseases. The main agent is the photosensitizer (PS, which is excited by light and converted to a triplet excited state. This latter species leads to the formation of singlet oxygen and radicals that oxidize biomolecules. The main motivation for this review is to suggest alternatives for achieving high-efficiency PDT protocols, by taking advantage of knowledge on the chemical and biological processes taking place during and after photosensitization. We defend that in order to obtain specific mechanisms of cell death and maximize PDT efficiency, PSes should oxidize specific molecular targets. We consider the role of subcellular localization, how PS photochemistry and photophysics can change according to its nanoenvironment, and how can all these trigger specific cell death mechanisms. We propose that in order to develop PSes that will cause a breakthrough enhancement in the efficiency of PDT, researchers should first consider tissue and intracellular localization, instead of trying to maximize singlet oxygen quantum yields in in vitro tests. In addition to this, we also indicate many open questions and challenges remaining in this field, hoping to encourage future research.

  17. Rice Photosynthetic Productivity and PSII Photochemistry under Nonflooded Irrigation

    Directory of Open Access Journals (Sweden)

    Haibing He

    2014-01-01

    Full Text Available Nonflooded irrigation is an important water-saving rice cultivation technology, but little is known on its photosynthetic mechanism. The aims of this work were to investigate photosynthetic characteristics of rice during grain filling stage under three nonflooded irrigation treatments: furrow irrigation with plastic mulching (FIM, furrow irrigation with nonmulching (FIN, and drip irrigation with plastic mulching (DI. Compared with the conventional flooding (CF treatment, those grown in the nonflooded irrigation treatments showed lower net photosynthetic rate (PN, lower maximum quantum yield (Fv/Fm, and lower effective quantum yield of PSII photochemistry (ΦPSII. And the poor photosynthetic characteristics in the nonflooded irrigation treatments were mainly attributed to the low total nitrogen content (TNC. Under non-flooded irrigation, the PN, Fv/Fm, and ΦPSII significantly decreased with a reduction in the soil water potential, but these parameters were rapidly recovered in the DI and FIM treatments when supplementary irrigation was applied. Moreover, The DI treatment always had higher photosynthetic productivity than the FIM and FIN treatments. Grain yield, matter translocation, and dry matter post-anthesis (DMPA were the highest in the CF treatment, followed by the DI, FIM, and FIN treatments in turn. In conclusion, increasing nitrogen content in leaf of rice plants could be a key factor to improve photosynthetic capacity in nonflooded irrigation.

  18. Studies in organic and physical photochemistry - an interdisciplinary approach.

    Science.gov (United States)

    Oelgemöller, Michael; Hoffmann, Norbert

    2016-08-21

    Traditionally, organic photochemistry when applied to synthesis strongly interacts with physical chemistry. The aim of this review is to illustrate this very fruitful interdisciplinary approach and cooperation. A profound understanding of the photochemical reactivity and reaction mechanisms is particularly helpful for optimization and application of these reactions. Some typical reactions and particular aspects are reported such as the Norrish-Type II reaction and the Yang cyclization and related transformations, the [2 + 2] photocycloadditions, particularly the Paternò-Büchi reaction, photochemical electron transfer induced transformations, different kinds of catalytic reactions such as photoredox catalysis for organic synthesis and photooxygenation are discussed. Particular aspects such as the structure and reactivity of aryl cations, photochemical reactions in the crystalline state, chiral memory, different mechanisms of hydrogen transfer in photochemical reactions or fundamental aspects of stereoselectivity are discussed. Photochemical reactions are also investigated in the context of chemical engineering. Particularly, continuous flow reactors are of interest. Novel reactor systems are developed and modeling of photochemical transformations and different reactors play a key role in such studies. This research domain builds a bridge between fundamental studies of organic photochemical reactions and their industrial application.

  19. On the photophysics and photochemistry of the water dimer

    Energy Technology Data Exchange (ETDEWEB)

    Segarra-Marti, Javier; Merchan, Manuela [Instituto de Ciencia Molecular, Universitat de Valencia, P.O. Box 22085, 46071 Valencia (Spain); Roca-Sanjuan, Daniel; Lindh, Roland [Department of Chemistry - Angstroem, Theoretical Chemistry Program, Uppsala University, Box 518, 75120 Uppsala (Sweden)

    2012-12-28

    The photochemistry of the water dimer irradiated by UV light is studied by means of the complete active space perturbation theory//complete active space self-consistent field (CASPT2//CASSCF) method and accurate computational approaches like as minimum energy paths. Both electronic structure computations and ab initio molecular dynamics simulations are carried out. The results obtained show small shifts relative to a single water molecule on the vertical excitation energies of the dimer due to the hydrogen bond placed between the water donor (W{sub D}) and the water acceptor (W{sub A}). A red-shift and a blue-shift are predicted for the W{sub D} and W{sub A}, respectively, supporting previous theoretical and experimental results. The photoinduced chemistry of the water dimer is described as a process occurring between two single water molecules in which the effect of the hydrogen bond plays a minor role. Thus, the photoinduced decay routes correspond to two photodissociation processes, one for each water molecule. The proposed mechanism for the decay channels of the lowest-lying excited states of the system is established as the photochemical production of a hydrogen-bonded H{sub 2}O Horizontal-Ellipsis HO species plus a hydrogen H atom.

  20. Two case studies on the interaction of large-scale transport, mesoscale photochemistry, and boundary-layer processes on the lower tropospheric ozone dynamics in early spring

    Directory of Open Access Journals (Sweden)

    S. Brönnimann

    2001-04-01

    Full Text Available The vertical distribution of ozone in the lower troposphere over the Swiss Plateau is investigated in detail for two episodes in early spring (February 1998 and March 1999. Profile measurements of boundary-layer ozone performed during two field campaigns with a tethered balloon sounding system and a kite are investigated using regular aerological and ozone soundings from a nearby site, measurements from monitoring stations at various altitudes, backward trajectories, and synoptic analyses of meteorological fields. Additionally, the effect of in situ photochemistry was estimated for one of the episodes employing the Metphomod Eulerian photochemical model. Although the meteorological situations were completely different, both cases had elevated layers with high ozone concentrations, which is not untypical for late winter and early spring. In the February episode, the highest ozone concentrations of 55 to 60 ppb, which were found at around 1100 m asl, were partly advected from Southern France, but a considerable contribution of in situ photochemistry is also predicted by the model. Below that elevation, the local chemical sinks and surface deposition probably overcompensated chemical production, and the vertical ozone distribution was governed by boundary-layer dynamics. In the March episode, the results suggest that ozone-rich air parcels, probably of stratospheric or upper tropospheric origin, were advected aloft the boundary layer on the Swiss Plateau.Key words. Atmospheric composition and structure (pollution – urban and regional; troposphere – composition and  chemistry – Meteorology and atmospheric dynamics (mesoscale meteorology

  1. Forward research on transmission characteristics of near-surface particulate-matter-polluted atmosphere in mining area combined with CFD method.

    Science.gov (United States)

    Wang, Wenzheng; Wang, Yanming; Shi, Guoqing

    2015-07-27

    The optical radiation and radiation transfer characteristics of atmospheric particulate matter (PM) in mining area of northwest China were simulated and analyzed in this paper. Computational fluid dynamics (CFD) method was adopted to simulate the distribution of PM considering the local desertification and mining activities. The 1-D radiative transfer equation was solved using discrete ordinates method combined with Mie scattering model based on the CFD simulation results. The spectral aerosol optical depth and transmission characteristics of PM polluted atmosphere in the wavelength of 1-25μm under different intensity of dust releases, wind speeds and dust compositions were obtained and analyzed. The simulation results show that: the transmission characteristics are obviously enhanced with the increase of wind speed and sand particles' proportion but greatly decreased with the increase of the intensity of dust release.

  2. Effect of a bacteriophage cocktail in combination with modified atmosphere packaging in controlling Listeria monocytogenes on fresh-cut spinach

    Directory of Open Access Journals (Sweden)

    Boyacioglu O.

    2016-06-01

    Full Text Available A Listeria monocytogenes-specific bacteriophage cocktail was evaluated for its activity against a nalidixic acid-resistant L. monocytogenes (Lm-NalR isolate on fresh-cut spinach stored under modified atmosphere packaging at various temperatures. Pieces (~2 × 2 cm2 of fresh spinach inoculated with 4.5 log CFU/cm2 Lm-NalR were sprayed with the phage cocktail (6.5 log plaque-forming units [PFU]/cm2 or a control. The samples were stored at 4°C or 10°C for up to 14 d in sealed packages filled with either atmospheric air (AA or modified atmosphere (MA. At 4°C under AA, the phages significantly (P ≤ 0.05 lowered the Lm-NalR populations on spinach, compared to control-treated inoculated samples, by 1.12 and 1.51 log CFU/cm2 after 1 and 14 d, respectively. At 4°C under MA, Lm-NalR was significantly reduced by 1.95 log CFU/cm2 compared to control leaves after both 1 and 14 d. At 10°C under AA, the phages significantly reduced Lm-NalR by 1.50 and 2.51 log CFU/cm2 after 1 and 14 d compared to the control. Again at 10°C under MA, the phages significantly reduced Lm-NalR by 1.71 and 3.24 log CFU/cm2 compared to control after 1 and 14 d, respectively. The results support the potential of lytic bacteriophages in effectively reducing populations of L. monocytogenes on freshcut leafy produce, under both AA and MA conditions.

  3. Variability in Arctic sea ice topography and atmospheric form drag: Combining IceBridge laser altimetry with ASCAT radar backscatter.

    Science.gov (United States)

    Petty, A.; Tsamados, M.; Kurtz, N. T.

    2016-12-01

    Here we present atmospheric form drag estimates over Arctic sea ice using high resolution, three-dimensional surface elevation data from NASA's Operation IceBridge Airborne Topographic Mapper (ATM), and surface roughness estimates from the Advanced Scatterometer (ASCAT). Surface features of the ice pack (e.g. pressure ridges) are detected using IceBridge ATM elevation data and a novel surface feature-picking algorithm. We use simple form drag parameterizations to convert the observed height and spacing of surface features into an effective atmospheric form drag coefficient. The results demonstrate strong regional variability in the atmospheric form drag coefficient, linked to variability in both the height and spacing of surface features. This includes form drag estimates around 2-3 times higher over the multiyear ice north of Greenland, compared to the first-year ice of the Beaufort/Chukchi seas. We compare results from both scanning and linear profiling to ensure our results are consistent with previous studies investigating form drag over Arctic sea ice. A strong correlation between ASCAT surface roughness estimates (using radar backscatter) and the IceBridge form drag results enable us to extrapolate the IceBridge data collected over the western-Arctic across the entire Arctic Ocean. While our focus is on spring, due to the timing of the primary IceBridge campaigns since 2009, we also take advantage of the autumn data collected by IceBridge in 2015 to investigate seasonality in Arctic ice topography and the resulting form drag coefficient. Our results offer the first large-scale assessment of atmospheric form drag over Arctic sea ice due to variable ice topography (i.e. within the Arctic pack ice). The analysis is being extended to the Antarctic IceBridge sea ice data, and the results are being used to calibrate a sophisticated form drag parameterization scheme included in the sea ice model CICE, to improve the representation of form drag over Arctic and

  4. Formation of reactive nitrogen oxides from urban grime photochemistry

    OpenAIRE

    Baergen, Alyson M.; Donaldson, D. James

    2016-01-01

    Impervious surfaces are ubiquitous in urban environments and constitute a substrate onto which atmospheric constituents can deposit and undergo photochemical and oxidative processing, giving rise to “urban grime” films. HNO3 and N2O5 are important sinks for NOx in the lower atmosphere and may be deposited onto these films, forming nitrate through surface hydrolysis. Although such deposition has been considered as a net loss of NOx from the atmosphere, there is increasing ...

  5. Atmospheric Photochemistry Studies of Pollutant Emissions from Transportation Vehicles Operating on Alternative Fuels

    Energy Technology Data Exchange (ETDEWEB)

    Jeffries, H.; Sexton, K.; Yu, J.

    1998-07-01

    This project was undertaken with the goal of improving our ability to predict the changes in urban ozone resulting from the widespread use of alternative fuels in automobiles. This report presents the results in detail.

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

    DEFF Research Database (Denmark)

    Mang, Stephen A.; Henricksen, Dana K.; Bateman, Adam P.

    2008-01-01

    The photodegradation of secondary organic aerosol (SOA) material by actinic UV radiation was investigated. SOA was generated via the dark reaction of ozone and d-limonene, collected onto quartz-fiber filters, and exposed to wavelength-tunable radiation. Photochemical production of CO was monitored...... was measured and compared with the photolysis action spectrum for the release of CO, a marker for Norrish type-1 photocleavage of carbonyls. Both spectra had a band at similar to 300 nm corresponding to the overlapping n -> pi* transitions in nonconjugated carbonyls. The effective extinction coefficient...

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

    Science.gov (United States)

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

    2008-09-11

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

  8. Apportionment of carbon dioxide over central Europe: insights from combined measurements of atmospheric CO2 mixing ratios and carbon isotope composition

    Science.gov (United States)

    Zimnoch, M.; Jelen, D.; Galkowski, M.; Kuc, T.; Necki, J.; Chmura, L.; Gorczyca, Z.; Jasek, A.; Rozanski, K.

    2012-04-01

    The European continent, due to high population density and numerous sources of anthropogenic CO2 emissions, plays an important role in the global carbon budget. Nowadays, precise measurements of CO2 mixing ratios performed by both global and regional monitoring networks, combined with appropriate models of carbon cycle, allow quantification of the European input to the global atmospheric CO2 load. However, measurements of CO2 mixing ratios alone cannot provide the information necessary for the apportionment of fossil-fuel related and biogenic contributions to the total CO2 burden of the regional atmosphere. Additional information is required, for instance obtained through measurements of radiocarbon content in atmospheric carbon dioxide. Radiocarbon is a particularly useful tracer for detecting fossil carbon in the atmosphere on different spatial and temporal scales. Regular observations of atmospheric CO2mixing ratios and their isotope compositions have been performed during the period of 2005-2009 at two sites located in central Europe (southern Poland). The sites, only ca. 100 km apart, represent two extreme environments with respect to the extent of anthropogenic pressure: (i) the city of Krakow, representing typical urban environment with numerous sources of anthropogenic CO2, and (ii) remote mountain site Kasprowy Wierch, relatively free of local influences. Regular, quasi-continuous measurements of CO2 mixing ratios have been performed at both sites. In addition, cumulative samples of atmospheric CO2 have been collected (weekly sampling regime for Krakow and monthly for Kasprowy Wierch) to obtain mean carbon isotope signature (14C/12C and 13C/12C ratios) of atmospheric CO2 at both sampling locations. Partitioning of the local atmospheric CO2 load at both locations has been performed using isotope- and mass balance approach. In Krakow, the average fossil-fuel related contribution to the local atmospheric CO2 load was equal to approximately 3.4%. The biogenic

  9. Stable lead isotopes and lake sediments--a useful combination for the study of atmospheric lead pollution history.

    Science.gov (United States)

    Renberg, I; Brännvall, M L; Bindler, R; Emteryd, O

    2002-06-20

    Analysis of stable lead isotopes and lead concentrations in lake-sediment deposits, not least in varved (annually-laminated) sediments, is a useful method to study lead pollution history. This paper presents details from a study of 31 lakes in Sweden. Using a strong acid digestion of sediment samples and ICP-MS analyses, we have found that Swedish lake sediments have a high natural (pre-pollution) 206[Pb]207[Pb] ratio (mean 1.52+/-0.18, range 1.28-2.01, n=31 lakes). In contrast, atmospheric lead pollution derived from metal smelting processes, coal burning and from alkyl-lead added to petrol has a lower ratio (pollution lead deposition began approximately 3500 years ago, the lead isotope ratio of the sediments started to decline, and in modern sediments it is typically pollution and natural lead in sediment samples can be calculated. The pollution lead records of the Swedish lake sediments show a consistent picture of the atmospheric lead pollution history. Some noticeable features are the Roman peak (approx. 0 AD), the large and permanent Medieval increase (approx. 1000 AD), peaks at approximately 1200 and 1530 AD, the rapid increase after World War II, the peak in the 1970s, and the large modern decline.

  10. Primary Photochemistry in the Photoactive Yellow Protein: The Prototype Xanthopsin

    Science.gov (United States)

    Larsen, D. S.; van Grondelle, R.; Hellingwerf, K. J.

    Light-sensing proteins, i.e., biological photoreceptors, are complexes composed of an apo-protein and a bound light-absorbing chromophore. They provide the opportunity to resolve and characterize how Nature has tuned proteins to convert photon energy into biological function. Such photoreceptor proteins can be triggered with (laser) flash illumination and because modern ultrafast lasers offer exceptional control of laser light pulses, excellent time-resolution is achievable in spectroscopic studies. Because photoreceptors are also signaltransduction proteins, one may anticipate the conformational transitions to be significant to allow participation in a macroscopic signal transduction pathway [1]. Furthermore, the variable color of these proteins functions as an excellent indicator for the number of discernable states involved in their transition( s). The various photoreceptor proteins that have been described in the literature can be classified into a limited number of families. This classification is primarily based on the chemical structure of the light-absorbing chromophores involved, but in addition, arguments derived from the protein sequence alignment have to be used (specifically to discriminate the many photoreceptor proteins that bind flavin derivatives). These families are the rhodopsins [2, 3] (containing retinal), the phytochromes [4] (binding a bilin derivative), the xanthopsins [5] (containing a covalently bound 4-hydroxycinnamic acid), and the cryptochromes [6], the phototropins [7] and the BLUF proteins [8] that all contain a flavin derivative. Activation of these photoreceptor proteins involves changes in the configuration of the corresponding embedded chromophores. For the first three families, this change in configuration is a trans/cis isomerization, but for theflavin-containing photoreceptors other types of photochemistry have been uncovered (like transient cysteinyladduct formation in the LOV domains of phototropins [9, 10]). This change in

  11. Physicochemical study of spiropyran-terthiophene derivatives: photochemistry and thermodynamics.

    Science.gov (United States)

    Zanoni, Michele; Coleman, Simon; Fraser, Kevin J; Byrne, Robert; Wagner, Klaudia; Gambhir, Sanjeev; Officer, David L; Wallace, Gordon G; Diamond, Dermot

    2012-07-07

    The photochemistry and thermodynamics of two terthiophene (TTh) derivatives bearing benzospiropyran (BSP) moieties, 1-(3,3″-dimethylindoline-6'-nitrobenzospiropyranyl)-2-ethyl 4,4″-didecyloxy-2,2':5',2″-terthiophene-3'-acetate (BSP-2) and 1-(3,3″-dimethylindoline-6'-nitrobenzospiropyranyl)-2-ethyl 4,4″-didecyloxy-2,2':5',2″-terthiophene-3'-carboxylate (BSP-3), differing only by a single methylene spacer unit, have been studied. The kinetics of photogeneration of the equivalent merocyanine (MC) isomers (MC-2 and MC-3, respectively), the isomerisation properties of MC-2 and MC-3, and the thermodynamic parameters have been studied in acetonitrile, and compared to the parent, non-TTh-functionalised, benzospiropyran derivative, BSP-1. Despite the close structural similarity of BSP-2 and BSP-3, their physicochemical properties were found to differ significantly; examples include activation energies (E(a(MC-2)) = 75.05 kJ mol(-1), E(a(MC-3)) = 100.39 kJ mol(-1)) and entropies of activation (ΔS = 43.38 J K(-1) mol(-1), ΔS = 37.78 J K(-1) mol(-1)) for the thermal relaxation from MC to BSP, with the MC-3 value much closer to the unmodified MC-1 value (46.48 J K(-1) mol(-1)) for this latter quantity. The thermal relaxation kinetics and solvatochromic behaviour of the derivatives in a range of solvents of differing polarity (ethanol, dichloromethane, acetone, toluene and diethyl ether) are also presented. Differences in the estimated values of these thermodynamic and kinetic parameters are discussed with reference to the molecular structure of the derivatives.

  12. Effects of soaking with natural additives in combinations with vacuum or modified atmosphere packaging on microbial populations and shelf life of fresh truffles (Chinese Tuber indicum).

    Science.gov (United States)

    Miao, Yuzhi; Chen, Cuiping; Ma, Qinqin; Wang, Yiding; Zhang, Xiaoyu; Guo, Fanglan; Li, Wei; Yong, Bin

    2014-10-01

    The objective of this study was to evaluate the relative effects and interactions of combined soaking treatment using citric acid (CTA) and apple polyphenol (APP) at mild heating temperatures for the inactivation of the external and internal microflora (mesophilic aerobic bacteria, mesophilic anaerobic bacteria, and fungi) in Chinese Tuber indicum, as well as to analyze the microbiological and sensory changes under modified atmosphere packaging (MAP)- and vacuum atmosphere packaging (VAC)-packed Chinese T. indicum stored at 4 °C for up to 55 d. Chinese T. indicum was soaked with CTA and APP alone or in combination for 10, 20, and 30 min at 35, 45, and 55 °C. A disinfection method using CTA and APP (3% CTA + 3% APP for 20 min at 45 °C) was obtained. Under this set of combination, the experimental values of microbial counts of mesophilic aerobic bacteria, mesophilic anaerobic bacteria, and fungi were 2.31 ± 0.4 log CFU/g, <1.0 log CFU/g, and <1.0 log CFU/g, respectively. Through the analysis of sensory qualities and microbial populations for MAP- or VAC-packed Chinese T. indicum, the shelf life of soaked truffles was prolonged to 45 or 40 d, respectively. The synergistic effect of CTA and APP may provide valuable insight into the reduction of microorganisms on fresh truffles. © 2014 Institute of Food Technologists®

  13. Photochemistry of hydrogen halides on water clusters: simulations of electronic spectra and photodynamics, and comparison with photodissociation experiments.

    Science.gov (United States)

    Ončák, Milan; Slavíček, Petr; Fárník, Michal; Buck, Udo

    2011-06-16

    The photochemistry of small HX·(H(2)O)(n), n = 4 and 5 and X = F, Cl, and Br, clusters has been modeled by means of ab initio-based molecular simulations. The theoretical results were utilized to support our interpretation of photodissociation experiments with hydrogen halides on ice nanoparticles HX·(H(2)O)(n), n ≈ 10(2)-10(3). We have investigated the HX·(H(2)O)(n) photochemistry for three structural types: covalently bound structures (CBS) and acidically dissociated structures in a form of contact ion pair (CIP) and solvent separated pair (SSP). For all structures, we have modeled the electronic absorption spectra using the reflection principle combined with a path integral molecular dynamics (PIMD) estimate of the ground state density. In addition, we have investigated the solvent effect of water on the absorption spectra within the nonequilibrium polarizable continuum model (PCM) scheme. The major conclusion from these calculations is that the spectra for ionic structures CIP and SSP are significantly red-shifted with respect to the spectra of CBS structures. We have also studied the photodynamics of HX·(H(2)O)(n) clusters using the Full Multiple Spawning method. In the CBS structures, the excitation led to almost immediate release of the hydrogen atom with high kinetic energy. The light absorption in ionically dissociated species generates the hydronium radical (H(3)O) and halogen radical (X) within a charge-transfer-to-solvent (CTTS) excitation process. The hydronium radical ultimately decays into a water molecule and hydrogen atom with a characteristic kinetic energy irrespective of the hydrogen halide. We have also investigated the dynamics of an isolated and water-solvated H(3)O radical that we view as a central species in water radiation chemistry. The theoretical findings support the following picture of the HX photochemistry on ice nanoparticles investigated in our molecular beam experiments: HX is acidically dissociated in the ground state on

  14. Developing Tighter Constraints on Exoplanet Biosignatures by Modeling Atmospheric Haze

    Science.gov (United States)

    Felton, Ryan; Neveu, Marc; Domagal-Goldman, Shawn David; Desch, Steven; Arney, Giada

    2018-01-01

    As we increase our capacity to resolve the atmospheric composition of exoplanets, we must continue to refine our ability to distinguish true biosignatures from false positives in order to ultimately distinguish a life-bearing from a lifeless planet. Of the possible true and false biosignatures, methane (CH4) and carbon dioxide (CO2) are of interest, because on Earth geological and biological processes can produce them on large scales. To identify a biotic, Earth-like exoplanet, we must understand how these biosignatures shape their atmospheres. High atmospheric abundances of CH4 produce photochemical organic haze, which dramatically alters the photochemistry, climate, and spectrum of a planet. Arney et al. (2017) have suggested that haze-bearing atmospheres rich in CO2 may be a type of biosignature because the CH4 flux required to produce the haze is similar to the amount of biogenic CH4 on modern Earth. Atmospheric CH4 and CO2 both affect haze-formation photochemistry, and the potential for hazes to form in Earth-like atmospheres at abiotic concentrations of these gases has not been well studied. We will explore a wide range of parameter space of abiotic concentration levels of these gases to determine what spectral signatures are possible from abiotic environments and look for measurable differences between abiotic and biotic atmospheres. We use a 1D photochemical model with an upgraded haze production mechanism to compare Archean and modern Earth atmospheres to abiotic versions while varying atmospheric CH4 and CO2 levels and atmospheric pressure. We will vary CO2 from a trace gas to an amount such that it dominates atmospheric chemistry. For CH4, there is uncertainty regarding the amount of abiotic CH4 that comes from serpentinizing systems. To address this uncertainty, we will model three cases: 1) assume all CH4 comes from photochemistry; 2) use estimates of modern-day serpentinizing fluxes, assuming they are purely abiotic; and 3) assume serpentinizing

  15. 2011 Photochemistry Gordon Research Conference (July10-15, 2011, Stonehill College, Easton, MA)

    Energy Technology Data Exchange (ETDEWEB)

    Prof. Gerald Meyer

    2011-07-15

    Photochemistry has wide implications on fundamental science with technological applications that range from synthetic and mechanistic organic and inorganic chemistry to sensing/manipulation in the biological sciences to viable solar energy conversion assemblies. The 2011 Gordon Research Conference on Photochemistry will highlight recent advances on photochemical reactions, their mechanisms, spectroscopic techniques and applications to materials, organic synthesis, and biology. The conference will continue its long tradition on dynamic discussions on recent advances and unsolved scientific problems. The format of lectures, poster presentations and informal discussions provides an ideal venue for students and post-doctoral fellows to interact with the leaders in the field. These junior scientists will have an opportunity to participate in the Gordon Research Seminar on Photochemistry to be held prior to the GRC. The GRS will focus on photochemical aspects of solar energy conversion. Four abstracts for posters at the GRC and presentations at the GRS will be selected as short talks at the GRC.

  16. Applications of Continuous-Flow Photochemistry in Organic Synthesis, Material Science, and Water Treatment.

    Science.gov (United States)

    Cambié, Dario; Bottecchia, Cecilia; Straathof, Natan J W; Hessel, Volker; Noël, Timothy

    2016-09-14

    Continuous-flow photochemistry in microreactors receives a lot of attention from researchers in academia and industry as this technology provides reduced reaction times, higher selectivities, straightforward scalability, and the possibility to safely use hazardous intermediates and gaseous reactants. In this review, an up-to-date overview is given of photochemical transformations in continuous-flow reactors, including applications in organic synthesis, material science, and water treatment. In addition, the advantages of continuous-flow photochemistry are pointed out and a thorough comparison with batch processing is presented.

  17. Retrieval of atmospheric-temperature and water-vapor profiles by use of combined satellite and ground-based infrared spectral-radiance measurements.

    Science.gov (United States)

    Ho, Shu-Peng; Smith, William L; Huang, Hung-Lung

    2002-07-10

    A nonlinear sounding retrieval algorithm is used to produce vertical-temperature and water-vapor profiles from coincident observations taken by the airborne High-resolution Interferometer Sounder (HIS) and the ground-based Atmospheric Emitted Radiance Interferometer (AERI) during the SUbsonic Contrails and Clouds Effects Special Study (SUCCESS). Also, clear sky Geostationary Operational Environmental Satellite (GOES) and AERI radiance measurements, achieved on a daily real-time basis at the Department of Energy's Oklahoma CART (Cloud and Radiation Testbed) site, are used to demonstrate the current profiling capability by use of simultaneous geostationary satellite and ground-based remote sensing observations under clear-sky conditions. The discrepancy principle, a method to find the proper smoothing parameters from the minimum value between the normalized spectral residual norm and the a priori upper bound, is used to demonstrate the feasibility and effectiveness of on-line simultaneous tuning of the multiple weighting and smoothing parameters from the combined satellite/airborne and ground-based measurements for the temperature and water-vapor retrieval in this nonlinear-retrieval process. An objective method to determine the degrees of freedom (d.f.) of the observation signal is derived. The d.f. of the radiance signal for the combined GOES and AERI measurements is larger than that for either instrument alone; while the d.f. of the observation signal for the combined GOES and AERI measurements is larger than that for either instrument alone and of the combined GOES and AERI measurements. The use of simultaneous clear-sky AERI and GOES data now provides improved vertical temperature and moisture soundings on an hourly basis for use in the Atmospheric Radiation Measurement program [J. Appl. Meteorol. 37, 875 (1998)].

  18. Combining in situ and laboratory measurements of soil-atmosphere carbonyl sulfide fluxes from four different biomes across Europe

    Science.gov (United States)

    Kitz, Florian; Gomez-Brandon, Maria; Hammerle, Albin; Spielmann, Felix M.; Insam, Heribert; Ibrom, Andreas; Migliavacca, Mirco; Moreno, Gerardo; Noe, Steffen M.; Wohlfahrt, Georg

    2017-04-01

    Flux partitioning, the quantification of photosynthesis and respiration, is a major uncertainty in modelling the carbon cycle and in times when robust models are needed to assess future global changes a persistent problem. A promising new approach is to derive gross primary production (GPP) from measurements of the carbonyl sulfide (COS) flux, the most abundant sulfur-containing trace gas in the atmosphere, with a mean concentration of about 500 pptv in the troposphere. This is possible because COS and CO2 enter the leaf via a similar pathway and are processed by the same enzyme (carbonic anhydrase). A prerequisite for using COS as a proxy for photosynthesis is a robust estimation of all non-leaf sources and sinks in an ecosystem. Past studies described soils either as a sink or source, depending on their properties like soil temperature and soil water content. In 2016 we conducted field campaigns in Austria (managed temperate mountain grassland), Spain (savannah), Denmark (temperate beech forest) and Estonia (hemiboreal forest) to estimate the soil-atmosphere COS fluxes under ambient conditions in different biomes. We used self-built fused silica soil chambers to avoid COS emissions from built-in materials and to assess the impact of radiation. At the grassland sites (Austria, Spain) vegetation was removed below the chambers, therefor more radiation reached the soil surface compared to natural conditions. The grassland sites were characterized by highly positive COS fluxes during daytime and COS fluxes around zero during nighttime. In contrast, the soils at the forest sites (Denmark, Estonia), characterized by less radiation on the soil surface, acted as a sink for COS. The impact of other abiotic factors, like soil water content and soil temperature, varied between the ecosystems. In addition to the field measurements soil and litter samples were taken at the study sites and used to measure COS fluxes under controlled conditions in the lab. Results from the

  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. Effect of combining nisin with modified atmosphere packaging on inhibition of Listeria monocytogenes in ready-to-eat turkey bologna.

    Science.gov (United States)

    Naas, Hesham; Martinez-Dawson, Rose; Han, Inyee; Dawson, Paul

    2013-07-01

    ABSTRACT The objective of this study was to evaluate the effect of nisin in combination with different types of packaging on the survival of Listeria monocytogenes in ready-to-eat low-fat turkey bologna. Bologna was inoculated with L. monocytogenes exposed to 1 of 6 treatments: 3 packaging treatments (100% CO2, air, vacuum), each with and without nisin. Bologna was refrigerated and sampled 9 times over 42 d. Nisin reduced initial L. monocytogenes populations by 1.5 to 2 log cycles and 100% CO2 packaging prevented outgrowth throughout 42 d of storage, whereas non-CO2 packaging displayed a 2-log increase in population during storage. Nisin (500 IU/mL) combined with 100% CO2 was effective in reducing Listeria and preventing outgrowth on bologna over 42 d of refrigerated storage.

  1. Combined chemical and topographic imaging at atmospheric pressure via microprobe laser desorption/ionization mass spectrometry-atomic force microscopy.

    Science.gov (United States)

    Bradshaw, James A; Ovchinnikova, Olga S; Meyer, Kent A; Goeringer, Douglas E

    2009-12-01

    The operational characteristics and imaging performance are described for a new instrument comprising an atomic force microscope coupled with a pulsed laser and a linear ion trap mass spectrometer. The operating mode of the atomic force microscope is used to produce topographic surface images having sub-micrometer spatial and height resolution. Spatially resolved mass spectra of ions, produced from the same surface via microprobe-mode laser desorption/ionization at atmospheric pressure, are also used to create a 100 x 100 microm chemical image. The effective spatial resolution of the image (approximately 2 microm) was constrained by the limit of detection (estimated to be 10(9)-10(10) molecules) rather than by the diameter of the focused laser spot or the step size of the sample stage. The instrument has the potential to be particularly useful for surface analysis scenarios in which chemical analysis of targeted topographic features is desired; consequently, it should have extensive application in a number of scientific areas. Because the number density of desorbed neutral species in laser desorption/ionization is known to be orders-of-magnitude greater than that of ions, it is expected that improvements in imaging performance can be realized by implementation of post-ionization methods.

  2. Control of Listeria monocytogenes on frankfurters and cooked pork chops by irradiation combined with modified atmosphere packaging.

    Science.gov (United States)

    Kudra, Li L; Sebranek, Joseph G; Dickson, James S; Larson, Elaine M; Mendonca, Aubrey F; Prusa, Kenneth J; Cordray, Joseph C; Jackson-Davis, Armitra; Lu, Zheng

    2012-06-01

    This study was conducted to investigate the efficacy of controlling Listeria monocytogenes on frankfurters and cooked pork chops with irradiation and modified atmosphere packaging (MAP) containing a high concentration of CO(2). Frankfurters and cooked pork chops were inoculated with a five-strain cocktail of L. monocytogenes and packaged in vacuum or high-CO(2) MAP. Irradiation was applied to each product at 0, 0.5, 1.0, or 1.5 kGy. No significant packaging effect was found for the radiation sensitivity of L. monocytogenes. Radiation D(10)-values for L. monocytogenes were 0.66 ± 0.03 and 0.70 ± 0.05 kGy on frankfurters and 0.60 ± 0.02 and 0.57 ± 0.02 kGy on cooked pork chops in vacuum and high-CO(2) MAP, respectively. High-CO(2) MAP was more effective than vacuum packaging for controlling the growth of survivors during refrigerated storage. These results indicate that irradiation and high-CO(2) MAP can be used to improve control of L. monocytogenes in ready-to-eat meats.

  3. Boundary layer photochemistry during a total solar eclipse

    Directory of Open Access Journals (Sweden)

    Peter Fabian

    2001-05-01

    Full Text Available Simultaneous measurements of radiation, photolysis frequencies, O3, CO, OH, PAN and NOx species were carried out in the boundary layer, along with pertinent meteorological parameters, under total solar eclipse conditions. This experiment performed at about 34 solar zenith angle and noontime conditions thus provided a case study about the interactions between radiation and photochemistry under fast ''day-night'' and ''night-day'' transitions, at high solar elevation. The results reveal a close correlation of photolysis frequencies jO(1D and jNO2with the UV radiation flux. All three parameters show, due to the decreasing fraction of direct radiation at shorter wavelengths, much weaker cloud shading effects than global solar radiation. NO and OH concentrations decrease to essentially zero during totality. Subsequently, NO and OH concentrations increased almost symmetrically to their decrease preceding totality. The NO/NO2 ratio was proportional to jNO2over 30 min before and after totality indicating that the partitioning of NOx species is determined by jNO2. Simple box model simulations show the effect of reduced solar radiation on the photochemical production of O3 and PAN. WÄhrend der totalen Sonnenfinsternis am 11. August 1999 wurden simultane und kontinuierliche Messungen von O3, CO, OH, PAN and NOx, Strahlung, Photolysefrequenzen und relevanten meteorologischen Parametern durchgefÜhrt. Dieses Experiment, durchgefÜhrt etwa am Mittag, bei 34 Zenithwinkel der Sonne, ermöglichte die Untersuchung der Interaktion von Strahlung und Photochemie fÜr schnelle Tag-Nacht und Nacht-Tag-ÜbergÄnge bei hohem Sonnenstand. Die Ergebnisse zeigen eine enge Korrelation der Photolysefrequenzen jO(1D und jNO2 mit dem UV-Strahlungsfluss. Alle drei Parameter zeigen, wegen des abnehmenden Anteils direkter Sonnenstrahlung bei kurzen WellenlÄngen, erheblich geringere AbschwÄchung durch Wolken als die Globalstrahlung. NO und OH gehen wÄhrend der

  4. Mutagenicity in Salmonella of a Simulated Urban-Smog Atmosphere Generated Using a Mobile Reaction Chamber

    Science.gov (United States)

    The EPA Mobile Reaction Chamber (MRC) is a 24-foot trailer containing a 14.3-m3 Teflon lined photochemical chamber used to generate simulated urban atmospheres. Photochemistry in the MRC is catalyzed by 120 fluorescent bulbs evenly mixed with black light bulbs and UV bulbs (300 &...

  5. Dynamic mineral clouds on HD 189733b. II. Monte Carlo radiative transfer for 3D cloudy exoplanet atmospheres: combining scattering and emission spectra

    Science.gov (United States)

    Lee, G. K. H.; Wood, K.; Dobbs-Dixon, I.; Rice, A.; Helling, Ch.

    2017-05-01

    Context. As the 3D spatial properties of exoplanet atmospheres are being observed in increasing detail by current and new generations of telescopes, the modelling of the 3D scattering effects of cloud forming atmospheres with inhomogeneous opacity structures becomes increasingly important to interpret observational data. Aims: We model the scattering and emission properties of a simulated cloud forming, inhomogeneous opacity, hot Jupiter atmosphere of HD 189733b. We compare our results to available Hubble Space Telescope (HST) and Spitzer data and quantify the effects of 3D multiple scattering on observable properties of the atmosphere. We discuss potential observational properties of HD 189733b for the upcoming Transiting Exoplanet Survey Satellite (TESS) and CHaracterising ExOPlanet Satellite (CHEOPS) missions. Methods: We developed a Monte Carlo radiative transfer code and applied it to post-process output of our 3D radiative-hydrodynamic, cloud formation simulation of HD 189733b. We employed three variance reduction techniques, I.e. next event estimation, survival biasing, and composite emission biasing, to improve signal to noise of the output. For cloud particle scattering events, we constructed a log-normal area distribution from the 3D cloud formation radiative-hydrodynamic results, which is stochastically sampled in order to model the Rayleigh and Mie scattering behaviour of a mixture of grain sizes. Results: Stellar photon packets incident on the eastern dayside hemisphere show predominantly Rayleigh, single-scattering behaviour, while multiple scattering occurs on the western hemisphere. Combined scattered and thermal emitted light predictions are consistent with published HST and Spitzer secondary transit observations. Our model predictions are also consistent with geometric albedo constraints from optical wavelength ground-based polarimetry and HST B band measurements. We predict an apparent geometric albedo for HD 189733b of 0.205 and 0.229, in the

  6. Short-Time Events, Coherence, and Structural Dynamics in Photochemistry of Aqueous Halogenated Transition Metal Dianions

    Directory of Open Access Journals (Sweden)

    Pascher T.

    2013-03-01

    Full Text Available Ultrafast pump-probe spectroscopy, time-resolved x-ray absorption, and computational photochemistry elucidate the photochemical pathway of hexabromoplatinate dianions that propagates through distortions of nascent penta-bromoplatinate anions caused by Jahn-Teller conical intersections and terminates at aquated product complexes.

  7. Photochemistry of solid interstellar molecular samples exposed to vacuum-ultraviolet synchrotron radiation

    Energy Technology Data Exchange (ETDEWEB)

    Lo, Jen-Iu; Chou, Sheng-Lung; Peng, Yu-Chain; Lin, Meng-Yeh; Lu, Hsiao-Chi; Cheng, Bing-Ming, E-mail: bmcheng@nsrrc.org.tw

    2014-10-15

    Highlights: • By means of an end station attached to synchrotron, we investigate the VUV photolysis of gaseous samples condensed at 3 K. • The end station is applicable to explore the VUV photochemistry of interstellar solid molecules. • We upgraded the end station with detection of absorption of IR light and of emission of UV–vis light. • As a demonstration, we recorded simultaneously absorption spectra of photoproduct N{sub 3} and emission from VUV excited N{sub 2}. • The end station is applicable to investigate cometary mixed-ice analogs excited with VUV light from the synchrotron. - Abstract: At the vacuum-ultraviolet (VUV) beamline of the Taiwan synchrotron, an end station for photochemistry coupled to instruments to record infrared absorption spectra and ultraviolet and visible emission spectra is used to investigate the photolysis of samples of gases condensed at 3 K. This end station is applicable to explore the VUV photochemistry of interstellar molecules in solid samples. For demonstration, we discuss the response of solid dinitrogen to VUV irradiation. In the future, the upgraded photochemistry end station is applicable to investigate the cometary mixed-ice analogs excited with VUV light from the synchrotron.

  8. Kinetics and Photochemistry of Ruthenium Bisbipyridine Diacetonitrile Complexes: An Interdisciplinary Inorganic and Physical Chemistry Laboratory Exercise

    Science.gov (United States)

    Rapp, Teresa L.; Phillips, Susan R.; Dmochowski, Ivan J.

    2016-01-01

    The study of ruthenium polypyridyl complexes can be widely applied across disciplines in the undergraduate curriculum. Ruthenium photochemistry has advanced many fields including dye-sensitized solar cells, photoredox catalysis, lightdriven water oxidation, and biological electron transfer. Equally promising are ruthenium polypyridyl complexes…

  9. Energy cascades, excited state dynamics, and photochemistry in cob(III)alamins and ferric porphyrins.

    Science.gov (United States)

    Rury, Aaron S; Wiley, Theodore E; Sension, Roseanne J

    2015-03-17

    Porphyrins and the related chlorins and corrins contain a cyclic tetrapyrrole with the ability to coordinate an active metal center and to perform a variety of functions exploiting the oxidation state, reactivity, and axial ligation of the metal center. These compounds are used in optically activated applications ranging from light harvesting and energy conversion to medical therapeutics and photodynamic therapy to molecular electronics, spintronics, optoelectronic thin films, and optomagnetics. Cobalt containing corrin rings extend the range of applications through photolytic cleavage of a unique axial carbon-cobalt bond, permitting spatiotemporal control of drug delivery. The photochemistry and photophysics of cyclic tetrapyrroles are controlled by electronic relaxation dynamics including internal conversion and intersystem crossing. Typically the electronic excitation cascades through ring centered ππ* states, ligand to metal charge transfer (LMCT) states, metal to ligand charge transfer (MLCT) states, and metal centered states. Ultrafast transient absorption spectroscopy provides a powerful tool for the investigation of the electronic state dynamics in metal containing tetrapyrroles. The UV-visible spectrum is sensitive to the oxidation state, electronic configuration, spin state, and axial ligation of the central metal atom. Ultrashort broadband white light probes spanning the range from 270 to 800 nm, combined with tunable excitation pulses, permit the detailed unravelling of the time scales involved in the electronic energy cascade. State-of-the-art theoretical calculations provide additional insight required for precise assignment of the states. In this Account, we focus on recent ultrafast transient absorption studies of ferric porphyrins and corrin containing cob(III)alamins elucidating the electronic states responsible for ultrafast energy cascades, excited state dynamics, and the resulting photoreactivity or photostability of these compounds. Iron

  10. Synergy of CuO and CeO2 combination for mercury oxidation under low-temperature selective catalytic reduction atmosphere

    KAUST Repository

    Li, Hailong

    2016-07-19

    Synergy for low temperature Hg0 oxidation under selective catalytic reduction (SCR) atmosphere was achieved when copper oxides and cerium oxides were combined in a CuO-CeO2/TiO2 (CuCeTi) catalyst. Hg0 oxidation efficiency as high as 99.0% was observed on the CuCeTi catalyst at 200 °C, even the gas hourly space velocity was extremely high. To analyze the synergistic effect, comparisons of catalyst performance in the presence of different SCR reaction gases were systematically conducted over CuO/TiO2 (CuTi), CeO2/TiO2 (CeTi) and CuCeTi catalysts prepared by sol-gel method. The interactions between copper oxides and cerium oxides in CuCeTi catalyst yielded more surface chemisorbed oxygen, and facilitated the conversion of gas-phase O2 to surface oxygen, which are favorable for Hg0 oxidation. Copper oxides in the combination interacted with NO forming more chemisorbed oxygen for Hg0 oxidation in the absence of gas-phase O2. Cerium oxides in the combination promoted Hg0 oxidation through enhancing the transformations of NO to NO2. In the absence of NO, NH3 exhibited no inhibitive effect on Hg0 oxidation, because enough Lewis acid sites due to the combination of copper oxides and cerium oxides scavenged the competitive adsorption between NH3 and Hg0. In the presence of NO, although NH3 lowered Hg0 oxidation rate through inducing reduction of oxidized mercury, complete recovery of Hg0 oxidation activity over the CuCeTi catalyst was quickly achieved after cutting off NH3. This study revealed the synergistic effect of the combination of copper oxides and cerium oxides on Hg0 oxidation, and explored the involved mechanisms. Such knowledge would help obtaining maximum Hg0 oxidation co-benefit from SCR units in coal-fired power plants.

  11. Combining tree-ring metal concentrations and lead, carbon and oxygen isotopes to reconstruct peri-urban atmospheric pollution

    Directory of Open Access Journals (Sweden)

    Annick Doucet

    2012-08-01

    Full Text Available In this study, we analysed the tree-ring metal concentrations and isotope ratios of five stands located in three contrasted settings to infer the diffuse air pollution history of the northern part of the Windsor–Québec City Corridor in eastern Canada. Tree-ring series show that the Cd and Zn accumulation rates were higher between 1960 and 1986 and that the long-term acidification of the soil (Ca/Al series was likely induced by NOx and SOx deposition (δ15N and δ13C trends as proxy. The Pb concentrations and 206Pb/207Pb ratios indicate that the dominant source of lead from 1880 to the 1920s was the combustion of north-eastern American coal, which was succeeded by the combustion of leaded gasoline from the 1920s to the end of the 1980s. Our modelling approach allows separating the climatic and anthropogenic effects on the tree-ring δ13C and δ18O responses. Diffuse air pollution caused an enrichment in 13C in all stands and a decrease of the δ18O values only in three of the stands. This study indicates that dendrogeochemistry can show contrasted responses to environmental changes and that the combination of several independent indicators constitutes a powerful tool to reconstruct the air pollution history in the complex context of peri-urban regions.

  12. The impact of urban canopy meteorological forcing on summer photochemistry

    Science.gov (United States)

    Huszár, Peter; Karlický, Jan; Belda, Michal; Halenka, Tomáš; Pišoft, Petr

    2018-03-01

    The regional climate model RegCM4.4, including the surface model CLM4.5, was offline coupled to the chemistry transport model CAMx version 6.30 in order to investigate the impact of the urban canopy induced meteorological changes on the longterm summer photochemistry over central Europe for the 2001-2005 period. First, the urban canopy impact on the meteorological conditions was calculated performing a reference experiment without urban landsurface considered and an experiment with urban surfaces modeled with the urban parameterization within the CLM4.5 model. In accordance with expectations, strong increases of urban surface temperatures (up to 2-3 K), decreases of wind speed (up to -1 ms-1) and increases of vertical turbulent diffusion coefficient (up to 60-70 m2s-1) were found. For the impact on chemistry, these three components were considered. Additionally, we accounted for the effect of temperature enhanced biogenic emission increase. Several experiments were performed by adding these effects one-by-one to the total impact: i.e., first, only the urban temperature impact was considered driving the chemistry model; secondly, the wind impact was added and so on. We found that the impact on biogenic emission account for minor changes in the concentrations of ozone (O3), oxides of nitrogen NOx = NO + NO2 and nitric acid (HNO3). On the other hand, the dominating component acting is the increased vertical mixing, resulting in up to 5 ppbv increase of urban ozone concentrations while causing -2 to -3 ppbv decreases and around 1 ppbv increases of NOx and HNO3 surface concentrations, respectively. The temperature impact alone results in reduction of ozone, increase in NO, decrease in NO2 and increases of HNO3. The wind impact leads, over urban areas, to ozone decreases, increases of NOx and a slight increase in HNO3. The overall impact is similar to the impact of increased vertical mixing alone. The Process Analysis (PA) technique implemented in CAMx was adopted to

  13. Modeling microbial spoilage and quality of gilthead seabream fillets: combined effect of osmotic pretreatment, modified atmosphere packaging, and nisin on shelf life.

    Science.gov (United States)

    Tsironi, Theofania N; Taoukis, Petros S

    2010-05-01

    The objective of the study was the kinetic modeling of the effect of storage temperature on the quality and shelf life of chilled fish, modified atmosphere-packed (MAP), and osmotically pretreated with the addition of nisin as antimicrobial agent. Fresh gilthead seabream (Sparus aurata) fillets were osmotically treated with 50% high dextrose equivalent maltodextrin (DE 47) plus 5% NaCl. Water loss, solid gain, salt content, and water activity were monitored throughout treatment and treatment conditions were selected for the shelf life study. Untreated and osmotically pretreated slices with and without nisin (2 x 10(4) IU/100 g osmotic solution), packed in air or modified atmosphere (50% CO(2)-50% air), and stored at controlled isothermal conditions (0, 5, 10, and 15 degrees C) were studied. Quality assessment and modeling were based on growth of several microbial indices, total volatile nitrogen, trimethylamine nitrogen, lipid oxidation (TBARS), and sensory scoring. Temperature dependence of quality loss rates was modeled by the Arrhenius equation, validated under dynamic conditions. Pretreated samples showed improved quality stability during subsequent refrigerated storage, in terms of microbial growth, chemical changes, and organoleptic degradation. Osmotic pretreatment with the addition of nisin in combination with MAP was the most effective treatment resulting in significant shelf life extension of gilthead seabream fillets (48 days compared to 10 days for the control at 0 degrees C).

  14. Atmospheric turbulence mitigation in an OAM-based MIMO free-space optical link using spatial diversity combined with MIMO equalization.

    Science.gov (United States)

    Ren, Yongxiong; Wang, Zhe; Xie, Guodong; Li, Long; Willner, Asher J; Cao, Yinwen; Zhao, Zhe; Yan, Yan; Ahmed, Nisar; Ashrafi, Nima; Ashrafi, Solyman; Bock, Robert; Tur, Moshe; Willner, Alan E

    2016-06-01

    We explore the mitigation of atmospheric turbulence effects for orbital angular momentum (OAM)-based free-space optical (FSO) communications with multiple-input multiple-output (MIMO) architecture. Such a system employs multiple spatially separated aperture elements at the transmitter/receiver, and each transmitter aperture contains multiplexed data-carrying OAM beams. We propose to use spatial diversity combined with MIMO equalization to mitigate both weak and strong turbulence distortions. In a 2×2 FSO link with each transmitter aperture containing two multiplexed OAM modes of ℓ=+1 and ℓ=+3, we experimentally show that at least two OAM data channels could be recovered under both weak and strong turbulence distortions using selection diversity assisted with MIMO equalization.

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

    Directory of Open Access Journals (Sweden)

    L. González Palacios

    2016-09-01

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

  16. Aliskiren alone or in combination with enalapril vs. enalapril among patients with chronic heart failure with and without diabetes: a subgroup analysis from the ATMOSPHERE trial.

    Science.gov (United States)

    Kristensen, Søren L; Mogensen, Ulrik M; Tarnesby, Georgia; Gimpelewicz, Claudio R; Ali, Mohammed A; Shao, Qing; Chiang, YannTong; Jhund, Pardeep S; Abraham, William T; Dickstein, Kenneth; McMurray, John J V; Køber, Lars

    2018-01-01

    Because of concerns about the safety of aliskiren in patients with diabetes, study treatment was stopped prematurely in the Aliskiren Trial of Minimizing OutcomeS for Patients with HEart failuRE (ATMOSPHERE). We examined outcomes and treatment effect in these patients compared with those without diabetes. ATMOSPHERE included 7016 patients with heart failure and a reduced ejection fraction (HFrEF) randomly assigned to enalapril plus aliskiren, aliskiren alone, or enalapril. At baseline, 1944 (27.7%) patients had diabetes. Median follow-up was shorter in patients with diabetes compared with those without (24 months vs. 46 months). Among patients with diabetes, the primary endpoint of cardiovascular death or hospitalization for heart failure occurred in 216 patients (33.1%) in the enalapril group (reference), 172 (27.4%) in the aliskiren group [hazard ratio (HR) 0.82, 95% confidence interval (CI) 0.67-1.00; P = 0.053], and 196 (29.5%) in the combination group (HR 0.86, 95% CI 0.71-1.04; P = 0.13). The effects of the treatments studied did not differ significantly compared with patients without diabetes. In patients with diabetes, aliskiren monotherapy was associated with a lower risk of symptomatic hypotension compared to enalapril [42 (6.7%) vs. 65 (10.0%); P = 0.04], whereas other adverse events were generally balanced between the three groups. In patients with HFrEF and diabetes, there was no signal of harm and a trend towards benefit when direct renin inhibition monotherapy was compared with an angiotensin-converting enzyme inhibitor, whereas combined aliskiren and enalapril treatment led to more adverse events with no improvement in outcomes. Treatment effects did not differ in patients with diabetes compared with those without. Clinical Trial Registration URL: http://www.clinicaltrials.gov. Unique identifier: NCT00853658. © 2017 The Authors. European Journal of Heart Failure © 2017 European Society of Cardiology.

  17. Surface O3 photochemistry over the South China Sea: Application of a near-explicit chemical mechanism box model.

    Science.gov (United States)

    Wang, Yu; Guo, Hai; Zou, Shichun; Lyu, Xiaopu; Ling, Zhenhao; Cheng, Hairong; Zeren, Yangzong

    2017-11-22

    A systematic field measurement was conducted at an island site (Wanshan Island, WSI) over the South China Sea (SCS) in autumn 2013. It was observed that mixing ratios of O3 and its precursors (such as volatile organic compounds (VOCs), nitrogen oxides (NOx = NO + NO2) and carbon monoxide (CO)) showed significant differences on non-episode days and episode days. Additional knowledge was gained when a photochemical box model incorporating the Master Chemical Mechanism (PBM-MCM) was applied to further investigate the differences/similarities of O3 photochemistry between non-episode and episode days, in terms of O3-precursor relationship, atmospheric photochemical reactivity and O3 production. The simulation results revealed that, from non-O3 episode days to episode days, 1) O3 production changed from both VOC and NOx-limited (transition regime) to VOC-limited; 2) OH radicals increased and photochemical reaction cycling processes accelerated; and 3) both O3 production and destruction rates increased significantly, resulting in an elevated net O3 production over the SCS. The findings indicate the complexity of O3 pollution over the SCS. Copyright © 2017 Elsevier Ltd. All rights reserved.

  18. Spatial Variability in Ozone and CO2 Flux during the Front Range Air Pollution and Photochemistry Experiment

    Science.gov (United States)

    Almand-Hunter, B.; Piedrahita, R.; Kaushik, A.; Noone, D. C.; Walker, J. T.; Hannigan, M.

    2014-12-01

    Air quality problems persist in the Northern Front-Range Metropolitan Area (NFRMA) of Colorado despite efforts to reduce emissions, and summertime ozone concentrations frequently exceed the NAAQS. Atmospheric modeling in the NFRMA is challenging due to the complex topography of the area, as well as diversity of pollutant sources (urban NOx and VOCs, power plants, oil and gas, agricultural emissions, biogenic emissions, and wildfires). An improved understanding of the local atmospheric chemistry will enable researchers to advance atmospheric models, which will subsequently be used to develop and test more effective air quality management strategies. The Front Range Air Pollution and Photochemistry Experiment (FRAPPE) investigates this problem through detailed examination of atmospheric chemistry in the NFRMA. Our project specifically explores the spatial variability in ozone (O3) concentration and dry deposition within the FRAPPE study area. One source of uncertainty in atmospheric models is O3 flux, which varies spatially due to local meteorology and variation in ambient concentration and deposition velocity. Model grid cells typically range in size from 10-100 km and 100-500 km, for regional and global models, respectively, and accurate representations of an entire grid cell cannot always be achieved. Large spatial variability within a model grid cell can lead to poor estimates of trace-gas flux and concentration. Our research addresses this issue by measuring spatial variability in O3 flux using low-cost dry-deposition flux chambers. We are measuring O3 and CO2 flux with 5 low-cost flux chambers and one eddy-covariance tower. The eddy-covariance tower is located at the Boulder Atmospheric Observatory in Erie, CO. All 5 chambers are within a 8.3 x 6 km square, with one chamber collocated with the eddy-covariance tower, and the other 4 chambers at distances of 0.33, 1.14, 3.22, and 7.55 km from the tower. The largest distance between any two chambers is 8.5 km. All

  19. Two case studies on the interaction of large-scale transport, mesoscale photochemistry, and boundary-layer processes on the lower tropospheric ozone dynamics in early spring

    Directory of Open Access Journals (Sweden)

    S. Brönnimann

    Full Text Available The vertical distribution of ozone in the lower troposphere over the Swiss Plateau is investigated in detail for two episodes in early spring (February 1998 and March 1999. Profile measurements of boundary-layer ozone performed during two field campaigns with a tethered balloon sounding system and a kite are investigated using regular aerological and ozone soundings from a nearby site, measurements from monitoring stations at various altitudes, backward trajectories, and synoptic analyses of meteorological fields. Additionally, the effect of in situ photochemistry was estimated for one of the episodes employing the Metphomod Eulerian photochemical model. Although the meteorological situations were completely different, both cases had elevated layers with high ozone concentrations, which is not untypical for late winter and early spring. In the February episode, the highest ozone concentrations of 55 to 60 ppb, which were found at around 1100 m asl, were partly advected from Southern France, but a considerable contribution of in situ photochemistry is also predicted by the model. Below that elevation, the local chemical sinks and surface deposition probably overcompensated chemical production, and the vertical ozone distribution was governed by boundary-layer dynamics. In the March episode, the results suggest that ozone-rich air parcels, probably of stratospheric or upper tropospheric origin, were advected aloft the boundary layer on the Swiss Plateau.

    Key words. Atmospheric composition and structure (pollution – urban and regional; troposphere – composition and  chemistry – Meteorology and atmospheric dynamics (mesoscale meteorology

  20. Combined effect of antagonistic yeast and modified atmosphere to control Penicillium expansum infection in sweet cherries cv. Ambrunés.

    Science.gov (United States)

    de Paiva, E; Serradilla, M J; Ruiz-Moyano, S; Córdoba, M G; Villalobos, M C; Casquete, R; Hernández, A

    2017-01-16

    Fruit decay caused by pathogenic moulds is a major concern in the postharvest quality and shelf life of fruit. Blue mould decay is caused by Penicillium expansum (P. expansum) and is one of the most important postharvest diseases in cherries (Prunus avium L.). Synthetic fungicides are the main medium used to control pathogenic moulds. However, alternative approaches are available for developing safer technologies to control postharvest disease. An integrated approach that combines biological control, using antagonistic yeasts and modified atmosphere packaging (MAP) with cold storage is a promising alternative to synthetic fungicide treatment. In this work, two microperforated films (M10 and M50) and two antagonistic yeast strains (Hanseniaspora opuntiae L479 and Metschnikowia pulcherrima L672) were evaluated for their effectiveness to control the development of P. expansum in wounded cherries stored at 1°C. Results showed that the microperforated films had fungistatic effects, particularly M50, due to the level of CO2 achieved (mean CO2 of 11.2kPa at 35days), and the decrease in disease severity. Antagonistic yeasts, particularly Metschnikowia pulcherrima L672, delayed the development of P. expansum and decreased disease incidence and severity. The combination of MAP and antagonistic yeasts was the most effective approach to control P. expansum, during cold storage. Copyright © 2016 Elsevier B.V. All rights reserved.

  1. Toward shrimp consumption without chemicals: Combined effects of freezing and modified atmosphere packaging (MAP) on some quality characteristics of Giant Red Shrimp (Aristaeomorpha foliacea) during storage.

    Science.gov (United States)

    Bono, Gioacchino; Okpala, Charles Odilichukwu R; Alberio, Giuseppina R A; Messina, Concetta M; Santulli, Andrea; Giacalone, Gabriele; Spagna, Giovanni

    2016-04-15

    The combined effects of freezing and modified atmosphere packaging (MAP) (100% N2 and 50% N2+50% CO2) on some quality characteristics of Giant Red Shrimp (GRS) (Aristaeomorpha foliacea) was studied during 12-month storage. In particular, the quality characteristics determined proximal and gas compositions, melanosis scores, pH, total volatile basic-nitrogen (TVB-N), thiobarbituric acid (TBA) as well as free amino acid (FAA). In addition, the emergent data were compared to those subject to vacuum packaging as well as conventional preservative method of sulphite treatment (SUL). Most determined qualities exhibited quantitative differences with storage. By comparisons, while pH and TVB-N statistically varied between treatments (P<0.05) and TBA that ranged between ∼0.15 and 0.30 mg MDA/kg appeared least at end of storage for 100% N2 treated-group, the latter having decreased melanosis scores showed such treatments with high promise to keep the colour of GRS sample hence, potential replacement for SUL group. By comparisons also, while some individual FAA values showed increases especially at the 100% N2-treated group, the total FAAs statistically differed with storage (P<0.05). The combination of freezing and MAP treatments as preservative treatment method shows high promise to influence some quality characteristics of GRS samples of this study. Copyright © 2015 Elsevier Ltd. All rights reserved.

  2. Reduction of methanol in brewed wine by the use of atmospheric and room-temperature plasma method and the combination optimization of malt with different adjuncts.

    Science.gov (United States)

    Liang, Ming-Hua; Liang, Ying-Jie; Chai, Jiang-Yan; Zhou, Shi-Shui; Jiang, Jian-Guo

    2014-11-01

    Methanol, often generated in brewed wine, is highly toxic for human health. To decrease the methanol content of the brewed wine, atmospheric and room-temperature plasma (ARTP) was used as a new mutagenesis tool to generate a mutant of Saccharomyces cerevisiae with lower methanol content. Headspace gas chromatography was used to determine the identity and concentration of methanol with butyl acetate as internal standard in brewed wine. With 47.4% higher and 26.3% positive mutation rates were obtained, the ARTP jet exhibited a strong effect on mutation breeding of S. cerevisiae. The mutant S. cerevisiae S12 exhibited the lowest methanol content, which was decreased by 72.54% compared with that of the wild-type strain. Subsequently, the mutant S. cerevisiae S12 was used to ferment different combinations of malt and adjuncts for lower methanol content and higher alcoholic content. It was shown that the culture 6#, which was 60% malt, 20% wheat, and 20% corn, was the best combinations of malt and adjuncts, with the lowest methanol content (104.8 mg/L), and a relatively higher alcoholic content (15.3%, v/v). The optimal malt-adjunct culture 6#, treated with the glucoamylase dose of 0.04 U/mg of grain released the highest reducing sugars (201.6 mg/mL). It was indicated that the variation in reducing sugars among the combinations of malt and different adjuncts could be due to the dose of exogenous enzymes. © 2014 Institute of Food Technologists®

  3. OCS and SO2 isotope effects in photochemistry: Implications for background and volcanic stratospheric sulfate aerosols (Invited)

    Science.gov (United States)

    Hattori, S.; Schmidt, J. A.; Danielache, S.; Ueno, Y.; Johnson, M. S.; Yoshida, N.

    2013-12-01

    The stratospheric sulfate aerosol (SSA) layer increases the Earth's albedo and modulates the concentration of ozone because of surface heterogeneous reactions. We present an analysis of the stratospheric sulfur cycle using sulfur isotopes. Carbonyl sulfide (OCS) is the most abundant sulfur containing gas in the atmosphere, with an average mole fraction of 500 ppt in the troposphere. Air currents carry OCS in to the stratosphere where it is decomposed by photolysis and reactions with OH and O(3P). According to our study of OCS sink reactions, reaction products will not enriched but rather depleted in 34S. In addition, based on the estimated OCS sulfur isotopic composition (δ34S = 11‰) and the reported value for background SSA (δ34S = 2.6‰), OCS is an acceptable source of background SSA. Quantifying the range of natural climate variation, including that caused by volcanoes, is the basis for identifying anthropogenic climate change. We describe a mechanism, photoexcitation of SO2, that links climate-impacting volcanism with the mass-independent sulfur isotope record preserved in cyospheric sulfate. A plume model was constructed including photochemistry, entrainment of background air, and sulfate deposition. Isotopologue-specifc photoexcitation rates were calculated based on the UV absorption cross-sections of 32SO2, 33SO2, 34SO2, and 36SO2 from 250 to 320 nm. The model shows that UV photoexcitation is enhanced with altitude, whereas mass-dependent oxidation, mainly SO2 + OH, is suppressed by in situ plume chemistry, allowing the production and preservation of a mass-independent sulfur isotope anomaly in the sulfate product. We have identified the process generating the mass-independent sulfur isotope anomalies observed in the modern atmosphere, and this mechanism is the basis of identifying the magnitude of historic volcanic events recorded in ice core sulfate.

  4. Combined dispersive solid-phase extraction-dispersive liquid-liquid microextraction-derivatization for gas chromatography-mass spectrometric determination of aliphatic amines on atmospheric fine particles.

    Science.gov (United States)

    Majedi, Seyed Mohammad; Lee, Hian Kee

    2017-02-24

    Short-chain aliphatic amines are ubiquitous in the atmospheric environment. They play an important role in the formation and growth of atmospheric particles. As such, there is a pressing need to monitor these particle-bound compounds present at trace quantities. The present work describes an efficient, one-step microextraction technique for the preconcentration and detection of trace levels of 10 aliphatic amines on fine particles (particulate matter of 2.5μm or less (PM2.5)) in the atmosphere. After extraction of amines from particles in acidified water samples, carbon-based sorbents (in dispersive solid-phase extraction mode), and vortex agitation were utilized for simultaneous derivatization-extraction and dispersive liquid-liquid microextraction. The approach significantly increased the recoveries and enrichment of the amine derivatives. This one-step, combined technique is proposed for the first time. Several influential factors including type and concentration of derivatization reagent (for gas chromatographic separation), type of buffer, sample pH, types and volumes of extraction and disperser solvents, type and amount of sorbent, vortex time and temperature, desorption solvent type and volume, and salt content were investigated and optimized. Under the optimum conditions, high enrichment factors (in the range of between 307 and 382) and good reproducibility (relative standard deviations, below 7.0%, n=5) were achieved. The linearity ranged from 0.1μg/L-100μg/L, and from 0.5μg/L-100μg/L, depending on the analytes. The limits of detection were between 0.02μg/L (corresponding to ∼0.01ng/m(3) in air) and 0.09μg/L (corresponding to ∼0.04ng/m(3) in air). The developed method was successfully applied to the analysis of PM2.5 samples collected by air sampling through polytetrafluoroethylene filters. The concentration levels of amines ranged from 1.04 to 4.16ng/m(3) in the air sampled. Copyright © 2016 Elsevier B.V. All rights reserved.

  5. The Radiation Environment of Exoplanet Atmospheres

    Directory of Open Access Journals (Sweden)

    Jeffrey L. Linsky

    2014-10-01

    Full Text Available Exoplanets are born and evolve in the radiation and particle environment created by their host star. The host star’s optical and infrared radiation heats the exoplanet’s lower atmosphere and surface, while the ultraviolet, extreme ultraviolet and X-radiation control the photochemistry and mass loss from the exoplanet’s upper atmosphere. Stellar radiation, especially at the shorter wavelengths, changes dramatically as a host star evolves leading to changes in the planet’s atmosphere and habitability. This paper reviews the present state of our knowledge concerning the time-dependent radiation emitted by stars with convective zones, that is stars with spectral types F, G, K, and M, which comprise nearly all of the host stars of detected exoplanets.

  6. Photochemistry of the ozone-water complex in cryogenic neon, argon, and krypton matrixes.

    Science.gov (United States)

    Tsuge, Masashi; Tsuji, Kazuhide; Kawai, Akio; Shibuya, Kazuhiko

    2013-12-12

    The photochemistry of ozone-water complexes and the wavelength dependence of the reactions were studied by matrix isolation FTIR spectrometry in neon, argon, and krypton matrixes. Hydrogen peroxide was formed upon the irradiation of UV light below 355 nm. Quantitative analyses of the reactant and product were performed to evaluate the matrix cage effect of the photoreaction. In argon and krypton matrixes, a bimolecular O((1)D) + H2O → H2O2 reaction was found to occur to form hydrogen peroxide, where the O((1)D) atom generated by the photolysis of ozone diffused in the cryogenic solids to encounter water. In a neon matrix, hydrogen peroxide was generated through intracage photoreaction of the ozone-water complex, indicating that a neon matrix medium is most appropriate to study the photochemistry of the ozone-water complex.

  7. 2009 Gordon Research Conference on Photochemistry: Formal Schedule and Speaker/Poster Program

    Energy Technology Data Exchange (ETDEWEB)

    Wasielewski, Michael [Northwestern Univ., Evanston, IL (United States)

    2009-07-05

    The impact of photochemistry on diverse fields ranging from materials and environmental science to biology and medicine has never been greater. The 2009 Gordon Conference on Photochemistry will highlight recent advances in these key areas while also presenting the latest research on new photochemical reactions and mechanistic studies. Session topics will include: development of new chromophores, light harvesting materials, solar energy conversion, photocontrolled biomolecules, light-triggered amplification reactions, and advanced bioimaging techniques. The Conference will continue its 45 year history of promoting interactions between fundamental and applied scientists, a hallmark of the Gordon Conferences. In addition, oral presentations, poster sessions and informal discussions will provide opportunities for junior scientists and students to present their own work and discuss their results with leaders in the field. Applicants to the Conference are encouraged to submit abstracts for poster presentations in order to gain visibility and feedback on their research. In addition, a number of poster abstracts will be selected for presentation as short talks.

  8. Maintenance of safety and quality of refrigerated ready-to-cook seasoned ground beef product (meatball) by combining gamma irradiation with modified atmosphere packaging.

    Science.gov (United States)

    Gunes, Gurbuz; Ozturk, Aylin; Yilmaz, Neriman; Ozcelik, Beraat

    2011-08-01

    Meatballs were prepared by mixing ground beef and spices and inoculated with E. coli O157:H7, L. monocytogenes, and S. enteritidis before packaged in modified atmosphere (3% O₂ + 50% CO₂ + 47% N₂) or aerobic conditions. The packaged samples were irradiated at 0.75, 1.5, and 3 kGy doses and stored at 4 °C for 21 d. Survival of the pathogens, total plate count, lipid oxidation, color change, and sensory quality were analyzed during storage. Irradiation at 3 kGy inactivated all the inoculated (approximately 10⁶ CFU/g) S. enteritidis and L. monocytogenes cells in the samples. The inoculated (approximately 10⁶ CFU/g) E. coli O157:H7 cells were totally inactivated by 1.5 kGy irradiation. D¹⁰-values for E. coli O157:H7, S. enteritidis, and L. monocytogenes were 0.24, 0.43, and 0.41 kGy in MAP and 0.22, 0.39, and 0.39 kGy in aerobic packages, respectively. Irradiation at 1.5 and 3 kGy resulted in 0.13 and 0.36 mg MDA/kg increase in 2-thiobarbituric acid-reactive substances (TBARS) reaching 1.02 and 1.49 MDA/kg, respectively, on day 1. Irradiation also caused significant loss of color and sensory quality in aerobic packages. However, MAP effectively inhibited the irradiation-induced quality degradations during 21-d storage. Thus, combining irradiation (3 kGy) and MAP (3% O₂ + 50% CO₂ + 47% N₂) controlled the safety risk due to the potential pathogens and maintained qualities of meatballs during 21-d refrigerated storage. Combined use of gamma irradiation and modified atmosphere packaging (MAP) can maintain quality and safety of seasoned ground beef (meatball). Seasoned ground beef can be irradiated at 3 kGy and packaged in MAP with 3% O₂ + 50% CO₂ + 47% N₂ gas mixture in a high barrier packaging materials. These treatments can significantly decrease risk due to potential pathogens including E. coli O157:H7, L. monocytogenes, and S. enteritidis in the product. The MAP would reduce the undesirable effects of

  9. Matrix photochemistry of small molecules: Influencing reaction dynamics on electronically excited hypersurfaces

    Energy Technology Data Exchange (ETDEWEB)

    Laursen, S.L.

    1990-01-01

    Investigations of chemical reactions on electronically excited reaction surfaces are presented. The role of excited-surface multiplicity is of particular interest, as are chemical reactivity and energy transfer in systems in which photochemistry is initiated through a metal atom sensitizer.'' Two approaches are employed: A heavy-atom matrix affords access to forbidden triplet reaction surfaces, eliminating the need for a potentially reactive sensitizer. Later, the role of the metal atom in the photosensitization process is examined directly.

  10. Photochemistry on TiO2: Mechanisms Behind the Surface Chemistry

    Science.gov (United States)

    2009-01-21

    containing known ppm levels of added hydrocarbon contamination [27]. Fig. 12. (a) Water droplet on non-irradiated TiO2 in mixed O2 + n-hexane (120 ppm...2003) 145. [10] A. Hagfeldt, M. Graetzel, Chem. Rev. 95 (1995) 49. [11] A. Fujishima, K. Hashimoto, T. Watanabe, TiO2 Photocatalysis : Fundamentals and...Photochemistry on TiO2 : Mechanisms behind the surface chemistry John T. Yates Jr. * Department of Chemistry, University of Virginia, Charlottesville

  11. The synthesis and photochemistry of nitric oxide containing organometallic compunds of iron

    OpenAIRE

    Maher, Kieran

    2002-01-01

    Nitric oxide has been shown in the recent past to have an important role in many biological systems, including an essential role in neurotransmission, blood clotting, and in combating tumour cells and intracellular parasites. This thesis investigates the photochemistry of a series of compounds containing NO as a ligand. The aim of this work is to investigate the possibility that NO could be released under photochemical conditions at specific biological sites, thus providing a novel means o...

  12. Looking at pollution control in a new light: Photochemistry for a cleaner environment

    Energy Technology Data Exchange (ETDEWEB)

    NONE

    1995-09-01

    This phamphet, from the National Renewable Energy Laboratory and Sandia National Laboratory, describes a major new development in the field of photochemistry. The NREL/Sandia team has developed a pollution control technique - photocatalytic oxidation (PCO) that uses the energy in light to destroy environmental contaminants. Applicable as both a waste clean-up and a pollution control technique, PCP could help thousands of businesses comply with environmental regulations.

  13. Mapping of the Energy Levels of Metallophthalocyanines via Electronic Spectroscopy, Electrochemistry, and Photochemistry.

    Science.gov (United States)

    1982-06-01

    various cxcited states, information of considerable value ill uiderstanding pliool-ctnical behavior. Al- though Ifw heavy transitioi metal ion...Photochemistry, Photocatalysis 20. ABSTRACT (Contfou., an rover** oldsi $necesar n’pwd isionvtr &j black mmsbeo) 4 The mapping of the energy levels In...thet nature of rhe electron transfer, that is, redox at metal or ligand. Well-defined correlations are shown to exist between the ease of oxidation or

  14. Mercury, trace elements and organic constituents in atmospheric fine particulate matter, Shenandoah National Park, Virginia, USA: A combined approach to sampling and analysis

    Science.gov (United States)

    Kolker, A.; Engle, M.A.; Orem, W.H.; Bunnell, J.E.; Lerch, H.E.; Krabbenhoft, D.P.; Olson, M.L.; McCord, J.D.

    2008-01-01

    Compliance with U.S. air quality regulatory standards for atmospheric fine particulate matter (PM2.5) is based on meeting average 24 hour (35 ?? m-3) and yearly (15 ??g m-3) mass-per-unit-volume limits, regardless of PM2.5 composition. Whereas this presents a workable regulatory framework, information on particle composition is needed to assess the fate and transport of PM2.5 and determine potential environmental/human health impacts. To address these important non-regulatory issues an integrated approach is generally used that includes (1) field sampling of atmospheric particulate matter on filter media, using a size-limiting cyclone, or with no particle-size limitation; and (2) chemical extraction of exposed filters and analysis of separate particulate-bound fractions for total mercury, trace elements and organic constituents, utilising different USGS laboratories optimised for quantitative analysis of these substances. This combination of sampling and analysis allowed for a more detailed interpretation of PM2.5 sources and potential effects, compared to measurements of PM2.5 abundance alone. Results obtained using this combined approach are presented for a 2006 air sampling campaign in Shenandoah National Park (Virginia, USA) to assess sources of atmospheric contaminants and their potential impact on air quality in the Park. PM2.5 was collected at two sampling sites (Big Meadows and Pinnacles) separated by 13.6 km. At both sites, element concentrations in PM2.5 were low, consistent with remote or rural locations. However, element/Zr crustal abundance enrichment factors greater than 10, indicating anthropogenic input, were found for Hg, Se, S, Sb, Cd, Pb, Mo, Zn and Cu, listed in decreasing order of enrichment. Principal component analysis showed that four element associations accounted for 84% of the PM 2.5 trace element variation; these associations are interpreted to represent: (1) crustal sources (Al, REE); (2) coal combustion (Se, Sb), (3) metal production

  15. Combined effect of oregano essential oil and modified atmosphere packaging on shelf-life extension of fresh chicken breast meat, stored at 4 degrees C.

    Science.gov (United States)

    Chouliara, E; Karatapanis, A; Savvaidis, I N; Kontominas, M G

    2007-09-01

    The combined effect of oregano essential oil (0.1% and 1% w/w) and modified atmosphere packaging (MAP) (30% CO2/70% N2 and 70% CO2/30% N2) on shelf-life extension of fresh chicken meat stored at 4 degrees C was investigated. The parameters that were monitored were: microbiological (TVC, Pseudomonas spp., lactic acid bacteria (LAB), yeasts, Brochothrix thermosphacta and Enterobacteriaceae), physico-chemical (pH, TBA, color) and sensory (odor and taste) attributes. Microbial populations were reduced by 1-5 log cfu/g for a given sampling day, with the more pronounced effect being achieved by the combination of MAP and oregano essential oil. TBA values for all treatments remained lower than 1 mg malondialdehyde (MDA) kg(-1) throughout the 25-day storage period. pH values varied between 6.4 (day 0) and 5.9 (day 25). The values of the color parameters L*, a* and b* were not considerably affected by oregano oil or by MAP. Finally, sensory analysis showed that oregano oil at a concentration of 1% imparted a very strong taste to the product for which reason these lots of samples were not scored. On the basis of sensory evaluation a shelf-life extension of breast chicken meat by ca. 3-4 days for samples containing 0.1% oregano oil, 2-3 days for samples under MAP and 5-6 days for samples under MAP containing 0.1% of oregano oil was attained. Thus oregano oil and MAP exhibited an additive preservation effect.

  16. Combined effects of antimicrobial coating, modified atmosphere packaging, and gamma irradiation on Listeria innocua present in ready-to-use carrots (Daucus carota).

    Science.gov (United States)

    Caillet, S; Millette, M; Salmiéri, S; Lacroix, M

    2006-01-01

    The objective of this study was to evaluate the effect of an edible antimicrobial coating combined with modified atmosphere (MA) packaging (60% O2, 30% CO2, and 10% N2) and gamma irradiation on peeled minicarrots inoculated with Listeria innocua. Carrots were inoculated with L. innocua (10(3) CFU/g) and then coated with an antimicrobial coating based on calcium caseinate containing trans-cinnamaldehyde. The same formulation without trans-cinnamaldehyde was used as an inactive coating. Coated and uncoated carrots were packed under the MA or under air, irradiated at 0.25 or 0.5 kGy, and stored at 4 +/- 1 degrees C for 21 days. Samples were evaluated periodically for enumeration of L. innocua. Unirradiated carrots stored under air had the highest concentrations of L. innocua after 21 days of storage: 2.23 CFU/g in the uncoated samples and 2.26 CFU/ g in samples coated with the inactive coating. These results suggest that the inactive coating did not have any antimicrobial effect against L. innocua. However, the addition of the antimicrobial coating resulted in a 1.29-log reduction in the concentration of L. innocua in carrots packed under air after 21 days of storage and a 1.08-log reduction in carrots packed under MA after 7 days of storage. After 7 days of storage, no L. innocua was detected in samples treated at 0.5 kGy under air or in samples treated at 0.25 kGy under MA. A complete inhibition of L. innocua was also observed during all storage periods in uncoated and coated samples treated at 0.5 kGy under MA. These results indicate that the combination of irradiation and MA conditions play an important role in the radiosensitization of L. innocua.

  17. Effects of vacuum or modified atmosphere packaging in combination with irradiation for control of Escherichia coli O157:H7 in ground beef patties.

    Science.gov (United States)

    Kudra, Li L; Sebranek, Joseph G; Dickson, James S; Mendonca, Aubrey F; Larson, Elaine M; Jackson-Davis, Armitra L; Lu, Zheng

    2011-12-01

    The efficacy of controlling Escherichia coli O157:H7 in ground beef patties by combining irradiation with vacuum packaging or modified atmosphere packaging (MAP) was investigated. Fresh ground beef patties were inoculated with a five-strain cocktail of E. coli O157:H7 at 5 log CFU/g. Single patties, packaged with vacuum or high-CO(2) MAP (99.6% CO(2) plus 0.4% CO), were irradiated at 0 (control), 0.5, 1.0, or 1.5 kGy. The D(10)-value for this pathogen was 0.47 ± 0.02 kGy in vacuum and 0.50 ± 0.02 kGy in MAP packaging. Irradiation with 1.5 kGy reduced E. coli O157:H7 by 3.0 to 3.3 log, while 0.5 and 1.0 kGy achieved reductions of 0.7 to 1.0, and 2.0 to 2.2 log, respectively. After irradiation, the numbers of survivors of this pathogen on beef patties in refrigerated storage (4°C) did not change significantly for 6 weeks. Temperature abuse (at 25°C) resulted in growth in vacuum-packaged patties treated with 0.5 and 1.5 kGy, but no growth in MAP packages. This study demonstrated that combining irradiation with MAP was similar in effectiveness to irradiation with vacuum packaging for control of E. coli O157:H7 in ground beef patties during refrigerated storage. However, high-CO(2) MAP appeared to be more effective after temperature abuse.

  18. Model Atmospheres and Transit Spectra for Hot Rocky Planets

    Science.gov (United States)

    Lupu, Roxana

    We propose to build a versatile set of self-consistent atmospheric models for hot rocky exoplanets and use them to predict their transit and eclipse spectra. Hot rocky exoplanets will form the majority of small planets in close-in orbits to be discovered by the TESS and Kepler K2 missions, and offer the best opportunity for characterization with current and future instruments. We will use fully non-grey radiative-convective atmospheric structure codes with cloud formation and vertical mixing, combined with a self-consistent treatment of gas chemistry above the magma ocean. Being in equilibrium with the surface, the vaporized rock material can be a good tracer of the bulk composition of the planet. We will derive the atmospheric structure and escape rates considering both volatile-free and volatile bearing compositions, which reflect the diversity of hot rocky planet atmospheres. Our models will inform follow- up observations with JWST and ground-based instruments, aid the interpretation of transit and eclipse spectra, and provide a better understanding of volatile loss in these atmospheres. Such results will help refine our picture of rocky planet formation and evolution. Planets in ultra-short period (USP) orbits are a special class of hot rocky exoplanets. As shown by Kepler, these planets are generally smaller than 2 Earth radii, suggesting that they are likely to be rocky and could have lost their volatiles through photo-evaporation. Being close to their host stars, these planets are ultra-hot, with estimated temperatures of 1000-3000 K. A number of USP planets have been already discovered (e.g. Kepler-78 b, CoRoT-7 b, Kepler-10 b), and this number is expected to grow by confirming additional planet candidates. The characterization of planets on ultra-short orbits is advantageous due to the larger number of observable transits, and the larger transit signal in the case of an evaporating atmosphere. Much advance has been made in understanding and characterizing

  19. Characterisation of the spoilage microbiota in raw salmon (Salmo salar) steaks stored under vacuum or modified atmosphere packaging combining conventional methods and PCR-TTGE.

    Science.gov (United States)

    Macé, Sabrina; Cornet, Josiane; Chevalier, Frédérique; Cardinal, Mireille; Pilet, Marie-France; Dousset, Xavier; Joffraud, Jean-Jacques

    2012-05-01

    In order to characterise the spoilage related to microbiota of raw salmon, a combination of culture-dependent and -independent methods, including PCR-TTGE, was used to analyse 3 raw salmon batches stored for 3 days at chilled temperature in modified atmosphere packaging (MAP) (50% CO₂/50% N₂) or under vacuum. Sensory evaluation, microbiological enumeration and chemical analysis were performed after 3, 7 and 10 days of storage. At the onset of spoilage, 65 bacterial isolates were picked from the plates. Thus, 13 different genera or species were identified by phenotypic and molecular tests: Serratia spp., Photobacterium phosphoreum, Yersinia intermedia, Hafnia alvei, Buttiauxella gaviniae, Pseudomonas sp., Carnobacterium maltaromaticum, Carnobacterium divergens, Lactococcus piscium, Lactobacillus fuchuensis, Vagococcus carniphilus, Leuconostoc gasicomitatum and Brochothrix thermosphacta. The PCR-TTGE profiles and band identification enabled a shift of the dominant populations during the storage to be visualised for all the batches, probably due to the temperature change and the packaging. At the beginning of storage, Pseudomonas sp. dominated the raw salmon microbiota while in the following days (7 and 10), P. phosphoreum and L. piscium were identified as the main bacterial groups. This study enhances the knowledge of MAP and vacuum-packed raw salmon spoilage microbiota. Copyright © 2011 Elsevier Ltd. All rights reserved.

  20. Combined Application of Antibrowning, Heat Treatment and Modified-Atmosphere Packaging to Extend the Shelf Life of Fresh-Cut Lotus Root.

    Science.gov (United States)

    Son, Jihye; Hyun, Jeong-Eun; Lee, Jo-Won; Lee, Sun-Young; Moon, BoKyung

    2015-06-01

    This work aimed to determine the effects of different concentrations of antibrowning treatments (that is, distilled water [DW], 1% ascorbic acid [AA], 0.5% chamomile [CM], and 1% AA + 0.5% CM) and heat-treatment (55 °C for 45 s) combined with packaging under 4 different modified-atmosphere gas compositions (that is, air, vacuum, 100% CO2 , 50% CO2 /50% N2 ) on the quality and microbiological characteristics of fresh-cut lotus root. The quality characteristics (that is, color, weight loss, texture, pH, polyphenoloxidase activity, and total phenolic content) of the AA + CM-dipped sample in 100% CO2 packaging were maintained significantly better than those of the other samples (P < 0.05). The microbiological counts observed in the DW-dipped sample during storage were higher than those of the AA, CM, and AA + CM samples, and heat-treatment retarded the microbiological deterioration of fresh-cut lotus root. Therefore, the results revealed that dipping in an antibrowning treatment (AA + CM), and 100% CO2 MAP with heat treatment effectively extend the shelf life of fresh-cut lotus root to 21 d at 5 °C. © 2015 Institute of Food Technologists®

  1. Staging atmospheres

    DEFF Research Database (Denmark)

    Bille, Mikkel; Bjerregaard, Peter; Sørensen, Tim Flohr

    2015-01-01

    The article introduces the special issue on staging atmospheres by surveying the philosophical, political and anthropological literature on atmosphere, and explores the relationship between atmosphere, material culture, subjectivity and affect. Atmosphere seems to occupy one of the classic...

  2. Atmospheric Science and the CFC Industry

    Science.gov (United States)

    Steed, J. M.

    2012-12-01

    Industry involvement with developing atmospheric science and subsequent regulations to protect ozone was unusual. Chlorofluorocarbon manufacturers were research-based businesses accustomed to understanding the science behind product-related issues. When Lovelock's measurements in 1971 implied most of the cumulative production of CFCs remained in the atmosphere, global CFC producers funded academic research to identify natural sinks for the materials. The Fluorocarbon Program Panel (FPP) began in 1972, but changed focus to atmospheric photochemistry following Rowland and Molina's work in 1974. Despite early vociferous opposition, especially by the CFC-using aerosol industry, to any regulations, leaders among the producers worked to build their scientific understanding, expanding FPP funding and launching internal work in modeling and ozone trend analysis. The key first question for industry was not how much depletion might occur, but whether it would occur at all. If so, regardless of the amount, regulations and a major transition would be required in CFC-using industries, and the response would need to be global and prompt. So long as that basic question was in doubt, some businesses and countries would resist the economic cost of action. In the meantime, the producing industry worked to identify potential alternatives and to communicate atmospheric science to the downstream industries. Although the industry science effort was often disparaged as an attack on "real" science, my only assignment when I joined DuPont's Central Research Department in 1979 was to understand and contribute to the science, keeping both the company and our customers informed. Our modeling results were published freely. FPP funding led to better knowledge of the ClO + O rate constant, significantly increasing depletion in model calculations; supported the development of the techniques used to measure in situ atmospheric ClO, so important in later strengthening the case for chlorine

  3. The long-term changes in summer-time photochemistry due to urban canopy induced meteorological forcing

    Science.gov (United States)

    Huszar, Peter; Karlicky, Jan; Bardachova, Tatsiana; Belda, Michal; Halenka, Tomas

    2017-04-01

    Urban surfaces are clearly distinguished from rural ones and represent a specific forcing on meteorological conditions resulting in higher temperatures (urban heat island - UHI), reduced wind speed, enhanced turbulence, reduced humidity etc. It is straightforward to expect that these effects have further impact on the chemistry over these surfaces. This study intends to evaluate the summertime changes in ozone photo-chemistry due to urban canopy meteorological effects using the regional climate model RegCM4 coupled to the CAMx chemistry transport model. Experiments cover the 2001-2010 period focusing on central Europe. In all experiments, emission are kept the same and only the individual elements of meteorological forcing are varied. The most important ones are considered: changes of temperature, horizontal wind and turbulence. The surface ozone response to the inclusion of urban induced temperature increase is, over urban centers, is rather negative. Decreased wind speeds further contribute to ozone reduction due to suppressed transport of NOx to the surrounding rural areas, which in turn, increases the titration. The enhanced vertical mixing however have a leading impact on ozone levels: stronger vertical eddy transport removes NOx from urban environment and thus supports ozone formation. The combined effect of the individual ones is an increase of ozone. As each of the urban induced meteorological effects (changes of temperature, wind, turbulence) have a clear daily cycle, we examined the daily cycle of the impact on ozone and its precursors as well, and, it is shown that different mechanism become important throughout the day.

  4. Detection of herbicide effects on pigment composition and PSII photochemistry in Helianthus annuus by Raman spectroscopy and chlorophyll a fluorescence

    Science.gov (United States)

    Vítek, Petr; Novotná, Kateřina; Hodaňová, Petra; Rapantová, Barbora; Klem, Karel

    2017-01-01

    The effects of herbicides from three mode-of-action groups - inhibitors of protoporphyrinogen oxidase (carfentrazone-ethyl), inhibitors of carotenoid biosynthesis (mesotrione, clomazone, and diflufenican), and inhibitors of acetolactate synthase (amidosulfuron) - were studied in sunflower plants (Helianthus annuus). Raman spectroscopy, chlorophyll fluorescence (ChlF) imaging, and UV screening of ChlF were combined to evaluate changes in pigment composition, photosystem II (PSII) photochemistry, and non-photochemical quenching in plant leaves 6 d after herbicide application. The Raman signals of phenolic compounds, carotenoids, and chlorophyll were evaluated and differences in their intensity ratios were observed. Strongly augmented relative content of phenolic compounds was observed in the case of amidosulfuron-treated plants, with a simultaneous decrease in the chlorophyll/carotenoid intensity ratio. The results were confirmed by in vivo measurement of flavonols using UV screening of ChlF. Herbicides from the group of carotenoid biosynthesis inhibitors significantly decreased both the maximum quantum efficiency of PSII and non-photochemical quenching as determined by ChlF. Resonance Raman imaging (mapping) data with high resolution (150,000-200,000 spectra) are presented, showing the distribution of carotenoids in H. annuus leaves treated by two of the herbicides acting as inhibitors of carotenoid biosynthesis (clomazone or diflufenican). Clear signs were observed that the treatment induced carotenoid depletion within sunflower leaves. The depletion spatial pattern registered differed depending on the type of herbicide applied.

  5. The combined efficacy of carvacrol and modified atmosphere packaging on the survival of Salmonella, Campylobacter jejuni and lactic acid bacteria on turkey breast cutlets.

    Science.gov (United States)

    Nair, Divek V T; Kiess, Aaron; Nannapaneni, Rama; Schilling, Wes; Sharma, Chander Shekhar

    2015-08-01

    The primary objective of this study was to determine the efficacy of carvacrol in combination with modified atmosphere packaging (MAP) in reducing Salmonella on turkey breast cutlets stored at 4 °C. In experiment I, carvacrol (0.5, 1, and 2% v/v) was applied as surface treatment and samples were stored under aerobic condition or as surface and dip treatments followed by storage in an environment of 100% carbon dioxide. The findings of the experiment I revealed the synergistic activity of carvacrol with carbon dioxide in reducing Salmonella when used as dip treatment compared to the surface treatment. In experiment II, turkey breast cutlets were dip treated with carvacrol (0.25, 0.5, and 1% v/v) for 30 s and stored under MAP (95% carbon dioxide and 5% oxygen) to evaluate the efficacy against Salmonella, Campylobacter jejuni and lactic acid bacteria on turkey breast cutlets. In experiment II, the combined application of carvacrol and MAP resulted in 1.0-2.0 log CFU/g reduction (P ≤ 0.05) of both Salmonella and Campylobacter on turkey breast cutlets for 7 d storage at 4 °C. MAP alone and in combination with carvacrol reduced lactic acid bacteria (P ≤ 0.05) on cutlets stored at 4 °C for 21 d period. There was no difference (P ≤ 0.05) in meat color among treatments and controls except for an increased paleness of meat (P ≤ 0.05) observed for the 1% carvacrol treated cutlets stored under MAP after 21 d of storage. The high concentration of carbon dioxide and carvacrol treatments did not cause any alteration in meat pH (P ≤ 0.05). In conclusion, carvacrol was effective at a low concentration of 0.25% (v/v) in reducing Salmonella and C. jejuni by ∼1.0 log CFU/g when stored under MAP. Copyright © 2015 Elsevier Ltd. All rights reserved.

  6. Combining external and internal mixing representation of atmospheric aerosol for optical properties calculations: focus on absorption properties over Europe and North America using AERONET observations and AQMEII simulations

    Science.gov (United States)

    Curci, Gabriele

    2017-04-01

    The calculation of optical properties from knowledge of the composition and abundance of atmospheric aerosol implies a certain number of assumptions. First and if not known or explicitly simulated, a size distribution must be assigned to each aerosol component (e.g. sulfate-like inorganic ions, organic and back carbon, soil dust, sea salt). Second, physical-chemical properties such as the shape, density, complex refractive index, and hygroscopic factors must be associated to each aerosol species. Third, a representation of how the aerosol species combine together must be made: among those, the most popular are the assumptions of external mixing, in which each particle is assumed to be formed of a single compound and the optical properties may be calculated separately for each species, or of internal core-shell arrangement, in which each particle consists of a water-insoluble core coated with a water-soluble shell and that requires more elaborate calculations for optical properties. Previous work found that the assumption on the mixing state (external or core-shell internal) is the one that introduces the highest uncertainty, quantified in about 30% uncertainty on the calculation of monthly mean aerosol optical depth (AOD) and single-scattering albedo (SSA). The external mixing assumption is generally more reasonable for freshly emitted aerosol, while the internal mixing case is associated with aged aerosol that had the time to form the coating around the core. Both approximations are thus regarded as valid, but in general a combination of the two mixing states may be expected in a given air mass. In this work, we test a simple empirical parameterization of the fraction of internally mixed particles (F_in) in a generic air mass. The F_in fraction is calculated in two alternative ways, one exploiting the NOz to NOx ratio (proxy of the photochemical aging), and the other using the relative abundance of black carbon with respect to other aerosol components (proxy of

  7. REY-Th-U Solute Dynamics in the Critical Zone: Combined Influence of Chemical Weathering, Atmospheric Deposit Leaching, and Vegetation Cycling (Mule Hole Watershed, South India)

    Science.gov (United States)

    Braun, Jean-Jacques; Riotte, Jean; Battacharya, Shrema; Violette, Aurélie; Prunier, Jonathan; Bouvier, Vincent; Candaudap, Frédéric; Maréchal, Jean-Christophe; Ruiz, Laurent; Panda, Smruthi Rekha; Subramanian, S.

    2017-12-01

    The source and proportion of REY, Th, and U exported by groundwater and by the ephemeral stream along with the elemental proportions passing through vegetation have been assessed in the subhumid tropical forested CZO of Mule Hole, Southern India. The study relies on a pluriannual hydrogeochemical monitoring combined with a hydrological model. The significant difference between the soil input (SI) and output (SO) solute fluxes (mmol/km2/yr) of LREE (SI-SO = 13,250-1,500), HREE (1,930-235), Th (64-12), and U (63-25) indicates a strong uptake by roots carried by canopy and forest floor processes. The contribution of atmospheric dust leaching can reach about 60% of LREE and 80% of HREE. At the watershed scale, the U solute flux exported by groundwater (180 mmol/km2/yr) mainly originates from the breakdown of primary U-bearing accessory minerals and dominates by a factor of 25 the stream flux. The precipitation of authigenic U-bearing phases and adsorption onto Fe-oxides and oxyhydroxides play a significant role for limiting the U mobility. In the groundwater, the plagioclase chemical weathering is efficiently traced by the positive Eu-anomaly. The very low (REY) to nil (Th) contents are explained by the precipitation of authigenic phases. In the stream flow, dominated by the overland flow (87% of the yearly stream flow), the solute exports (in mmol/km2/yr) of REY (1,080 for LREE and 160 for HREE) and of Th (14) dominate those by groundwater. Their mobility is enhanced by chelation with organic ligands produced by forest floor and canopy processes.

  8. A Combined Subaru/VLT/MMT 1-5 Micrometer Study of Planets Orbiting HR 8799: Implications For Atmospheric Properties, Masses and Formation

    Science.gov (United States)

    Currie, Thayne; Burrows, Adam; Itoh, Yoichi; Matsumura, Soko; Fukagawa, Misato; Apai, Daniel; Madhusudhan, Nikku; Hinz, Philip M.; Rodigas, T. J.; Kasper, Markus; hide

    2011-01-01

    We present new 1-1.25 micron (z and J band) Subaru/IRCS and 2 micron (K band) VLT/NaCo data for HR 8799 and a rereduction of the 3-5 micron MMT/Clio data first presented by Hinz et al. Our VLT/NaCo data yield a detection of a fourth planet at a projected separation of approximately 15 AU--"HR 8799e ." We also report new, albeit weak detections of HR 8799b at 1.03 micron and 3.3 micron. Empirical comparisons to field brown dwarfs show that at least HR 8799b and HR 8799c, and possibly HR 8799d, have near-to-mid-IR colors/ magnitudes significantly discrepant from the L/T dwarf sequence. Standard cloud deck atmosphere models appropriate for brown dwarfs provide only (marginally) statistically meaningful fits to HR 8799b and c for unphysically small radii. Models with thicker cloud layers not present in brown dwarfs reproduce the planets' spectral energy distributions far more accurately and without the need for resealing the planets' radii. Our preliminary modeling suggests that HR 8799b has log(g) = 4-4.5, T(sub eff) = 900 K. while HR 8799c, d, and (by inference) e have log(g) = 4-4.5, T(sub eff) = 1000-1200 K. Combining results from planet evolution models and new dynamical stability limits implies that the masses of HR 8799b, c, d, and e are 6-7 M(sub j), 7-10 M(sub j), 7-10 M(sub j), and 7-10 M(sub j). "Patchy" cloud prescriptions may provide even better fits to the data and may lower the estimated surface gravities and masses. Finally, contrary to some recent claims, forming the HR 8799 planets by core accretion is still plausible, although such systems are likely rare.

  9. Visible light driven plasmonic photochemistry on nano-textured silver.

    Science.gov (United States)

    Walia, Jaspreet; Guay, Jean-Michel; Krupin, Oleksiy; Variola, Fabio; Berini, Pierre; Weck, Arnaud

    2017-12-20

    Plasmon assisted generation of silver sulfate from dodecanethiol is demonstrated on a nano-textured silver substrate with a strong surface plasmon resonance in the visible range. The observed photo-physical processes are attributed to hot charge carriers that are generated from the excitation of surface plasmon resonances using 532 nm laser light. Excited charge carriers are responsible for cleaving the alkane chain, and for generating reactive oxygen species which rapidly photooxidize the exposed sulfur atoms. The ability to drive photochemical reactions with photon energies in the visible range rather than in the UV, on nano-textured silver surfaces, will enable researchers to study photochemical transformations for a wide variety of applications. The strong optical absorbance across the visible range, combined with the fact that the substrates can be fabricated over large areas, naturally makes them candidates for solar driven photochemical applications, and for large scale plasmonic reactors.

  10. Two-photon excitation based photochemistry and neural imaging

    Science.gov (United States)

    Hatch, Kevin Andrew

    Two-photon microscopy is a fluorescence imaging technique which provides distinct advantages in three-dimensional cellular and molecular imaging. The benefits of this technology may extend beyond imaging capabilities through exploitation of the quantum processes responsible for fluorescent events. This study utilized a two-photon microscope to investigate a synthetic photoreactive collagen peptidomimetic, which may serve as a potential material for tissue engineering using the techniques of two-photon photolysis and two-photon polymerization. The combination of these techniques could potentially be used to produce a scaffold for the vascularization of engineered three-dimensional tissues in vitro to address the current limitations of tissue engineering. Additionally, two-photon microscopy was used to observe the effects of the application of the neurotransmitter dopamine to the mushroom body neural structures of Drosophila melanogaster to investigate dopamine's connection to cognitive degeneration.

  11. Benzene formation in Titan's lower atmosphere

    Science.gov (United States)

    Plane, J. M. C.; Douglas, K.; Blitz, M. A.; Heard, D. E.; Seakins, P. W.; Feng, W.; Willacy, K.

    2017-09-01

    The most distinctive feature of Saturn's moon Titan is that it is covered in a thick haze. The haze consists of organic particles called tholins, of which benzene is thought to be an important precursor. Here we examine two pathways to form benzene. The first involves reactions on cosmic dust particles, which mostly do not ablate when entering Titan's atmosphere and accumulate in the lower atmosphere. We have shown in the laboratory that acetylene molecules stick on synthetic cosmic dust at low temperatures, and react efficiently to make benzene. The second pathway is through gas phase reactions involving radical species formed through methane photochemistry. A new lab study shows that the rates of critical reactions involving these radicals vary unexpectedly at low temperatures, leading to significant changes in important benzene precursors.

  12. Effects of climate change on surface-water photochemistry: a review.

    Science.gov (United States)

    De Laurentiis, Elisa; Minella, Marco; Maurino, Valter; Minero, Claudio; Vione, Davide

    2014-10-01

    Information concerning the link between surface-water photochemistry and climate is presently very scarce as only a few studies have been dedicated to the subject. On the basis of the limited knowledge that is currently available, the present inferences can be made as follows: (1) Warming can cause enhanced leaching of ionic solutes from the catchments to surface waters, including cations and more biologically labile anions such as sulphate. Preferential sulphate biodegradation followed by removal as organic sulphides in sediment could increase alkalinity, favouring the generation of the carbonate radical, CO3 (·-). However, this phenomenon would be easily offset by fluctuations of the dissolved organic carbon (DOC), which is strongly anticorrelated with CO3 (·-). Therefore, obtaining insight into DOC evolution is a key issue in understanding the link between photochemistry and climate. (2) Climate change could exacerbate water scarcity in the dry season in some regions. Fluctuations in the water column could deeply alter photochemistry that is usually favoured in shallower waters. However, the way water is lost would strongly affect the prevailing photoinduced processes. Water outflow without important changes in solute concentration would mostly favour reactions induced by the hydroxyl and carbonate radicals (·OH and CO3 (·-)). In contrast, evaporative concentration would enhance reactions mediated by singlet oxygen ((1)O2) and by the triplet states of chromophoric dissolved organic matter ((3)CDOM*). (3) In a warmer climate, the summer stratification period of lakes would last longer, thereby enhancing photochemical reactions in the epilimnion but at the same time keeping the hypolimnion water in the dark for longer periods.

  13. Reactivity of biogenic manganese oxide for metal sequestration and photochemistry: Computational solid state physics study

    Energy Technology Data Exchange (ETDEWEB)

    Kwon, K.D.; Sposito, G.

    2010-02-01

    Many microbes, including both bacteria and fungi, produce manganese (Mn) oxides by oxidizing soluble Mn(II) to form insoluble Mn(IV) oxide minerals, a kinetically much faster process than abiotic oxidation. These biogenic Mn oxides drive the Mn cycle, coupling it with diverse biogeochemical cycles and determining the bioavailability of environmental contaminants, mainly through strong adsorption and redox reactions. This mini review introduces recent findings based on quantum mechanical density functional theory that reveal the detailed mechanisms of toxic metal adsorption at Mn oxide surfaces and the remarkable role of Mn vacancies in the photochemistry of these minerals.

  14. Photoactive energetic materials: linear and nonlinear photochemistry of chromophore linked energetic materials

    Science.gov (United States)

    Greenfield, Margo; McGrane, Shawn; Bolme, Cindy; Chavez, David; Veauthier, Jacqueline; Hanson, Susan; Myers, Thomas; Scharff, Jason

    2015-06-01

    In general, conventional molecular explosives are white to off-white in color and only absorb ultraviolet light. A novel approach to synthetically link optically active energetic chromophores to existing molecular energetic materials has resulted in increased photoactivity in the visible (532 nm) region of the electromagnetic spectrum. Tetrazine, an energetic optically active chromophore, which absorbs around 532 nm, has been derivatized with various energetic materials including pentaeythritol tetranitrate (PETN), nitroglycerine (NG) and dinitroazetidine (DNAZ). We report the corresponding photochemistry and photochemical quantum yields of these new materials under various wavelength and intensity regimes.

  15. Assessment of the Contribution of the Atmosphere to Uncertainties in Normalized Water-Leaving Radiance: A Combined Modeling and Data Analysis Approach. Chapter 21

    Science.gov (United States)

    Stamnes, Knut; Li, Wei; Chen, Bing-Quan

    2001-01-01

    Our research for the Sensor Intercomparison and Merger for Biological and Interdisciplinary Oceanic Studies (SIMBIOS) program has been focused on modeling and simulation studies as well as the development of atmospheric correction algorithms. Based on our original proposal and discussions at the SIMBIOS team meetings and workshops, the objectives of our research can be summarized as follows: (1) Use our radiative transfer model for the coupled atmosphere-ocean system to simulate the radiation field at arbitrary levels and in any desired direction in the atmosphere and ocean so as to provide a firm connection between the signal received by the satellite sensor and by a sensor looking down into the water column just above the surface and just below it; (2) Use the simulations to quantify the influence of atmospheric aerosols on the water-leaving radiance, and to quantify the error in the water-leaving radiance as a function of uncertainties in the aerosol optical properties, mass loading and vertical extent; (3) Use the model simulations in conjunction with validation measurements taken by other SIMBIOS investigators (for satellite overpasses) to assess our understanding of the radiative transfer process in the coupled atmosphere-ocean column, and to examine the extent to which the model provides a realistic prediction of simultaneously measured in situ water-leaving radiance and the radiance received by the satellite sensor; (4) Modify and improve an existing atmospheric correction algorithm, based on the work above, as needed by constructing new look-up tables that include scattering by ocean particles; and (5) Carry out approaches to developing an atmospheric correction algorithm for ocean color imagery with strongly absorbing aerosols.

  16. Reduction of hexavalent chromium: photocatalysis and photochemistry and their application in wastewater remediation.

    Science.gov (United States)

    Machado, Tiele Caprioli; Lansarin, Marla Azário; Matte, Natália

    2014-01-01

    Hexavalent chromium present in wastewater discharge of galvanic industries is toxic to most microorganisms and potentially harmful to human health. This work examines the photochemical reduction of Cr(VI) with ethanol under ultraviolet (UV) and visible radiation, and photocatalytic reduction of Cr(VI) with TiO2 in the presence of ethanol under UV radiation. By means of different experimental designs, this study investigates the influence of the initial pH, ethanol amount, catalyst concentration and initial Cr(VI) concentration on total Cr(VI) reduction. The results obtained showed that photochemistry with ethanol under UV radiation (96.10%) was more efficient than photochemistry with ethanol under visible light (48.07%). Furthermore, photocatalysis with TiO2 in the presence of ethanol under UV radiation showed high values of total Cr(VI) reduction: 94.15%, under the optimal conditions established by the experimental design. Finally, experiments were carried out with wastewater discharge from an electroplating plant in its original concentration, and higher values of total Cr(VI) reduction were observed.

  17. UV Resonance Raman Investigation of Pentaerythritol Tetranitrate Solution Photochemistry and Photoproduct Hydrolysis.

    Science.gov (United States)

    Gares, Katie L; Bykov, Sergei V; Asher, Sanford A

    2017-10-19

    Ultraviolet resonance Raman spectroscopy (UVRR) is being developed for standoff trace explosives detection. To accomplish this, it is important to develop a deep understanding of the accompanying UV excited photochemistry of explosives, as well as the impact of reactions on the resulting photoproducts. In the work here we used 229 nm excited UVRR spectroscopy to monitor the photochemistry of pentaerythritol tetranitrate (PETN) in acetonitrile. We find that solutions of PETN in CD3CN photodegrade with a quantum yield of 0.08 ± 0.02, as measured by high performance liquid chromatography (HPLC). The initial step in the 229 nm UV photolysis of PETN in CD3CN is cleavage of an O-NO2 bond to form NO2. The accompanying photoproduct is pentaerythritol trinitrate (PETriN), (CH2ONO2)3CCH2OH formed by photolysis of a single O-NO2. The resulting UVRR spectra show a dominant photoproduct band at ∼1308 cm-1, which derives from the symmetric stretch of dissolved NO2. This photoproduct NO2 is hydrolyzed by trace amounts of water, which downshifts this 1308 cm-1 NO2 Raman band due to the formation of molecular HNO3. The dissociation of HNO3 to NO3- in the presence of additional water results in an intense NO3- symmetric stretching UVRR band at 1044 cm-1.

  18. A Combined Atmospheric Rivers and Geopotential Height Analysis for the Detection of High Streamflow Event Probability Occurrence in UK and Germany

    Science.gov (United States)

    Rosario Conticello, Federico; Cioffi, Francesco; Lall, Upmanu; Merz, Bruno

    2017-04-01

    The role of atmospheric rivers (ARs) in inducing High Streamflow Events (HSEs) in Europe has been confirmed by numerous studies. Here, we assume as HSEs the streamflows exceeding the 99th percentile of daily flowrate time series measured at streamflow gauges. Among the indicators of ARs are: the Integrated Water Vapor (IWV) and Integrated Water Vapor Transport (IVT). For both indicators the literature suggests thresholds in order to identify ARs. Furthermore, local thresholds of such indices are used to assess the occurrence of HSEs in a given region. Recent research on ARs still leaves room for open issues: 1) The literature is not unanimous in defining which of the two indicators is better. 2) The selection of the thresholds is based on subjective assessments. 3) The predictability of HSEs at the local scale associated with these indices seems to be weak and to exist only in the winter months. In order to address these issues, we propose an original methodology: (i) to choose between the two indicators which one is the most suitable for HSEs predictions; (ii) to select IWT and/or IVT (IVT/IWV) local thresholds in a more objective way; (iii) to implement an algorithm able to determine whether a IVT/IWV configuration is inducing HSEs, regardless of the season. In pursuing this goal, besides IWV and IVT fields, we introduce as further predictor the geopotential height at 850 hPa (GPH850) field, that implicitly contains information about the pattern of temperature, direction and intensity of the winds. In fact, the introduction of the GPH850 would help to improve the assessment of the occurrence of HSEs throughout the year. It is also plausible to hypothesize, that IVT/IWV local thresholds could vary in dependence of the GPH850 configuration. In this study, we propose a model to statistically relate these predictors, IVT/IWV and GPH850, to the simultaneous occurrence of HSEs in one or more streamflow gauges in UK and Germany. Historical data from 57 streamflow gauges

  19. Laser Photochemistry.

    Science.gov (United States)

    1981-07-01

    HAB + HAA + HABA + HA, (18) where HA and HB are the unperturbed Hamiltonians of the active (A) mode and the bath (B) modes, respectively and HAB is...equations of motion for the average excitation of the active mode in which the many-body effects of the phonon bath modes (HAB and HABA ) and the active...relaxation rates induced by the many-body effects of the Hamiltonians HAA, HAB and HABA ; n is a Bose-Einstein function for the bath modes; and 2c <n> is the

  20. Mechanistic studies on the OH-initiated atmospheric oxidation of selected aromatic hydrocarbons

    Energy Technology Data Exchange (ETDEWEB)

    Nehr, Sascha

    2012-07-01

    Benzene, toluene, the xylenes, and the trimethylbenzenes are among the most abundant aromatic trace constituents of the atmosphere mainly originating from anthropogenic sources. The OH-initiated atmospheric photo-oxidation of aromatic hydrocarbons is the predominant removal process resulting in the formation of O{sub 3} and secondary organic aerosol. Therefore, aromatics are important trace constituents regarding air pollution in urban environments. Our understanding of aromatic photo-oxidation processes is far from being complete. This work presents novel approaches for the investigation of OH-initiated atmospheric degradation mechanisms of aromatic hydrocarbons. Firstly, pulsed kinetic studies were performed to investigate the prompt HO{sub 2} formation from OH+ aromatic hydrocarbon reactions under ambient conditions. For these studies, the existing OH reactivity instrument, based on the flash photolysis/laser-induced fluorescence (FP/LIF) technique, was extended to the detection of HO{sub 2} radicals. The experimental design allows for the determination of HO{sub 2} formation yields and kinetics. Results of the pulsed kinetic experiments complement previous product studies and help to reduce uncertainties regarding the primary oxidation steps. Secondly, experiments with aromatic hydrocarbons were performed under atmospheric conditions in the outdoor atmosphere simulation chamber SAPHIR (Simulation of Atmospheric PHotochemistry In a large Reaction chamber) located at Forschungszentrum Juelich. The experiments were aimed at the evaluation of up-to-date aromatic degradation schemes of the Master Chemical Mechanism (MCMv3.2). The unique combination of analytical instruments operated at SAPHIR allows for a detailed investigation of HO{sub x} and NO{sub x} budgets and for the determination of primary phenolic oxidation product yields. MCMv3.2 deficiencies were identified and most likely originate from shortcomings in the mechanistic representation of ring

  1. Bactericidal efficiency and mode of action: a comparative study of photochemistry and photocatalysis.

    Science.gov (United States)

    Pigeot-Rémy, S; Simonet, F; Atlan, D; Lazzaroni, J C; Guillard, C

    2012-06-15

    In order to compare the disinfection potential of photocatalysis and photochemistry, the effects of these two processes on bacteria in water were investigated under exposure to UV-A and UV-C. The well-known bacterial model Escherichia coli (E. coli) was used as the experimental organism. Radiation exposure was produced with an HPK 125 W lamp and the standard TiO(2) Degussa P-25 was used as the photocatalyst. Firstly, the impact of photocatalysis and photochemistry on the cultivability of bacterial cells was investigated. UV-A radiation resulted in low deleterious effects on bacterial cultivability but generated colonies of size smaller than average. UV-C photocatalysis demonstrated a greater efficiency than UV-A photocatalysis in altering bacterial cultivability. From a cultivability point of view only, UV-C radiation appeared to be the most deleterious treatment. A rapid epifluorescence staining method using the LIVE/DEAD Bacterial Viability Kit was then used to assess the modifications in bacterial membrane permeability. UV-A radiation did not induce any alterations in bacterial permeability for 420 min of exposure whereas only a few minutes of exposure to UV-C radiation, with the same total radiance intensity, induced total loss of permeability. Moreover, after 20 and 60 min of exposure to UV-C and UV-A photocatalysis respectively, all bacteria lost their membrane integrity, suggesting that the bacterial envelope is the primary target of reactive oxygen species (ROS) generated at the surface of TiO(2) photocatalyst. These results were further confirmed by the formation of malondialdehyde (MDA) during the photocatalytic inactivation of bacterial cells and suggest that destruction of the cell envelope is a key step in the bactericidal action of photocatalysis. The oxidation of bacterial membrane lipids was also correlated with the monitoring of carboxylic acids, which can be considered as representatives of lipid peroxidation by-products. Finally, damages to

  2. The Upper Atmosphere Research Satellite: From Coffee Table Art to Quantitative Science

    Science.gov (United States)

    Douglass, Anne R.

    1999-01-01

    The Upper Atmosphere Research Satellite (UARS) has provided an unprecedented set of observations of constituents of the stratosphere. When used in combination with data from other sources and appropriate modeling tools, these observations are useful for quantitative evaluation of stratospheric photochemical processes. This is illustrated by comparing ozone observations from airborne Differential Absorption Lidar (DIAL), from the Polar Ozone and Aerosol Measurement (POAM), from the Microwave Limb Sounder (MLS), and from the Halogen occultation Experiment (HALOE) with ozone fields generated with a three dimensional model. For 1995-96, at polar latitudes, observations from DIAL flights on December 9 and January 30, and POAM and MLS between late December and late January are compared with ozone fields from the GSFC 3D chemistry and transport model. Data from the three platforms consistently show that the observed ozone has a negative trend relative to the modeled ozone, and that the trend is uniform in time between early and mid winter, with no obvious dependence on proximity to the vortex edge. The importance of chlorine catalyzed photochemistry to this ozone loss is explored by comparing observations from MLS and HALOE with simulations for other northern winters, particularly 1997-98.

  3. Impact of Clouds and Aerosols on Photochemistry During the TexAQS II Radical and Aerosol Measurement Project

    Science.gov (United States)

    Flynn, J. H.; Lefer, B. L.; Rappenglueck, B.; Olson, J. R.; Chen, G.

    2007-12-01

    Photochemistry is responsible for the production of tropospheric ozone, the primary component of smog. In 2006, Houston, Texas experienced 20 days with a 1-hour ozone average in excess of 125 ppbv, and 36 days with an 8-hour average over 85 ppbv. Two models were used to assess the impact of clouds and aerosols on the photochemical production and loss of ozone and radicals in a polluted urban environment. The NASA Langley Research Center (LaRC) 0-D photochemical box model was used to assess the changes in the photochemical budgets due to varying cloud and aerosol conditions. The NCAR Tropospheric Ultraviolet and Visible (TUV) radiative transfer model was used to calculate photolysis frequencies for clear sky conditions with a variety of aerosol profiles. These tools were used to analyze the data set collected during the Texas Air Quality Study II Radical and Aerosol Measurement Project (TRAMP) with respect to ozone and radical budgets. Measurements of trace gasses, aerosols, meteorological parameters, and radiation were collected between mid-August and early October 2006 at the University of Houston. The photochemical model was run using various photolysis rates that reflect a range of atmospheric conditions impacting the actinic flux. Rates from real-time actinic flux measurements include the impact of both the clouds and aerosols that are present. Photolysis rates for clear-sky (cloud-free) conditions, both with and without aerosol profiles were calculated using the TUV radiative transfer model. A comparison of the photochemical ozone and radical budgets resulting from these different rates indicate those sensitivities to the presence of aerosols and clouds. Approximately seven of the 50 days during the campaign were cloud-free and were compared to LaRC-TUV results to show the effects of aerosols. The remaining days show the effects of both aerosols and cloud conditions that varied from partly cloudy to heavy overcast conditions. A cloud camera was used to

  4. Potential sources and processes affecting speciated atmospheric mercury at Kejimkujik National Park, Canada: comparison of receptor models and data treatment methods

    Science.gov (United States)

    Xu, Xiaohong; Liao, Yanyin; Cheng, Irene; Zhang, Leiming

    2017-01-01

    Source apportionment analysis was conducted with positive matrix factorization (PMF) and principal component analysis (PCA) methods using concentrations of speciated mercury (Hg), i.e., gaseous elemental mercury (GEM), gaseous oxidized mercury (GOM), and particulate-bound mercury (PBM), and other air pollutants collected at Kejimkujik National Park, Nova Scotia, Canada, in 2009 and 2010. The results were largely consistent between the 2 years for both methods. The same four source factors were identified in each year using PMF method. In both years, factor photochemistry and re-emission had the largest contributions to atmospheric Hg, while the contributions of combustion emission and industrial sulfur varied slightly between the 2 years. Four components were extracted with air pollutants only in each year using PCA method. Consistencies between the results of PMF and PCA include (1) most or all PMF factors overlapped with PCA components, (2) both methods suggest strong impact of photochemistry but little association between ambient Hg and sea salt, and (3) shifting of PMF source profiles and source contributions from one year to another was echoed in PCA. Inclusion of meteorological parameters led to identification of an additional component, Hg wet deposition in PCA, while it did not affect the identification of other components. The PMF model performance was comparable in 2009 and 2010. Among the three Hg forms, the agreements between model-reproduced and observed annual mean concentrations were excellent for GEM, very good for PBM, and acceptable for GOM. However, on a daily basis, the agreement was very good for GEM but poor for GOM and PBM. Sensitivity tests suggest that increasing sample size by imputation is not effective in improving model performance, while reducing the fraction of concentrations below method detection limit, by either scaling GOM and PBM to higher concentrations or combining them to reactive mercury, is effective. Most of the data

  5. Detection of CO2 leaks from carbon capture and storage sites to the atmosphere with combined CO2 and O2 measurements

    Science.gov (United States)

    van Leeuwen, Charlotte; Meijer, Harro A. J.

    2015-04-01

    One of the main issues in carbon capture and storage (CCS) is the possibility of leakage of CO2 from the storage reservoir to the atmosphere, both from a public health and a climate change combat perspective. Detecting these leaks in the atmosphere is difficult due to the rapid mixing of the emitted CO2 with the surrounding air masses and the high natural variability of the atmospheric CO2 concentration. Instead of measuring only the CO2 concentration of the atmosphere, its isotopes or chemical tracers that are released together with the CO2, our method uses O2 measurements in addition to CO2 measurements to detect a leak from a CCS site. CO2 and O2 are coupled in most processes on earth. In photosynthesis, plants take up CO2 and release O2 at the same time. In respiration and fossil fuel burning, O2 is consumed while CO2 is released. In case of a leak from a CCS site, however, there is no relationship between CO2 and O2. A CO2 leak can therefore be distinguished from other sources of CO2 by looking at the atmospheric CO2-O2 ratio. A natural increase of the CO2 concentration is accompanied by a drop in the O2 concentration, while an increase in the CO2 concentration caused by a leak from a CCS site does not have any effect on the O2 concentration. To demonstrate this leak detection strategy we designed and built a transportable CO2 and O2 measurement system, that is capable of measuring the relatively minute (ppm's variations on a 21% concentration) changes in the O2 concentration. The system comprises of three cases that contain the instrumentation and gas handling equipment, the gas cylinders used as reference and calibration gases and a drying system, respectively. Air is pumped to the system from an air inlet that is placed in a small tower in the field. At the conference, we will demonstrate the success of leak detection with our system by showing measurements of several CO2 release experiments, where CO2 was released at a small distance from the air inlet of

  6. Planetary Atmosphere and Surfaces Chamber (PASC): A Platform to Address Various Challenges in Astrobiology

    Science.gov (United States)

    Mateo-Marti, Eva

    2014-08-01

    The study of planetary environments of astrobiological interest has become a major challenge. Because of the obvious technical and economical limitations on in situ planetary exploration, laboratory simulations are one of the most feasible research options to make advances both in planetary science and in developing a consistent description of the origin of life. With this objective in mind, we applied vacuum technology to the design of versatile vacuum chambers devoted to the simulation of planetary atmospheres' conditions. These vacuum chambers are able to simulate atmospheres and surface temperatures representative of the majority of planetary objects, and they are especially appropriate for studying the physical, chemical and biological changes induced in a particular sample by in situ irradiation or physical parameters in a controlled environment. Vacuum chambers are a promising potential tool in several scientific and technological fields, such as engineering, chemistry, geology and biology. They also offer the possibility of discriminating between the effects of individual physical parameters and selected combinations thereof. The implementation of our vacuum chambers in combination with analytical techniques was specifically developed to make feasible the in situ physico-chemical characterization of samples. Many wide-ranging applications in astrobiology are detailed herein to provide an understanding of the potential and flexibility of these experimental systems. Instruments and engineering technology for space applications could take advantage of our environment-simulation chambers for sensor calibration. Our systems also provide the opportunity to gain a greater understanding of the chemical reactivity of molecules on surfaces under different environments, thereby leading to a greater understanding of interface processes in prebiotic chemical reactions and facilitating studies of UV photostability and photochemistry on surfaces. Furthermore, the

  7. A Leaf-Inspired Luminescent Solar Concentrator for Energy-Efficient Continuous-Flow Photochemistry.

    Science.gov (United States)

    Cambié, Dario; Zhao, Fang; Hessel, Volker; Debije, Michael G; Noël, Timothy

    2017-01-19

    The use of solar light to promote chemical reactions holds significant potential with regard to sustainable energy solutions. While the number of visible light-induced transformations has increased significantly, the use of abundant solar light has been extremely limited. We report a leaf-inspired photomicroreactor that constitutes a merger between luminescent solar concentrators (LSCs) and flow photochemistry to enable green and efficient reactions powered by solar irradiation. This device based on fluorescent dye-doped polydimethylsiloxane collects sunlight, focuses the energy to a narrow wavelength region, and then transports that energy to embedded microchannels where the flowing reactants are converted. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  8. The road to hot electron photochemistry at surfaces: A personal recollection

    Science.gov (United States)

    Gadzuk, J. W.

    2012-09-01

    A very important part of contemporary fs-laser surface photochemistry (SPC) is based on a proposed mechanism in which a laser pulse incident upon an adsorbate-covered surface photoexcites substrate electrons which in turn inelastically scatter from atoms and molecules (chemists may call them "reactants") in or on the surface. The present narrative outlines my own very personal SPC saga that began with early exposure to the wonders of and fascination with inelastic resonant electron scattering from gas phase atoms and molecules that dominated the Atomic and Electron Physics activities at NBS (now NIST) in 1968 when I arrived. How this lead to a fundamental understanding of important aspects of SPC is the focus of this essay.

  9. A model for the origin of photosynthesis--III. The ultraviolet photochemistry of uroporphyrinogen

    Science.gov (United States)

    Mercer-Smith, J. A.; Raudino, A.; Mauzerall, D. C.

    1985-01-01

    The photochemical ramifications of the high ultraviolet flux on the primordial earth prior to the formation of the ozone layer have been considered in a study of the ultraviolet photochemistry of uroporphyrinogen (urohexahydroporphyrin), a colorless compound which absorbs strongly at wavelengths less than 220 nanometers. Urohexahydroporphyrin was investigated since it is the first macrocycle formed on the biosynthetic pathway of chlorophyll and can be used to test the hypothesis that the biosynthetic pathway to chlorophyll recapitulates the evolutionary history of photosynthesis. When urohexahydroporphyrin is illuminated in aqueous anaerobic solution, hydrogen gas is produced. More hydrogen gas is produced in the presence of a colloidal platinum catalyst. The products of the photooxidation of urohexahydroporphyrin are urotetrahydroporphyrin (uroporphomethene) and uroporphyrin. This research shows how the oxidation of uroporphyrinogen to uroporphyrin, the first biogenetic porphyrin, could have occurred anaerobically and abiotically on the primordial earth.

  10. Solution and solid trinitrotoluene (TNT) photochemistry: persistence of TNT-like ultraviolet (UV) resonance Raman bands.

    Science.gov (United States)

    Gares, Katie L; Bykov, Sergei V; Godugu, Bhaskar; Asher, Sanford A

    2014-01-01

    We examined the 229 nm deep-ultraviolet resonance Raman (DUVRR) spectra of solution and solid-state trinitrotoluene (TNT) and its solution and solid-state photochemistry. Although TNT photodegrades with a solution quantum yield of ϕ ∼ 0.015, the initial photoproducts show DUVRR spectra extraordinarily similar to pure TNT, due to the similar photoproduct enhancement of the -NO2 stretching vibrations. This results in TNT-like DUVRR spectra even after complete TNT photolysis. These ultraviolet resonance Raman spectral bands enable DUVRR of trace as well as DUVRR standoff TNT detection. We determined the structure of various initial TNT photoproducts by using liquid chromatography-mass spectrometry and tandem mass spectrometry. Similar TNT DUVRR spectra and photoproducts are observed in the solution and solid states.

  11. The Ultraviolet Photochemistry and Photobiology of Vegetative Cells and Spores of Bacillus megaterium

    Science.gov (United States)

    Donnellan, J. E.; Stafford, R. S.

    1968-01-01

    The ultraviolet (UV) photochemistry and photobiology of spores and vegetative cells of Bacillus megaterium have been studied. The response of vegetative cells of B. megaterium appears qualitatively similar to those of Escherichia coli, Micrococcus radiodurans, and Bacillus subtilis with respect to photoproduct formation and repair mechanisms. UV irradiation, however, does not produce cyclobutane-type thymine dimers in the DNA of spores, although other thymine photo-products are produced. The photoproducts do not disappear after photoreactivation, but they are eliminated from the DNA by a dark-repair mechanism different from that found for dimers in vegetative cells. Irradiations performed at three wavelengths produce the same amounts of spore photoproduct and give the same survival curves. Variation of the sporulation medium before irradiation results in comparable alterations in the rate of spore photoproduct production and in survival. PMID:4966691

  12. Model assessing the impact of biomass burning on air quality and photochemistry in Mexico City

    Science.gov (United States)

    Lei, W.; Li, G.; Wiedinmyer, C.; Yokelson, R. J.; Molina, L. T.

    2010-12-01

    Biomass burning is a major global emission source for trace gases and particulates. Various multi-platform measurements during the Mexico City Metropolitan Area (MCMA)-2003 and Megacity Initiative: Local and Global Research Observations (MILAGRO)-2006 campaigns suggest significant influences of biomass burning (BB) on air quality in Mexico City during the dry season, and the observations show emissions from BB impose viable yet highly variable impacts on organic aerosols (OA) in and around Mexico City. We have developed emission inventories for forest fires surrounding Mexico City based on measurement-estimated emission factors and MODIS fire counts, and for garbage fires in Mexico City based on in situ-measured emission factors and the population distribution and socioeconomic data. In this study, we will comprehensively assess the impact of biomass burning on the aerosol loading, chemical composition, OA formation and photochemistry in Mexico City using WRF-Chem. Analysis of the model results, in conjunction with concurrent field measurements, will be presented.

  13. Photochemistry at high temperatures - potential of ZnO as a high temperature photocatalyst

    Energy Technology Data Exchange (ETDEWEB)

    Schubnell, M.; Beaud, P.; Kamber, I. [Paul Scherrer Inst. (PSI), Villigen (Switzerland)

    1997-06-01

    Direct conversion of solar radiation into useful, storeable and transportable chemical products is the primary goal of solar chemistry. In this paper we discuss some fundamental aspects of photochemistry at elevated temperatures. We show that luminescence can serve as an indicator of the potential use of a system as a photoconverter. As an example we present experimental data on the chemical potential and on the lifetime of the excited states of ZnO. The low luminescence quantum yield together with a lifetime of about 200 ps indicate that an efficient photochemical conversion on ZnO is highly improbable. We believe this to be a general feature of chemical systems based on a semiconductor photocatalyst, in particular of photoreactions at a solid/gas interface. (author) 3 figs., 6 refs

  14. Surface photochemistry: alloxazine within nanochannels of Na+ and H + ZSM-5 zeolites.

    Science.gov (United States)

    Ferreira, L F Vieira; Costa, A I; Machado, I Ferreira; do Rego, A M Botelho; Sikorska, E; Sikorskie, M

    2009-07-21

    This work reports the surface photochemistry study of alloxazine adsorbed within nanochannels of MFI zeolites, namely in a series of Na+ and H+ ZSM-5 zeolites where the hydrophobic and hydrophilic character of the host varies systematically. Laser-induced room temperature and 77 K luminescence of air-equilibrated solid powdered samples of alloxazine adsorbed onto the two sets of zeolites, which we will name NaZSM-5 and HZSM-5, revealed the existence of a single emission of alloxazine as a broad band centred at about 450 nm in some cases, while in others an emission with a maximum at about 510 nm was detected. The decay times of the alloxazine emission vary greatly going from solution to entrapment within the nanochannels of the ZSM-5 zeolites. In the latter case a lifetime distribution analysis has shown that the longest lifetime for the alloxazine fluorescence emission exists in the case where an isoalloxazine-type emission was detected, i.e. whenever the hydrophobic character of the host increases. Alloxazine entrapped in the more acidic zeolites exists in the form of emissive monomers. However, alloxazine emits both from monomeric and aggregated emissive forms in the case of the hydrophobic zeolites. These data indicate the formation of planar dimers of alloxazine whenever the number of active sites in the zeolite decreases. These dimers have to be formed at the intersections of the zig-zag and linear nanochannels of the zeolite since there is no space available for their formation inside the zeolite channels. The isoalloxazine tautomers are formed due to the existence of alloxazine dimers which may undergo double proton transfer in the excited state, following laser excitation. Delayed fluorescence of alloxazine was also detected for the HZSM-5 and NaZSM-5 entrapment both at room temperature and at 77 K. The present study is paradigmatic as regards the host influence on the photochemistry of the guest.

  15. The photochemistry of thymine in frozen aqueous solution: trimeric and minor dimeric products.

    Science.gov (United States)

    Shetlar, Martin D; Basus, Vladimir J

    2013-01-01

    Early work identified three compounds, namely the c,s cyclobutane dimer, the so-called (6-4) photoproduct (5-hydroxy-6-4'-(5-methylpyrimidin-2'-one)-5,6-dihydrothymine) and a trimer hydrate, as products formed upon UV irradiation of thymine in frozen aqueous solution. More recent work has shown that an (α-4) product, namely α-4'-(5'-methylpyrimidine-2'-one)-thymine, is a likely product formed under these reaction conditions. During a thorough reinvestigation of the photochemistry of Thy in ice at -78.5°C, we found that a variety of other products could be detected. In addition to the c,s dimer, the other three known cyclobutane dimers, namely the c,a, t,s and t,a forms, are produced, although in considerably smaller amounts. The so-called "spore product" of thymine (5,6-dihydro-5-(α-thyminyl)thymine) is likewise formed. Two other dimers have been identified as minor products; one of these has been determined to be 5-(thymin-3-yl)-5,6-dihydrothymine and the other has been tentatively assigned to be a (5-4) adduct (6-hydroxy-5-4'-(5-methylpyrimidin-2'-one)-5,6-dihydrothymine). Compounds with the behavior expected of true trimeric compounds have been isolated via HPLC and characterized by mass spectrometry and photochemical behavior. One of these materials, putatively containing an oxetane ring, decomposes thermally to a secondary trimeric product that is then converted into the known trimer hydrate. © 2013 Wiley Periodicals, Inc. Photochemistry and Photobiology © 2013 The American Society of Photobiology.

  16. Confirmation and efficacy tests against codling moth and oriental fruit moth in peaches and nectarines using combination heat and controlled atmosphere treatments.

    Science.gov (United States)

    Neven, Lisa G; Rehfield-Ray, Linda M; Obenland, David

    2006-10-01

    Two high-temperature, forced air treatments under controlled atmosphere conditions, called CATTS for controlled atmosphere/temperature treatment system, were developed for control of all life stages of codling moth, Cydia pomonella (L.), and oriental fruit moth, Grapholita molesta (Busck), infesting peaches and nectarines (both Prunus spp.). These treatments were used in efficacy and confirmation tests to kill > 5,000 fourth instar oriental fruit moths and > 30,000 fourth instar codling moths with zero survivors. The treatments consist of linear heating rates of either 12 or 24 degrees C/h to a final chamber temperature under a 1% O2, 15% CO2, and > 90% RH atmosphere with air speed between 1.2 and 2.0 m/s. At a 12 degrees C linear chamber heating rate, treatment takes approximately 3 h to reach a final chamber temperature of 46 degrees C. The average lowest core temperatures of the fruit reached 43.8 degrees C within the last 30 min of the treatment. At a 24 degrees C linear chamber heating rate, it takes approximately 2.5 h to reach a final chamber temperature of 46 degrees C. The average lowest core temperatures of the fruit reached 44.6 degrees C for the last 15 min of the treatment. It also was determined that both treatments did not significantly alter the quality parameters that were evaluated to a degree that would have negatively influenced the marketability of the fruit. Positive benefits of treatment included a slower ripening of treated fruit and an inhibition of the loss of juiciness during storage in some cultivars. These treatments may be used to replacement to methyl bromide fumigation for conventional fruit or as a new treatment for organic fruit contingent upon importing country approval.

  17. Atmospheric Dispositifs

    DEFF Research Database (Denmark)

    Wieczorek, Izabela

    2015-01-01

    Through the coupling of dispositif with atmosphere this paper engages in a discussion of the atmospherics as both a form of knowledge and a material practice. In doing so the objective is to provide an inventory of tools and methodologies deployed in the construction of atmosphere understood......, the conceptual foundations and protocols for the production of atmosphere in architecture might be found beneath the surface of contemporary debates. In this context, the notion of atmospheric dispositif – illustrated through an oeuvre of the German architect Werner Ruhnau and its theoretical and historical...

  18. Aerosol optical extinction during the Front Range Air Pollution and Photochemistry Éxperiment (FRAPPÉ) 2014 summertime field campaign, Colorado, USA

    National Research Council Canada - National Science Library

    Justin H Dingle; Eric C Apel; Teresa L Campos; Alan J Hills; Rebecca S Hornbrook; Denise D Montzka; John B Nowak; Joseph R Roscioli

    2016-01-01

      Summertime aerosol optical extinction (βext) was measured in the Colorado Front Range and Denver metropolitan area as part of the Front Range Air Pollution and Photochemistry Éxperiment (FRAPPÉ...

  19. Collision-Induced Dissociation Study of Strong Hydrogen-Bonded Cluster Ions Y−(HF)n (Y=F, O2) Using Atmospheric Pressure Corona Discharge Ionization Mass Spectrometry Combined with a HF Generator

    OpenAIRE

    Sakamoto, Kenya; Sekimoto, Kanako; Takayama, Mitsuo

    2017-01-01

    Hydrogen fluoride (HF) was produced by a homemade HF generator in order to investigate the properties of strong hydrogen-bonded clusters such as (HF)n. The HF molecules were ionized in the form of complex ions associated with the negative core ions Y− produced by atmospheric pressure corona discharge ionization (APCDI). The use of APCDI in combination with the homemade HF generator led to the formation of negative-ion HF clusters Y−(HF)n (Y=F, O2), where larger clusters with n≥4 were not dete...

  20. Articulating Atmospheres

    DEFF Research Database (Denmark)

    Kinch, Sofie

    2011-01-01

    This paper presents an architectural approach to designing computational interfaces by articulating the notion of atmosphere in the field of interaction design. It draws upon the concept of kinesthetic interaction and a philosophical notion on atmosphere emphasizing the importance of bodily exper......” implications and qualities of the approach are identified through concrete examples of a design case, which also investigates the qualities and implications of addressing atmospheres both as design concern and user experience.......This paper presents an architectural approach to designing computational interfaces by articulating the notion of atmosphere in the field of interaction design. It draws upon the concept of kinesthetic interaction and a philosophical notion on atmosphere emphasizing the importance of bodily...... experience in space, presented as middle ground experience. In the field of HCI, middle ground experiences complete the unarticulated spectrum between designing for foreground of attention or background awareness. When “Articulating Atmospheres through Middle Ground Experiences in Interaction Design...

  1. Titan 2D: Understanding Titan’s Seasonal Atmospheric Cycles

    Science.gov (United States)

    Wong, Michael; Zhang, X.; Li, C.; Hu, R.; Shia, R.; Newman, C.; Müller-Wodarg, I.; Yung, Y.

    2013-10-01

    In this study, we present results from a novel two-dimensional (2D) model that simulates the physics and chemistry of Titan’s atmosphere. Despite being an icy moon of Saturn, Titan is the only Solar System object aside from Earth that is sheathed by a thick nitrogen-dominated atmosphere. This vulnerable gaseous envelope—an embodiment of a delicate coupling between photochemistry, radiation, and dynamics—is Nature’s laboratory for the synthesis of complex organic molecules. Titan’s large obliquity generates pronounced seasonal cycles in its atmosphere, and the Cassini spacecraft has been observing these variations since 2004. In particular, Cassini measurements show that the latitudinal distribution of Titan’s rich mélange of hydrocarbon species follows seasonal patterns. The mixing ratios of hydrocarbons increase with latitude towards the winter pole, suggesting a pole-to-pole circulation that reverses after equinox. Using a one-dimensional photochemical model of Titan’s atmosphere, we show that photochemistry alone cannot produce the observed meridional hydrocarbon distribution. This necessitates the employment of a 2D chemistry-transport model that includes meridional circulation as well as diffusive processes and photochemistry. Of additional concern, no previous 2D model of Titan extends beyond 500 km altitude—a critical limitation since the peak of methane photolysis is at 800 km. Our 2D model is the first to include Titan’s stratosphere, mesosphere, and thermosphere. The meridional circulation in our 2D model is derived from the outputs of two general circulation models (GCMs): the TitanWRF GCM (Newman et al. 2011) covering the troposphere, stratosphere, and lower mesosphere, and a thermosphere general circulation model (TGCM) covering the remainder of the atmosphere through the thermosphere (Müller-Wodarg et al. 2003; 2008). This presentation will focus on the utilization of these advances applied to the 2D Caltech/JPL KINETICS model to

  2. Atmospheric electricity

    CERN Document Server

    Chalmers, J Alan

    1957-01-01

    Atmospheric Electricity brings together numerous studies on various aspects of atmospheric electricity. This book is composed of 13 chapters that cover the main problems in the field, including the maintenance of the negative charge on the earth and the origin of the charges in thunderstorms. After a brief overview of the historical developments of atmospheric electricity, this book goes on dealing with the general principles, results, methods, and the MKS system of the field. The succeeding chapters are devoted to some aspects of electricity in the atmosphere, such as the occurrence and d

  3. Atmospheric Neutrinos

    Directory of Open Access Journals (Sweden)

    Takaaki Kajita

    2012-01-01

    Full Text Available Atmospheric neutrinos are produced as decay products in hadronic showers resulting from collisions of cosmic rays with nuclei in the atmosphere. Electron-neutrinos and muon-neutrinos are produced mainly by the decay chain of charged pions to muons to electrons. Atmospheric neutrino experiments observed zenith angle and energy-dependent deficit of muon-neutrino events. It was found that neutrino oscillations between muon-neutrinos and tau-neutrinos explain these data well. This paper discusses atmospheric neutrino experiments and the neutrino oscillation studies with these neutrinos.

  4. Ring-opening photochemistry in cyclohexadiene derivatives: Ultrafast dynamics in solution and model membranes

    Science.gov (United States)

    Arruda, Brenden C.

    The ultrafast dynamics of molecules in condensed phases is an area of research that has the possibility to inform the design of molecules for functional nano-devices as well as improve on understanding of biological processes. Presented in this thesis are experiments probing the excited and ground state dynamics of molecules based on the 1,3-cyclohexadiene (CHD) chromophore. The reversible photochemistry of these molecules is applicable to the study of photo-switching systems under consideration for molecular memory devices as well as the photobiological synthesis of Vitamin D3. The full reaction mechanism for a number of CHD derivatives is deduced from ultrafast broadband transient absorption spectroscopy and supporting density functional calculations. Steric groups on the cyclohexadiene backbone can affect both the excited state properties as well as the dynamic approach to equilibrium for the hexatriene photoproducts following excitation of CHD. The photoreaction was characterized in multiple solvent environments with a range of viscosity, polarity, hydrogen-bonding capacity, and packing density. The conformational dynamics of the photoproducts depend on the substitution pattern and solvent. The alpha-phellandrene photoproduct relaxes to a fully trans form much like hexatriene, while alpha-terpinene and 7-dehydrocholesterol photoproducts are limited to certain conformations by steric clashes. The solvent affects the relaxation timescales differently for each photoproduct, but all of the dynamics occur within 5 - 10 ps. The ring opening of DHC that occurs in the biological synthesis of Vitamin D3 is also examined in a liposomal model for the cell membrane. In this anisotropic environment, the excited state dynamics are significantly lengthened to ~ 11 -- 50 ps depending on the liposome properties. This suggests significant interaction between DHC and the lipids that affects the ring-opening reaction coordinate. The excited state and photoproduct conformational

  5. Urban atmospheres.

    Science.gov (United States)

    Gandy, Matthew

    2017-07-01

    What is an urban atmosphere? How can we differentiate an 'atmosphere' from other facets of urban consciousness and experience? This essay explores some of the wider cultural, political, and philosophical connotations of atmospheres as a focal point for critical reflections on space and subjectivity. The idea of an 'affective atmosphere' as a distinctive kind of mood or shared corporeal phenomenon is considered in relation to recent developments in phenomenology, extended conceptions of agency, and new understandings of materialism. The essay draws in particular on the changing characteristics of air and light to reflect on different forms of sensory experience and their wider cultural and political connotations. The argument highlights some of the tensions and anomalies that permeate contemporary understandings of urban atmospheres.

  6. Photochemistry of excited-state species in natural waters: a role for particulate organic matter.

    Science.gov (United States)

    Cottrell, Barbara A; Timko, Stephen A; Devera, Lianne; Robinson, Alice K; Gonsior, Michael; Vizenor, Ashley E; Simpson, André J; Cooper, William J

    2013-09-15

    Laser flash photolysis (LFP) was used to characterize a triplet excited state species isolated from Black River and San Joaquin wetlands particulate organic matter (POM). The solubilized organic matter, isolated from POM by pH-independent diffusion in distilled water, was named PdOM. UV-visible absorption spectroscopy, excitation-emission matrix spectroscopy (EEMs), and (1)H NMR were used to characterize the PdOM. While LFP of dissolved organic matter (DOM) is known to generate the solvated electron, LFP of the PdOM transient in argon-, air-, and nitrous oxide-saturated solutions indicated that this was a triplet excited state species ((3)PdOM*). The lifetime and the reactivity of (3)PdOM* with sorbic acid, a triplet state quencher, were compared with that of the triplet excited state of benzophenone, a DOM proxy. A second excited state species (designated DOM*), with a longer lifetime, was reported in a number of previous studies but not characterized. The lifetime of DOM*, measured for seventeen organic matter isolates, lignin, tannic acid, and three wetlands plant extracts, was shown to differentiate allochthonous from autochthonous DOM. (3)POM* and DOM* were also observed in lake water and a constructed wetlands' water. Aqueous extracts of fresh and aged plant material from the same wetland were shown to be one source of these excited state species. This study provides evidence of a role for POM in the photochemistry of natural and constructed wetland waters. Copyright © 2013 Elsevier Ltd. All rights reserved.

  7. Photochemistry of naphthalene diimides: EPR study of free radical formation via photoredox process.

    Science.gov (United States)

    Reszka, Krzysztof J; Takayama, Masami; Sik, Robert H; Chignell, Colin F; Saito, Isao

    2005-01-01

    Earlier studies have shown that on exposure to UVA, hydroperoxynaphthalene diimide (IA) generates hydroxyl radicals, induces DNA strand scission, and kills cells. Here we employed electron paramagnetic resonance (EPR) and spin trapping to investigate the free radical photochemistry of IA and that of related naphthalene diimides, which are devoid of the hydroperoxyl moiety (N,N'-bis[2-methyl]-1,4,5,8-naphthaldiimide [IB], N,N'-bis[2-thiomethyl-2-methoxyethyl]-1,4,5,8-naphthaldiimide [IC]) and therefore are unable to generate hydroxyl radicals. It is shown that on UV irradiation (>300 nm) in air-free methanol or ethanol solutions all these naphthalene diimides undergo one-electron reduction to corresponding anion radicals, positively identified by EPR. With EPR and a spin trap 5,5-dimethyl-1-pyrroline N-oxide (DMPO), we found that the photogeneration of the naphthalene diimide radicals is concomitant with the formation of radicals from the solvents, presumably through electron/hydrogen atom abstraction by photoactivated diimides. Irradiation of IA, IB or IC in the presence of oxygen generates superoxide, which was detected as a DMPO adduct. The high photoreactivity of IB and IC supports the notion that hydroperoxide IA can induce oxidative damage via photoprocesses that are independent of *OH generation. These observations could be pertinent to the application of naphthalene diimides as selective photonucleases, PDT anticancer agents or both.

  8. Photochemistry of Solutes in Different Locations in/on Ice. Part II: Reaction Rate Measurements

    Science.gov (United States)

    Hullar, T.; Anastasio, C.

    2014-12-01

    Particularly in polar regions, photochemical reactions in snowpacks can be an important mechanism for transforming organic and inorganic compounds. Chemicals within snow and ice are found in three different compartments: distributed in the bulk ice, concentrated in liquid-like regions (LLRs) within the ice matrix (such as at grain boundaries), or in quasi-liquid layers at the air-ice interface. While some experiments suggest reaction rates may vary in these different compartments, it is not clear if the reaction rates are different or if the changes are due to variations in the reaction environment (such as photon flux). A companion presentation discusses our work identifying solute location in laboratory ice samples; here, we describe experimental measurements of reaction rates in different ice compartments. Polycyclic aromatic hydrocarbons (PAHs) are common pollutants in snow and ice. We first prepared aqueous solutions of a single PAH. We then froze these samples using various methods that segregate the solute into different locations in the ice matrix. With simulated sunlight, we illuminated these samples and measured photon flux (using 2-nitrobenzaldehyde) and the photodecay of the PAH. We will discuss differences in PAH photochemistry as a function of location in the ice sample and the implications of these results for environmental snow and ice.

  9. High-Power 365 nm UV LED Mercury Arc Lamp Replacement for Photochemistry and Chemical Photolithography.

    Science.gov (United States)

    Hölz, K; Lietard, J; Somoza, M M

    2017-01-03

    Ultraviolet light emitting diodes (UV LEDs) have become widespread in chemical research as highly efficient light sources for photochemistry and photopolymerization. However, in more complex experimental setups requiring highly concentrated light and highly spatially resolved patterning of the light, high-pressure mercury arc lamps are still widely used because they emit intense UV light from a compact arc volume that can be efficiently coupled into optical systems. Advances in the deposition and p-type doping of gallium nitride have recently permitted the manufacture of UV LEDs capable of replacing mercury arc lamps also in these applications. These UV LEDs exceed the spectral radiance of mercury lamps even at the intense I-line at 365 nm. Here we present the successful exchange of a high-pressure mercury arc lamp for a new generation UV LED as a light source in photolithographic chemistry and its use in the fabrication of high-density DNA microarrays. We show that the improved light radiance and efficiency of these LEDs offer substantial practical, economic and ecological advantages, including faster synthesis, lower hardware costs, very long lifetime, an >85-fold reduction in electricity consumption and the elimination of mercury waste and contamination.

  10. Photochemistry-based immune modulation in the treatment of cutaneous leishmaniasis

    Science.gov (United States)

    Akilov, Oleg E.; Kosaka, Sachiko; Hasan, Tayyaba

    2009-06-01

    The destruction of infectious pathogens by photodynamic therapy (PDT) is an emerging modality. We demonstrated the efficacy of PDT for the management of cutaneous leishmaniasis in our previous studies. However, much remains to be done for the improvement of PDT regimens. The modulation of the immune response by photochemistry is an exciting but under-explored area of PDT research. The goal of this study is to understand the mechanisms of the augmentation of the host immune response after PDT of cutaneous leishmaniasis (CL). We found that PDT with phenoxiazine analogues was capable for induction of Th1 immune response due to stimulation of IL- 12 production by dendritic cells. Single PDT treatment facilitated fast healing of the CL lesions due to effective parasite eradication and augmentation of the immune system. Comparative study with different photosensitizers (PS) (porphyrins, pehnoxiazines) demonstrated different immunomodulating properties of PDT depending on chemical class of PS. Knowing the particular profiles and immunomodulating properties of the pertinent PSs allows us to select the optimal PS with regards to both the photodestructive and immunostimulating potential.

  11. Photochemistry of nanoporous carbons: Perspectives in energy conversion and environmental remediation.

    Science.gov (United States)

    Gomis-Berenguer, Alicia; Velasco, Leticia F; Velo-Gala, Inmaculada; Ania, Conchi O

    2017-03-15

    The interest in the use of nanoporous carbon materials in applications related to energy conversion and storage, either as catalysts or additives, has grown over recent decades in various disciplines. Since the early studies reporting the benefits of the use of nanoporous carbons as inert supports of semiconductors and as electron acceptors that enhance the splitting of the photogenerated excitons, many researchers have investigated the key role of carbon matrices coupled to all types of photoactive materials. More recently, our group has demonstrated the ability of semiconductor-free nanoporous carbons to convert the absorbed photons into chemical reactions (i.e. oxidation of pollutants, water splitting, reduction of surface groups) opening new opportunities beyond conventional applications in light energy conversion. The aim of this paper is to review the recent progress on the application of nanoporous carbons in photochemistry using varied illumination conditions (UV, simulated solar light) and covering their role as additives to semiconductors as well as their use as photocatalysts in various fields, describing the photochemical quantum yield of nanoporous carbons for different reactions, and discussing the mechanisms postulated for the carbon/light interactions in confined pore spaces. Copyright © 2016 The Authors. Published by Elsevier Inc. All rights reserved.

  12. FTIR Studies of the Photochemistry of Deuterated Formic Acid in a Parahydrogen Matrix

    Science.gov (United States)

    Anderson, David T.

    2014-06-01

    We report new FTIR studies of the 193 nm photochemistry of deuterated formic acid (DCOOD) trapped in parahydrogen matrices. In our 2011 preliminary report, we showed the 193 nm in situ photolysis of formic acid (HCOOH) produces small amounts of HCO and HOCO and that after the laser is turned off, we observe continued slow growth in the HOCO radical for up to 10 hours after photolysis. At that time we were unsure of the detailed chemical mechanism by which the HOCO continues to grow after photolysis, but we suspected it had to do with reactions of mobile H-atoms with the HCOOH precursor that remains at significant concentrations after photolysis under these conditions. The present deuterated formic acid photolysis studies provide strong circumstantial evidence that H-atom reactions with formic acid are the source of the continued HOCO growth. Further, variable-temperature kinetic studies conducted with the deuterated formic acid sample show a strong inverse temperature dependence to the reaction kinetics. Essentially, the reaction that leads to HOCO growth only occurs at temperatures below 2.4 K. We are currently trying to model the kinetics using standard methods and the most recent analysis will be presented at the meeting. David T. Anderson, Leif O. Paulson, 66th Ohio State University International Symposium on Molecular Spectroscopy, talk FE02 (2011).

  13. High-Power 365 nm UV LED Mercury Arc Lamp Replacement for Photochemistry and Chemical Photolithography

    Science.gov (United States)

    2016-01-01

    Ultraviolet light emitting diodes (UV LEDs) have become widespread in chemical research as highly efficient light sources for photochemistry and photopolymerization. However, in more complex experimental setups requiring highly concentrated light and highly spatially resolved patterning of the light, high-pressure mercury arc lamps are still widely used because they emit intense UV light from a compact arc volume that can be efficiently coupled into optical systems. Advances in the deposition and p-type doping of gallium nitride have recently permitted the manufacture of UV LEDs capable of replacing mercury arc lamps also in these applications. These UV LEDs exceed the spectral radiance of mercury lamps even at the intense I-line at 365 nm. Here we present the successful exchange of a high-pressure mercury arc lamp for a new generation UV LED as a light source in photolithographic chemistry and its use in the fabrication of high-density DNA microarrays. We show that the improved light radiance and efficiency of these LEDs offer substantial practical, economic and ecological advantages, including faster synthesis, lower hardware costs, very long lifetime, an >85-fold reduction in electricity consumption and the elimination of mercury waste and contamination. PMID:28066690

  14. Prebiotic significance of extraterrestrial ice photochemistry: detection of hydantoin in organic residues.

    Science.gov (United States)

    de Marcellus, Pierre; Bertrand, Marylène; Nuevo, Michel; Westall, Frances; Le Sergeant d'Hendecourt, Louis

    2011-11-01

    The delivery of extraterrestrial organic materials to primitive Earth from meteorites or micrometeorites has long been postulated to be one of the origins of the prebiotic molecules involved in the subsequent apparition of life. Here, we report on experiments in which vacuum UV photo-irradiation of interstellar/circumstellar ice analogues containing H(2)O, CH(3)OH, and NH(3) led to the production of several molecules of prebiotic interest. These were recovered at room temperature in the semi-refractory, water-soluble residues after evaporation of the ice. In particular, we detected small quantities of hydantoin (2,4-imidazolidinedione), a species suspected to play an important role in the formation of poly- and oligopeptides. In addition, hydantoin is known to form under extraterrestrial, abiotic conditions, since it has been detected, along with various other derivatives, in the soluble part of organic matter of primitive carbonaceous meteorites. This result, together with other related experiments reported recently, points to the potential importance of the photochemistry of interstellar "dirty" ices in the formation of organics in Solar System materials. Such molecules could then have been delivered to the surface of primitive Earth, as well as other telluric (exo-) planets, to help trigger first prebiotic reactions with the capacity to lead to some form of primitive biomolecular activity.

  15. Photochemistry of Coronene in Cosmic Water Ice Analogs at Different Concentrations

    Science.gov (United States)

    de Barros, A. L. F.; Mattioda, A. L.; Ricca, A.; Cruz-Diaz, G. A.; Allamandola, L. J.

    2017-10-01

    This work presents the photochemistry of ultraviolet (UV) irradiated coronene in water ices at 15 K studied using mid-infrared Fourier transform (FTIR) spectroscopy for C24H12:H2O at concentrations of (1:50), (1:150), (1:200), (1:300), and (1:400). Previous UV irradiation studies of anthracene:H2O, pyrene:H2O, and benzo[ghi]perylene:H2O ices at 15 K have shown that aromatic alcohols and ketones, as well as CO2 and H2CO, are formed at very low temperatures. Likewise, here, in addition to the coronene cation, hydroxy-, keto-, and protonated coronene (coronene H+) are formed. The rate constants for the decay of neutral coronene and for the formation of photoproducts have been derived. It is shown that Polycyclic Aromatic Hydrocarbons (PAHs) and their UV induced PAH:H2O photoproducts have mid-infrared spectroscopic signatures in the 5-8 μm region that can contribute to the interstellar ice components described by Boogert et al. as C1-C5. Our results suggest that oxygenated and hydrogenated PAHs could be in UV-irradiated regions of the interstellar medium where water-rich ices are important.

  16. Atmospheric Infancy

    DEFF Research Database (Denmark)

    Roald, Tone; Pedersen, Ida Egmose; Levin, Kasper

    2017-01-01

    In this article we establish intersubjective meaning-making in infancy as atmospheric. Through qualitative descriptions of five mother–infant dyads in a video-recorded, experimental setting when the infant is 4, 7, 10, and 13 months, we discovered atmospheric appearances with a developmental...... pattern of atmospheric variations. These appearances, we argue, are contextual and intersubjective monologues. The monologues are similar to what Daniel Stern describes with his concept of “vitality affects,” but they arise as a unified force that envelops the mother and child. As such, we present a new...

  17. 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.

  18. Atmosphere Impact Losses

    Science.gov (United States)

    Schlichting, Hilke E.; Mukhopadhyay, Sujoy

    2018-02-01

    } ρ0 (π h R)^{3/2}, r_{cap}˜25 km for the current Earth), that are able to eject all the atmosphere above the tangent plane of the impact site, where h, R and ρ0 are the atmospheric scale height, radius of the target, and its atmospheric density at the ground. 3) Small impactors (m_{min}>4 πρ0 h3, r_{min}˜ 1 km for the current Earth), that are only able to eject a fraction of the atmospheric mass above the tangent plane. We demonstrate that per unit impactor mass, small impactors with r_{min} efficient impactors in eroding the atmosphere. In fact for the current atmospheric mass of the Earth, they are more than five orders of magnitude more efficient (per unit impactor mass) than giant impacts, implying that atmospheric mass loss must have been common. The enormous atmospheric mass loss efficiency of small impactors is due to the fact that most of their impact energy and momentum is directly available for local mass loss, where as in the giant impact regime a lot of energy and momentum is 'wasted' by having to create a strong shock that can transverse the entirety of the planet such that global atmospheric loss can be achieved. In the absence of any volatile delivery and outgassing, we show that the population of late impactors inferred from the lunar cratering record containing 0.1% M_{\\oplus } is able to erode the entire current Earth's atmosphere implying that an interplay of erosion, outgassing and volatile delivery is likely responsible for determining the atmospheric mass and composition of the early Earth. Combining geochemical observations with impact models suggest an interesting synergy between small and big impacts, where giant impacts create large magma oceans and small and larger impacts drive the atmospheric loss.

  19. 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

  20. Ultraviolet spectrum and photochemistry of the simplest Criegee intermediate CH2OO.

    Science.gov (United States)

    Beames, Joseph M; Liu, Fang; Lu, Lu; Lester, Marsha I

    2012-12-12

    Ozonolysis of alkenes in the troposphere produces Criegee intermediates, which have eluded detection in the gas phase until very recently. This laboratory has synthesized the simplest Criegee intermediate within a quartz capillary tube affixed to a pulsed valve to cool and isolate CH(2)OO in a supersonic expansion. UV excitation resonant with the B (1)A' ← X (1)A' transition depletes the ground-state population of CH(2)OO, which is detected by single-photon ionization at 118 nm. The large UV-induced depletion (approaching 100%) near the peak of the profile at 335 nm is indicative of rapid dissociation, consistent with the repulsive B (1)A' potential along the O-O coordinate computed theoretically. The experimental spectrum is in very good accord with the absorption spectrum calculated using the one-dimensional reflection principle. The B ← X spectrum is combined with the solar actinic flux to estimate an atmospheric lifetime for CH(2)OO at midday on the order of ∼1 s with respect to photodissociation.

  1. Planetary Atmosphere and Surfaces Chamber (PASC: A Platform to Address Various Challenges in Astrobiology

    Directory of Open Access Journals (Sweden)

    Eva Mateo-Marti

    2014-08-01

    Full Text Available The study of planetary environments of astrobiological interest has become a major challenge. Because of the obvious technical and economical limitations on in situ planetary exploration, laboratory simulations are one of the most feasible research options to make advances both in planetary science and in developing a consistent description of the origin of life. With this objective in mind, we applied vacuum technology to the design of versatile vacuum chambers devoted to the simulation of planetary atmospheres’ conditions. These vacuum chambers are able to simulate atmospheres and surface temperatures representative of the majority of planetary objects, and they are especially appropriate for studying the physical, chemical and biological changes induced in a particular sample by in situ irradiation or physical parameters in a controlled environment. Vacuum chambers are a promising potential tool in several scientific and technological fields, such as engineering, chemistry, geology and biology. They also offer the possibility of discriminating between the effects of individual physical parameters and selected combinations thereof. The implementation of our vacuum chambers in combination with analytical techniques was specifically developed to make feasible the in situ physico-chemical characterization of samples. Many wide-ranging applications in astrobiology are detailed herein to provide an understanding of the potential and flexibility of these experimental systems. Instruments and engineering technology for space applications could take advantage of our environment-simulation chambers for sensor calibration. Our systems also provide the opportunity to gain a greater understanding of the chemical reactivity of molecules on surfaces under different environments, thereby leading to a greater understanding of interface processes in prebiotic chemical reactions and facilitating studies of UV photostability and photochemistry on surfaces

  2. Possible combined influences of absorbing aerosols and anomalous atmospheric circulation on summertime diurnal temperature range variation over the middle and lower reaches of the Yangtze River

    Science.gov (United States)

    Cai, Jiaxi; Guan, Zhaoyong; Ma, Fenhua

    2016-12-01

    Based on the temperature data from the China Meteorological Administration, NCEP-NCAR reanalysis data, and the TOMS Aerosol Index (AI), we analyze the variations in the summertime diurnal temperature range (DTR) and temperature maxima in the middle and lower reaches of the Yangtze River (MLRYR) in China. The possible relationships between the direct warming effect of the absorbing aerosol and temperature variations are further investigated, although with some uncertainties. It is found that the summertime DTR exhibits a decreasing trend over the most recent 50 years, along with a slight increasing tendency since the 1980s. The trend of the maximum temperature is in agreement with those of the DTR and the absorbing aerosols. To investigate the causes of the large anomalies in the temperature maxima, composite analyses of the circulation anomalies are performed. When anomalous AI and anomalous maximum temperature over the MLRYR have the same sign, an anomalous circulation with a quasi-barotropic structure occurs there. This anomalous circulation is modulated by the Rossby wave energy propagations from the regions northwest of the MLRYR and influences the northwestern Pacific subtropical high over the MLRYR. In combination with aerosols, the anomalous circulation may increase the maximum temperature in this region. Conversely, when the anomalous AI and anomalous maximum temperature in the MLRYR have opposite signs, the anomalous circulation is not equivalently barotropic, which possibly offsets the warming effect of aerosols on the maximum temperature changes in this region. These results are helpful for a better understanding of the DTR changes and the occurrences of temperature extremes in the MLRYR region during boreal summer.

  3. Atmospheric neutrinos

    Energy Technology Data Exchange (ETDEWEB)

    Kajita, Takaaki [Research Center for Cosmic Neutrinos, Institute for Cosmic Ray Research, University of Tokyo, Kashiwa-no-ha 5-1-5, Kashiwa, Chiba 277-8582 (Japan)

    2004-12-01

    Neutrino oscillation was discovered through the study of atmospheric neutrinos. Atmospheric neutrinos are produced as decay products in hadronic showers resulting from collisions of cosmic rays with nuclei in the atmosphere. Electron neutrinos and muon neutrinos are produced mainly by the decay chain of charged pions to muons and electrons. Depending on the energy of the neutrinos, atmospheric neutrinos are observed as fully contained events, partially contained events and upward-going muon events. The energy range covered by these events is from a few hundred MeV to >1 TeV. Data from various experiments showed zenith angle- and energy-dependent deficit of {nu}{sub {mu}} events, while {nu}{sub e} events did not show any such effect. It was also shown that the {nu}{sub {mu}} survival probability obeys the sinusoidal function as predicted by neutrino oscillations. Two-flavour {nu}{sub {mu}} {r_reversible} {nu}{sub {tau}} oscillations, with sin{sup 2} 2{theta} > 0.90 and {delta}m{sup 2} in the region of 1.9 x 10{sup -3} to 3.0 x 10{sup -3} eV{sup 2}, explain all these data. Various detailed studies using high statistics atmospheric neutrino data excluded the alternative hypotheses that were proposed to explain the {nu}{sub {mu}} deficit.

  4. The catalytic role of water in the photochemistry of ammonia ice: from diluted to concentrated phase

    Science.gov (United States)

    Jonusas, Mindaugas; Krim, Lahouari

    2017-10-01

    Using infrared spectroscopy as an in situ probe for reactions occurring in the solid phase, we investigated the influence of water molecules on the photochemistry of ammonia ices. Experiments were carried out in diluted and concentrated phases and between 3 and 130 K. We showed that the photolysis of NH3-H2O (2 per cent of H2O) ices using continuous radiation from 115 to 400 nm produces NH2OH as the main photoproduct, but also that such a photoinduced reaction strongly depends on both the initial ice temperature and the environment where the primary reactants NH3 and H2O are trapped. Our experimental results highlight the catalytic role played by H2O molecules in enhancing the formation yield of NH2 during the photolysis process through the NH3 + OH → NH2 + H2O hydrogen abstraction reaction, which is only favored at low temperatures in the range of 3-60 K. During heating of such irradiated ammonia-water ices, the amount of NH2OH keeps rising while that of NH2, is greatly reduced only from 70 K onwards. These behaviours are attributed to the competition that occurs between NH2 formation from the NH3 + OH reaction and its consumption from the NH2 + OH radical recombination. These results might explain the variable abundances of NH2 and NH3 provided by previous astronomical observations, where the NH2/NH3 ratio ranges from 0.02 to 0.5 depending on the regions of the interstellar medium that were analysed.

  5. Provenance effect on carbon assimilation, photochemistry and leaf morphology in Mediterranean Cistus species under chilling stress.

    Science.gov (United States)

    Puglielli, G; Cuevas Román, F J; Catoni, R; Moreno Rojas, J M; Gratani, L; Varone, L

    2017-07-01

    The potential resilience of shrub species to environmental change deserves attention in those areas threatened by climate change, such as the Mediterranean Basin. We asked if leaves produced under different climate conditions through the winter season to spring can highlight the leaf traits involved in determining potential resilience of three Cistus spp. to changing environmental conditions and to what extent intraspecific differences affect such a response. We analysed carbon assimilation, maximum quantum efficiency of PSII photochemistry (F v /F m ) and leaf morphological control of the photosynthetic process in leaves formed through the winter season into spring in C. creticus subsp. eriocephalus (CE), C. salvifolius (CS) and C. monspeliensis (CM) grown from seed of different provenances under common garden conditions. Intraspecific differences were found in F v /F m for CE and CS. Carbon assimilation-related parameters were not affected by provenance. Moreover, our analysis highlighted that the functional relationships investigated can follow seasonal changes and revealed patterns originating from species-specific differences in LMA arising during the favourable period. Cistus spp. have great ability to modify the structure and function of their leaves in the mid-term in order to cope with changing environmental conditions. The F v /F m response to chilling reveals that susceptibility to photoinhibition is a trait under selection in Cistus species. Concerning carbon assimilation, differing ability to control stomatal opening was highlighted between species. Moreover, seasonal changes of the functional relationships investigated can have predictable consequences on species leaf turnover strategies. © 2017 German Botanical Society and The Royal Botanical Society of the Netherlands.

  6. Photochemistry and photobiology of actinic erythema: defensive and reparative cutaneous mechanisms

    Directory of Open Access Journals (Sweden)

    A.C. Tedesco

    1997-05-01

    Full Text Available Sunlight is part of our everyday life and most people accept it as beneficial to our health. With the advance of our knowledge in cutaneous photochemistry, photobiology and photomedicine over the past four decades, the terrestrial solar radiation has become a concern of dermatologists and is considered to be a major damaging environmental factor for our skin. Most photobiological effects (e.g., sunburn, suntanning, local and systemic immunosuppression, photoaging or dermatoheliosis, skin cancer and precancer, etc. are attributed to ultraviolet radiation (UVR and more particularly to UVB radiation (290-320 nm. UVA radiation (320-400 nm also plays an important role in the induction of erythema by the photosensitized generation of reactive oxygen species (singlet oxygen (1O2, superoxide (O2.- and hydroxyl radicals (.OH that damage DNA and cellular membranes, and promote carcinogenesis and the changes associated with photoaging. Therefore, research efforts have been directed at a better photochemical and photobiological understanding of the so-called sunburn reaction, actinic or solar erythema. To survive the insults of actinic damage, the skin appears to have different intrinsic defensive mechanisms, among which antioxidants (enzymatic and non-enzymatic systems play a pivotal role. In this paper, we will review the basic aspects of the action of UVR on the skin: a photochemical reactions resulting from photon absorption by endogenous chromophores; b the lipid peroxidation phenomenon, and c intrinsic defensive cutaneous mechanisms (antioxidant systems. The last section will cover the inflammatory response including mediator release after cutaneous UVR exposure and adhesion molecule expression

  7. Vacuum ultraviolet spectroscopy and photochemistry of zinc dihydride and related molecules in low-temperature matrices.

    Science.gov (United States)

    Henchy, Chris; Kilmartin, Una; McCaffrey, John G

    2013-09-26

    Optical absorption spectra of thin film samples, formed by the codeposition of zinc vapor with D2 and CH4, have been recorded with synchrotron radiation. With sufficiently low metal vapor flux, samples deposited at 4 K were found to consist exclusively of isolated zinc atoms for both solids. The atomic absorption bands in the quantum solids D2 and CH4 were found to exhibit large bandwidths, behavior related to the high lattice frequencies of these low mass solids. The reactivity of atomic zinc was promoted with (1)P state photolysis leading to the first recording of electronic absorption spectra for the molecules ZnD2 and CH3ZnH in the vacuum ultraviolet (VUV) region. (3)P state luminescence of atomic zinc observed in the Zn/CH4 system points to the involvement of the spin triplet state in the relaxation of CH3ZnH system as it evolves into the C3v ground state. This state is not involved in the relaxation of the higher symmetry molecule ZnD2. Time dependent density functional theory (TD-DFT) calculations were conducted to predict the electronic transitions of the inserted molecular species. Comparisons with experimental data indicate the predicted transition energies are approximately 0.5 eV less than the recorded values. Possible reasons for the discrepancy are discussed. The molecular photochemistry of ZnD2 and CH3ZnH observed in the VUV was modeled successfully with a simple four-valence electron AH2 Walsh-type diagram.

  8. The photochemistry of pyrimidine in realistic astrophysical ices and the production of nucleobases

    Energy Technology Data Exchange (ETDEWEB)

    Nuevo, Michel; Materese, Christopher K.; Sandford, Scott A., E-mail: michel.nuevo-1@nasa.gov [NASA Ames Research Center, MS 245-6, Moffett Field, CA 94035 (United States)

    2014-10-01

    Nucleobases, together with deoxyribose/ribose and phosphoric acid, are the building blocks of DNA and RNA for all known life. The presence of nucleobase-like compounds in carbonaceous chondrites delivered to the Earth raises the question of an extraterrestrial origin for the molecules that triggered life on our planet. Whether these molecules are formed in interstellar/protostellar environments, in small parent bodies in the solar system, or both, is currently unclear. Recent experiments show that the UV irradiation of pyrimidine (C{sub 4}H{sub 4}N{sub 2}) in H{sub 2}O-rich ice mixtures that contain NH{sub 3}, CH{sub 3}OH, or CH{sub 4} leads to the formation of the pyrimidine-based nucleobases uracil, cytosine, and thymine. In this work, we discuss the low-temperature UV irradiation of pyrimidine in realistic astrophysical ice mixtures containing H{sub 2}O, CH{sub 3}OH, and NH{sub 3}, with or without CH{sub 4}, to search for the production of nucleobases and other prebiotic compounds. These experiments show the presence of uracil, urea, glycerol, hexamethylenetetramine, small amino acids, and small carboxylic acids in all samples. Cytosine was only found in one sample produced from ices irradiated with a higher UV dose, while thymine was not found in any sample, even after irradiation with a higher UV dose. Results are discussed to evaluate the role of the photochemistry of pyrimidine in the inventory of organic molecules detected in meteorites and their astrophysical/astrobiological implications.

  9. Aerosol effects on the photochemistry in Mexico City during MCMA-2006/MILAGRO campaign

    Directory of Open Access Journals (Sweden)

    G. Li

    2011-06-01

    Full Text Available In the present study, the impact of aerosols on the photochemistry in Mexico City is evaluated using the WRF-CHEM model for the period from 24 to 29 March during the MCMA-2006/MILAGRO campaign. An aerosol radiative module has been developed with detailed consideration of aerosol size, composition, and mixing. The module has been coupled into the WRF-CHEM model to calculate the aerosol optical properties, including optical depth, single scattering albedo, and asymmetry factor. Calculated aerosol optical properties are in good agreement with the surface observations and aircraft and satellite measurements during daytime. In general, the photolysis rates are reduced due to the absorption by carbonaceous aerosols, particularly in the early morning and late afternoon hours with a long aerosol optical path. However, with the growth of aerosol particles and the decrease of the solar zenith angle around noontime, aerosols can slightly enhance photolysis rates when ultraviolet (UV radiation scattering dominates UV absorption by aerosols at the lower-most model layer. The changes in photolysis rates due to aerosols lead to about 2–17 % surface ozone reduction during daytime in the urban area in Mexico City with generally larger reductions during early morning hours near the city center, resulting in a decrease of OH level by about 9 %, as well as a decrease in the daytime concentrations of nitrate and secondary organic aerosols by 5–6 % on average. In addition, the rapid aging of black carbon aerosols and the enhanced absorption of UV radiation by organic aerosols contribute substantially to the reduction of photolysis rates.

  10. 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...

  11. 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

  12. Effect of modified atmosphere packaging and addition of calcium hypochlorite on the atmosphere composition, colour and microbial quality of mushrooms

    CSIR Research Space (South Africa)

    Kuyper, L

    1993-01-01

    Full Text Available The effect of modified atmosphere packaging in combination with the addition of calcium hypochlorite on the atmosphere composition, colour and microbial quality of mushrooms was investigated. A modified atmosphere which slowed down discolouration...

  13. Alarming atmospheres

    DEFF Research Database (Denmark)

    Højlund, Marie; Kinch, Sofie

    2014-01-01

    Nurses working in the Neuro-Intensive Care Unit at Aarhus University Hospital lack the tools to prepare children for the alarming atmosphere they will enter when visiting a hospitalised relative. The complex soundscape dominated by alarms and sounds from equipment is mentioned as the main stressor...

  14. Atmospheric humidity

    Science.gov (United States)

    Water vapor plays a critical role in earth's atmosphere. It helps to maintain a habitable surface temperature through absorption of outgoing longwave radiation, and it transfers trmendous amounts of energy from the tropics toward the poles by absorbing latent heat during evaporation and subsequently...

  15. Combination of electrospray ionization, atmospheric pressure photoionization and laser desorption ionization Fourier transform ion cyclotronic resonance mass spectrometry for the investigation of complex mixtures – Application to the petroleomic analysis of bio-oils

    Energy Technology Data Exchange (ETDEWEB)

    Hertzog, Jasmine [LCP-A2MC, FR 2843 Institut Jean Barriol de Chimie et Physique Moléculaires et Biomoléculaires, FR 3624 Réseau National de Spectrométrie de Masse FT-ICR à très haut champ, Université de Lorraine, ICPM, 1 boulevard Arago, 57078 Metz Cedex 03 (France); Carré, Vincent, E-mail: vincent.carre@univ-lorraine.fr [LCP-A2MC, FR 2843 Institut Jean Barriol de Chimie et Physique Moléculaires et Biomoléculaires, FR 3624 Réseau National de Spectrométrie de Masse FT-ICR à très haut champ, Université de Lorraine, ICPM, 1 boulevard Arago, 57078 Metz Cedex 03 (France); Le Brech, Yann [LRGP, CNRS, Université de Lorraine, ENSIC, 1, Rue Grandville, 54000 Nancy (France); Mackay, Colin Logan [SIRCAMS, School of Chemistry, University of Edinburgh, Edinburgh, EH9 3FJ, Scotland (United Kingdom); Dufour, Anthony [LRGP, CNRS, Université de Lorraine, ENSIC, 1, Rue Grandville, 54000 Nancy (France); Mašek, Ondřej [UK Biochar Research Center, School of Geosciences, University of Edinburgh, Kings Buildings, Edinburgh, EH9 3JN (United Kingdom); and others

    2017-05-29

    The comprehensive description of complex mixtures such as bio-oils is required to understand and improve the different processes involved during biological, environmental or industrial operation. In this context, we have to consider how different ionization sources can improve a non-targeted approach. Thus, the Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR MS) has been coupled to electrospray ionization (ESI), laser desorption ionization (LDI) and atmospheric pressure photoionization (APPI) to characterize an oak pyrolysis bio-oil. Close to 90% of the all 4500 compound formulae has been attributed to C{sub x}H{sub y}O{sub z} with similar oxygen class compound distribution. Nevertheless, their relative abundance in respect with their double bound equivalent (DBE) value has evidenced significant differences depending on the ion source used. ESI has allowed compounds with low DBE but more oxygen atoms to be ionized. APPI has demonstrated the efficient ionization of less polar compounds (high DBE values and less oxygen atoms). The LDI behavior of bio-oils has been considered intermediate in terms of DBE and oxygen amounts but it has also been demonstrated that a significant part of the features are specifically detected by this ionization method. Thus, the complementarity of three different ionization sources has been successfully demonstrated for the exhaustive characterization by petroleomic approach of a complex mixture. - Highlights: • Non-targeted mass spectrometry by combining electrospray ionization, atmospheric pressure photoionization and laser/desorption ionization. • Exhaustive description of pyrolytic bio-oil components. • Distinction of sugaric derivatives, lignin derivatives and lipids contained in a woody-based pyrolytic bio-oil.

  16. The influence of scales of atmospheric motion on air pollution over Portugal

    Science.gov (United States)

    Russo, Ana; Trigo, Ricardo; Mendes, Manuel; Jerez, Sonia; Gouveia, Célia Marina

    2014-05-01

    Air pollution is determined by the combination of different factors, namely, emissions, physical constrains, meteorology and chemical processes [1,2,3]. The relative importance of such factors is influenced by their interaction on diverse scales of atmospheric motion. Each scale depicts different meteorological conditions, which, when combined with the different air pollution sources and photochemistry, result in varying ambient concentrations [2]. Identifying the dominant scales of atmospheric motion over a given airshed can be of great importance for many applications such as air pollution and pollen dispersion or wind energy management [2]. Portugal has been affected by numerous air pollution episodes during the last decade. These episodes are often related to peak emissions from local industry or transport, but can also be associated to regional transport from other urban areas or to exceptional emission events, such as forest fires. This research aims to identify the scales of atmospheric motion which contribute to an increase of air pollution. A method is proposed for differentiating between the scales of atmospheric motion that can be applied on a daily basis from data collected at several wind-measuring sites in a given airshed and to reanalysis datasets. The method is based on the daily mean wind recirculation and the mean and standard deviation between sites. The determination of the thresholds between scales is performed empirically following the approach of Levy et al. [2] and also through a automatic statistical approach computed taking into account the tails of the distributions (e.g. 95% and 99% percentile) of the different wind samples. A comparison is made with two objective approaches: 1) daily synoptic classification for the same period over the region [4] and 2) a 3-D backward trajectory approach [5,6] for specific episodes. Furthermore, the outcomes are expected to support the Portuguese authorities on the implementation of strategies for a

  17. Atmospheric Change on Pluto

    Science.gov (United States)

    Person, Michael

    2013-10-01

    We propose to use SOFIA with HIPO and FLITECAM (FLIPO) to measure the parameters of Pluto's atmosphere (temperature, pressure, possible particulate haze) by observing a stellar occultation by Pluto on 15 November 2014. Due to its highly elliptical orbit and seasonally variable obliquity, Pluto's atmosphere is predicted to condense onto its surface within the next ~10 years and possibly within the next few years and thus frequent observations are critical. Detection of the occultation central flash will allow measurement of the structure of Pluto's lower atmosphere and atmospheric oblateness. We will use FLIPO to measure the refracted starlight contemporaneously at visible and infrared wavelengths; this approach is needed to differentiate between two competing explanations for the deficiency in the observed light refracted from Pluto's lower atmosphere (strong thermal gradients versus variable particulate extinction). Only an airborne platform such as SOFIA has the flexibility to place a large telescope in the center of the shadow path of this brief event while at the same time nearly eliminating the possibility of missing time-critical observations due to unfortunate weather systems. Occultation predictions will be updated throughout the period preceding the observations with the goal of achieving sufficient prediction accuracy at the event time to place SOFIA directly in the path of Pluto's central flash. This SOFIA observation will be combined with our ongoing ground-based observing program whose goal is to measure the temporal variability of Pluto's atmosphere in response to its changing seasonal obliquity (and resulting ice migration) and recession from the sun. For the NASA New Horizons mission to Pluto and the Kuiper Belt, this Pluto occultation event represents the last chance, prior to the spacecraft closest approach to the Pluto/Charon system (July 2015), to provide input to the mission for encounter planning, as well as context and supporting atmospheric

  18. Exogenous Calcium Enhances the Photosystem II Photochemistry Response in Salt Stressed Tall Fescue

    Directory of Open Access Journals (Sweden)

    Guangyang Wang

    2017-11-01

    Full Text Available Calcium enhances turfgrass response to salt stress. However, little is known about PSII photochemical changes when exogenous calcium was applied in salinity-stressed turfgrass. Here, we probe into the rearrangements of PSII electron transport and endogenous ion accumulation in tall fescue (Festuca arundinacea Schreber treated with exogenous calcium under salt stress. Three-month-old seedlings of genotype “TF133” were subjected to the control (CK, salinity (S, salinity + calcium nitrate (SC, and salinity + ethylene glycol tetraacetic acid (SE. Calcium nitrate and ethylene glycol tetraacetic acid was used as exogenous calcium donor and calcium chelating agent respectively. At the end of a 5-day duration treatment, samples in SC regime had better photochemistry performance on several parameters than salinity only. Such as the Area (equal to the plastoquinone pool size, N (number of QA- redox turnovers until Fm is reached, ψE0, or δRo (Efficiencdy/probability with which a PSII trapped electron is transferred from QA to QB or PSI acceptors, ABS/RC (Absorbed photon flux per RC. All the above suggested that calcium enhanced the electron transfer of PSII (especially beyond QA- and prevented reaction centers from inactivation in salt-stressed tall fescue. Furthermore, both grass shoot and root tissues generally accumulated more C, N, Ca2+, and K+ in the SC regime than S regime. Interrelated analysis indicated that ψE0, δRo, ABS/RC, C, and N content in shoots was highly correlated to each other and significantly positively related to Ca2+ and K+ content in roots. Besides, high salt increased ATP6E and CAMK2 transcription level in shoot at 1 and 5 day, respectively while exogenous calcium relieved it. In root, CAMK2 level was reduced by Salinity at 5 day and exogenous calcium recovered it. These observations involved in electron transport capacity and ion accumulation assist in understanding better the protective role of exogenous calcium in tall

  19. Lysozyme Photochemistry as a Function of Temperature. The Protective Effect of Nanoparticles on Lysozyme Photostability.

    Directory of Open Access Journals (Sweden)

    Catarina Oliveira Silva

    Full Text Available The presence of aromatic residues and their close spatial proximity to disulphide bridges makes hen egg white lysozyme labile to UV excitation. UVB induced photo-oxidation of tryptophan and tyrosine residues leads to photochemical products, such as, kynurenine, N-formylkynurenine and dityrosine and to the disruption of disulphide bridges in proteins. We here report that lysozyme UV induced photochemistry is modulated by temperature, excitation power, illumination time, excitation wavelength and by the presence of plasmonic quencher surfaces, such as gold, and by the presence of natural fluorescence quenchers, such as hyaluronic acid and oleic acid. We show evidence that the photo-oxidation effects triggered by 295 nm at 20°C are reversible and non-reversible at 10°C, 25°C and 30°C. This paper provides evidence that the 295 nm damage threshold of lysozyme lies between 0.1 μW and 0.3 μW. Protein conformational changes induced by temperature and UV light have been detected upon monitoring changes in the fluorescence emission spectra of lysozyme tryptophan residues and SYPRO® Orange. Lysozyme has been conjugated onto gold nanoparticles, coated with hyaluronic acid and oleic acid (HAOA. Steady state and time resolved fluorescence studies of free and conjugated lysozyme onto HAOA gold nanoparticles reveals that the presence of the polymer decreased the rate of the observed photochemical reactions and induced a preference for short fluorescence decay lifetimes. Size and surface charge of the HAOA gold nanoparticles have been determined by dynamic light scattering and zeta potential measurements. TEM analysis of the particles confirms the presence of a gold core surrounded by a HAOA matrix. We conclude that HAOA gold nanoparticles may efficiently protect lysozyme from the photochemical effects of UVB light and this nanocarrier could be potentially applied to other proteins with clinical relevance. In addition, this study confirms that the

  20. Photochemistry and kinetics of gas phase reactions involving HO and Cl radicals

    Energy Technology Data Exchange (ETDEWEB)

    Nelson, H.H.

    1980-11-01

    The kinetics of the reaction of the HO radical with HNO/sub 3/ and H/sub 2/O/sub 2/, the kinetics of Cl atom reactions with ClNO and ClNO/sub 2/, and the photochemistry of ClNO/sub 2/ and ClONO/sub 2/ were examined. The ultraviolet absorption cross sections of HNO/sub 3/ and ClNO/sub 2/ were also determined as part of the kinetics work. The rate constant for the reaction of HO with HNO/sub 3/ at room temperature was measured to be (8.2 +- 1.8) x 10/sup -14/ cm/sup 3/ molecule/sup -1/ s/sup -1/, where the uncertainty reported here and in all cases reflects twice the experimental standard deviation plus an estimate of systematic errors. The rate constant for the reaction HO + H/sub 2/O/sub 2/ was measured as (1.57 +- 0.23) x 10/sup -12/ cm/sup 3/ molecule/sup -1/ s/sup -1/. This agrees well with the two latest determinations and serves as a calibration of the experimental apparatus used. The Cl + ClNO reaction rate constant was determined to be (1.65 +- 0.32) x 10/sup -11/ cm/sup 3/ molecule/sup -1/ s/sup -1/. The rate constant for the reaction of Cl + ClNO/sub 2/ was found to be (5.05 +- 0.75) x 10/sup -12/ cm/sup 3/ molecule/sup -1/ s/sup -1/. This is the first direct measurement of this rate constant. The photodissociation of ClNO/sub 2/ was studied in great detail. The absorption cross sections were measured in the ultraviolet and found to be substantially lower than the literature values in the Cl/sub 2/ absorption region (300 to 360 nm). Two product channels were investigated; products representative of the two channels were Cl and O atoms. Absolute calibration for the product detection systems was provided by Cl/sub 2/ and NO/sub 2/ photolysis respectively. The quantum uields measured for photolysis at 350 nm, calcualted using the absorption spectrum measured in this work, are: 0.93 +- 0.1 for Cl and less than or equal to 0.025 for O. An upper limit of 0.1 was measured for the O atom channel in ClOHO/sub 2/ photolysis.

  1. Atmospheric materiality

    DEFF Research Database (Denmark)

    Wieczorek, Izabela

    2016-01-01

    A disjunction between the material and the immaterial has been at the heart of the architectural debate for decades. In this dialectic tension, the notion of atmosphere which increasingly claims attention in architectural discourse seems to be parallactic, leading to the re-evaluation of perceptual...... experience and, consequently, to the conceptual and methodological shifts in the production of space, and hence in the way we think about materiality. In this context, architectural space is understood as a contingent construction – a space of engagement that appears to us as a result of continuous...... and complex interferences revealed through our perception; ‘the atmospheric’ is explored as a spatial and affective quality as well as a sensory background, and materiality as a powerful and almost magical agency in shaping of atmosphere. Challenging existing dichotomies and unraveling intrinsic...

  2. [A Study of Data From the Photochemistry of Ozone Loss in the Arctic Region In Summer (POLARIS) Mission

    Science.gov (United States)

    Newman, Paul A.; Fahey, David W.; Brune, William H.; Kurylo, Michael J.; Kawa, S. Randolph

    1999-01-01

    The Photochemistry of Ozone Loss in the Arctic Region In Summer (POLARIS) mission was designed to investigate the natural summer decrease of stratospheric ozone levels. Both polar regions have large and distinct annual cycles of ozone column amounts. In northern spring, the average level is over 450 Dobson units (DU), decreasing to less than 275 DU by September. In order to cover this period of ozone decrease, POLARIS was conducted in three deployment phases from Fairbanks, Alaska, (650N) during the summer of 1997. The principal measurement platforms were the NASA ER-2 high-altitude aircraft and stratospheric balloons. Additional measurements were provided by ground-based instruments, sondes, and satellites. POLARIS observations included ozone, meteorological variables, particles, long-lived chemicals, and short-lived radicals. During the field deployments, several modeling and theoretical groups participated in flight planning and data evaluation activities. The interpretive studies in this Special Section of the Journal of Geophysical Research are a first comprehensive examination of the POLARIS data set, addressing stratospheric ozone abundances and its changes; the role of aerosols; details of the photochemistry of reactive species; transport of stratospheric air and the correlations of long-lived species; and measurement intercomparisons.

  3. Actinometric measurements of NO2 photolysis frequencies in the atmosphere simulation chamber SAPHIR

    Directory of Open Access Journals (Sweden)

    B. Bohn

    2005-01-01

    Full Text Available The simulation chamber SAPHIR at Forschungszentrum Jülich has UV permeable teflon walls facilitating atmospheric photochemistry studies under the influence of natural sunlight. Because the internal radiation field is strongly affected by construction elements, we use external, radiometric measurements of spectral actinic flux and a model to calculate mean photolysis frequencies for the chamber volume Bohn04B. In this work we determine NO2 photolysis frequencies j(NO2 within SAPHIR using chemical actinometry by injecting NO2 and observing the chemical composition during illumination under various external conditions. In addition to a photo-stationary approach, a time-dependent method was developed to analyse the data. These measurements had two purposes. Firstly, to check the model predictions with respect to diurnal and seasonal variations in the presence of direct sunlight and secondly to obtain an absolute calibration factor for the combined radiometry-model approach. We obtain a linear correlation between calculated and actinometric j(NO2. A calibration factor of 1.34±0.10 is determined, independent of conditions in good approximation. This factor is in line with expectations and can be rationalised by internal reflections within the chamber. Taking into account the uncertainty of the actinometric j(NO2, an accuracy of 13% is estimated for the determination of j(NO2 in SAPHIR. In separate dark experiments a rate constant of (1.93±0.12x10-14 cm3 s-1 was determined for the NO+O3 reaction at 298K using analytical and numerical methods of data analysis.

  4. Mapping Vinyl Cyanide and Other Nitriles in Titan’s Atmosphere Using ALMA

    Energy Technology Data Exchange (ETDEWEB)

    Lai, J. C.-Y.; Cordiner, M. A.; Nixon, C. A.; Achterberg, R. K.; Molter, E. M.; Palmer, M. Y.; Charnley, S. B.; Lindberg, J. E.; Mumma, M. J. [NASA Goddard Space Flight Center, 8800 Greenbelt Road, Greenbelt, MD 20771 (United States); Teanby, N. A. [School of Earth Sciences, University of Bristol, Wills Memorial Building, Queen’s Road, Bristol, BS8 1RJ (United Kingdom); Kisiel, Z. [Institute of Physics, Polish Academy of Sciences, Al. Lotnikøw 32/46, 02-668 Warszawa (Poland); Irwin, P. G. J., E-mail: martin.cordiner@nasa.gov [Atmospheric, Oceanic and Planetary Physics, Clarendon Laboratory, University of Oxford, Parks Road, Oxford, OX1 3PU (United Kingdom)

    2017-11-01

    Vinyl cyanide (C{sub 2}H{sub 3}CN) is theorized to form in Titan’s atmosphere via high-altitude photochemistry and is of interest regarding the astrobiology of cold planetary surfaces due to its predicted ability to form cell membrane-like structures (azotosomes) in liquid methane. In this work, we follow up on the initial spectroscopic detection of C{sub 2}H{sub 3}CN on Titan by Palmer et al. with the detection of three new C{sub 2}H{sub 3}CN rotational emission lines at submillimeter frequencies. These new, high-resolution detections have allowed for the first spatial distribution mapping of C{sub 2}H{sub 3}CN on Titan. We present simultaneous observations of C{sub 2}H{sub 5}CN, HC{sub 3}N, and CH{sub 3}CN emission, and obtain the first (tentative) detection of C{sub 3}H{sub 8} (propane) at radio wavelengths. We present disk-averaged vertical abundance profiles, two-dimensional spatial maps, and latitudinal flux profiles for the observed nitriles. Similarly to HC{sub 3}N and C{sub 2}H{sub 5}CN, which are theorized to be short-lived in Titan’s atmosphere, C{sub 2}H{sub 3}CN is most abundant over the southern (winter) pole, whereas the longer-lived CH{sub 3}CN is more concentrated in the north. This abundance pattern is consistent with the combined effects of high-altitude photochemical production, poleward advection, and the subsequent reversal of Titan’s atmospheric circulation system following the recent transition from northern to southern winter. We confirm that C{sub 2}H{sub 3}CN and C{sub 2}H{sub 5}CN are most abundant at altitudes above 200 km. Using a 300 km step model, the average abundance of C{sub 2}H{sub 3}CN is found to be 3.03 ± 0.29 ppb, with a C{sub 2}H{sub 5}CN/C{sub 2}H{sub 3}CN abundance ratio of 2.43 ± 0.26. Our HC{sub 3}N and CH{sub 3}CN spectra can be accurately modeled using abundance gradients above the tropopause, with fractional scale-heights of 2.05 ± 0.16 and 1.63 ± 0.02, respectively.

  5. Mapping Vinyl Cyanide and Other Nitriles in Titan’s Atmosphere Using ALMA

    Science.gov (United States)

    Lai, J. C.-Y.; Cordiner, M. A.; Nixon, C. A.; Achterberg, R. K.; Molter, E. M.; Teanby, N. A.; Palmer, M. Y.; Charnley, S. B.; Lindberg, J. E.; Kisiel, Z.; Mumma, M. J.; Irwin, P. G. J.

    2017-11-01

    Vinyl cyanide (C2H3CN) is theorized to form in Titan’s atmosphere via high-altitude photochemistry and is of interest regarding the astrobiology of cold planetary surfaces due to its predicted ability to form cell membrane-like structures (azotosomes) in liquid methane. In this work, we follow up on the initial spectroscopic detection of C2H3CN on Titan by Palmer et al. with the detection of three new C2H3CN rotational emission lines at submillimeter frequencies. These new, high-resolution detections have allowed for the first spatial distribution mapping of C2H3CN on Titan. We present simultaneous observations of C2H5CN, HC3N, and CH3CN emission, and obtain the first (tentative) detection of C3H8 (propane) at radio wavelengths. We present disk-averaged vertical abundance profiles, two-dimensional spatial maps, and latitudinal flux profiles for the observed nitriles. Similarly to HC3N and C2H5CN, which are theorized to be short-lived in Titan’s atmosphere, C2H3CN is most abundant over the southern (winter) pole, whereas the longer-lived CH3CN is more concentrated in the north. This abundance pattern is consistent with the combined effects of high-altitude photochemical production, poleward advection, and the subsequent reversal of Titan’s atmospheric circulation system following the recent transition from northern to southern winter. We confirm that C2H3CN and C2H5CN are most abundant at altitudes above 200 km. Using a 300 km step model, the average abundance of C2H3CN is found to be 3.03 ± 0.29 ppb, with a C2H5CN/C2H3CN abundance ratio of 2.43 ± 0.26. Our HC3N and CH3CN spectra can be accurately modeled using abundance gradients above the tropopause, with fractional scale-heights of 2.05 ± 0.16 and 1.63 ± 0.02, respectively.

  6. Aerosol influence on energy balance of the middle atmosphere of Jupiter

    Science.gov (United States)

    Zhang, Xi; West, Robert A.; Irwin, Patrick G. J.; Nixon, Conor A.; Yung, Yuk L.

    2015-12-01

    Aerosols are ubiquitous in planetary atmospheres in the Solar System. However, radiative forcing on Jupiter has traditionally been attributed to solar heating and infrared cooling of gaseous constituents only, while the significance of aerosol radiative effects has been a long-standing controversy. Here we show, based on observations from the NASA spacecraft Voyager and Cassini, that gases alone cannot maintain the global energy balance in the middle atmosphere of Jupiter. Instead, a thick aerosol layer consisting of fluffy, fractal aggregate particles produced by photochemistry and auroral chemistry dominates the stratospheric radiative heating at middle and high latitudes, exceeding the local gas heating rate by a factor of 5-10. On a global average, aerosol heating is comparable to the gas contribution and aerosol cooling is more important than previously thought. We argue that fractal aggregate particles may also have a significant role in controlling the atmospheric radiative energy balance on other planets, as on Jupiter.

  7. Aerosol influence on energy balance of the middle atmosphere of Jupiter.

    Science.gov (United States)

    Zhang, Xi; West, Robert A; Irwin, Patrick G J; Nixon, Conor A; Yung, Yuk L

    2015-12-22

    Aerosols are ubiquitous in planetary atmospheres in the Solar System. However, radiative forcing on Jupiter has traditionally been attributed to solar heating and infrared cooling of gaseous constituents only, while the significance of aerosol radiative effects has been a long-standing controversy. Here we show, based on observations from the NASA spacecraft Voyager and Cassini, that gases alone cannot maintain the global energy balance in the middle atmosphere of Jupiter. Instead, a thick aerosol layer consisting of fluffy, fractal aggregate particles produced by photochemistry and auroral chemistry dominates the stratospheric radiative heating at middle and high latitudes, exceeding the local gas heating rate by a factor of 5-10. On a global average, aerosol heating is comparable to the gas contribution and aerosol cooling is more important than previously thought. We argue that fractal aggregate particles may also have a significant role in controlling the atmospheric radiative energy balance on other planets, as on Jupiter.

  8. Astronomy and Atmospheric Optics

    Science.gov (United States)

    Cowley, Les; Gaina, Alex

    2011-12-01

    The authors discusse the insuccess of the observation of the Total Eclipse of the Moon from 10 december 2011 in Romania and relate them with meteoconditions. Only a very short part of the last penumbral phase was observed, while the inital part and the totality was not observed due to very dense clouds. The change in color and brightness during this phase was signaled. Meanwhile, there is an area of science where clouds are of great use and interest. This area is Atmospheric optics, while the science which study clouds is meteorology. Clouds in combination with Solar and Moon light could give rise to a variety of strange, rare and unobvious phenomena in the atmosphere (sky), sometimes confused with Unidentified Flying Objects (UFO). The importance of meteorology for astronomy and atmospheric optics is underlined and an invitation to astronomers to use unfavourable days for athmospheric observations was sent. The web address of the site by Les Cowley, designed for atmospheric optics phenomena is contained in the text of the entry.

  9. Atmospheric Production of Perchlorate on Earth and Mars

    Science.gov (United States)

    Claire, M.; Catling, D. C.; Zahnle, K. J.

    2009-12-01

    Natural production and preservation of perchlorate on Earth occurs only in arid environments. Isotopic evidence suggests a strong role for atmospheric oxidation of chlorine species via pathways including ozone or its photochemical derivatives. As the Martian atmosphere is both oxidizing and drier than the driest places on Earth, we propose an atmospheric origin for the Martian perchlorates measured by NASA's Phoenix Lander. A variety of hypothetical formation pathways can be proposed including atmospheric photochemical reactions, electrostatic discharge, and gas-solid reactions. Here, we investigate gas phase formation pathways using a 1-D photochemical model (Catling et al. 2009, accepted by JGR). Because perchlorate-rich deposits in the Atacama desert are closest in abundance to perchlorate measured at NASA's Phoenix Lander site, we start with a study of the means to produce Atacama perchlorate. We found that perchlorate can be produced in sufficient quantities to explain the abundance of perchlorate in the Atacama from a proposed gas phase oxidation of chlorine volatiles to perchloric acid. These results are sensitive to estimated reaction rates for ClO3 species. The feasibility of gas phase production for the Atacama provides justification for further investigations of gas phase photochemistry as a possible source for Martian perchlorate. In addition to the Atacama results, we will present a preliminary study incorporating chlorine chemistry into an existing Martian photochemical model (Zahnle et al. JGR 2008).

  10. Heterofunctional Glycopolypeptides by Combination of Thiol-Ene Chemistry and NCA Polymerization.

    Science.gov (United States)

    Krannig, Kai-Steffen; Schlaad, Helmut

    2016-01-01

    Glycopolypeptides are prepared either by the polymerization of glycosylated amino acid N-carboxyanhydrides (NCAs) or by the post-polymerization functionalization of polypeptides with suitable functional groups. Here we present a method for the in-situ functionalization and (co-) polymerization of allylglycine N-carboxyanhydride in a facile one-pot procedure, combining radical thiol-ene photochemistry and nucleophilic ring-opening polymerization techniques, to yield well-defined heterofunctional glycopolypeptides.

  11. Scientific investigations of atmospheric processes

    Science.gov (United States)

    1994-01-01

    Research was performed in atmospheric, dynamical, and thermodynamical processes and in other disciplines necessary to accomplish the following tasks: develop procedures for combining generalized radiative transfer codes with dynamic atmospheric model codes; perform diagnostic analysis of atmospheric processes to gain a better understanding of the evolution and development of mesoscale circulation systems and their precipitation structures; and to develop algorithms and software necessary to graphically display diagnostic sets on the MSFC McIDAS and EADS to facilitate scientific study and sensor capability evaluation. Research activities during this reporting period are detailed.

  12. Photochemistry and electron-transfer mechanism of transition metal oxalato complexes excited in the charge transfer band.

    Science.gov (United States)

    Chen, Jie; Zhang, Hua; Tomov, Ivan V; Ding, Xunliang; Rentzepis, Peter M

    2008-10-07

    The photoredox reaction of trisoxalato cobaltate (III) has been studied by means of ultrafast extended x-ray absorption fine structure and optical transient spectroscopy after excitation in the charge-transfer band with 267-nm femtosecond pulses. The Co-O transient bond length changes and the optical spectra and kinetics have been measured and compared with those of ferrioxalate. Data presented here strongly suggest that both of these metal oxalato complexes operate under similar photoredox reaction mechanisms where the primary reaction involves the dissociation of a metal-oxygen bond. These results also indicate that excitation in the charge-transfer band is not a sufficient condition for the intramolecular electron transfer to be the dominant photochemistry reaction mechanism.

  13. Estimated SAGE II ozone mixing ratios in early 1993 and comparisons with Stratospheric Photochemistry, Aerosols and Dynamic Expedition measurements

    Science.gov (United States)

    Yue, G. K.; Veiga, R. E.; Poole, L. R.; Zawodny, J. M.; Proffitt, M. H.

    1994-01-01

    An empirical time-series model for estimating ozone mixing ratios based on Stratospheric Aerosols and Gas Experiment II (SAGE II) monthly mean ozone data for the period October 1984 through June 1991 has been developed. The modeling results for ozone mixing ratios in the 10- to 30- km region in early months of 1993 are presented. In situ ozone profiles obtained by a dual-beam UV-absorption ozone photometer during the Stratospheric Photochemistry, Aerosols and Dynamics Expedition (SPADE) campaign, May 1-14, 1993, are compared with the model results. With the exception of two profiles at altitudes below 16 km, ozone mixing ratios derived by the model and measured by the ozone photometer are in relatively good agreement within their individual uncertainties. The identified discrepancies in the two profiles are discussed.

  14. Collision-Induced Dissociation Study of Strong Hydrogen-Bonded Cluster Ions Y−(HF)n (Y=F, O2) Using Atmospheric Pressure Corona Discharge Ionization Mass Spectrometry Combined with a HF Generator

    Science.gov (United States)

    Sakamoto, Kenya; Sekimoto, Kanako; Takayama, Mitsuo

    2017-01-01

    Hydrogen fluoride (HF) was produced by a homemade HF generator in order to investigate the properties of strong hydrogen-bonded clusters such as (HF)n. The HF molecules were ionized in the form of complex ions associated with the negative core ions Y− produced by atmospheric pressure corona discharge ionization (APCDI). The use of APCDI in combination with the homemade HF generator led to the formation of negative-ion HF clusters Y−(HF)n (Y=F, O2), where larger clusters with n≥4 were not detected. The mechanisms for the formation of the HF, F−(HF)n, and O2−(HF)n species were discussed from the standpoints of the HF generator and APCDI MS. By performing energy-resolved collision-induced dissociation (CID) experiments on the cluster ions F−(HF)n (n=1–3), the energies for the loss of HF from F−(HF)3, F−(HF)2, and F−(HF) were evaluated to be 1 eV or lower, 1 eV or higher, and 2 eV, respectively, on the basis of their center-of-mass energy (ECM). These ECM values were consistent with the values of 0.995, 1.308, and 2.048 eV, respectively, obtained by ab initio calculations. The stability of [O2(HF)n]− (n=1–4) was discussed on the basis of the bond lengths of O2H–F−(HF)n and O2−H–F(HF)n obtained by ab initio calculations. The calculations indicated that [O2(HF)4]− separated into O2H and F−(HF)3. PMID:28966900

  15. Collision-Induced Dissociation Study of Strong Hydrogen-Bonded Cluster Ions Y-(HF) n (Y=F, O2) Using Atmospheric Pressure Corona Discharge Ionization Mass Spectrometry Combined with a HF Generator.

    Science.gov (United States)

    Sakamoto, Kenya; Sekimoto, Kanako; Takayama, Mitsuo

    2017-01-01

    Hydrogen fluoride (HF) was produced by a homemade HF generator in order to investigate the properties of strong hydrogen-bonded clusters such as (HF) n . The HF molecules were ionized in the form of complex ions associated with the negative core ions Y - produced by atmospheric pressure corona discharge ionization (APCDI). The use of APCDI in combination with the homemade HF generator led to the formation of negative-ion HF clusters Y - (HF) n (Y=F, O 2 ), where larger clusters with n ≥4 were not detected. The mechanisms for the formation of the HF, F - (HF) n , and O 2 - (HF) n species were discussed from the standpoints of the HF generator and APCDI MS. By performing energy-resolved collision-induced dissociation (CID) experiments on the cluster ions F - (HF) n ( n =1-3), the energies for the loss of HF from F - (HF) 3 , F - (HF) 2 , and F - (HF) were evaluated to be 1 eV or lower, 1 eV or higher, and 2 eV, respectively, on the basis of their center-of-mass energy ( E CM ). These E CM values were consistent with the values of 0.995, 1.308, and 2.048 eV, respectively, obtained by ab initio calculations. The stability of [O 2 (HF) n ] - ( n =1-4) was discussed on the basis of the bond lengths of O 2 H-F - (HF) n and O 2 - H-F(HF) n obtained by ab initio calculations. The calculations indicated that [O 2 (HF) 4 ] - separated into O 2 H and F - (HF) 3 .

  16. Compact Solid-State 213 nm Laser Enables Standoff Deep Ultraviolet Raman Spectrometer: Measurements of Nitrate Photochemistry.

    Science.gov (United States)

    Bykov, Sergei V; Mao, Michael; Gares, Katie L; Asher, Sanford A

    2015-08-01

    We describe a new compact acousto-optically Q-switched diode-pumped solid-state (DPSS) intracavity frequency-tripled neodymium-doped yttrium vanadate laser capable of producing ~100 mW of 213 nm power quasi-continuous wave as 15 ns pulses at a 30 kHz repetition rate. We use this new laser in a prototype of a deep ultraviolet (UV) Raman standoff spectrometer. We use a novel high-throughput, high-resolution Echelle Raman spectrograph. We measure the deep UV resonance Raman (UVRR) spectra of solid and solution sodium nitrate (NaNO3) and ammonium nitrate (NH4NO3) at a standoff distance of ~2.2 m. For this 2.2 m standoff distance and a 1 min spectral accumulation time, where we only monitor the symmetric stretching band, we find a solid state NaNO3 detection limit of ~100 μg/cm(2). We easily detect ~20 μM nitrate water solutions in 1 cm path length cells. As expected, the aqueous solutions UVRR spectra of NaNO3 and NH4NO3 are similar, showing selective resonance enhancement of the nitrate (NO3(-)) vibrations. The aqueous solution photochemistry is also similar, showing facile conversion of NO3(-) to nitrite (NO2(-)). In contrast, the observed UVRR spectra of NaNO3 and NH4NO3 powders significantly differ, because their solid-state photochemistries differ. Whereas solid NaNO3 photoconverts with a very low quantum yield to NaNO2, the NH4NO3 degrades with an apparent quantum yield of ~0.2 to gaseous species.

  17. Informal Conference on Photochemistry Held in Atlanta, Georgia on 26 April-1 May, 1992

    Science.gov (United States)

    1992-05-01

    Cloud Waters" 3 4:10 - 4:30 L3 G.N. Robinson, D.R Worsnop, M.S. Zahniser, C.E. Kolb, W.DeBruyn, S. Duan, and P. Davidovits , "Heterogeneous Chemistry...and Paul Davidovits , - Boston College, Chestnut Hill, MA 02167 3 Heterogeneous gas/liquid processes play an important role in atmospheric chemical...B4 Davidovits , P ....................................... L3 Davis, D. D

  18. Combined 2-m and Interpolated 10-m Bathymetric Grid of National Oceanic and Atmospheric Administration (NOAA) Survey H12013 Off the Entrance to the Connecticut River in Northeastern Long Island Sound (H12013_INTGEO, Geographic, WGS-84)

    Data.gov (United States)

    U.S. Geological Survey, Department of the Interior — The U.S. Geological Survey (USGS), in cooperation with the National Oceanic and Atmospheric Administration (NOAA) and the Connecticut Department of Energy and...

  19. Rate Constant for the Reaction CH3 + CH3 Yields C2H6 at T = 155 K and Model Calculation of the CH3 Abundance in the Atmospheres of Saturn and Neptune

    Science.gov (United States)

    Cody, Regina J.; Romani, Paul N.; Nesbitt, Fred L.; Iannone, Mark A.; Tardy, Dwight C.; Stief, Louis J.

    2003-01-01

    The column abundances of CH3 observed by the Infrared Space Observatory (ISO) satellite on Saturn and Neptune were lower than predicted by atmospheric photochemical models, especially for Saturn. It has been suggested that the models underestimated the loss of CH3 due to poor knowledge of the rate constant k of the CH3 + CH3 self-reaction at the low temperatures and pressures of these atmospheres. Motivated by this suggestion, we undertook a combined experimental and photochemical modeling study of the CH3 + CH3 reaction and its role in determining planetary CH3 abundances. In a discharge flow-mass spectrometer system, k was measured at T = 155 K and three pressures of He. The results in units of cu cm/molecule/s are k(0.6 Torr) = 6.82 x 10(exp -11), k(1.0 Torr) = 6.98 x 10(exp -11), and k(1.5 Torr) = 6.91 x 10(exp -11). Analytical expressions for k were derived that (1) are consistent with the present laboratory data at T = 155 K, our previous data at T = 202 K and 298 K, and those of other studies in He at T = 296-298 K and (2) have some theoretical basis to provide justification for extrapolation. The derived analytical expressions were then used in atmospheric photochemical models for both Saturn and Neptune. These model results reduced the disparity with observations of Saturn, but not with observations of Neptune. However, the disparity for Neptune is much smaller. The solution to the remaining excess CH3 prediction in the models relative to the ISO observations lies, to a large extent, elsewhere in the CH3 photochemistry or transport, not in the CH3 + CH3 rate.

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

    Science.gov (United States)

    Imanaka, Hiroshi; Smith, Mark A.

    2010-01-01

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

  1. 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.

  2. Chasing Neoproterozoic Atmospheric Oxygen Ghosts

    Science.gov (United States)

    Bjerrum, C. J.; Canfield, D. E.; Dahl, T. W.

    2016-12-01

    Increasing atmospheric oxygen has been considered a necessary condition for the evolution of animal life for over half a century. While direct proxies for atmospheric oxygen are difficult to obtain, a number of indirect proxies have been giving us a ghost image of rising atmospheric oxygen at the close of the Precambrian. In this context, redox sensitive elements and isotopes represent the hallmark for a significant reduction in anoxic areas of the world ocean, implicating a significant rise of atmospheric oxygen during the Neoproterozoic. Here, we test to what degree redox sensitive elements in ancient marine sediments are proxies of atmospheric oxygen. We model the redox-chemical evolution of the shelf seas and ocean using a combination of 3D high resolution shelf sea models and a simpler global ocean biogeochemical model including climate weathering feedbacks, a free sea level and parameterized icecaps. We find that ecosystem evolution would have resulted in reorganization of the nutrient and redox balance of the shelf-ocean system causing a significant increase in oxygenated areas that permitted a boosting of trace metal concentrations in the remaining anoxic areas. While this reorganization takes place there is limited net change in the modelled atmospheric oxygen, warning us against interpreting changing trace metal concentrations and isotopes as reflecting a rise in atmospheric oxygen.

  3. Atmospheric contamination during ultrasonic scaling

    NARCIS (Netherlands)

    Timmerman, MF; Menso, L; Steinfort, J; van Winkelhoff, AJ; van der Weijden, GA

    Objective: The aim of this study was to determine the microbial atmospheric contamination during initial periodontal treatment using a piezoelectric ultrasonic scaler in combination with either high-volume evacuation (HVE) or conventional dental suction (CDS). Methods: The study included 17

  4. Cl2O photochemistry: ultraviolet/vis absorption spectrum temperature dependence and O(3P) quantum yield at 193 and 248 nm.

    Science.gov (United States)

    Papanastasiou, Dimitrios K; Feierabend, Karl J; Burkholder, James B

    2011-05-28

    The photochemistry of Cl(2)O (dichlorine monoxide) was studied using measurements of its UV/vis absorption spectrum temperature dependence and the O((3)P) atom quantum yield, Φ(Cl(2)O)(O)(λ), in its photolysis at 193 and 248 nm. The Cl(2)O UV/vis absorption spectrum was measured over the temperature range 201-296 K between 200 and 500 nm using diode array spectroscopy. Cl(2)O absorption cross sections, σ(Cl(2)O)(λ,T), at temperatures <296 K were determined relative to its well established room temperature values. A wavelength and temperature dependent parameterization of the Cl(2)O spectrum using the sum of six Gaussian functions, which empirically represent transitions from the ground (1)A(1) electronic state to excited states, is presented. The Gaussian functions are found to correlate well with published theoretically calculated vertical excitation energies. O((3)P) quantum yields in the photolysis of Cl(2)O at 193 and 248 nm were measured using pulsed laser photolysis combined with atomic resonance fluorescence detection of O((3)P) atoms. O((3)P) quantum yields were measured to be 0.85 ± 0.15 for 193 nm photolysis at 296 K and 0.20 ± 0.03 at 248 nm, which was also found to be independent of temperature (220-352 K) and pressure (17 and 28 Torr, N(2)). The quoted uncertainties are at the 2σ (95% confidence) level and include estimated systematic errors. ClO radical temporal profiles obtained following the photolysis of Cl(2)O at 248 nm, as reported previously in Feierabend et al. [J. Phys. Chem. A 114, 12052, (2010)], were interpreted to establish a <5% upper-limit for the O + Cl(2) photodissociation channel, which indicates that O((3)P) is primarily formed in the three-body, O + 2Cl, photodissociation channel at 248 nm. The analysis also indirectly provided a Cl atom quantum yield of 1.2 ± 0.1 at 248 nm. The results from this work are compared with previous studies where possible. © 2011 American Institute of Physics

  5. Conservação da qualidade de caqui 'Fuyu' em ambiente refrigerado pela combinação de 1-MCP e atmosfera modificada Quality maintenance of 'Fuyu' persimmon in cold storage by combining 1-MCP and modified atmosphere

    Directory of Open Access Journals (Sweden)

    Luiz Carlos Argenta

    2009-06-01

    AM sobre a redução desses distúrbios e do amolecimento dos frutos foram consistentes para todos os pomares. Os resultados indicam que a combinação de 1-MCP e AM é um método efetivo para retardar a deterioração de caqui 'Fuyu' durante e após a armazenagem refrigerada.This study examined the effects of ethylene action inhibitor 1-MCP (1-methylcyclopropene,MA (modified atmosphere and ethylene oxidant KMnO4 (potassium permanganate on the quality of 'Fuyu'persimmon fruit after cold storage. The factors 1-MCP, MA and KMnO were combined in four manners corresponding to the following treatments: T1 Control + MA + KMnO4, T2(4 1-MCP + MA + KMnO4, T3 1-MCP + MA, and T4 1-MCP + AA (AA= atmosphere of air. Mature-firm fruit with predominant yellow colorwere harvested from seven commercial orchards in the northeast of Rio Grande do Sul state. Some of fruit were exposed to 0.3 µL L-1 of 1-MCP for 12 h in 24 h after the harvest. After that, fruit were stored in AA or MA induced by polyethylene bags (0.04 mm thick, by 20, 40, 60 or 80 days at -0.1±0.8ºC. Two pellets of 8.5 g alumina-KMnO4 were added into the polyethylene bags of treatments one and two before they weresealed. Fruit were analyzed after 0, 3, 6 or 9 days of shelf in AA at 22±1ºC. 1-MCP treatment delayed fleshsoftening, but did not consistently affect the development of skin disorders (lined dark dots and blackspots on fruit stored in MA containing KMnO4. However, the incidence of skin disorders on 1-MCP treated fruit stored in MA was significantly less than that of 1-MCP treated fruit stored in AA. There were additiveeffects of 1-MCP and MA on the retention of firmness and on the reduction of chilling injury appeared bythe formation of firm gel texture of flesh and translucent stains on the skin. The use of KMnO4 did not improve the retention of fruit quality when treated with 1-MCP and stored in MA. The development of skindisorders was orchard- and storage period-dependent. However, the benefits of 1-MCP

  6. Characterization of atmospheric trace gases and particulate matter in Hangzhou, China

    Directory of Open Access Journals (Sweden)

    G. Zhang

    2018-02-01

    suggested the combined importance of local atmospheric photochemistry and synoptic conditions during the accumulation (related with anticyclones and dilution process (related with cyclones. Apart from supplementing a general picture of the air pollution state in the city of Hangzhou in the YRD region, this study specifically elucidates the role of local emission and regional transport, and it interprets the physical and photochemical processes during haze and photochemical pollution episodes. Moreover, this work suggests that cross-regional control measures are crucial to improve air quality in the YRD region, and it further emphasizes the importance of local thermally induced circulation for air quality.

  7. Atmospheric pollution.

    Science.gov (United States)

    Schlesinger, R B

    1992-06-01

    Air pollution has been directly responsible for increases in mortality and morbidity in the general population during periods known as episodes, when pollutant levels were elevated well above those that occur on a regular basis. The major concern today regarding pollution and health is, however, more subtle--namely, whether the lower levels of pollution to which we are exposed daily are harmful to health. It is extremely difficult to relate specific health problems to specific pollutants, because other environmental and lifestyle factors may contribute to decrements in health. Furthermore, people are generally exposed to mixtures of pollutants, making it difficult to extract the effects caused by individual components, or to determine which combinations are the most hazardous. Community air pollution results from various sources: mobile sources, such as vehicles; stationary sources, such as power plants and factories; and indoor sources, such as building material. Complicating the picture is the fact that many chemicals released into the air may react, producing additional secondary pollutants. This article provides an overview of the major air pollutants that may be of concern in terms of public health.

  8. User's Manual for SAG-2 SHARC/SAMM Atmosphere Generator

    National Research Council Canada - National Science Library

    Shroll, Robert

    2003-01-01

    The SHARC Atmosphere Generator (SAG) is a stand-alone, interactive program that utilizes a combination of empirical models to generate atmospheric profiles for Air Force IR radiation codes that account for systematic variability...

  9. Atmospheric Climate Experiment Plus

    Science.gov (United States)

    Lundahl, K.

    ACE+ is an atmospheric sounding mission using radio occultation techniques and is a combination of the two Earth Explorer missions ACE and WATS earlier proposed to ESA. ACE was highly rated by ESA in the Call for Earth Explorer Opportunity Missions in 1999 and was prioritised as number three and selected as a "hot-stand-by". A phase A study was carried out during 2000 and 2001. ACE will observe atmospheric parameters using radio occultations from an array of 6 micro-satellites which track the L- band signal of GPS satellites to map the detailed refractivity and thermal structure of the global atmosphere from surface to space. Water vapour and wind in Atmospheric Troposphere and Stratosphere WATS was the response to ESA's Call for Ideas for the next Earth Explorer Core Missions in 2001. WATS combines ACE GPS atmospheric occultations and LEO-LEO cross-link occultations. Cross-links strongly enhance the capability of measuring humidity relative to the ACE mission. The Earth Science Advisory Committée at ESA noted that the LEO-GNSS occultation technique is already well established through several missions in recent years and could not recommend WATS for a Phase A study as an Earth Explorer Core Mission. The ESAC was, however, deeply impressed by the LEO-LEO component of the WATS proposal and would regard it as regrettable if this science would be lost and encourages the ACE/WATS team to explore other means to achieve its scientific goal. ACE+ is therefore the response to ESA's 2nd Call for Earth Explorer Opportunity Missions in 2001 and will contribute in a significant manner to ESA's Living Planet Programme. ACE+ will considerably advance our knowledge about atmosphere physics and climate change processes. The mission will demonstrate a highly innovative approach using radio occultations for globally measuring profiles of humidity and temperature throughout the atmosphere and stratosphere. A constellation of 4 small satellites, tracking L-band GPS/GALILEO signals and

  10. Biomass burning at Cape Grim: exploring photochemistry using multi-scale modelling

    Science.gov (United States)

    Lawson, Sarah J.; Cope, Martin; Lee, Sunhee; Galbally, Ian E.; Ristovski, Zoran; Keywood, Melita D.

    2017-10-01

    We have tested the ability of a high-resolution chemical transport model (CTM) to reproduce biomass burning (BB) plume strikes and ozone (O3) enhancements observed at Cape Grim in Tasmania, Australia, from the Robbins Island fire. The CTM has also been used to explore the contribution of near-field BB emissions and background sources to O3 observations under conditions of complex meteorology. Using atmospheric observations, we have tested model sensitivity to meteorology, BB emission factors (EFs) corresponding to low, medium, and high modified combustion efficiency (MCE), and spatial variability. The use of two different meteorological models (TAPM-CTM and CCAM-CTM) varied the first (BB1) plume strike time by up to 15 h and the duration of impact between 12 and 36 h, and it varied the second (BB2) plume duration between 50 and 57 h. Meteorology also had a large impact on simulated O3, with one model (TAPM-CTM) simulating four periods of O3 enhancement, while the other model (CCAM) simulating only one period. Varying the BB EFs, which in turn varied the non-methane organic compound (NMOC) / oxides of nitrogen (NOx) ratio, had a strongly non-linear impact on simulated O3 concentration, with either destruction or production of O3 predicted in different simulations. As shown in previous work (Lawson et al., 2015), minor rainfall events have the potential to significantly alter EF due to changes in combustion processes. Models that assume fixed EF for O3 precursor species in an environment with temporally or spatially variable EF may be unable to simulate the behaviour of important species such as O3. TAPM-CTM is used to further explore the contribution of the Robbins Island fire to the observed O3 enhancements during BB1 and BB2. Overall, TAPM-CTM suggests that the dominant source of O3 observed at Cape Grim was aged urban air (age = 2 days), with a contribution of O3 formed from local BB emissions. This work shows the importance of assessing model sensitivity to

  11. Evolution of Earth-like Extrasolar Planetary Atmospheres: Assessing the Atmospheres and Biospheres of Early Earth Analog Planets with a Coupled Atmosphere Biogeochemical Model.

    Science.gov (United States)

    Gebauer, S; Grenfell, J L; Stock, J W; Lehmann, R; Godolt, M; von Paris, P; Rauer, H

    2017-01-01

    masks its biosphere over a wide range of conditions). Key Words: Early Earth-Proterozoic-Archean-Oxygen-Atmosphere-Biogeochemistry-Photochemistry-Biosignatures-Earth-like planets. Astrobiology 16, 27-54.

  12. Kinetics programs for simulation of tropospheric photochemistry on the global scale

    Energy Technology Data Exchange (ETDEWEB)

    Elliott, S.; Kao, C.Y.J. [Los Alamos National Lab., NM (US); Turco, R.P.; Zhao, X.P. [California Univ., Los Angeles, CA (US). Dept. of Atmospheric Sciences

    1993-08-01

    The study of tropospheric kinetics underlies global change because key greenhouse gases are photochemically active. Modeling of tropospheric chemistry on a global scale is essential because some indirect greenhouse gases are short-lived and interact in a non-linear fashion. It is also extremely challenging, however; the global change grid is extensive in both the physical and temporal domains, and critical lower atmospheric species include the organics and their oxidized derivatives, which are numerous. Several types of optimization may be incorporated into kinetics modules to enhance their ability to simulate the complete lower atmospheric gas phase chemical system. (1) The photochemical integrator can be accelerated by avoiding matrix and iterative solutions and by establishing families. Accuracy and mass conservation are sacrificed in the absence of iteration, but atom balancing is restorable post hoc. (2) Chemistry can be arranged upon the massive grid to exploit parallel processing, and solutions to its continuity equations can be automated to permit experimentation with species and reaction lists or family definitions. Costs in programming effort will be incurred in these cases. (3) Complex hydrocarbon decay sequences can be streamlined either through structural lumping methods descended from smog investigations, which require considerable calibration, or by defining surrogates for classes of compounds, with a loss in constituent detail. From among the available options, the most advantageous permutations will vary with the specific nature of any eventual global scale study, and there is likely to be demand for many approaches. Tracer transport codes serve as a foundation upon which tropospheric chemistry packages will be tested. Encroachment of the NO{sub x} sphere of influence upon tropical rain forests and the upper free troposphere are two examples of specific problems to which full three-dimensional chemical simulations might be applied.

  13. Photoreactivity of condensed species in Titan lower atmosphere

    Science.gov (United States)

    Fleury, Benjamin; Gudipati, Murthy; Couturier-Tamburelli, Isabelle; Carrasco, Nathalie

    2017-10-01

    Photochemical processes initiated in the thermosphere of Titan at about 1000 km by the dissociation and the ionization of N2 and CH4 by the VUV solar photons [1] lead to the formation of a number of hydrocarbons and nitriles species. Some of these species can condense in the troposphere and the lower stratosphere of Titan ( 300 nm) can reach these lower atmospheric layers [4], ongoing possible further solid-state chemistry as demonstrated experimentally [5]. We will present here an experimental study simulating the reactivity of ices in the atmosphere of Titan and will discuss the photoreactivity occurring in the lower atmospheric layers of Titan despite the absorption of the most energetic photons.AcknowledgmentsThis work is supported by NASA Solar System Workings grant " Photochemistry in Titan’s Lower Atmosphere". The research work has been carried out at the Jet Propulsion Laboratory, California Institute of Technology under a contract with the National Aeronautics and Space Administration. NC acknowledges the European Research Council for their financial support (ERC Starting Grant PRIMCHEM, grant agreement n°636829).References[1] Waite, J. H., et al., The process of Tholin formation in Titan’s upper atmosphere, (2007), Science 316, 870-875.[2] Barth, E. L., Modeling survey of ices in Titan’s stratosphere, (2017), Planetary and Space Science 137, 20-31.[3] Fulchignoni, M., et al., In situ measurements of the physical characteristics of Titan’s environment, (2005), Nature 438, 785-791.[4] Tomasko, M. G., et al., Rain, winds and haze during the Huygens probe’s descent to Titan’s surface, (2005), Nature 438, 765-778.[5] Gudipati, M. S., et al., Photochemical activity of Titan’s low-altitude condensed haze, (2013), Nature Communications, 4: p1648.

  14. Martian atmospheric O3 retrieval development for the NOMAD-UVIS spectrometer

    Science.gov (United States)

    Hewson, W.; Mason, J. P.; Leese, M.; Hathi, B.; Holmes, J.; Lewis, S. R.; Iriwin, P. G. J.; Patel, M. R.

    2017-09-01

    The composition of atmospheric trace gases and aerosols is a highly variable and poorly constrained component of the martian atmosphere, and by affecting martian climate and UV surface dose, represents a key parameter in the assessment of suitability for martian habitability. The ExoMars Trace Gas Orbiter (TGO) carries the Open University (OU) designed Ultraviolet and VIsible Spectrometer (UVIS) instrument as part of the Belgian-led Nadir and Occultation for MArs Discovery (NOMAD) spectrometer suite. NOMAD will begin transmitting science observations of martian surface and atmosphere back-scattered UltraViolet (UV) and visible radiation in Spring 2018, which will be processed to derive spatially and temporally averaged atmospheric trace gas and aerosol concentrations, intended to provide a better understanding of martian atmospheric photo-chemistry and dynamics, and will also improve models of martian atmospheric chemistry, climate and habitability. Work presented here illustrates initial development and testing of the OU's new retrieval algorithm for determining O3 and aerosol concentrations from the UVIS instrument.

  15. Photochemistry of bacteriochlorophylls in human blood plasma: 2. Reaction mechanism investigated by product analysis and deuterium isotope effect.

    Science.gov (United States)

    Dandler, Jörg; Wilhelm, Brigitte; Scheer, Hugo

    2010-01-01

    Transmetalated (Pd) bacteriochlorophyll derivatives are currently being clinically tested as sensitizers for photodynamic therapy. Protocols using short delay times between injection and irradiation generate interest in the photochemistry of these pigments in the blood. Using near-infrared irradiation where these pigments absorb strongly, we have studied the mechanism of photo-oxidation in two lipoprotein fractions, low- and high-density lipoproteins, derived from human blood plasma that preferentially accumulate these pigments (Dandler et al. [2009] Photochem. Photobiol., 85, in press). Using quenchers of reactive oxygen species, and chemical reporters, in particular peroxides generated from cholesterol as an inherent component of the lipoproteins, a Type II mechanism generating singlet oxygen has been demonstrated for Pd- and Zn-bacteriopheophorbides. In homogeneous systems, accelerated bleaching in D(2)O, compared with H(2)O, supports this mechanism. An unusual deuterium isotope effect was observed, by contrast, in heterogeneous amphiphilic-water systems. In the early phase, and under high oxygen concentrations, again a positive D-isotope effect is observed which later, in a second phase, is reversed to a negative D-isotope effect. The latter cannot be explained by heterogeneous pigment populations in the amphiphilic system; we, therefore, conclude a mechanistic switch, and discuss a possible mechanism.

  16. Photochemistry of HI on argon and water nanoparticles: hydronium radical generation in HI·(H2O)n.

    Science.gov (United States)

    Poterya, Viktoriya; Fedor, Juraj; Pysanenko, Andriy; Tkáč, Ondřej; Lengyel, Jozef; Ončák, Milan; Slavíček, Petr; Fárník, Michal

    2011-02-14

    Photochemistry of HI molecules on large Ar(n) and (H(2)O)(n), n ∼ 100-500, clusters was investigated after excitation with 243 nm and 193 nm laser radiation. The measured H-fragment kinetic energy distributions pointed to a completely different photodissociation mechanism of HI on water than on argon clusters. Distinct features corresponding to the fragment caging (slow fragments) and direct exit (fast fragments) were observed in the spectra from HI photodissociation on Ar(n) clusters. On the other hand, the fast fragments were entirely missing in the spectrum from HI·(H(2)O)(n) and the slow-fragment part of the spectrum had a different shape from HI·Ar(n). The HI·(H(2)O)(n) spectrum was interpreted in terms of the acidic dissociation of HI on (H(2)O)(n) in the ground state, and hydronium radical H(3)O formation following the UV excitation of the ionically dissociated species into states of a charge-transfer-to-solvent character. The H(3)O generation was proved by experiments with deuterated species DI and D(2)O. The experiment was complemented by ab initio calculations of structures and absorption spectra for small HI·(H(2)O)(n) clusters, n = 0-5, supporting the proposed model.

  17. Solution and Solid Hexahydro-1,3,5-trinitro-1,3,5-triazine (RDX) Ultraviolet (UV) 229 nm Photochemistry.

    Science.gov (United States)

    Gares, Katie L; Bykov, Sergei V; Brinzer, Thomas; Asher, Sanford A

    2015-05-01

    We measured the 229 nm deep-ultraviolet resonance Raman (DUVRR) spectra of solution and solid-state hexahydro-1,3,5-trinitro-1,3,5-triazine (RDX). We also examined the photochemistry of RDX both in solution and solid states. RDX quickly photodegrades with a solution quantum yield of φ ~ 0.35 as measured by high-performance liquid chromatography (HPLC). New spectral features form over time during the photolysis of RDX, indicating photoproduct formation. The photoproduct(s) show stable DUVRR spectra at later irradiation times that allow standoff detection. In the solution-state photolysis, nitrate is a photoproduct that can be used as a signature for detection of RDX even after photolysis. We used high-performance liquid chromatography-high-resolution mass spectrometry (HPLC-HRMS) and gas chromatography mass spectrometry (GCMS) to determine some of the major solution-state photoproducts. X-ray photoelectron spectroscopy (XPS) was also used to determine photoproducts formed during solid-state RDX photolysis.

  18. Synthesis of Superparamagnetic Iron Oxide Nanoparticles Modified with MPEG-PEI via Photochemistry as New MRI Contrast Agent

    Directory of Open Access Journals (Sweden)

    Yancong Zhang

    2015-01-01

    Full Text Available Novel method for synthesis of superparamagnetic iron oxide nanoparticles (SPIONs coated with polyethylenimine (PEI and modified with poly(ethylene glycol methyl ether (MPEG, MPEG-PEI-SPIONs, was developed. PEI-SPIONs were successfully prepared in aqueous system via photochemistry, and their surface was modified with poly(ethylene glycol methyl ether (MPEG. The so-obtained MPEG-PEI-SPIONs had a uniform hydrodynamic particle size of 34 nm. The successful coating of MPEG-PEI on the SPIONs was ascertained from FT-IR analysis, and the PEI and MPEG fractions in MPEG-PEI-SPIONs were calculated to account for 31% and 12%, respectively. Magnetic measurement revealed that the saturated magnetization of MPEG-PEI-SPIONs reached 46 emu/g and the nanoparticles showed the characteristic of being superparamagnetic. The stability experiment revealed that the MPEG-PEI modification improved the nanoparticles stability greatly. T2 relaxation measurements showed that MPEG-PEI-SPIONs show similar R2 value to the PEI-SPIONs. The T2-weighted magnetic resonance imaging (MRI of MPEG-PEI-SPIONs showed that the magnetic resonance signal was enhanced significantly with increasing nanoparticle concentration in water. These results indicated that the MPEG-PEI-SPIONs had great potential for application in MRI.

  19. Electron transfer mechanism and photochemistry of ferrioxalate induced by excitation in the charge transfer band.

    Science.gov (United States)

    Chen, Jie; Zhang, Hua; Tomov, Ivan V; Rentzepis, Peter M

    2008-03-17

    The photoredox reaction of ferrioxalate after 266/267 nm excitation in the charge transfer band has been studied by means of ultrafast extended X-ray absorption fine structure (EXAFS) analysis, optical transient spectroscopy, and quantum chemistry calculations. The Fe-O bond length changes combined with the transient spectra and kinetics have been measured and in combination with ultrahigh frequency density functional theory (UHF/DFT) calculations are used to determine the photochemical mechanism for the Fe(III) to Fe(II) redox reaction. The present data and the results obtained with 266/267 nm excitations strongly suggest that the primary reaction is the dissociation of the Fe-O bond before intramolecular electron transfer occurs. Low quantum yield electron photodetachment from ferrioxalate has also been observed.

  20. Atmosphere: Power, Critique, Politics

    DEFF Research Database (Denmark)

    Albertsen, Niels

    2016-01-01

    This paper hans three interrelated parts. First, atmosphere is approached through the concept of power. Atmospheres 'grip' us directly or mediate power indirectly by manipulating moods and evoking emotions. How does atmosphere relate to different conceptions of power? Second, atmospheric powers may...

  1. Impacts of brown carbon from biomass burning on surface UV and ozone photochemistry in the Amazon Basin

    KAUST Repository

    Mok, Jungbin

    2016-11-11

    The spectral dependence of light absorption by atmospheric particulate matter has major implications for air quality and climate forcing, but remains uncertain especially in tropical areas with extensive biomass burning. In the September-October 2007 biomass-burning season in Santa Cruz, Bolivia, we studied light absorbing (chromophoric) organic or “brown” carbon (BrC) with surface and space-based remote sensing. We found that BrC has negligible absorption at visible wavelengths, but significant absorption and strong spectral dependence at UV wavelengths. Using the ground-based inversion of column effective imaginary refractive index in the range 305–368 nm, we quantified a strong spectral dependence of absorption by BrC in the UV and diminished ultraviolet B (UV-B) radiation reaching the surface. Reduced UV-B means less erythema, plant damage, and slower photolysis rates. We use a photochemical box model to show that relative to black carbon (BC) alone, the combined optical properties of BrC and BC slow the net rate of production of ozone by up to 18% and lead to reduced concentrations of radicals OH, HO2, and RO2 by up to 17%, 15%, and 14%, respectively. The optical properties of BrC aerosol change in subtle ways the generally adverse effects of smoke from biomass burning.

  2. Impacts of Brown Carbon from Biomass Burning on Surface UV and Ozone Photochemistry in the Amazon Basin

    Science.gov (United States)

    Mok, Jungbin; Krotkov, Nickolay A.; Arola, Antti; Torres, Omar; Jethva, Hiren; Andrade, Marcos; Labow, Gordon; Eck, Thomas F.; Li, Zhangqing; Dickerson, Russell R.; hide

    2016-01-01

    The spectral dependence of light absorption by atmospheric particulate matter has major implications for air quality and climate forcing, but remains uncertain especially in tropical areas with extensive biomass burning. In the September-October 2007 biomass-burning season in Santa Cruz, Bolivia, we studied light absorbing (chromophoric) organic or brown carbon (BrC) with surface and space-based remote sensing. We found that BrC has negligible absorption at visible wavelengths, but significant absorption and strong spectral dependence at UV wavelengths. Using the ground-based inversion of column effective imaginary refractive index in the range 305368nm, we quantified a strong spectral dependence of absorption by BrC in the UV and diminished ultraviolet B (UV-B) radiation reaching the surface. Reduced UV-B means less erythema, plant damage, and slower photolysis rates. We use a photochemical box model to show that relative to black carbon (BC) alone, the combined optical properties of BrC and BC slow the net rate of production of ozone by up to 18 and lead to reduced concentrations of radicals OH, HO2, and RO2 by up to 17, 15, and 14, respectively. The optical properties of BrC aerosol change in subtle ways the generally adverse effects of smoke from biomass burning.

  3. Impacts of brown carbon from biomass burning on surface UV and ozone photochemistry in the Amazon Basin

    Science.gov (United States)

    Mok, Jungbin; Krotkov, Nickolay A.; Arola, Antti; Torres, Omar; Jethva, Hiren; Andrade, Marcos; Labow, Gordon; Eck, Thomas F.; Li, Zhanqing; Dickerson, Russell R.; Stenchikov, Georgiy L.; Osipov, Sergey; Ren, Xinrong

    2016-11-01

    The spectral dependence of light absorption by atmospheric particulate matter has major implications for air quality and climate forcing, but remains uncertain especially in tropical areas with extensive biomass burning. In the September-October 2007 biomass-burning season in Santa Cruz, Bolivia, we studied light absorbing (chromophoric) organic or “brown” carbon (BrC) with surface and space-based remote sensing. We found that BrC has negligible absorption at visible wavelengths, but significant absorption and strong spectral dependence at UV wavelengths. Using the ground-based inversion of column effective imaginary refractive index in the range 305-368 nm, we quantified a strong spectral dependence of absorption by BrC in the UV and diminished ultraviolet B (UV-B) radiation reaching the surface. Reduced UV-B means less erythema, plant damage, and slower photolysis rates. We use a photochemical box model to show that relative to black carbon (BC) alone, the combined optical properties of BrC and BC slow the net rate of production of ozone by up to 18% and lead to reduced concentrations of radicals OH, HO2, and RO2 by up to 17%, 15%, and 14%, respectively. The optical properties of BrC aerosol change in subtle ways the generally adverse effects of smoke from biomass burning.

  4. Ultrafast photochemistry with two product channels: Wavepacket motion through two distinct conical intersections

    Science.gov (United States)

    Riedle, Eberhard; Roos, Matthias K.; Thallmair, Sebastian; Sailer, Christian F.; Krebs, Nils; Fingerhut, Benjamin P.; de Vivie-Riedle, Regina

    2017-09-01

    Light induced bond cleavage is an ubiquitous process in large molecules, yet its quantum nature is not fully understood. We present a comprehensive description of the ultrafast light induced Csbnd Cl bond cleavage in diarylmethyl chlorides combining femtosecond transient absorption measurements with ab initio calculations. We observe a delayed appearance of radicals (80 fs) and cations (125 fs). The excited state wavepacket moves initially toward two conical intersections and the passing through these intersections determines the partitioning into the differing product channels. Different locations of the conical intersections explain the observed delay times.

  5. Research on artificial neural network intrusion detection photochemistry based on the improved wavelet analysis and transformation

    Science.gov (United States)

    Li, Hong; Ding, Xue

    2017-03-01

    This paper combines wavelet analysis and wavelet transform theory with artificial neural network, through the pretreatment on point feature attributes before in intrusion detection, to make them suitable for improvement of wavelet neural network. The whole intrusion classification model gets the better adaptability, self-learning ability, greatly enhances the wavelet neural network for solving the problem of field detection invasion, reduces storage space, contributes to improve the performance of the constructed neural network, and reduces the training time. Finally the results of the KDDCup99 data set simulation experiment shows that, this method reduces the complexity of constructing wavelet neural network, but also ensures the accuracy of the intrusion classification.

  6. Time dependences of atmospheric Carbon dioxide fluxes

    CERN Document Server

    DeSalvo, Riccardo

    2014-01-01

    Understanding the lifetime of CO2 in the atmosphere is critical for predictions regarding future climate changes. A simple mass conservation analysis presented here generates tight estimations for the atmosphere's retention time constant. The analysis uses a leaky integrator model that combines the observed deficit (only less than 40% of CO2 produced from combustion of fossil fuels is actually retained in the atmosphere, while more than 60% is continuously shed) with the exponential growth of fossil fuel burning. It reveals a maximum characteristic time of less than 23 year for the transfer of atmospheric CO2 to a segregation sink. This time constant is further constrained by the rapid disappearance of 14C after the ban of atmospheric atomic bomb tests, which provides a lower limit of 18 years for this transfer. The study also generates evaluations of other CO2 fluxes, exchange time constants and volumes exchanged. Analysis of large harmonic oscillations of atmospheric CO2 concentration, often neglected in th...

  7. The spectroscopy and photochemistry of quinioline structural isomers: (E)- and (Z)-phenylvinylnitrile

    Energy Technology Data Exchange (ETDEWEB)

    Mehta-Hurt, Deepali N.; Korn, Joseph A.; Navotnaya, Polina; Parobek, Alexander P.; Clayton, Rachel M.; Zwier, Timothy S., E-mail: zwier@purdue.edu [Department of Chemistry, Purdue University, 560 Oval Drive, West Lafayette, Indiana 47907-2084 (United States)

    2015-08-21

    In Titan’s atmosphere, photochemical pathways that lead to nitrogen heteroaromatics may incorporate photoisomerization of their structural isomers as a final step. (E)- and (Z)-phenylvinylnitrile ((E)- and (Z)-PVN, C{sub 6}H{sub 5} —CH=CHCN) are structural isomers of quinoline that themselves possess extensive absorptions in the ultraviolet, and thus may engage in such photoisomerization pathways. The present study explores the vibronic spectroscopy and photo-induced isomerization of gas-phase (E)- and (Z)-PVN in the 33,600-35,850 cm{sup −1} region under jet-cooled conditions. The S{sub 0}-S{sub 1} origins for (E)- and (Z)-PVN have been identified at 33 827 cm{sup −1} and 33 707 cm{sup −1}, respectively. Isomer-specific UV-UV hole-burning and UV depletion spectra reveal sharp vibronic structure that extends over almost 2000 cm{sup −1}, with thresholds for fast non-radiative decay identified by a comparison between hole-burning and UV depletion spectra. Dispersed fluorescence spectra of the two isomers enable the assignment of many low frequency transitions in both molecules, aided by harmonic frequency calculations (B3LYP/6-311++G(d,p)) and a comparison with the established spectroscopy of phenylvinylacetylene, the ethynyl counterpart to PVN. Both isomers are proven to be planar in both the S{sub 0} ground and S{sub 1} electronic excited states. (E)-PVN exhibits extensive Duschinsky mixing involving out-of-plane modes whose frequencies and character change significantly in the ππ{sup ∗} transition, which modulates the degree of single- and double-bond character along the vinylnitrile substituent. This same mixing is much less evident in (Z)-PVN. The spectroscopic characterization of (E)- and (Z)-PVN served as the basis for photoisomerization experiments using ultraviolet hole-filling spectroscopy carried out in a reaction tube affixed to the pulsed valve. Successful interconversion between (E) and (Z)-PVN was demonstrated via ultraviolet hole

  8. The contribution to nitrogen deposition and ozone formation in South Norway from atmospheric emissions related to the petroleum activity in the North Sea

    Energy Technology Data Exchange (ETDEWEB)

    Solberg, S.; Walker, S.-E.; Knudsen, S.; Lazaridis, M.; Beine, H.J.; Semb, A

    1999-03-01

    A photochemical plume model has been developed and refined. The model is designed to simulate the advection and photochemistry for several simultaneous point sources as well as the atmospheric mixing. the model has been used to calculate nitrogen deposition and ozone formation due to offshore emissions in the North Sea. Based on meteorological data for 1992 the calculations give a total contribution of 60-80 mg (N)/m{sub 2} at most in South Norway. Emission from British and Norwegian sector is calculated to contribute less than 5% each to the AOT40 index for ozone. (author)

  9. 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.

  10. Atmosphere-Ionosphere Coupling via Atmospheric Waves

    Science.gov (United States)

    Koucka Knizova, Petra; Lastovicka, Jan

    2017-04-01

    The Earth atmosphere and ionosphere is complicated and highly variable system which displays oscillations on wide range scales. The most important factor influencing the ionosphere is certainly the solar and geomagnetic activity. However, the processes even in distant regions in the neutral atmosphere cannot be simply neglected. This contribution reviews aspects of ionospheric variability originating in the lower laying atmosphere. It focuses especially on the generation and propagation of the atmospheric waves from their source region up to the heights of the ionosphere. We will show the role of infrasound, gravity waves, tides and planetary waves in the atmosphere-ionosphere coupling. Particularly gravity waves are of high importance for the ionosphere. Recent theoretical and experimental results will briefly be reviewed.

  11. Reactive nitrogen in Rocky Mountain National Park during the Front Range Air Pollution and Photochemistry Experiment (FRAPPÉ)

    Science.gov (United States)

    Prenni, A. J.; Benedict, K. B.; Evanoski-Cole, A. R.; Zhou, Y.; Sullivan, A.; Day, D.; Sive, B. C.; Zondlo, M. A.; Schichtel, B. A.; Vimont, J.; Collett, J. L., Jr.

    2014-12-01

    The Front Range Air Pollution and Photochemistry Éxperiment (FRAPPÉ) took place in July-August 2014. This collaborative study was aimed at characterizing those processes which control air quality along Colorado's Front Range. Although the study was largely focused on ozone, an additional goal of the study included characterizing contributions from Front Range sources and long-range transport to total reactive nitrogen in Rocky Mountain National Park (ROMO). Import of reactive nitrogen into ROMO and other pristine, high elevation areas has the potential to negatively impact terrestrial and aquatic ecosystems. We present measurements of reactive nitrogen species measured within ROMO during FRAPPÉ, and compare these data to measurements made in the surrounding areas. At our monitoring site in ROMO, co-located with IMPROVE and CASTNet monitoring, measurements of NO, NO2, NOx, NOy, NH3, and total reactive nitrogen (TNx) were made at high time resolution. Additional measurements of NH3, HNO3 and PM2.5 ions were made at hourly resolution using a MARGA and also at 24-hour time resolution using URG denuder-filter pack sampling. Precipitation samples also were collected to quantify wet deposition of ammonium, nitrate, and organic nitrogen. Finally, measurements of organic gases were made using online gas chromatography and proton transfer reaction-mass spectrometry. Preliminary results for ammonia show both a diel pattern, with concentrations increasing each morning, and a strong dependence on wind direction, implicating the importance of transport. Higher concentrations of NOx and NOy also were observed in the daytime, but in general these patterns differed from that of ammonia. Several upslope events were observed during the measurement period during which NOx, NH3, 2-propylnitrate, 2-butylnitrate, ethane, butane, and pentane were observed to increase in concentration along with ozone.

  12. Microfabrication of extracellular matrix structures using multipohoton-excited photochemistry: Application to modeling ovarian tissue in vitro

    Science.gov (United States)

    Ajeti, Visar

    The extracellular matrix plays a crucial role in tissue development, differentiation and homeostasis by providing the necessary biophysical and biochemical cues for the cells. In tumors, the composition and the structure of the microenvironment is thought to be manipulated by the cancers cells to support proliferative growth and enhanced migration as means of facilitated metastasis. Current in vitro tools to address these mechanistic events in tumor progression are lacking in part due to the difficulty in recapitulating the complexity of the composition and nanoarchitecture of the tumor microenvironment. In this thesis, we explore the feasibility of multiphoton-excited photochemistry as a fabrication tool for generating in vitro scaffolds that are highly repeatable, biologically relevant and relatively affordable in a research setting. The power of this technique lays in the capabilities of crosslinking whole extracellular matrix proteins in three dimensions (3D) to recreate key topographical features of the tissue with sub-micron resolution and high fidelity. The technological developments we present here enable direct translation of matrix topographies by using the high resolution image data of the tissue samples as a fabrication template. To this effect, we have applied the fabrication technique to generate gradients of crosslinked proteins as means of studying the role of haptotaxis in ovarian and breast cancers. Our findings show that cancer cells modulate their migration velocity and persistence in response to the changes in the composition of the extracellular matrix. In addition, we have examined structural features of the stroma in relation to cancer migration dynamics. We find that by recreating highly aligned nanoarchitectural features prevalent in cancer stroma, we see permissive and enhanced cell migration with cell morphologies similar to in vivo. We believe multiphoton fabrication to be an enabling tool in the next generation of tissue scaffolding

  13. New insights into the aquatic photochemistry of fluoroquinolone antibiotics: Direct photodegradation, hydroxyl-radical oxidation, and antibacterial activity changes

    Energy Technology Data Exchange (ETDEWEB)

    Ge, Linke; Na, Guangshui [Key Laboratory for Ecological Environment in Coastal Areas (SOA), National Marine Environmental Monitoring Center, Dalian 116023 (China); Zhang, Siyu [Institute of Applied Ecology, Chinese Academy of Sciences, Shenyang 110016 (China); Li, Kai [Key Laboratory for Ecological Environment in Coastal Areas (SOA), National Marine Environmental Monitoring Center, Dalian 116023 (China); Zhang, Peng, E-mail: pzhang@nmemc.org.cn [Key Laboratory for Ecological Environment in Coastal Areas (SOA), National Marine Environmental Monitoring Center, Dalian 116023 (China); Ren, Honglei; Yao, Ziwei [Key Laboratory for Ecological Environment in Coastal Areas (SOA), National Marine Environmental Monitoring Center, Dalian 116023 (China)

    2015-09-15

    The ubiquity and photoreactivity of fluoroquinolone antibiotics (FQs) in surface waters urge new insights into their aqueous photochemical behavior. This study concerns the photochemistry of 6 FQs: ciprofloxacin, danofloxacin, levofloxacin, sarafloxacin, difloxacin and enrofloxacin. Methods were developed to calculate their solar direct photodegradation half-lives (t{sub d,E}) and hydroxyl-radical oxidation half-lives (t{sub ·OH,E}) in sunlit surface waters. The t{sub d,E} values range from 0.56 min to 28.8 min at 45° N latitude, whereas t{sub ·OH,E} ranges from 3.24 h to 33.6 h, suggesting that most FQs tend to undergo fast direct photolysis rather than hydroxyl-radical oxidation in surface waters. However, a case study for levofloxacin and sarafloxacin indicated that the hydroxyl-radical oxidation induced risky photochlorination and resulted in multi-degradation pathways, such as piperazinyl hydroxylation and clearage. Changes in the antibacterial activity of FQs caused by photodegradation in various waters were further examined using Escherichia coli, and it was found that the activity evolution depended on primary photodegradation pathways and products. Primary intermediates with intact FQ nuclei retained significant antibacterial activity. These results are important for assessing the fate and risk of FQs in surface waters. - Highlights: • It is first reported on hydroxyl-radical oxidation of 6 fluoroquinolone antibiotics. • Methods were developed to assess photolysis and oxidation fate in surface waters. • The neutral form reacted faster with hydroxyl radical than protonated forms. • The main oxidation intermediates and transformation pathways were clarified. • The antibacterial activity changes depend on dominant photolysis pathways.

  14. Observations of Dinitrogen Pentoxide and Nitryl Chloride at two inland sites in North China: Abundances, Origins, and Impact on Photochemistry

    Science.gov (United States)

    LI, Q.; Xue, L.; Tham, Y. J.; Wang, W.; Yun, H.; Wang, T.; Wang, Z.; Wang, X.; Zhang, L.; Yao, L.; Wen, L.; Lu, K.; Zhang, Y.; Wang, W.

    2015-12-01

    Dinitrogen pentoxide (N2O5) and nitryl chloride (ClNO2) are key players in the nocturnal tropospheric chemistry, and also have potential to perturb the next-day's photochemistry. We here present the first ambient measurements of N2O5 and ClNO2 in inland regions of northern China, which is suffering from severe photochemical smog and haze pollution. A chemical ionization mass spectrometer (CIMS) was deployed at a semi-rural site in Wangdu, Hebei and on the top of Mt Tai, Shandong (1500 m a.s.l.) during the summer of 2014. At Wangdu, significant levels of ClNO2 were observed persistently throughout the campaign, with the maximum concentration of up to 2.1 ppbv (1-min data). N2O5 were generally in small concentrations but on few occasions reached up to hundreds of pptv. Clear variation of ClNO2 and N2O5 from night to night suggests the variability of N2O5 heterogeneous reactivity under different conditions over the region. On the mountain-top, elevated ClNO2-laden plumes were frequently observed around mid-night with a 1-min maximum of 2.1 ppbv, whilst N2O5 was always in very low levels indicating a fast N2O5 hydrolysis. The elevated ClNO2 levels at both locations were significantly influenced by the high NOx-saturated urban plumes and non-oceanic sources of chloride like biomass burning and coal-fired power plants in the region. MCM (Master Chemical Mechanism) modeling analyses indicate the significance of ClNO2 photolysis to the daytime radical and ozone production. Our study implies that the N2O5 reactivity and chlorine activation are significant in North China, and should be also important in other non-marine regions of China where NOx and particle chloride are in great abundances.

  15. The Inclusion of Raman Scattering Effects in the Combined Ocean-Atmosphere Radiative Transfer Model MOMO to Estimate the Influence of Raman Scattering in Case 1 Waters on Satellite Ocean Remote Sensing Applications

    Science.gov (United States)

    von Bismarck, J.; Fischer, J.

    2011-12-01

    Raman scattering of the solar lightfield, due to energy absorption by vibrational modes of water molecules, may contribute significantly to the signals observed by remote sensing satellites over water. The inelastic fraction of the water-leaving radiance for clear water reaches values of 30% in the red part of the visible spectrum, and still reaches values of several percent in moderately turbid waters. Furthermore, inelastic scattering due to chlorophyll and yellow substance fluorescence adds to this fraction. For these reasons the inclusion of inelastic scattering sources into radiative-transfer models, used in ocean remote sensing applications or atmosphere remote sensing over the ocean, can be important. MOMO is a computer code based on the matrix-operator method designed to calculate the lightfield in the stratified atmosphere-ocean system. It has been developed at the Institute for Space Sciences of the Freie Universität Berlin and provides the full polarization state (in the newest version) and an air-sea interface accounting for radiative effects of the wind roughened water surface. The inclusion of Raman scattering effects is done by a processing module, that starts a primary MOMO program run with a high spectral resolution, to calculate the radiative energy available for inelastic scattering at each model layer boundary. The processing module then calculates the first order Raman source-terms for every observation wavelength at every layer boundary, accounting for the non-isotropicity (including the azimuthal dependence) of the Raman phase-function, the spectral redistribution, and the spectral dependence of the Raman scattering coefficient. These elementary source-terms then serve as input for the second program run, which then calculates the source-terms of all model layers, using the doubling-adding method, and the resulting radiance field. Higher orders of the Raman contribution can be computed with additional program runs. Apart from the Raman

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

    Directory of Open Access Journals (Sweden)

    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

  17. 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

  18. Photochemistry and enzymology of photosynthesis. Progress report, November 1, 1978-May 31, 1981

    Energy Technology Data Exchange (ETDEWEB)

    Radmer, R.; Golbeck, J.; Velthuys, B.

    1981-05-01

    Three different aspects of photosynthesis are being investigated. Three different technical approaches are being used (i.e., mass spectrometry; biochemical techniques; and a combination of polarographic, spectroscopic, and fluorescence techniques). In the first group of experiments, a specially designed mass spectrometer system was used to monitor the gas exchange in chloroplasts in response to single short flashes of light. Several gases and their isotopes (e.g., N/sub 2/, /sup 15/N/sub 2/, /sup 18/O/sub 2/, etc.) were monitored to study photosystem II reactions in chloroplasts, particularly those reactions that use donors other than H/sub 2/ /sup 16/O (and evolve products other than /sup 16/O/sub 2/). Our goal was to obtain a better understanding of the O/sub 2/-evolving system. The second topic studied was the role of copper in photosynthesis. Biochemical techniques were applied to investigating the role of nonplastocyanin copper in photosystem II- and photosystem I-mediated O/sub 2/ uptake via polyphenol oxidase. The third area of study was light harvesting and electron transport in C/sub 4/ plants. Many aspects of carbon flow in C/sub 4/ plants seem to be well understood; however, the distribution of photons and the flow of electrons in the two tissues of the leaves of C/sub 4/ plants remain enigmatic. We used polarographic, spectroscopic, and fluorescence techniques to gain an understanding of these processes.

  19. Ultraviolet photochemistry of 2-bromothiophene explored using universal ionization detection and multi-mass velocity-map imaging with a PImMS2 sensor

    OpenAIRE

    Ingle, Rebecca A.; Hansen, Christopher S; Elsdon, Emma; Bain, Matthew; King, Simon J.; Lee, Jason W. L.; Brouard, Mark; Vallance, Claire; Turchetta, Renato; Ashfold, Michael N. R.

    2017-01-01

    This project is funded by EPSRC Programme Grant No. EP/L005913/1. The raw ion events data and calculation log files can be retrieved from the University of Bristol’s research data repository and can be accessed using the following DOI:10.5523/bris.k35bi3pqsdbh2b5moo2e3puxf. The ultraviolet photochemistry of 2-bromothiophene (C4H3SBr) has been studied across the wavelength range 265-245 nm using a velocity-map imaging (VMI) apparatus recently modified for multi-mass imaging and vacuum ultra...

  20. Atmospheric structure from Phoenix atmospheric entry data

    Science.gov (United States)

    Catling, D. C.

    2008-12-01

    The atmospheric structure at the time of landing of NASA's Phoenix probe has been derived from measurements of the aerodynamic drag of the spacecraft during atmospheric entry and descent. The result provides the first atmospheric structure in Mars' polar environment obtained from in situ measurements. Phoenix was equipped with an inertial measurement unit (IMU) that used accelerometers for linear acceleration measurement in three Cartesian axes and ring-laser gyroscopes to measure the three- dimensional orientation of the probe (Taylor et al., 2008). The temperature structure of the atmosphere along the flight path was calculated via a four-step process: (i) integrating forward the IMU data to obtain the time history of the spacecraft velocity vector relative to the atmosphere as a function of altitude; (ii) calculating atmospheric density from drag, with iteration for aerodynamic coefficient dependence on density; (iii) integrating the hydrostatic equation to derive the vertical pressure; and (iv) calculating atmospheric temperature from the equation of state. Initial profile reconstruction shows reasonable agreement with predictions in the middle atmosphere for the given season and time of day (landing occurred at 16h 33min 37sec in local solar time expressed as a 24-hour clock). However, the derived lower atmospheric structure below ~0.1 mbar is generally warmer than predicted. A possible explanation could be a shallower vertical distribution of dust that usually assumed. References: P. A. Taylor, D. C. Catling, M. Daly, C. S. Dickinson, H. O. Gunnlaugsson, A-M. Harri, C. F. Lange, Temperature, pressure and wind instrumentation on the Phoenix meteorological package, J. Geophys. Res., 113, EA0A10, doi:10.1029/2007JE003015, 2008.

  1. Planetary Atmospheric Electricity

    CERN Document Server

    Leblanc, F; Yair, Y; Harrison, R. G; Lebreton, J. P; Blanc, M

    2008-01-01

    This volume presents our contemporary understanding of atmospheric electricity at Earth and in other solar system atmospheres. It is written by experts in terrestrial atmospheric electricity and planetary scientists. Many of the key issues related to planetary atmospheric electricity are discussed. The physics presented in this book includes ionisation processes in planetary atmospheres, charge generation and separation, and a discussion of electromagnetic signatures of atmospheric discharges. The measurement of thunderstorms and lightning, including its effects and hazards, is highlighted by articles on ground and space based instrumentation, and new missions.Theory and modelling of planetary atmospheric electricity complete this review of the research that is undertaken in this exciting field of space science. This book is an essential research tool for space scientists and geoscientists interested in electrical effects in atmospheres and planetary systems. Graduate students and researchers who are new to t...

  2. Mirador - Atmospheric Composition

    Data.gov (United States)

    National Aeronautics and Space Administration — Earth Science data access made simple. Atmospheric Composition is focused on the composition of Earth's atmosphere in relation to climate prediction, solar effects,...

  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

    conversion of NO2 to HONO leads to persistent reactivity over long times (7 hours). Uptake coefficients increased linearly with the irradiation intensity indicating that the number of reactive sites at the soot surface is proportional to the number of photoactivated species. We suggest that nitrogen-containing organic compounds are also produced on the soot surface as a consequence of the heterogeneous reaction with NO2 under irradiation. These compounds can then be photolyzed and release NO and HONO in a NOx-free atmosphere. An estimation of the HONO production rate indicates that heterogeneous soot photochemistry may contribute to the daytime HONO concentration (1). When soot particles are exposed to high concentrations of O3 under irradiation there is an increase in hydrophobicity as it was previously observed for organic surface films(2). (1)ME Monge, B D'Anna, L Mazri, A Giroir-Fendler, M Ammann, D. J. Donaldson, and C George. Light changes the atmospheric reactivity of soot. PNAS, 2010, doi:10.1073/ pnas.0908341107 In press (2)L Nieto-Gligorovski, S Net, S Gligorovski, C Zetzsch, A Jammoul, B D'Anna, C George. Interactions of ozone with organic surface films in the presence of simulated sunlight: impact on wettability of aerosols. Physical Chemistry Chemical Physics 10, 2008, 2964-2971.

  4. Photochemistry of Pyrimidine in Astrophysical Ices: Formation of Nucleobases and Other Prebiotic Species

    Science.gov (United States)

    Nuevo, Michel; Sandford, Scott A.; Materese, Christopher K.; Milam, Stefanie N.

    2012-01-01

    Nucleobases are N-heterocycles that are the informational subunits of DNA and RNA. They are divided into two molecular groups: pyrimidine bases (uracil, cytosine, and thymine) and purine bases (adenine and guanine). Nucleobases have been detected in meteorites, and their extraterrestrial origin confirmed by isotopic measurements. Although no N-heterocycles have ever been observed in the ISM, the positions of the 6.2- m interstellar emission features suggest a population of such molecules is likely to be present. However, laboratory experiments have shown that the ultraviolet (UV) irradiation of pyrimidine in ices of astrophysical relevance such as H2O, NH3, CH3OH, CH4, CO, or combinations of these at low temperature (less than or equal to 20 K) leads to the formation of several pyrimidine derivatives including the nucleobases uracil and cytosine, as well as precursors such as 4(3H)-pyrimidone and 4-aminopyrimidine. Quantum calculations on the formation of 4(3H)-pyrimidone and uracil from the irradiation of pyrimidine in pure H2O ices are in agreement with their experimental formation pathways.10 In those residues, other species of prebiotic interest such as urea as well as the amino acids glycine and alanine could also be identified. However, only very small amounts of pyrimidine derivatives containing CH3 groups could be detected, suggesting that the addition of methyl groups to pyrimidine is not an efficient process. For this reason, the nucleobase thymine was not observed in any of the samples. In this work, we study the formation of nucleobases and other photo-products of prebiotic interest from the UV irradiation of pyrimidine in ices containing H2O, NH3, CH3OH, and CO, mixed in astrophysical proportions.

  5. Atmospheric refraction : a history

    NARCIS (Netherlands)

    Lehn, WH; van der Werf, S

    2005-01-01

    We trace the history of atmospheric refraction from the ancient Greeks up to the time of Kepler. The concept that the atmosphere could refract light entered Western science in the second century B.C. Ptolemy, 300 years later, produced the first clearly defined atmospheric model, containing air of

  6. Nitric oxide delta band emission in the earth's atmosphere - Comparison of a measurement and a theory

    Science.gov (United States)

    Rusch, D. W.; Sharp, W. E.

    1981-01-01

    Attention is given to the altitude dependent emission rate in the delta-bands of nitric oxide as measured in the earth's atmosphere at night by a scanning ultraviolet spectrometer. It is noted that the reaction responsible is the two-body association of nitrogen and oxygen atoms. The measurements show a vertical intensity beneath the layer for the delta-band system of 19 R. The horizontal emission rate is found to increase from 70 R at 117 km to 140 R at 150 km. The data are analyzed with a one-dimensional, time-dependent, vertical-transport model of odd nitrogen photochemistry. The calculated and measured intensities agree so long as the quenching of N(2D) by atomic oxygen is near 5 x 10 to the -13 cu cm/sec.

  7. Evaluation of local versus remote areas of CH4 sources at IC3 stations using a combined analysis of 222Rn tracer and Atmospheric Particles Transport Model (APTM) results. Application at the Gredos and Iruelas station (GIC3), Spain.

    Science.gov (United States)

    Grossi, Claudia; Morguí, Josep Anton; Curcoll, Roger; Àgueda, Alba; Arnold, Delia; Batet, Oscar; Cañas, Lidia; Nofuentes, Manel; Occhipinti, Paola; Vogel, Felix; Vargas, Arturo; Rodó, Xavier

    2014-05-01

    The Gredos and Iruelas station (GIC3) is part of the IC3 (Institut Català de Ciències del Clima) atmospheric monitoring network. This station is located in the Gredos Natural Park (40.22º N; -5.14º E) in the Spanish central plateau. The IC3 network consists of 8 stations distributed across Spain. It has been developed with the aim of studying climatic processes and the responses of impacted systems at different temporal and spatial scales. Since 2012, CO2, CH4, 222Rn (a natural radioactive gas) and meteorological variables are continuously measured at GIC3 at 20 m a.g.l. (1100 m a.s.l.). Furthermore, 4-days backward simulations are run daily for each IC3 station using the FLEXPART model. Simulations use ECMWF meteorological data as input and a horizontal spatial resolution of 0.2 degrees. The Laboratory of the Atmosphere and the Oceans (LAO) of the IC3 has elaborated a new approach to evaluate the local or remote greenhouse gases emissions using the radon gas as tracer and the atmospheric particles transport model FLEXPART under nocturnal and winter conditions. The ratios between the normalized and rescaled measured concentrations of CH4 and 222Rn during nocturnal hours (21h, 00h, 03h and 06h) and in the winter season, in order to reduce local radon flux and methane source due to seasonal livestock migration and to get stable atmospheric conditions, have been analyzed in relation to the influence of the local area (set to an initial dimension of 20x20 km2). The influence area (IA) has been defined as the percentage of the ratio between the residence time of the fictitious particles released in FLEXPART simulations over the area of interest (TLocal Area) and the residence time of these fictitious particles over the total area included in the simulation (TTotal Area ), i.e. IA = (TLocal Area/TTotal Area * 100). First results considering an area of interest of 20x20 km2 show a linear increase of the radon concentration with IA until reaching a maximum when IA is

  8. Development of a coupled diffusion denuder system combined with gas chromatography/mass spectrometry for the separation and quantification of molecular iodine and the activated iodine compounds iodine monochloride and hypoiodous acid in the marine atmosphere.

    Science.gov (United States)

    Huang, Ru-Jin; Hoffmann, Thorsten

    2009-03-01

    This study concerns the development of a coupled diffusion denuder system capable of separating and quantifying gaseous molecular iodine (I(2)) and two other highly reactive iodine species, ICl and HOI, which are collectively named activated iodine compounds (AIC). Both I(2) and AIC are key species in the atmospheric chemistry of iodine. 1,3,5-Trimethoxybenzene (1,3,5-TMB)- and alpha-cyclodextrin/(129)I(-) (alpha-CD/(129)I(-))-coated denuders proved to be suitable for the collection of gaseous AIC and I(2), respectively. The experimental collection efficiencies for AIC (tested as ICl) and I(2) agreed well with the theoretical values for gas flow rates in the range between 300 and 1800 mL min(-1). The coupled denuder system (1,3,5-TMB-coated denuder as front-denuder coupled upstream of an alpha-CD/(129)I(-)-coated denuder) was applied successfully to separate test gas mixtures of ICl and I(2) at various mixing ratios in the laboratory. The operation of both denuder systems was demonstrated to be independent of relative humidity (0-100%) and storage period (at least 2 weeks prior to and after sampling). Detection limits were achieved at sub-parts-per-trillion-by-volume (sub-pptv) level. The presented method provides a reliable and practical approach for the speciation of gaseous iodine compounds. In addition, we report for the first time ambient air measurements of AIC mixing ratios, carried out at the atmospheric research station in Mace Head, Ireland. A maximum concentration of AIC of 30.2 pptv was observed for nighttime measurements and 6.0 pptv for daytime measurements. A similar diurnal pattern was found for I(2) with an average concentration level of 23.2 pptv during daytime and 85.1 pptv during nighttime, indicating a strong correlation with AIC.

  9. Ozone in the atmosphere. Basic principles, natural and human impacts

    Energy Technology Data Exchange (ETDEWEB)

    Fabian, Peter [Technical Univ. Munich (Germany). Immission Research; Dameris, Martin [German Aerospace Center (DLR), Oberpfaffenhofen-Wessling (Germany). Inst. of Atmospheric Physics

    2014-09-01

    Comprehensive coverage of ozone both in the upper and the lower atmosphere. Essential overview of atmospheric ozone research written by two experienced and acknowledged experts. Numerous qualified references to the scientific literature. Peter Fabian and Martin Dameris provide a concise yet comprehensive overview of established scientific knowledge about ozone in the atmosphere. They present both ozone changes and trends in the stratosphere, as well as the effects of overabundance in the troposphere including the phenomenon of photosmog. Aspects such as photochemistry, atmospheric dynamics and global ozone distribution as well as various techniques for ozone measurement are treated. The authors outline the various causes for ozone depletion, the effects of ozone pollution and the relation to climate change. The book provides a handy reference guide for researchers active in atmospheric ozone research and a useful introduction for advanced students specializing in this field. Non-specialists interested in this field will also profit from reading the book. Peter Fabian can look back on a life-long active career in ozone research, having first gained international recognition for his measurements of the global distribution of halogenated hydrocarbons. He also pioneered photosmog investigations in the metropolitan areas of Munich, Berlin, Athens and Santiago de Chile, and his KROFEX facility provided controlled ozone fumigation of adult tree canopies for biologists to investigate the effects of ozone increases on forests. Besides having published a broad range of scientific articles, he has also been the author or editor of numerous books. From 2002 to 2005 he served the European Geosciences Union (EGU) as their first and Founding President. Martin Dameris is a prominent atmospheric modeler whose interests include the impacts of all kinds of natural and man-made disturbances on the atmospheric system. His scientific work focuses on the connections between ozone and

  10. Atmospheric Habitable Zones in Y Dwarf Atmospheres

    Energy Technology Data Exchange (ETDEWEB)

    Yates, Jack S.; Palmer, Paul I. [School of GeoSciences, University of Edinburgh (United Kingdom); Biller, Beth; Cockell, Charles S., E-mail: j.s.yates@ed.ac.uk [Centre for Exoplanet Science, University of Edinburgh (United Kingdom)

    2017-02-20

    We use a simple organism lifecycle model to explore the viability of an atmospheric habitable zone (AHZ), with temperatures that could support Earth-centric life, which sits above an environment that does not support life. To illustrate our model, we use a cool Y dwarf atmosphere, such as WISE J085510.83–0714442.5, whose 4.5–5.2 μ m spectrum shows absorption features consistent with water vapor and clouds. We allow organisms to adapt to their atmospheric environment (described by temperature, convection, and gravity) by adopting different growth strategies that maximize their chance of survival and proliferation. We assume a constant upward vertical velocity through the AHZ. We found that the organism growth strategy is most sensitive to the magnitude of the atmospheric convection. Stronger convection supports the evolution of more massive organisms. For a purely radiative environment, we find that evolved organisms have a mass that is an order of magnitude smaller than terrestrial microbes, thereby defining a dynamical constraint on the dimensions of life that an AHZ can support. Based on a previously defined statistical approach, we infer that there are of the order of 10{sup 9} cool Y brown dwarfs in the Milky Way, and likely a few tens of these objects are within 10 pc from Earth. Our work also has implications for exploring life in the atmospheres of temperate gas giants. Consideration of the habitable volumes in planetary atmospheres significantly increases the volume of habitable space in the galaxy.

  11. Coupled Photochemical and Condensation Model for the Venus Atmosphere

    Science.gov (United States)

    Bierson, Carver; Zhang, Xi; Mendonca, Joao; Liang, Mao-Chang

    2017-10-01

    Ground based and Venus Express observations have provided a wealth of information on the vertical and latitudinal distribution of many chemical species in the Venus atmosphere [1,2]. Previous 1D models have focused on the chemistry of either the lower [3] or middle atmosphere [4,5]. Photochemical models focusing on the sulfur gas chemistry have also been independent from models of the sulfuric acid haze and cloud formation [6,7]. In recent years sulfur-bearing particles have become important candidates for the observed SO2 inversion above 80 km [5]. To test this hypothesis it is import to create a self-consistent model that includes photochemistry, transport, and cloud condensation.In this work we extend the domain of the 1D chemistry model of Zhang et al. (2012) [5] to encompass the region between the surface to 110 km. This model includes a simple sulfuric acid condensation scheme with gravitational settling. It simultaneously solves for the chemistry and condensation allowing for self-consistent cloud formation. We compare the resulting chemical distributions to observations at all altitudes. We have also validated our model cloud mass against pioneer Venus observations [8]. This updated full atmosphere chemistry model is also being applied in our 2D solver (altitude and altitude). With this 2D model we can model how the latitudinal distribution of chemical species depends on the meridional circulation. This allows us to use the existing chemical observations to place constraints on Venus GCMs [9-11].References: [1] Arney et al., JGR:Planets, 2014 [2] Vandaele et al., Icarus 2017 (pt. 1 & 2) [3] Krasnopolsky, Icarus, 2007 [4] Krasnopolsky, Icarus, 2012 [5] Zhang et al., Icarus 2012 [6] Gao et al., Icarus, 2014 [7] Krasnopolsky, Icarus, 2015 [8] Knollenberg and Hunten, JGR:Space Physics, 1980 [9] Lee et al., JGR:Planets, 2007 [10] Lebonnois et al., Towards Understanding the Climate of Venus, 2013 [11] Mendoncca and Read, Planetary and Space Science, 2016

  12. Functionalization of the PEG Corona of Nanoparticles by Clip Photochemistry in Water: Application to the Grafting of RGD Ligands on PEGylated USPIO Imaging Agent.

    Science.gov (United States)

    Pourcelle, Vincent; Laurent, Sophie; Welle, Alexandre; Vriamont, Nicolas; Stanicki, Dimitri; Vander Elst, Luce; Muller, Robert N; Marchand-Brynaert, Jacqueline

    2015-05-20

    The fast development of nanomedicines requires more and more reliable chemical tools in order to accurately design materials and control the surface properties of the nano-objects used in biomedical applications. In this study we describe a smooth and simple photografting technique, i.e., the clip photochemistry, that allows the introduction of molecules of interest in inert polymers or on stealth nanoparticles directly in aqueous solution. First we developed the methodology on polyethylene glycol (PEG) and looked for critical parameters of the process (irradiation times, concentrations, washings) by using several molecular probes and adapted analytical techniques ((19)F qNMR, EA, LSC). We found that the clip photochemistry in water is a robust and efficient method to functionalize PEG. Second we applied it on PEGylated USPIO (USPIO-PEG) magnetic resonance imaging agent and succeeded in introducing RGD peptide and homemade peptidomimetics on their PEG segments. The magnetic abilities of the conjugated nanoparticles were unchanged by the derivatization process as evidenced by their relaxometric properties and their NMRD profile. When tested on Jurkat lymphocyte T Cells, which express αvβ3 integrins, the USPIO conjugated with RGD ligands leads to an increase of the transverse relaxation rate (R2) by a factor 10 to 14 as compared to USPIO-PEG. Consequently, it makes them good candidates for targeted imaging technology in cancer therapy.

  13. UV extinction in the atmosphere and its spatial variation in North China

    Science.gov (United States)

    Bai, Jianhui

    2017-04-01

    It is important to determine the distribution of solar radiation between the top of the atmosphere and the surface. Based on an empirical model for estimating hourly ultraviolet radiation irradiance (UVI) under all sky conditions in North China, UVI at the surface and at the top of the atmosphere were obtained. An important phenomenon of UV utilization by ;water vapor or absorbing factor; in the 290-400 nm range was studied, its mechanism was that UV energy can be absorbed indirectly once they react OH radicals and H2O and/or consumed directly by gases, liquids, particles (GLPs). The UVI loss in the atmosphere contributed by ;absorbing; and scattering materials were 19.30 and 35.31 W m-2, respectively, which depend on the region and season. The energy loss related to the ;absorbing substances; would exist in other regions and should be considered in models (e.g., radiative transfer, chemistry and photochemistry, climate) for better understanding the basic processes in the atmosphere.

  14. Oh where OH where is Oh? Measuring the Elusive Hydroxyl Radical in the Atmosphere Using Laser-Induced Fluorescence

    Science.gov (United States)

    Stevens, Philip S.

    2016-06-01

    The hydroxyl radical (OH) plays a central role in the chemistry of the atmosphere. In addition to controlling the lifetimes of many trace gases important to issues of global climate change and stratospheric ozone depletion, the OH radical initiates the oxidation of carbon monoxide and volatile organic compounds which in the presence of nitrogen oxides can lead to the production of ground-level ozone and secondary organic aerosols, the primary components of photochemical smog. Accurate measurements of OH radical concentrations in the atmosphere can provide critical tests of our understanding of atmospheric chemistry and ground-level ozone production in urban and rural areas. Because of its high reactivity, mixing ratios of OH in the atmosphere are extremely low (typically less than 0.1 parts per trillion) and its chemical lifetime very short (less than 1 second). As a result, measurements of OH present a serious analytical challenge, especially on the timescale necessary to test our understanding of the fast photochemistry of the atmosphere. This presentation will describe the Indiana University laser-induced fluorescence instrument for the sensitive detection of OH radicals in the atmosphere, including recent results from several measurement campaigns in both urban and rural environments.

  15. Atmospheric origins of perchlorate on Mars and in the Atacama

    Science.gov (United States)

    Catling, D. C.; Claire, M. W.; Zahnle, K. J.; Quinn, R. C.; Clark, B. C.; Hecht, M. H.; Kounaves, S.

    2010-01-01

    Isotopic studies indicate that natural perchlorate is produced on Earth in arid environments by the oxidation of chlorine species through pathways involving ozone or its photochemical products. With this analogy, we propose that the arid environment on Mars may have given rise to perchlorate through the action of atmospheric oxidants. A variety of hypothetical pathways can be proposed including photochemical reactions, electrostatic discharge, and gas-solid reactions. Because perchlorate-rich deposits in the Atacama desert are closest in abundance to perchlorate measured at NASA's Phoenix Lander site, we made a preliminary study of the means to produce Atacama perchlorate to help shed light on the origin of Martian perchlorate. We investigated gas phase pathways using a 1-D photochemical model. We found that perchlorate can be produced in sufficient quantities to explain the abundance of perchlorate in the Atacama from a proposed gas phase oxidation of chlorine volatiles to perchloric acid. The feasibility of gas phase production for the Atacama provides justification for future investigations of gas phase photochemistry as a possible source for Martian perchlorate.

  16. Levels, trends and health concerns of atmospheric PAHs in Europe

    Science.gov (United States)

    Garrido, Adrián; Jiménez-Guerrero, Pedro; Ratola, Nuno

    2014-12-01

    Changes in climate can affect the concentration patterns of polycyclic aromatic hydrocarbons (PAHs) by altering the dispersion (wind speed, mixing layer height, convective fronts), deposition by precipitation, dry deposition, photochemistry, natural emissions and background concentrations. This means the evolution trends of these pollutants have to be studied under a multi-scale perspective, allowing the establishment of transport patterns and distribution of PAHs. In this sense, this work tries to unveil the atmospheric behaviour of these pollutants using temporal data series collected in different stations from the European Monitoring and Evaluation Programme (EMEP) air sampling network. These sites are thought to avoid the direct influence of emitting areas (background stations), allowing the study of long-range transport effects, intra- and trans-annual variability, relationships between concentrations patterns and meteorological variables and latitudinal gradients of PAH levels in Europe. Overall, a typical high concentration pattern was found for the colder months (and an opposite behaviour is found for summertime). Negative trends were detected over high latitudes, for instance, in Svalbard (Norway), whereas for the United Kingdom the pattern is the inverse. Also, negative latitudinal gradients were observed in 4 of the 15 PAHs studied. Finally, air quality parameters revealed concern over human health issues, given the recent increase of BaP levels in Europe.

  17. The PHOCUS Project: Atmospheric Composition

    Science.gov (United States)

    Hedin, J.; Gumbel, J.; Khaplanov, M.

    2012-12-01

    On the morning of July 21, 2011, the PHOCUS sounding rocket was launched from Esrange, Sweden, into strong noctilucent clouds (NLC) and polar mesosphere summer echoes (PMSE). The aim of the PHOCUS project (Particles, Hydrogen and Oxygen Chemistry in the Upper Summer mesosphere) is to study mesospheric particles (ice and meteoric smoke) and their interaction with their neutral and charged environment. Interactions of interest comprise the charging and nucleation of particles, the relationship between meteoric smoke and ice, and the influence of these particles on gas-phase chemistry. Here we will describe the optical measurements of the atmospheric composition and present first results including comparison to the other simultaneous measurements. The atmospheric composition was probed by a set of optical instruments from Stockholm University. The idea behind the instrument setup was to combine the advantages of the sensitive resonance fluorescence with well-calibrated airglow photometry. The set of instruments consisted of two resonance fluorescence probes (each containing a lamp and a detector), one for atomic oxygen and one for atomic hydrogen, and two IR photometers for O2 and OH dayglow emissions in the near IR. The O2 IR Atmospheric system at 1.27 μm is related to the photolysis of O3, which during the day is in steady state with O and a retrieval of O is possible. The OH Meinel emission is produced by the reaction between mesospheric O3 and H, and H concentrations can be deduced by combining information from both photometers. Unfortunately, some of these measurements were corrupted by instrument problems or payload glow. O3 and O profiles will be presented and compared to the simultaneous measurements of ice and meteoric smoke particles, water vapour and the state of the background neutral and charged atmosphere.

  18. Measurement of the Atmospheric $\

    CERN Document Server

    Aartsen, M G; Abdou, Y; Ackermann, M; Adams, J; Aguilar, J A; Ahlers, M; Altmann, D; Andeen, K; Auffenberg, J; Bai, X; Baker, M; Barwick, S W; Baum, V; Bay, R; Beattie, K; Beatty, J J; Bechet, S; Tjus, J Becker; Becker, K -H; Bell, M; Benabderrahmane, M L; BenZvi, S; Berdermann, J; Berghaus, P; Berley, D; Bernardini, E; Bertrand, D; Besson, D Z; Bindig, D; Bissok, M; Blaufuss, E; Blumenthal, J; Boersma, D J; Bohaichuk, S; Bohm, C; Bose1, D; Boser, S; Botner, O; Brayeur, L; Brown, A M; Bruijn, R; Brunner, J; Buitink, S; Carson, M; Casey, J; Casier, M; Chirkin, D; Christy, B; Clark, K; Clevermann, F; Cohen, S; Cowen, D F; Silva, A H Cruz; Danninger, M; Daughhetee, J; Davis, J C; De Clercq, C; De Ridder, S; Descamps, F; Desiati, P; de Vries-Uiterweerd, G; DeYoung, T; Diaz-Velez, J C; Dreyer, J; Dumm, J P; Dunkman, M; Eagan, R; Eberhardt, B; Eisch, J; Ellsworth, R W; Engdegard, O; Euler, S; Evenson, P A; Fadiran, O; Fazely, A R; Fedynitch, A; Feintzeig, J; Feusels, T; Filimonov, K; Finley, C; Fischer-Wasels, T; Flis, S; Franckowiak, A; Franke, R; Frantzen, K; Fuchs, T; Gaisser, T K; Gallagher, J; Gerhardt, L; Gladstone, L; Glusenkamp, T; Goldschmidt, A; Golup, G; Goodman, J A; Gora, D; Grant, D; Gross, A; Grullon, S; Gurtner, M; Ha, C; Ismail, A Haj; Hallgren, A; Halzen, F; Hanson, K; Heereman, D; Heimann, P; Heinen, D; Helbing, K; Hellauer, R; Hickford, S; Hill, G C; Hoffman, K D; Hoffmann, R; Homeier, A; Hoshina, K; Huelsnitz, W; Hulth, P O; Hultqvist, K; Hussain, S; Ishihara, A; Jacobi, E; Jacobsen, J; Japaridze, G S; Jlelati, O; Kappes, A; Karg, T; Karle, A; Kiryluk, J; Kislat, F; Klas, J; Klein, S R; Kohne, J -H; Kohnen, G; Kolanoski, H; Kopke, L; Kopper, C; Kopper, S; Koskinen, D J; Kowalski, M; Krasberg, M; Kroll, G; Kunnen, J; Kurahashi, N; Kuwabara, T; Labare, M; Landsman, H; Larson, M J; Lauer, R; Lesiak-Bzdak, M; Lunemann, J; Madsen, J; Maruyama, R; Mase, K; Matis, H S; McNally, F; Meagher, K; Merck, M; Meszaros, P; Meures, T; Miarecki, S; Middell, E; Milke, N; Miller, J; Mohrmann, L; Montaruli, T; Morse, R; Nahnhauer, R; Naumann, U; Nowicki, S C; Nygren, D R; Obertacke, A; Odrowski, S; Olivas, A; Olivo, M; O'Murchadha, A; Panknin, S; Paul, L; Pepper, J A; Heros, C Perez de los; Pieloth, D; Pirk, N; Posselt, J; Price, P B; Przybylski, G T; Radel, L; Rawlins, K; Redl, P; Resconi, E; Rhode, W; Ribordy, M; Richman, M; Riedel, B; Rodrigues, J P; Rott, C; Ruhe, T; Ruzybayev, B; Ryckbosch, D; Saba, S M; Salameh, T; Sander, H -G; Santander, M; Sarkar, S; Schatto, K; Scheel, M; Scheriau, F; Schmidt, T; Schmitz, M; Schoenen, S; Schoneberg, S; Schonherr, L; Schonwald, A; Schukraft, A; Schulte, L; Schulz, O; Seckel, D; Seo, S H; Sestayo, Y; Seunarine, S; Sheremata, C; Smith, M W E; Soiron, M; Soldin, D; Spiczak, G M; Spiering, C; Stamatikos, M; Stanev, T; Stasik, A; Stezelberger, T; Stokstad, R G; Stoss, A; Strahler, E A; Strom, R; Sullivan, G W; Taavola, H; Taboada, I; Tamburro, A; Ter-Antonyan, S; Tilav, S; Toale, P A; Toscano, S; Usner, M; van der Drift, D; van Eijndhoven, N; Van Overloop, A; van Santen, J; Vehring, M; Voge1, M; Vraeghe, M; Walck, C; Waldenmaier, T; Wallraff, M; Walter, M; Wasserman, R; Weaver, Ch; Wendt, C; Westerhoff, S; Whitehorn, N; Wiebe, K; Wiebusch, C H; Williams, D R; Wissing, H; Wolf, M; Wood, T R; Woschnagg, K; Xu, C; Xu, D L; Xu, X W; Yanez, J P; Yodh, G; Yoshida, S; Zarzhitsky, P; Ziemann, J; Zierke, S; Zilles, A; Zoll, M

    2012-01-01

    We report the first observation in a high energy neutrino telescope of cascades induced by atmospheric electron neutrinos and by neutral current interactions of atmospheric neutrinos of all flavors. Using data recorded during the first year of operation of IceCube's DeepCore low energy extension, a sample of 1029 events is observed in 281 days of data. The number of observed cascades is $N_{\\rm cascade} = 496 \\pm 66 (stat.) \\pm 88(syst.)$ and the rest of the sample consists of residual backgrounds due to atmospheric muons and charged current interactions of atmospheric muon neutrinos. The flux of the atmospheric electron neutrinos is determined in the energy range between approximately 80 GeV and 6 TeV and is consistent with models of atmospheric neutrinos.

  19. Atmospheric Circulation of Exoplanets

    OpenAIRE

    Showman, Adam P.; Cho, James Y-K.; Menou, Kristen

    2009-01-01

    We survey the basic principles of atmospheric dynamics relevant to explaining existing and future observations of exoplanets, both gas giant and terrestrial. Given the paucity of data on exoplanet atmospheres, our approach is to emphasize fundamental principles and insights gained from Solar-System studies that are likely to be generalizable to exoplanets. We begin by presenting the hierarchy of basic equations used in atmospheric dynamics, including the Navier-Stokes, primitive, shallow-wate...

  20. Chemical kinetics and photochemistry

    Science.gov (United States)

    1982-01-01

    A compilation of rate constant data for use in stratospheric modeling is presented. The tabulations are divided into two categories: bimolecular and termolecular. Explanations are given for anomalous pressure and temperature dependences.

  1. Photochemistry at Interfaces

    Energy Technology Data Exchange (ETDEWEB)

    Eisenthal, Kenneth B [Columbia Univ., New York, NY (United States)

    2015-02-24

    We have advanced our capabilities to investigate ultrafast excited state dynamics at a liquid interface using a pump to excite molecules to higher electronic states and then probe the subsequent time evolution of the interfacial molecules with femtosecond time delayed vibrational SFG.

  2. Photochemistry of metalloporphyrins

    Energy Technology Data Exchange (ETDEWEB)

    Spiro, T.G.

    1990-01-01

    During the current period our efforts have been focussed on the characterization of porphyrin radical cations, anions, and excited states, and of oxo-metal prophyrins, using resonance Raman (RR) spectroscopy. RR spectra of octaethyl porphyrin and tetraphenylporphyrin radical cations showed different frequency shift patterns, which were interpreted in terms of the expected behavior of a{sub 1u} and a{sub 2u} radicals. Anomalously polarized RR bands were discovered whose frequencies and isotope shifts differed greatly from those of the neutral parents, and which signalled pseudo-Jahn-Teller activity in A{sub 2g} modes which mix the A{sub 1u} and A{sub 2u} ground and low-lying excited states. The RR spectrum of the ZnTPP radical anion showed modest frequency downshifts in Jahn-Teller (J-T) active B{sub 1g} and B{sub 2g} modes, but no significant polarized scattering from these modes, indicating that the J-T effect is dynamic in character. Manganyl porphyrins were found to have anomalously low metal-oxo stretching frequencies, and the weakness of the bond was related to electronic properties of the d{sup 3} Mn(IV) ion and its interactions with the porphyrin orbitals. Vanadyl porphyrins were used to assess the influence of solvents and axial ligands and of the effects of porphyrin radical cation formation on the metal-oxo bond. 13 refs.

  3. Designing Dynamic Atmospheres

    DEFF Research Database (Denmark)

    Kinch, Sofie; Højlund, Marie

    2012-01-01

    This paper addresses the notion of atmospheres from a designerly perspective, and discusses temporal challenges facing interaction designers when acknowledging the dynamic character of it. As atmospheres are created in the relation between body, space, and time, a pragmatic approach seems useful,....... The potentials and implica-­‐ tions are presented through a design case, Kidkit, highlighting temporality as design parametre within interaction design.......This paper addresses the notion of atmospheres from a designerly perspective, and discusses temporal challenges facing interaction designers when acknowledging the dynamic character of it. As atmospheres are created in the relation between body, space, and time, a pragmatic approach seems useful...

  4. Atmospheric Measurements Laboratory (AML)

    Data.gov (United States)

    Federal Laboratory Consortium — The Atmospheric Measurements Laboratory (AML) is one of the nation's leading research facilities for understanding aerosols, clouds, and their interactions. The AML...

  5. Possible atmospheric research with Aristoteles

    Science.gov (United States)

    Barlier, Francois

    1991-12-01

    Use of the Aristoteles mission in measuring atmospheric parameters is discussed. The total density of the thermosphere, the temperature of the stratosphere and the total electron count of the ionosphere are identified as three areas in which the Aristoteles mission could be of great use in carrying out research. Combining the accelerometer measurements yields the gravity tensor as well as the nongravitational acceleration acting upon the satellite. Ways in which the temperature of the stratosphere around the Earth, and the annual, seasonal and secular variations it goes through could be measured are discussed.

  6. Controlled Atmosphere Stunning

    NARCIS (Netherlands)

    Lambooij, E.; Gerritzen, M.A.

    2009-01-01

    Controlled atmosphere (CAS) stunning includes several variations of gaseous mixtures given to induce an anaesthetic state before slaughter poultry. One method of multi phase CAS is to unload the birds out of the crate on a conveyor belt and subject the birds to an atmosphere of 30% O2, 40% CO2 and

  7. Proterozoic atmospheric oxygen

    DEFF Research Database (Denmark)

    Canfield, Donald Eugene

    2014-01-01

    This article is concerned with the evolution of atmospheric oxygen concentrations through the Proterozoic Eon. In particular, this article will seek to place the history of atmospheric oxygenation through the Proterozoic Eon in the context of the evolving physical environment including the history...

  8. The Power of Atmosphere

    DEFF Research Database (Denmark)

    Wieczorek, Izabela

    2014-01-01

    composed of bubbles of affects – that is, the particles that are charged with power and normativity. References Grtiffero, T. (2014 (2010)). Atmospheres: Aesthetics of Emotional Spaces. Ashgate Philippopoulos-Mihalopoulos, A. (2013). Atmospheres of law: Senses, affects, lawscapes, in Emotion, Space...

  9. Designing Dynamic Atmospheres

    DEFF Research Database (Denmark)

    Højlund, Marie; Kinch, Sofie

    2012-01-01

    This paper addresses the notion of atmospheres from a designerly perspective, and discusses temporal challenges facing interaction designers when acknowledging the dynamic character of it. As atmospheres are created in the relation between body, space, and time, a pragmatic approach seems useful....... The potentials and implications are presented through a design case, Kidkit, highlighting temporality as design parametre within interaction design....

  10. Modeling the Martian Atmosphere with the LMD Global Climate Model

    Science.gov (United States)

    Forget, F.; Millour, E.; Gonzalez-Galindo, F.; Lebonnois, S.; Madeleine, J.-B.; Meslin, P.-Y.; Montabone, L.; Spiga, A.; Hourdin, F.; Lefevre, F.; Montmessin, F.; Lewis, S. R.; Read, P.; Lopez-Valverde, M. A.; Gilli, G.

    2008-11-01

    The Global Climate Model developed at LMD (Paris) in collaboration with IAA (Spain), AOPP and the OU (UK) has been improved. It is used for many applications (water, dust, CO2, radon cycles, photochemistry, thermosphere, ionosphere, etc.).

  11. Reflections on O2 as a Biosignature in Exoplanetary Atmospheres

    Science.gov (United States)

    Meadows, Victoria S.

    2017-10-01

    Oxygenic photosynthesis is Earth's dominant metabolism, having evolved to harvest the largest expected energy source at the surface of most terrestrial habitable zone planets. Using CO2 and H2O - molecules that are expected to be abundant and widespread on habitable terrestrial planets - oxygenic photosynthesis is plausible as a significant planetary process with a global impact. Photosynthetic O2 has long been considered particularly robust as a sign of life on a habitable exoplanet, due to the lack of known "false positives" - geological or photochemical processes that could also produce large quantities of stable O2. O2 has other advantages as a biosignature, including its high abundance and uniform distribution throughout the atmospheric column and its distinct, strong absorption in the visible and near-infrared. However, recent modeling work has shown that false positives for abundant oxygen or ozone could be produced by abiotic mechanisms, including photochemistry and atmospheric escape. Environmental factors for abiotic O2 have been identified and will improve our ability to choose optimal targets and measurements to guard against false positives. Most of these false-positive mechanisms are dependent on properties of the host star and are often strongest for planets orbiting M dwarfs. In particular, selecting planets found within the conservative habitable zone and those orbiting host stars more massive than 0.4 M⊙ (M3V and earlier) may help avoid planets with abundant abiotic O2 generated by water loss. Searching for O4 or CO in the planetary spectrum, or the lack of H2O or CH4, could help discriminate between abiotic and biological sources of O2 or O3. In advance of the next generation of telescopes, thorough evaluation of potential biosignatures - including likely environmental context and factors that could produce false positives - ultimately works to increase our confidence in life detection.

  12. The ultraviolet photochemistry of diacetylene - Direct detection of primary products of the metastable C4H2* + C4H2 reaction

    Science.gov (United States)

    Bandy, Ralph E.; Lakshminarayan, Chitra; Frost, Rex K.; Zwier, Timothy S.

    1993-01-01

    The products of diacetylene's ultraviolet photochemistry over the 245-220 nm region were directly determined in experiments where C4H2 was excited within a small reaction tube attached to a pulsed nozzle. The products formed in the collisions of C4H2* with C4H2 were subsequently ionized by vacuum UV radiation (at 118 nm) in the ion source of a time-of-flight mass spectrometer. It was found that the reaction of C4H2* with C4H2 produces C6H2 (+C2H2), C8H2 (+2H,H2), and C8H3 (+H), confirming the results of Glicker and Okabe (1987). Under certain conditions, secondary products were observed. Mechanisms for the observed reactions are proposed.

  13. Assessment of a 2016 Mission Concept: The Search for Trace Gases in the Atmosphere of Mars

    Science.gov (United States)

    Zurek, Richard W.; Chicarro, Augustin; Allen, Mark A.; Bertauz, Jean-Loup; Clancy, R. Todd; Daerden, Frank; Formisano, Vittorio; Garvin, James B.; neukum, Gerhard; Smith, Michael D.

    2011-01-01

    The reported detection of methane in the atmosphere of Mars as well as its potentially large seasonal spatial variations challenge our understanding of both the sources and sinks of atmospheric trace gases. The presence of methane suggests ongoing exchange between the subsurface and the atmosphere of potentially biogenic trace gases, while the spatial and temporal variations cannot be accounted for with current knowledge of martian photochemistry. A Joint Instrument Definition Team (JIDT) was asked to assess concepts for a mission that might follow up on these discoveries within the framework of a series of joint missions being considered by ESA and NASA for possible future exploration of Mars. The following is based on the report of the JIDT to the space agencies (Zurek et al., 2009); a synopsis of the report was presented at the Workshop on Mars Methane held in Frascati, Italy, in November 2009. To summarize, the JIDT believed that a scientifically exciting and credible mission could be conducted within the evolving capabilities of the science/telecommunications orbiter being considered by ESA and NASA for possible launch in the 2016 opportunity for Mars.

  14. Sat-J: a satellite-derived dataset of global atmospheric photolysis rates

    Science.gov (United States)

    Holmes, C. D.

    2016-12-01

    Photolysis—the breaking of chemical bonds by sunlight—is the primary driving force for reactive atmospheric chemistry. Photolysis reactions directly and indirectly control a host of air pollutants and greenhouse, particularly through the production of the hydroxyl radical (OH), the main oxidizing agent in the troposphere, by photolysis of ozone (O3). Despite the critical importance of atmospheric photochemistry for understanding and predicting air pollution and greenhouse gas levels, the rates of photolysis reactions (J values) are highly uncertain. State-of-the-art air quality and climate models differ in their global-mean J values by a factor of 2, and likely much more on regional and seasonal scales. We describe a new, global, 3-D dataset of photolysis rates that is derived from satellite observations of clouds, aerosols, and trace gases, together with a computationally efficient photolysis code. This "Sat-J" product is validated against in situ observations from aircraft and used to evaluate a 3-D atmospheric chemistry model.

  15. Atmospheric composition change: Ecosystems–Atmosphere interactions

    DEFF Research Database (Denmark)

    Fowler, D.; Pilegaard, Kim; Sutton, M.A.

    2009-01-01

    in the size range 1 nm–10 μm including organic and inorganic chemical species. The main focus of the review is on the exchange between terrestrial ecosystems, both managed and natural and the atmosphere, although some new developments in ocean–atmosphere exchange are included. The material presented is biased...... and techniques in micrometeorology. For some of the compounds there have been paradigm shifts in approach and application of both techniques and assessment. These include flux measurements over marine surfaces and urban areas using micrometeorological methods and the up-scaling of flux measurements using...... aircraft and satellite remote sensing. The application of a flux-based approach in assessment of O3 effects on vegetation at regional scales is an important policy linked development secured through improved quantification of fluxes. The coupling of monitoring, modelling and intensive flux measurement...

  16. Constraining the Volatile Composition and Coma Photochemistry in Jupiter Family Comet 41P/Tuttle-Giacobini-Kresak with High Resolution IR and Optical Spectroscopy

    Science.gov (United States)

    McKay, Adam; DiSanti, Michael; Cochran, Anita; Dello Russo, Neil; Bonev, Boncho; Vervack, Ronald; Gibb, Erika; Roth, Nathan; Kawakita, Hideyo

    2018-01-01

    Over the past 20 years optical and IR spectroscopy of cometary comae has expanded our understanding both of cometary volatile composition and coma photochemistry. However, these observations tend to be biased towards Nearly Isotropic Comets (NIC'S) from the Oort Cloud, rather than the generally fainter and less active Jupiter Family Comets (JFC's) that are thought to originate from the Scattered Disk. However, early 2017 provided a rare opportunity to study several JFC's. We present preliminary results from IR and optical spectroscopy of JFC 41P/Tuttle-Giacobini-Kresak obtained during its 2017 apparition. IR spectra were obtained with the NIRSPEC instrument on Keck II and the new iSHELL spectrograph on NASA IRTF. High spectral resolution optical spectra were obtained with the Tull Coude spectrograph on the 2.7-meter Harlan J. Smith Telescope at McDonald Observatory. We will discuss mixing ratios of HCN, NH3, C2H6, C2H2, H2CO, and CH3OH compared to H2O and compare these to previous observations of comets. Preliminary results from the NIRSPEC observations indicate that 41P has typical C2H2 and HCN abundances compared to other JFC's, while the C2H6 abundance is similar to that of NIC's, but is enriched compared to other JFC's. H2CO appears to be heavily depleted in 41P. Analysis of the iSHELL spectra is underway and we will include results from these observations, which complement those from NIRSPEC and extend the scope or our compositional study by measuring additional molecules. We will also present abundances for CN, C2, NH2, C3, and CH obtained from the optical spectra and discuss the implications for the coma photochemistry.This work is supported by the NASA Postdoctoral Program, administered by the Universities Space Research Association, with additional funding from the NSF and NASA PAST.

  17. Constraining the Volatile Composition and Coma Photochemistry in Jupiter Family Comet 41P/Tuttle-Giacobini-Kresak with High Resolution IR and Optical Spectroscopy

    Science.gov (United States)

    McKay, Adam; DiSanti, Michael A.; Cochran, Anita L.; Dello Russo, Neil; Bonev, Boncho P.; Vervack, Ronald J.; Gibb, Erika L.; Roth, Nathan X.; Kawakita, Hideyo

    2017-10-01

    Over the past 20 years optical and IR spectroscopy of cometary comae has expanded our understanding both of cometary volatile composition and coma photochemistry. However, these observations tend to be biased towards Nearly Isotropic Comets (NIC's) from the Oort Cloud, rather than the generally fainter and less active Jupiter Family Comets (JFC's) that are thought to originate from the Scattered Disk. However, early 2017 provided a rare opportunity to study several JFC's. We present preliminary results from IR and optical spectroscopy of JFC 41P/Tuttle-Giacobini-Kresak obtained during its 2017 apparition. IR spectra were obtained with the NIRSPEC instrument on Keck II and the new iSHELL spectrograph on NASA IRTF. High spectral resolution optical spectra were obtained with the Tull Coude spectrograph on the 2.7-meter Harlan J. Smith Telescope at McDonald Observatory. We will discuss mixing ratios of HCN, NH3, C2H6, C2H2, H2CO, and CH3OH compared to H2O and compare these to previous observations of comets. Preliminary results from the NIRSPEC observations indicate that 41P has typical C2H2 and HCN abundances compared to other JFC's, while the C2H6 abundance is similar to that of NIC's, but is enriched compared to other JFC's. H2CO appears to be heavily depleted in 41P. Analysis of the iSHELL spectra is underway and we will include results from these observations, which complement those from NIRSPEC and extend the scope or our compositional study by measuring additional molecules. We will also present abundances for CN, C2, NH2, C3, and CH obtained from the optical spectra and discuss the implications for the coma photochemistry.This work is supported by the NASA Postdoctoral Program, administered by the Universities Space Research Association, with additional funding from the NSF and NASA PAST.

  18. VUV-absorption cross section of CO2 at high temperatures and impact on exoplanet atmospheres

    Directory of Open Access Journals (Sweden)

    Venot Olivia

    2014-02-01

    Full Text Available Ultraviolet (UV absorption cross sections are an essential ingredient of photochemical atmosphere models. Exoplanet searches have unveiled a large population of short-period objects with hot atmospheres, very different from what we find in our solar system. Transiting exoplanets whose atmospheres can now be studied by transit spectroscopy receive extremely strong UV fluxes and have typical temperatures ranging from 400 to 2500 K. At these temperatures, UV photolysis cross section data are severely lacking. Our goal is to provide high-temperature absorption cross sections and their temperature dependency for important atmospheric compounds. This study is dedicated to CO2, which is observed and photodissociated in exoplanet atmospheres. We performed these measurements for the 115 - 200 nm range at 300, 410, 480, and 550 K. In the 195 - 230 nm range, we worked at seven temperatures between 465 and 800 K. We found that the absorption cross section of CO2 is very sensitive to temperature, especially above 160 nm. Within the studied range of temperature, the CO2 cross section can vary by more than two orders of magnitude. This, in particular, makes the absorption of CO2 significant up to wavelengths as high as 230 nm, while it is negligible above 200 nm at 300 K. To investigate the influence of these new data on the photochemistry of exoplanets, we implemented the measured cross section into a 1D photochemical model. The model predicts that accounting for this temperature dependency of CO2 cross section can affect the computed abundances of NH3, CO2, and CO by one order of magnitude in the atmospheres of hot Jupiter and hot Neptune.

  19. Dynamics of Massive Atmospheres

    Science.gov (United States)

    Chemke, Rei; Kaspi, Yohai

    2017-10-01

    The many recently discovered terrestrial exoplanets are expected to hold a wide range of atmospheric masses. Here the dynamic-thermodynamic effects of atmospheric mass on atmospheric circulation are studied using an idealized global circulation model by systematically varying the atmospheric surface pressure. On an Earth analog planet, an increase in atmospheric mass weakens the Hadley circulation and decreases its latitudinal extent. These changes are found to be related to the reduction of the convective fluxes and net radiative cooling (due to the higher atmospheric heat capacity), which, respectively, cool the upper troposphere at mid-low latitudes and warm the troposphere at high latitudes. These together decrease the meridional temperature gradient, tropopause height and static stability. The reduction of these parameters, which play a key role in affecting the flow properties of the tropical circulation, weakens and contracts the Hadley circulation. The reduction of the meridional temperature gradient also decreases the extraction of mean potential energy to the eddy fields and the mean kinetic energy, which weakens the extratropical circulation. The decrease of the eddy kinetic energy decreases the Rhines wavelength, which is found to follow the meridional jet scale. The contraction of the jet scale in the extratropics results in multiple jets and meridional circulation cells as the atmospheric mass increases.

  20. Atmospheric refraction: a history

    Science.gov (United States)

    Lehn, Waldemar H.; van der Werf, Siebren

    2005-09-01

    We trace the history of atmospheric refraction from the ancient Greeks up to the time of Kepler. The concept that the atmosphere could refract light entered Western science in the second century B.C. Ptolemy, 300 years later, produced the first clearly defined atmospheric model, containing air of uniform density up to a sharp upper transition to the ether, at which the refraction occurred. Alhazen and Witelo transmitted his knowledge to medieval Europe. The first accurate measurements were made by Tycho Brahe in the 16th century. Finally, Kepler, who was aware of unusually strong refractions, used the Ptolemaic model to explain the first documented and recognized mirage (the Novaya Zemlya effect).

  1. New atmospheric program

    Science.gov (United States)

    The National Science Foundation's Division of Atmospheric Sciences has established an Upper Atmospheric Facilities program within its Centers and Facilities section. The program will support the operation of and the scientific research that uses the longitudinal chain of incoherent scatter radars. The program also will ensure that the chain is maintained as a state-of-the-art research tool available to all interested and qualified scientists.For additional information, contact Richard A. Behnke, Division of Atmospheric Sciences, National Science Foundation, 1800 G Street, N.W., Washington, DC 20550 (telephone: 202-357-7390).

  2. Discovery of atmospheric neutrino oscillations

    Energy Technology Data Exchange (ETDEWEB)

    Kajita, Takaaki [Tokyo Univ., Inst. for Cosmic Ray Research, Kashiwa, Chiba (Japan)

    2003-05-01

    Cosmic ray particles entering the atmosphere interact with the air nuclei produce neutrinos. These neutrinos are called atmospheric neutrinos. The atmospheric neutrino anomaly observed in Kamiokande is now understood as due to neutrino oscillations by high statistics measurements of the atmospheric neutrinos in Super-Kamiokande. The studies of the atmospheric neutrinos have matured into detailed studies of neutrino masses and mixings. (author)

  3. Effects of Deep Convection on Atmospheric Chemistry

    Science.gov (United States)

    Pickering, Kenneth E.

    2007-01-01

    parameterizations for global chemical transport models. The range of mean values (factor of 3) of NO production per flash (or per meter of lightning channel length) that have been deduced from the model will be shown and compared with values of production in the literature that have been deduced using other methods, Results show that on a per flash basis, IC flashes are nearly as productive of NO as CG flashes. When combined with the global flash rate of 44 flashes per second from NASA's Optical Transient Detector (OTD) measurements, these estimates and the results from other techniques yield global NO production rates of 2-9 TgN/year. Vertical profiles of lightning NOx mass at the end of the 3-D storm simulations have been summarized to yield suggested profiles for use in global models. Simulations of the photochemistry over the 24 hours following a storm have been performed to determine the additional ozone production which can be attributed to lightning NO.

  4. A population study of hot Jupiter atmospheres

    Science.gov (United States)

    Tsiaras, Angelos; Waldmann, Ingo; Zingales, Tiziano; Rocchetto, Marco; Morello, Giuseppe; Damiano, Mario; Karpouzas, Konstantinos; Tinetti, Giovanna; McKemmish, Laura; Tennyson, Jonathan; Yurchenko, Sergey

    2017-10-01

    In the past two decades, we have learnt that every star hosts more than one planet. While the hunt for new exoplanets is on-going, the current sample of more than 3500 confirmed planets reveals a wide spectrum of planetary characteristics. While small planets appear to be the most common, the big and gaseous planets play a key role in the process of planetary formation. We present here the analysis of 30 gaseous extra-solar planets, with temperatures between 600 and 2400 K and radii between 0.35 and 1.9 Jupiter radii. These planets were spectroscopically observed with the Wide Field Camera 3 on-board the Hubble Space Telescope, which is currently one of the most successful instruments for observing exoplanetary atmospheres. The quality of the HST/WFC3 spatially-scanned data combined with our specialised analysis tools, allows us to create the largest and most self-consistent sample of exoplanetary transmission spectra to date and study the collective behaviour of warm and hot gaseous planets rather than isolated case-studies. We define a new metric, the Atmospheric Detectability Index (ADI) to evaluate the statistical significance of an atmospheric detection and find statistically significant atmospheres around 16 planets. For most of the Jupiters in our sample we find the detectability of their atmospheres to be dependent on the planetary radius but not on the planetary mass. This indicates that planetary gravity is a secondary factor in the evolution of planetary atmospheres. We detect the presence of water vapour in all the statistically detectable atmospheres and we cannot rule out its presence in the atmospheres of the others. In addition, TiO and/or VO signatures are detected with 4σ confidence in WASP-76 b, and they are most likely present on WASP-121 b. We find no correlation between expected signal-to-noise and atmospheric detectability for most targets. This has important implications for future large-scale surveys.

  5. Atmospheric Transport Modeling Resources

    Energy Technology Data Exchange (ETDEWEB)

    Mazzola, Carl A. [Stone and Webster Engineering Corporation, Aiken, SC (United States); Addis, Robert P. [Westinghouse Savannah River Company, Aiken, SC (United States)

    1995-03-01

    The purpose of this publication is to provide DOE and other federal agency emergency managers with an in-depth compilation and description of atmospheric dispersion models available to DOE and other Federal sites.

  6. Atmospheric Heavy Metal Pollution

    Indian Academy of Sciences (India)

    Home; Journals; Resonance – Journal of Science Education; Volume 6; Issue 4. Atmospheric Heavy Metal Pollution - Development of Chronological Records and Geochemical Monitoring. Rohit Shrivastav. General Article Volume 6 Issue 4 April 2001 pp 62-68 ...

  7. Students 'Weigh' Atmospheric Pollution.

    Science.gov (United States)

    Caporaloni, Marina

    1998-01-01

    Describes a procedure developed by students that measures the mass concentration of particles in a polluted urban atmosphere. Uses a portable fan and filters of various materials. Compares students' data with official data. (DDR)

  8. Our Changing Atmosphere.

    Science.gov (United States)

    Clearing, 1988

    1988-01-01

    Summarizes what is known about two major variables involved in certain types of chemical pollution that seem to be changing the structure of the Earth's atmosphere. Discusses the greenhouse effect and the ozone layer. (TW)

  9. Global atmospheric changes.

    OpenAIRE

    Piver, W T

    1991-01-01

    Increasing concentrations of CO2 and other greenhouse gases in the atmosphere can be directly related to global warming. In terms of human health, because a major cause of increasing atmospheric concentrations of CO2 is the increased combustion of fossil fuels, global warming also may result in increases in air pollutants, acid deposition, and exposure to ultraviolet (UV) radiation. To understand better the impacts of global warming phenomena on human health, this review emphasizes the proces...

  10. Dynamics in Atmospheric Physics

    Science.gov (United States)

    Lindzen, Richard A.

    2005-08-01

    Motion is manifest in the atmosphere in an almost infinite variety of ways. In Dynamics in Atmospheric Physics, Dr. Richard Lindzen describes the nature of motion in the atmosphere, develops fluid dynamics relevant to the atmosphere, and explores the role of motion in determining the climate and atmospheric composition. The author presents the material in a lecture note style, and the emphasis throughout is on describing phenomena that are at the frontiers of current research, but due attention is given to the methodology of research and to the historical background of these topics. The author's treatment and choice of topics is didactic. Problems at the end of each chapter will help students assimilate the material. In general the discussions emphasize physical concepts, and throughout Dr. Lindzen makes a concerted effort to avoid the notion that dynamic meteorology is simply the derivation of equations and their subsequent solution. His desire is that interested students will delve further into solution details. The book is intended as a text for first year graduate students in the atmospheric sciences. Although the material in the book is self contained, a familiarity with differential equations is assumed; some background in fluid mechanics is helpful.

  11. Use of Optical Oxygen Sensors in Non-Destructively Determining the Levels of Oxygen Present in Combined Vacuum and Modified Atmosphere Packaged Pre-Cooked Convenience-Style Foods and the Use of Ethanol Emitters to Extend Product Shelf-Life.

    Science.gov (United States)

    Hempel, Andreas W; Papkovsky, Dmitri B; Kerry, Joseph P

    2013-11-18

    O₂ sensors were used to non-destructively monitor O₂ levels in commercially packed pre-cooked, convenience modified atmosphere packaging (MAP) foods. A substantial level of O₂ (>15%) was present in packs resulting in a shorter than expected shelf-life, where the primary spoilage mechanism was found to be mould. Various combinations of vacuum (0-0.6 MPa) and gas flush (0.02-0.03 MPa) (30% CO₂/70% N₂) settings were assessed as treatments that result in the desired shelf-life (28 days). This was achieved using the combined treatment of vacuum 0.35 MPa and gas flush 0.02 MPa which resulted in a reduction of 6%-9% O2 in all three samples (battered sausages (BS), bacon slices (BA), and meat and potato pies (PP)). Reduced O₂ levels reflect the microbial quality of products, which has been successfully reduced. Duplicate samples of all product packs were produced using ethanol emitters (EE) to see if shelf-life could be further extended. Results showed a further improvement in shelf-life to 35 days. Sensory analysis showed that ethanol flavour and aroma was not perceived by panellists in two of the three products assessed. This study demonstrates how smart packaging technologies, both intelligent and active, can be used to assist in the modification of conventional packaging systems in order to enhance product quality and safety and through the extension of product shelf-life.

  12. Combination vaccines

    Directory of Open Access Journals (Sweden)

    David AG Skibinski

    2011-01-01

    Full Text Available The combination of diphtheria, tetanus, and pertussis vaccines into a single product has been central to the protection of the pediatric population over the past 50 years. The addition of inactivated polio, Haemophilus influenzae, and hepatitis B vaccines into the combination has facilitated the introduction of these vaccines into recommended immunization schedules by reducing the number of injections required and has therefore increased immunization compliance. However, the development of these combinations encountered numerous challenges, including the reduced response to Haemophilus influenzae vaccine when given in combination; the need to consolidate the differences in the immunization schedule (hepatitis B; and the need to improve the safety profile of the diphtheria, tetanus, and pertussis combination. Here, we review these challenges and also discuss future prospects for combination vaccines.

  13. Atmospheric Circulation of Exoplanets

    Science.gov (United States)

    Showman, A. P.; Cho, J. Y.-K.; Menou, K.

    2010-12-01

    We survey the basic principles of atmospheric dynamics relevant to explaining existing and future observations of exoplanets, both gas giant and terrestrial. Given the paucity of data on exoplanet atmospheres, our approach is to emphasize fundamental principles and insights gained from solar system studies that are likely to be generalizable to exoplanets. We begin by presenting the hierarchy of basic equations used in atmospheric dynamics, including the Navier-Stokes, primitive, shallow-water, and two-dimensional nondivergent models. We then survey key concepts in atmospheric dynamics, including the importance of planetary rotation, the concept of balance, and simple scaling arguments to show how turbulent interactions generally produce large-scale east-west banding on rotating planets. We next turn to issues specific to giant planets, including their expected interior and atmospheric thermal structures, the implications for their wind patterns, and mechanisms to pump their east-west jets. Hot Jupiter atmospheric dynamics are given particular attention, as these close-in planets have been the subject of most of the concrete developments in the study of exoplanetary atmospheres. We then turn to the basic elements of circulation on terrestrial planets as inferred from solar system studies, including Hadley cells, jet streams, processes that govern the large-scale horizontal temperature contrasts, and climate, and we discuss how these insights may apply to terrestrial exoplanets. Although exoplanets surely possess a greater diversity of circulation regimes than seen on the planets in our solar system, our guiding philosophy is that the multidecade study of solar system planets reviewed here provides a foundation upon which our understanding of more exotic exoplanetary meteorology must build.

  14. High-Resolution Mass Spectrometry and Molecular Characterization of Aqueous Photochemistry Products of Common Types of Secondary Organic Aerosols

    Energy Technology Data Exchange (ETDEWEB)

    Romonosky, Dian E.; Laskin, Alexander; Laskin, Julia; Nizkorodov, Sergey

    2015-03-19

    A significant fraction of atmospheric organic compounds is predominantly found in condensed phases, such as aerosol particles and cloud droplets. Many of these compounds are photolabile and can degrade through direct photolysis or indirect photooxidation processes on time scales that are comparable to the typical lifetimes of aqueous droplets (hours) and particles (days). This paper presents a systematic investigation of the molecular level composition and the extent of aqueous photochemical processing in different types of secondary organic aerosol (SOA) from biogenic and anthropogenic precursors including α-pinene, β-pinene, β-myrcene, d- limonene, α-humulene, 1,3,5-trimethylbenzene, and guaiacol, oxidized by ozone (to simulate a remote atmosphere) or by OH in the presence of NOx (to simulate an urban atmosphere). Chamber- and flow tube-generated SOA samples were collected, extracted in a methanol/water solution, and photolyzed for 1 h under identical irradiation conditions. In these experiments, the irradiation was equivalent to about 3-8 h of exposure to the sun in its zenith. The molecular level composition of the dissolved SOA was probed before and after photolysis with direct-infusion electrospray ionization high-resolution mass spectrometry (ESI-HR-MS). The mass spectra of unphotolyzed SOA generated by ozone oxidation of monoterpenes showed qualitatively similar features, and contained largely overlapping subsets of identified compounds. The mass spectra of OH/NOx generated SOA had more unique visual appearance, and indicated a lower extent of products overlap. Furthermore, the fraction of nitrogen containing species (organonitrates and nitroaromatics) was highly sensitive to the SOA precursor. These observations suggest that attribution of high-resolution mass spectra in field SOA samples to specific SOA precursors should be more straightforward under OH/NOx oxidation conditions compared to the ozone driven oxidation. Comparison of the SOA constituents

  15. Fundamentals of Atmospheric Radiation

    Science.gov (United States)

    Bohren, Craig F.; Clothiaux, Eugene E.

    2006-02-01

    This textbook fills a gap in the literature for teaching material suitable for students of atmospheric science and courses on atmospheric radiation. It covers the fundamentals of emission, absorption, and scattering of electromagnetic radiation from ultraviolet to infrared and beyond. Much of the book applies to planetary atmosphere. The authors are physicists and teach at the largest meteorology department of the US at Penn State. Craig T. Bohren has taught the atmospheric radiation course there for the past 20 years with no book. Eugene Clothiaux has taken over and added to the course notes. Problems given in the text come from students, colleagues, and correspondents. The design of the figures especially for this book is meant to ease comprehension. Discussions have a graded approach with a thorough treatment of subjects, such as single scattering by particles, at different levels of complexity. The discussion of the multiple scattering theory begins with piles of plates. This simple theory introduces concepts in more advanced theories, i.e. optical thickness, single-scattering albedo, asymmetry parameter. The more complicated theory, the two-stream theory, then takes the reader beyond the pile-of-plates theory. Ideal for advanced undergraduate and graduate students of atmospheric science.

  16. Atmospheric pollution in Lisbon urban atmosphere

    Science.gov (United States)

    Oliveira, C.

    2009-04-01

    Lisbon is the capital city of Portugal with about 565,000 residents in 2008 and a population density of 6,600 inhabitants per square kilometre. Like several other major metropolis, the town is surrounded by satellite cities, forming together a region known as "Lisbon Metropolitan Area" with about 3 million inhabitants, a quarter of the overall Portuguese population. Besides their local residents, it is estimated that more than one million citizens come into the Lisbon area every day from the outskirts, leading to elevated traffic densities and intense traffic jams, with important consequences on air pollution levels and obvious negative impacts on human health. Airborne particulate matter limit values are frequently exceeded, making urgent the existence of consistent programs to monitor and help taking measures to control them. Within the Portuguese project PAHLIS (Polycyclic Aromatic Hydrocarbons Contamination in Lisbon Urban Atmosphere) financed by the Portuguese Science Foundation ("Fundação para a Ciência e a Tecnologia"), an aerosol and vapour phase sampling program is being implemented in the city of Lisbon at two selected contrasting zones, namely a typically busy area with intense road traffic and frequent exceedences of the particulate matter standard for the maximum allowable concentration, and a residential quieter area, thus with a cleaner atmosphere characterised as an urban background site. An one month-long sampling campaign was performed during the summer of 2008, where particulate matter was collected in two fractions (coarse 2.5µmcommunication, the results of both organic and inorganic analyses of aerosol samples from these two sites will be presented, compared and discussed. Results of this work are expected to cover a lack of reliable information regarding sources of atmospheric pollutants in Portugal and present, for the first time, systematic data of PAHs levels in Lisbon. Acknowledgement: This work was performed under Project PAHLIS (PTDC

  17. Phenomenology of atmospheric neutrinos

    Directory of Open Access Journals (Sweden)

    Fedynitch Anatoli

    2016-01-01

    Full Text Available The detection of astrophysical neutrinos, certainly a break-through result, introduced new experimental challenges and fundamental questions about acceleration mechanisms of cosmic rays. On one hand IceCube succeeded in finding an unambiguous proof for the existence of a diffuse astrophysical neutrino flux, on the other hand the precise determination of its spectral index and normalization requires a better knowledge about the atmospheric background at hundreds of TeV and PeV energies. Atmospheric neutrinos in this energy range originate mostly from decays of heavy-flavor mesons, which production in the phase space relevant for prompt leptons is uncertain. Current accelerator-based experiments are limited by detector acceptance and not so much by the collision energy. This paper recaps phenomenological aspects of atmospheric leptons and calculation methods, linking recent progress in flux predictions with particle physics at colliders, in particular the Large Hadron Collider.

  18. Intensifying the Atmospheric

    DEFF Research Database (Denmark)

    Liebst, Lasse Suonperä

    2012-01-01

    The phenomenological concept of urban atmospheres is more often applied as an aesthetic description of the metropolitan space as such. This conceptualization is supported in this paper; however, I strive to give the concept a post-phenomenological axial turn. While phenomenology, due to its under...... sufficiently intense. All things considered, the paper should be read as a sociological contribution to theoretically reconstruct the concept of urban atmospheres in the light of spatial morphology.......The phenomenological concept of urban atmospheres is more often applied as an aesthetic description of the metropolitan space as such. This conceptualization is supported in this paper; however, I strive to give the concept a post-phenomenological axial turn. While phenomenology, due to its...

  19. Atmospheric pollution; Pollution atmospherique

    Energy Technology Data Exchange (ETDEWEB)

    Lambrozo, J.; Guillossou, G. [EDF-Gas de France, Service des Etudes Medicales, 75 - Paris (France)

    2008-10-15

    The atmosphere is the reservoir of numerous pollutants (nitrogen oxides, sulfur oxides, carbon oxides, particulates, volatile organic compounds, polycyclic aromatic hydrocarbons) from natural origin or anthropogenic origin ( industry, transport, agriculture, district heating). With epidemiologic studies the atmospheric pollution is associated with an increase of respiratory and cardiovascular diseases. At the european level, the technological progress, the legislation have allowed a reduction of pollutant emissions, however these efforts have to be continued because the sanitary impact of atmospheric pollution must not be underestimated, even if the risks appear less important that these ones in relation with tobacco, inside pollution or others factors of cardiovascular risks. Indeed, on these last factors an individual action is possible for the exposure to air pollution people have no control. (N.C.)

  20. Atmosphere and Ambient Space

    DEFF Research Database (Denmark)

    Schmidt, Ulrik

    Atmosphere and Ambient Space This paper explores the relation between atmosphere and ambient space. Atmosphere and ambient space share many salient properties. They are both ontologically indeterminate, constantly varying and formally diffuse and they are both experienced as a subtle, non......-signifying property of a given space. But from a certain point of view, the two concepts also designate quite dissimilar experiences of space. To be ’ambient’ means to surround. Accordingly, ambient space is that space, which surrounds something or somebody. (Gibson 1987: 65) Since space is essentially...... of a surrounding character, all space can thus be described as having a fundamentally ambient character. So what precisely is an ambient space, then? As I will argue in my presentation, ambient space is a sensory effect of spatiality when a space is experienced as being particularly surrounding: a ‘space effect...

  1. Atmospheric Infrared Radiance Variability.

    Science.gov (United States)

    1981-05-27

    ATMOSPHERIC VARIABILITY ON INFRARED RADIANCE PREDICTIONS - T. C. Degges 53 5. ATMOSPHERIC STRUCTURE - C.H. HLmphrey, C.R. Philbrick, S.M. Silverman , T.F. Tuan...variations similar to those shown in Figure 2. In arctic and subarctic regions, sudden warmings and coolings of the winter stratosphere and mesosphere... Silverman \\Jr I",rre. (;.L~~sIalmratorN Hanscom Air Force Base, Manss. T.F. Tuan Universitv of Cincinnati Cincinnati, (tio M. Anapol S.S.G.. Inc. Waltham

  2. Atmosphere and Heritage

    DEFF Research Database (Denmark)

    Ventzel Riis, Nina

    2012-01-01

    -between of the materials. This is what we identify as atmosphere, an enveloping phenomenon that surrounds and affects our sensuous system and well-being when we approach, enter, stay or move in a building. When we leave the building again we carry this atmospheric multi-sensory experience with us without adequate methods...... to describe and document it. In this paper I will introduce both new and traditional approaches to document the architectural heritage with the final conclusion to describe both tangible and intangible values, it requires an objective and geometrical approach as well as a subjective and phenomenological...

  3. Atmosphere, Ocean and Climate Dynamics An Introductory Text

    CERN Document Server

    Marshall, John

    1961-01-01

    For advanced undergraduate and beginning graduate students in atmospheric, oceanic, and climate science, Atmosphere, Ocean and Climate Dynamics is an introductory textbook on the circulations of the atmosphere and ocean and their interaction, with an emphasis on global scales. It will give students a good grasp of what the atmosphere and oceans look like on the large-scale and why they look that way. The role of the oceans in climate and paleoclimate is also discussed. The combination of observations, theory and accompanying illustrative laboratory experiments sets this text apart by making i

  4. Regional Ecosystem-Atmosphere CO2 Exchange Via Atmospheric Budgets

    Energy Technology Data Exchange (ETDEWEB)

    Davis, K J; Richardson, S J; Miles, N L

    2007-03-07

    are captured. Influence functions, derived using a Lagrangian Particle Dispersion model driven by the CSU Regional Atmospheric Modeling System and nudged to NCEP reanalysis meteorological fields, are used to determine source regions for the towers. The influence functions are combined with satellite vegetation observations to interpret the observed trends in CO2 concentration. Full inversions will combine these elements in a more formal analytic framework.

  5. combination Dictionary

    African Journals Online (AJOL)

    rbr

    advanced-level Spanish-speaking EFL learners. 2. Word combinations ... a certain process of segregation as a separate branch of linguistics. While lexi- ... As substantiated by Ilson's investigation of lexicographic practices, most dictionaries ...

  6. Evaluation of satellites and remote sensors for atmospheric pollution measurements

    Science.gov (United States)

    Carmichael, J.; Eldridge, R.; Friedman, E.; Keitz, E.

    1976-01-01

    An approach to the development of a prioritized list of scientific goals in atmospheric research is provided. The results of the analysis are used to estimate the contribution of various spacecraft/remote sensor combinations for each of several important constituents of the stratosphere. The evaluation of the combinations includes both single-instrument and multiple-instrument payloads. Attention was turned to the physical and chemical features of the atmosphere as well as the performance capability of a number of atmospheric remote sensors. In addition, various orbit considerations were reviewed along with detailed information on stratospheric aerosols and the impact of spacecraft environment on the operation of the sensors.

  7. Results from atmospheric neutrinos

    Indian Academy of Sciences (India)

    With the announcement of new evidence for muon neutrino disappearance observed by the super-Kamiokande experiment, the more than a decade old atmospheric neutrino anomaly moved from a possible indication for neutrino oscillations to an apparently inescapable fact. The evidence is reviewed, and new indications ...

  8. Photochemistry and aerosol in alpine region: mixing and transport; Photochimie et aerosol en region alpine: melange et transport

    Energy Technology Data Exchange (ETDEWEB)

    Chaxel, E

    2006-11-15

    The Alpine arc deeply interacts with general circulation of atmosphere. By studying configurations in summer and winter over various Alpine areas, this work explains how mixing and transport of airborne pollutants happen, both gaseous and particulate matter, from their emission sources to free troposphere. Using observational results and a comprehensive Eulerian modelling system, one focuses on mechanisms of pollution by ozone in summer and by particulate matter and benzene in winter. After having validated the modelling system using datasets from field experiments POVA, GRENOPHOT and ESCOMPTE, it is applied on two periods with principal interest in the Grenoble area: one is the heat-wave August 2003 and the other is a long episode of thermal inversion in February 2005. Uncertainties are also calculated. One finishes by applying the modelling chain to understand how a stratospheric intrusion following a tropopause fold affected the Alpine region in July 2004. (author)

  9. ESA Atmospheric Toolbox

    Science.gov (United States)

    Niemeijer, Sander

    2017-04-01

    The ESA Atmospheric Toolbox (BEAT) is one of the ESA Sentinel Toolboxes. It consists of a set of software components to read, analyze, and visualize a wide range of atmospheric data products. In addition to the upcoming Sentinel-5P mission it supports a wide range of other atmospheric data products, including those of previous ESA missions, ESA Third Party missions, Copernicus Atmosphere Monitoring Service (CAMS), ground based data, etc. The toolbox consists of three main components that are called CODA, HARP and VISAN. CODA provides interfaces for direct reading of data from earth observation data files. These interfaces consist of command line applications, libraries, direct interfaces to scientific applications (IDL and MATLAB), and direct interfaces to programming languages (C, Fortran, Python, and Java). CODA provides a single interface to access data in a wide variety of data formats, including ASCII, binary, XML, netCDF, HDF4, HDF5, CDF, GRIB, RINEX, and SP3. HARP is a toolkit for reading, processing and inter-comparing satellite remote sensing data, model data, in-situ data, and ground based remote sensing data. The main goal of HARP is to assist in the inter-comparison of datasets. By appropriately chaining calls to HARP command line tools one can pre-process datasets such that two datasets that need to be compared end up having the same temporal/spatial grid, same data format/structure, and same physical unit. The toolkit comes with its own data format conventions, the HARP format, which is based on netcdf/HDF. Ingestion routines (based on CODA) allow conversion from a wide variety of atmospheric data products to this common format. In addition, the toolbox provides a wide range of operations to perform conversions on the data such as unit conversions, quantity conversions (e.g. number density to volume mixing ratios), regridding, vertical smoothing using averaging kernels, collocation of two datasets, etc. VISAN is a cross-platform visualization and

  10. OCEANET-Atmosphere - The Autonomous Measurement Container

    Science.gov (United States)

    Kalisch, John; Macke, Andreas; Althausen, Dietrich; Bumke, Karl; Engelmann, Ronny; Kanitz, Thomas; Kleta, Henry; Zoll, Yann

    2010-05-01

    OCEANET-Atmosphere is a joint venture project of IFM-GEOMAR and IFT to study the mass and energy transfer of ocean and atmosphere by introducing a special measurement container, which is suitable to perform a large spectrum of atmospheric underway measurements on offshore research vessels and cargo ships. The container combines state-of-the-art measurement devices and connect them to its own computer network to realize a comprehensive system for remote sensing. A Raman-lidar measures marine and anthropogenic optical aerosol properities by analyzing the elastic signal and the vibration-rotation Raman signal of nitrogen. Our passive microwave radiometer determines the integrated water vapor and the liquid water path of the atmospheric column, as well as vertical temperature and humidity profiles. Carbon dioxide is measured high-frequent. Turbulence measurements are performed by means of a sonic anemometer. In combination with fast humidity sensors the fluxes of momentum, latent and sensible heat are derived. An automatic full sky imager monitors the state of the cloudy sky. A selection of standard meteorological devices measure air temperature, humidity, wind velocity, wind speed and downward shortwave and longwave radiative fluxes. The GPS sensors register navigational data. For an almost real time monitoring of a data subset our telemetry system is sending short hourly data reports via satellite. OCEANET-Atmosphere is set up to improve the quantity and the quality of atmospheric data sets on intercontinental oceanic transects, where the previous data base is still weak. A first research mission has been performed onboard RV Polarstern at ANT XXVI/1.

  11. Use of Optical Oxygen Sensors in Non-Destructively Determining the Levels of Oxygen Present in Combined Vacuum and Modified Atmosphere Packaged Pre-Cooked Convenience-Style Foods and the Use of Ethanol Emitters to Extend Product Shelf-Life

    Directory of Open Access Journals (Sweden)

    Andreas W. Hempel

    2013-11-01

    Full Text Available O2 sensors were used to non-destructively monitor O2 levels in commercially packed pre-cooked, convenience modified atmosphere packaging (MAP foods. A substantial level of O2 (>15% was present in packs resulting in a shorter than expected shelf-life, where the primary spoilage mechanism was found to be mould. Various combinations of vacuum (0–0.6 MPa and gas flush (0.02–0.03 MPa (30% CO2/70% N2 settings were assessed as treatments that result in the desired shelf-life (28 days. This was achieved using the combined treatment of vacuum 0.35 MPa and gas flush 0.02 MPa which resulted in a reduction of 6%–9% O2 in all three samples (battered sausages (BS, bacon slices (BA, and meat and potato pies (PP. Reduced O2 levels reflect the microbial quality of products, which has been successfully reduced. Duplicate samples of all product packs were produced using ethanol emitters (EE to see if shelf-life could be further extended. Results showed a further improvement in shelf-life to 35 days. Sensory analysis showed that ethanol flavour and aroma was not perceived by panellists in two of the three products assessed. This study demonstrates how smart packaging technologies, both intelligent and active, can be used to assist in the modification of conventional packaging systems in order to enhance product quality and safety and through the extension of product shelf-life.

  12. 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.

  13. Determining solar effects in Neptune's atmosphere

    Science.gov (United States)

    Aplin, K. L.; Harrison, R. G.

    2016-07-01

    Long-duration observations of Neptune's brightness at two visible wavelengths provide a disk-averaged estimate of its atmospheric aerosol. Brightness variations were previously associated with the 11-year solar cycle, through solar-modulated mechanisms linked with either ultraviolet or galactic cosmic ray (GCR) effects on atmospheric particles. Here, we use a recently extended brightness data set (1972-2014), with physically realistic modelling to show, rather than alternatives, ultraviolet and GCR are likely to be modulating Neptune's atmosphere in combination. The importance of GCR is further supported by the response of Neptune's atmosphere to an intermittent 1.5- to 1.9-year periodicity, which occurred preferentially in GCR (not ultraviolet) during the mid-1980s. This periodicity was detected both at Earth, and in GCR measured by Voyager 2, then near Neptune. A similar coincident variability in Neptune's brightness suggests nucleation onto GCR ions. Both GCR and ultraviolet mechanisms may occur more rapidly than the subsequent atmospheric particle transport.

  14. Photogeneration of reactive transient species upon irradiation of natural water samples: Formation quantum yields in different spectral intervals, and implications for the photochemistry of surface waters.

    Science.gov (United States)

    Marchisio, Andrea; Minella, Marco; Maurino, Valter; Minero, Claudio; Vione, Davide

    2015-04-15

    Chromophoric dissolved organic matter (CDOM) in surface waters is a photochemical source of several transient species such as CDOM triplet states ((3)CDOM*), singlet oxygen ((1)O2) and the hydroxyl radical (OH). By irradiation of lake water samples, it is shown here that the quantum yields for the formation of these transients by CDOM vary depending on the irradiation wavelength range, in the order UVB > UVA > blue. A possible explanation is that radiation at longer wavelengths is preferentially absorbed by the larger CDOM fractions, which show lesser photoactivity compared to smaller CDOM moieties. The quantum yield variations in different spectral ranges were definitely more marked for (3)CDOM* and OH compared to (1)O2. The decrease of the quantum yields with increasing wavelength has important implications for the photochemistry of surface waters, because long-wavelength radiation penetrates deeper in water columns compared to short-wavelength radiation. The average steady-state concentrations of the transients ((3)CDOM*, (1)O2 and OH) were modelled in water columns of different depths, based on the experimentally determined wavelength trends of the formation quantum yields. Important differences were found between such modelling results and those obtained in a wavelength-independent quantum yield scenario. Copyright © 2015 Elsevier Ltd. All rights reserved.

  15. Ultraviolet photochemistry of 2-bromothiophene explored using universal ionization detection and multi-mass velocity-map imaging with a PImMS2 sensor

    Science.gov (United States)

    Ingle, R. A.; Hansen, C. S.; Elsdon, E.; Bain, M.; King, S. J.; Lee, J. W. L.; Brouard, M.; Vallance, C.; Turchetta, R.; Ashfold, M. N. R.

    2017-07-01

    The ultraviolet photochemistry of 2-bromothiophene (C4H3SBr) has been studied across the wavelength range 265-245 nm using a velocity-map imaging (VMI) apparatus recently modified for multi-mass imaging and vacuum ultraviolet (VUV, 118.2 nm) universal ionization. At all wavelengths, molecular products arising from the loss of atomic bromine were found to exhibit recoil velocities and anisotropies consistent with those reported elsewhere for the Br fragment [J. Chem. Phys. 142, 224303 (2015)]. Comparison between the momentum distributions of the Br and C4H3S fragments suggests that bromine is formed primarily in its ground (2P3/2) spin-orbit state. These distributions match well at high momentum, but relatively fewer slow moving molecular fragments were detected. This is explained by the observation of a second substantial ionic product, C3H3+. Analysis of ion images recorded simultaneously for several ion masses and the results of high-level ab initio calculations suggest that this fragment ion arises from dissociative ionization (by the VUV probe laser) of the most internally excited C4H3S fragments. This study provides an excellent benchmark for the recently modified VMI instrumentation and offers a powerful demonstration of the emerging field of multi-mass VMI using event-triggered, high frame-rate sensors, and universal ionization.

  16. VUV photochemistry of the H2OCO complex in noble-gas matrices: formation of the OHCO complex and the HOCO radical.

    Science.gov (United States)

    Ryazantsev, Sergey V; Duarte, Luís; Feldman, Vladimir I; Khriachtchev, Leonid

    2016-12-21

    Vacuum ultraviolet (VUV, 130-170 nm) photochemistry of the H2OCO complex is studied by matrix-isolation infrared spectroscopy. The H2OCO complexes in Ne, Ar, Kr, and Xe matrices are generated by ultraviolet (UV, 193 and 250 nm) photolysis of formic acid (HCOOH). VUV photolysis of the H2OCO complexes is found to lead to the formation of the OHCO radical-molecule complexes and trans-HOCO radicals. It is shown that the matrix material, local matrix morphology, and possibly the H2OCO complex geometry strongly affect the VUV photolysis pathways. The intrinsic reactivity of the matrix-isolated OHCO complex resulting in the formation of trans-HOCO is directly demonstrated for the first time. This reaction occurs in Ar, Kr, and Xe matrices upon annealing above 25 K and may proceed over the barrier. The case of a Ne matrix is very special because the formation of trans-HOCO from the OHCO complex is observed even at the lowest experimental temperature (4.5 K), which is in sharp contrast to the other matrices. It follows that quantum tunneling is probably involved in this process in the Ne matrix at such a low temperature. Infrared light also promotes this reaction in the Ne matrix at 4.5 K, which is not the case in the other matrices. The last findings show the effect of the environment on the tunneling and infrared-induced rates of this fundamental chemical reaction.

  17. Measurements of spectrally integrated atmospheric transmittance in the O2 Schumann-Runge bands and derived oxygen column densities - 76-102 km

    Science.gov (United States)

    Longmire, M. S.; Bartoe, J.-D. F.; Brown, C. M.; Brueckner, G. E.; Tousey, R.

    1979-01-01

    Atmospheric transmittances integrated over wavelength intervals corresponding approximately to the (15-0) through (4-0) Schumann-Runge bands of O2 have been determined from EUV solar spectra (wavelengths between 1768 and 1948 A) photographed at seven altitudes between 102 and 76 km with a rocket-borne spectrograph having a resolution of 0.07 A. The observed transmittances are compared with atmospheric transmittances predicted from three models of the O2 absorption cross section. The predicted transmittances have also been used to derive column densities of atmospheric O2 from the observations. The results are compared with values calculated from the U.S. Standard Atmosphere (1976) and with oxygen column densities determined by Prinz and Brueckner (1977) from EUV solar spectra of the Schumann-Runge continuum (wavelength below 1750 A) and of the H-Lyman alpha line (1216 A) recorded on the same films used in the present research. The comparisons test the utility of the models for studies of atmospheric photochemistry, suggest which models may be best for this purpose, and indicate how the models can be improved.

  18. 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....

  19. Investigating CO2 Reservoirs at Gale Crater and Evidence for a Dense Early Atmosphere

    Science.gov (United States)

    Niles, P. B.; Archer, P. D.; Heil, E.; Eigenbrode, J.; McAdam, A.; Sutter, B.; Franz, H.; Navarro-Gonzalez, R.; Ming, D.; Mahaffy, P. R.; hide

    2015-01-01

    Hesperian/Noachian boundary. Likewise, the absence of carbonates suggests that CO2- weathering processes similar to those present on Earth were not dominant. Instead it is possible that more exotic CO2 deposition has occurred driven by atmospheric photochemistry and/or degradation of organic carbon.

  20. Anoxic atmospheres on Mars driven by volcanism: Implications for past environments and life

    Science.gov (United States)

    Sholes, Steven F.; Smith, Megan L.; Claire, Mark W.; Zahnle, Kevin J.; Catling, David C.

    2017-07-01

    Mars today has no active volcanism and its atmosphere is oxidizing, dominated by the photochemistry of CO2 and H2O. Mars experienced widespread volcanism in the past and volcanic emissions should have included reducing gases, such as H2 and CO, as well as sulfur-bearing gases. Using a one-dimensional photochemical model, we consider whether plausible volcanic gas fluxes could have switched the redox-state of the past martian atmosphere to reducing conditions. In our model, the total quantity and proportions of volcanic gases depend on the water content, outgassing pressure, and oxygen fugacity of the source melt. We find that, with reasonable melt parameters, the past martian atmosphere (∼3.5 Gyr to present) could have easily reached reducing and anoxic conditions with modest levels of volcanism, >0.14 km3 yr-1, which are well within the range of estimates from thermal evolution models or photogeological studies. Counter-intuitively we also find that more reducing melts with lower oxygen fugacity require greater amounts of volcanism to switch a paleo-atmosphere from oxidizing to reducing. The reason is that sulfur is more stable in such melts and lower absolute fluxes of sulfur-bearing gases more than compensate for increases in the proportions of H2 and CO. These results imply that ancient Mars should have experienced periods with anoxic and reducing atmospheres even through the mid-Amazonian whenever volcanic outgassing was sustained at sufficient levels. Reducing anoxic conditions are potentially conducive to the synthesis of prebiotic organic compounds, such as amino acids, and are therefore relevant to the possibility of life on Mars. Also, anoxic reducing conditions should have influenced the type of minerals that were formed on the surface or deposited from the atmosphere. We suggest looking for elemental polysulfur (S8) as a signature of past reducing atmospheres. Finally, our models allow us to estimate the amount of volcanically sourced atmospheric

  1. Atmospheric lepton fluxes

    Directory of Open Access Journals (Sweden)

    Gaisser Thomas K.

    2015-01-01

    Full Text Available This review of atmospheric muons and neutrinos emphasizes the high energy range relevant for backgrounds to high-energy neutrinos of astrophysical origin. After a brief historical introduction, the main distinguishing features of atmospheric νμ and νe are discussed, along with the implications of the muon charge ratio for the νµ / ν̅µ ratio. Methods to account for effects of the knee in the primary cosmic-ray spectrum and the energy-dependence of hadronic interactions on the neutrino fluxes are discussed and illustrated in the context of recent results from IceCube. A simple numerical/analytic method is proposed for systematic investigation of uncertainties in neutrino fluxes arising from uncertainties in the primary cosmic-ray spectrum/composition and hadronic interactions.

  2. Habituating alarming atmospheres

    DEFF Research Database (Denmark)

    Højlund, Marie

    This paper proposes embodied rhythmic sound habituation as a possible resource when designing contextualized technologies in critical atmospheres. The main contribution is collating the concept of rhythm as presented by Henri Lefebvre with the concept of sound habituation to help operationalize...... essential dynamic parameters when designing atmospheres. This research is based on the development of the novel research artefact Kidkit, designed for children, who are going to meet a hospitalized relative with fatal injuries in a Neuro–Intensive Care Unit. Sounds from hospital equipment have important...... functionality for the staff, but are stressful for visitors and patients, as they are designed to demand attention even though they have no direct functional meaning to them. By introducing sounds from the ward, integrated in the furniture as simple sound sample triggers, KidKit invites children to become...

  3. Atmosphere beyond Poetics

    DEFF Research Database (Denmark)

    Wieczorek, Izabela

    2014-01-01

    , the notion of atmosphere is presented as parallactic for designing experience in architectural fields, since it transgresses formal and material boundaries of bodies, opening a new gap that exposes the orthodox space-body-environment relationships to questions. It leads to the dissolution...... of the architectural ‘object’ and its fixity and offers a new understanding of context and space – approached as a field of dynamic relationships. It calls for a re-evaluation of perceptual experience, offering to architecture an expanded domain in which architecture manifests itself, including qualities – besides...... poetics and beauty – that architecture has long resisted. That is, it defines space as a contingent construction, performative and intensely affective. Accordingly, the intention is to critically analyse what the term atmosphere entails in architecture, and to expand its notion in terms of affective...

  4. Contaminants in the Atmosphere

    DEFF Research Database (Denmark)

    Skov, H.; Bossi, R.; Wåhlin, P.

    This report presents the results of atmospheric monitoring in Nuuk, Greenland. A long series of heavy metals and persistent organic Pollutants (POPs) have been measured and model calculations have been carried out supporting the interpretation of the results. Financially, the Danish Environmental...... Protection Agency supported this work with means from the MIKA/DANCEA funds for Environmental Support to the Arctic Region and the work is part of the Danish contribution to Arctic Monitoring and Assessment Programme, AMAP......This report presents the results of atmospheric monitoring in Nuuk, Greenland. A long series of heavy metals and persistent organic Pollutants (POPs) have been measured and model calculations have been carried out supporting the interpretation of the results. Financially, the Danish Environmental...

  5. Winning Combinations

    DEFF Research Database (Denmark)

    Criscuolo, Paola; Laursen, Keld; Reichstein, Toke

    2017-01-01

    Searching for the most rewarding sources of innovative ideas remains a key challenge in management of technological innovation. Yet, little is known about which combinations of internal and external knowledge sources are triggers for innovation. Extending theories about searching for innovation, ...

  6. Haze in Pluto's atmosphere

    Science.gov (United States)

    Cheng, A. F.; Summers, M. E.; Gladstone, G. R.; Strobel, D. F.; Young, L. A.; Lavvas, P.; Kammer, J. A.; Lisse, C. M.; Parker, A. H.; Young, E. F.; Stern, S. A.; Weaver, H. A.; Olkin, C. B.; Ennico, K.

    2017-07-01

    Haze in Pluto's atmosphere was detected in images by both the Long Range Reconnaissance Imager (LORRI) and the Multispectral Visible Imaging Camera (MVIC) on New Horizons. LORRI observed haze up to altitudes of at least 200 km above Pluto's surface at solar phase angles from ∼20° to ∼169°. The haze is structured with about ∼20 layers, and the extinction due to haze is greater in the northern hemisphere than at equatorial or southern latitudes. However, more haze layers are discerned at equatorial latitudes. A search for temporal variations found no evidence for motions of haze layers (temporal changes in layer altitudes) on time scales of 2 to 5 hours, but did find evidence of changes in haze scale height above 100 km altitude. An ultraviolet extinction attributable to the atmospheric haze was also detected by the ALICE ultraviolet spectrograph on New Horizons. The haze particles are strongly forward-scattering in the visible, and a microphysical model of haze is presented which reproduces the visible phase function just above the surface with 0.5 μm spherical particles, but also invokes fractal aggregate particles to fit the visible phase function at 45 km altitude and account for UV extinction. A model of haze layer generation by orographic excitation of gravity waves is presented. This model accounts for the observed layer thickness and distribution with altitude. Haze particles settle out of the atmosphere and onto Pluto's surface, at a rate sufficient to alter surface optical properties on seasonal time scales. Pluto's regional scale albedo contrasts may be preserved in the face of the haze deposition by atmospheric collapse.

  7. DREAMING OF ATMOSPHERES

    Energy Technology Data Exchange (ETDEWEB)

    Waldmann, I. P., E-mail: ingo@star.ucl.ac.uk [Department of Physics and Astronomy, University College London, Gower Street, WC1E 6BT (United Kingdom)

    2016-04-01

    Here, we introduce the RobERt (Robotic Exoplanet Recognition) algorithm for the classification of exoplanetary emission spectra. Spectral retrieval of exoplanetary atmospheres frequently requires the preselection of molecular/atomic opacities to be defined by the user. In the era of open-source, automated, and self-sufficient retrieval algorithms, manual input should be avoided. User dependent input could, in worst-case scenarios, lead to incomplete models and biases in the retrieval. The RobERt algorithm is based on deep-belief neural (DBN) networks trained to accurately recognize molecular signatures for a wide range of planets, atmospheric thermal profiles, and compositions. Reconstructions of the learned features, also referred to as the “dreams” of the network, indicate good convergence and an accurate representation of molecular features in the DBN. Using these deep neural networks, we work toward retrieval algorithms that themselves understand the nature of the observed spectra, are able to learn from current and past data, and make sensible qualitative preselections of atmospheric opacities to be used for the quantitative stage of the retrieval process.

  8. Dreaming of Atmospheres

    Science.gov (United States)

    Waldmann, I. P.

    2016-04-01

    Here, we introduce the RobERt (Robotic Exoplanet Recognition) algorithm for the classification of exoplanetary emission spectra. Spectral retrieval of exoplanetary atmospheres frequently requires the preselection of molecular/atomic opacities to be defined by the user. In the era of open-source, automated, and self-sufficient retrieval algorithms, manual input should be avoided. User dependent input could, in worst-case scenarios, lead to incomplete models and biases in the retrieval. The RobERt algorithm is based on deep-belief neural (DBN) networks trained to accurately recognize molecular signatures for a wide range of planets, atmospheric thermal profiles, and compositions. Reconstructions of the learned features, also referred to as the “dreams” of the network, indicate good convergence and an accurate representation of molecular features in the DBN. Using these deep neural networks, we work toward retrieval algorithms that themselves understand the nature of the observed spectra, are able to learn from current and past data, and make sensible qualitative preselections of atmospheric opacities to be used for the quantitative stage of the retrieval process.

  9. Balancing atmospheric carbon dioxide

    Energy Technology Data Exchange (ETDEWEB)

    Goreau, T.J. (Discovery Bay Marine Laboratory, Univ. of the West Indies (JM))

    1990-01-01

    Rising carbon dioxide and global temperatures are causing increasing worldwide concern, and pressure towards an international law of the atmosphere is rapidly escalating, yet widespread misconceptions about the greenhouse effect's inevitability, time scale, and causes have inhibited effective consensus and action. Observations from Antarctic ice cores, Amazonian rain forests, and Carribean coral reefs suggest that the biological effects of climate change may be more severe than climate models predict. Efforts to limit emissions from fossil-fuel combustion alone are incapable of stabilizing levels of carbon dioxide in the atmosphere. Stabilizing atmospheric carbon dioxide requires coupled measures to balance sources and sinks of the gas, and will only be viable with large-scale investments in increased sustainable productivity on degraded tropical soils, and in long-term research on renewable energy and biomass product development in the developing countries. A mechanism is outlined which directly links fossil-fuel combustion sources of carbon dioxide to removal via increasing biotic productivity and storage. A preliminary cost-benefit analysis suggests that such measures are very affordable, costing far less than inaction. (With 88 refs.).

  10. Evolution of the atmosphere.

    Science.gov (United States)

    Nunn, J F

    1998-01-01

    Planetary atmospheres depend fundamentally upon their geochemical inventory, temperature and the ability of their gravitational field to retain gases. In the case of Earth and other inner planets, early outgassing released mainly carbon dioxide and water vapour. The secondary veneer of comets and meteorites added further volatiles. Photodissociation caused secondary changes, including the production of traces of oxygen from water. Earth's gravity cannot retain light gases, including hydrogen. but retains oxygen. Water vapour generally does not pass the cold trap at the stratopause. In the archaean, early evolution of life, probably in hydrothermal vents, and the subsequent development of photosynthesis in surface waters, produced oxygen, at 3500 Ma or even earlier, becoming a significant component of the atmosphere from about 2000 Ma. Thereafter banded iron formations became rare, and iron was deposited in oxidized red beds. Atmospheric levels of carbon dioxide and oxygen have varied during the Phanerozoic: major changes may have caused extinctions. particularly the Permian/Triassic. The declining greenhouse effect due to the long-term decrease in carbon dioxide has largely offset increasing solar luminosity, and changes in carbon dioxide levels relate strongly to cycles of glaciation.

  11. Multispectral Resource Sampler (MPS): Proof of Concept. Literature survey of atmospheric corrections

    Science.gov (United States)

    Schowengerdt, R. A.; Slater, P. N.

    1981-01-01

    Work done in combining spectral bands to reduce atmospheric effects on spectral signatures is described. The development of atmospheric models and their use with ground and aerial measurements in correcting spectral signatures is reviewed. An overview of studies of atmospheric effects on the accuracy of scene classification is provided.

  12. Determination of the Atmospheric Neutrino Fluxes from Atmospheric Neutrino Data

    NARCIS (Netherlands)

    Gonzalez-Garcia, M. C.; Maltoni, M.; Rojo, J.

    2006-01-01

    The precise knowledge of the atmospheric neutrino fluxes is a key ingredient in the interpretation of the results from any atmospheric neutrino experiment. In the standard atmospheric neutrino data analysis, these fluxes are theoretical inputs obtained from sophisticated numerical calculations based

  13. 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

  14. NOAA's Tropical Atmosphere Ocean Project

    Data.gov (United States)

    National Oceanic and Atmospheric Administration, Department of Commerce — Realtime El Nino and La Nina data from the tropical Pacific Ocean is provided by the Tropical Atmosphere Ocean / Triangle Trans-Ocean buoy network (TAO/TRITON) of...

  15. Atmospheric corrosion of mild steel

    OpenAIRE

    Morcillo, M.; de la Fuente, D.; Díaz, I.; Cano, H.

    2011-01-01

    The atmospheric corrosion of mild steel is an extensive topic that has been studied by many authors in different regions throughout the world. This compilation paper incorporates relevant publications on the subject, in particular about the nature of atmospheric corrosion products, mechanisms of atmospheric corrosion and kinetics of the atmospheric corrosion process, paying special attention to two matters upon which relatively less information has been published: a) the morphology of steel c...

  16. Atmospheric corrosion of mild steel

    OpenAIRE

    Morcillo, Manuel; Fuente, Daniel de la; Díaz, Iván; Cano, H.

    2011-01-01

    The atmospheric corrosion of mild steel is an extensive topic that has been studied by many authors in different regions throughout the world. This compilation paper incorporates relevant publications on the subject, in particular about the nature of atmospheric corrosion products, mechanisms of atmospheric corrosion and kinetics of the atmospheric corrosion process, paying special attention to two matters upon which relatively less information has been published: a) the morpholog...

  17. Combined homicide

    Directory of Open Access Journals (Sweden)

    Slović Živana

    2017-01-01

    Full Text Available Introduction: Combined homicide is a combination of two or more different modes of killing. These homicides occur when multiple perpetrators have different mode of killing, to hide the true manner of death, or when an initially unsuccessful attack with one weapon is abandoned and changed by another mode which is more successful, or due to availability of weapons at the scene of homicide, or unexpected appearance of possible eyewitness, or else. Case report: This case report is about 65-year old woman who was found in her residence on the floor next to the bed lying on her back with two kitchen knives in her neck. Autopsy revealed an abrasion on the frontal part of the neck and a bruise of the soft tissues of the neck with a double fracture of both greater horns of the hyoid bone and a fracture of both superior horns of the thyroid cartilage. The cause of death was exsanguination into right half of the thoracic cavity from the left subclavian artery which was cut, on the spot of stab wound in the neck. Conclusion: Hemorrhage in the soft tissue near broken hyoid bone and thyroid cartilage indicate that the victim was first strangulated and then stabbed with kitchen knives. Combined homicides are caused by one or more killers in order to accelerate the killing, or to be sure to provide the fatal outcome. This case is also interesting because the killer left weapon in the victim's neck.

  18. the Martian atmospheric boundary layer

    DEFF Research Database (Denmark)

    Petrosyan, A.; Galperin, B.; Larsen, Søren Ejling

    2011-01-01

    The planetary boundary layer (PBL) represents the part of the atmosphere that is strongly influenced by the presence of the underlying surface and mediates the key interactions between the atmosphere and the surface. On Mars, this represents the lowest 10 km of the atmosphere during the daytime...

  19. Earle K. Plyler Prize for Molecular Spectroscopy & Dynamics: Photochemistry of Phenol: A Full-Dimensional Semiclassical Simulation

    Science.gov (United States)

    Truhlar, Donald

    This lecture will present a simulation of the photodissociation of phenol that is made possible by combining four methods in a complementary way: (1) the fourfold way for generating diabatic electronic states, based on diabatic molecular orbitals and configurational uniformity; (2) anchor points reactive potentials for fitting the 33-dimensional diabatic potentials; (3) coherent switches with decay of mixing for multistate dynamics governed by coupled potential energy surfaces, including density matrix coherence and decoherence; (4) army ants tunneling, including electronically nonadiabatic tunneling. By combining all these methods, one can thoroughly sample an ensemble of trajectories with potential energy surfaces and couplings that include multireference dynamic electron correlation. By including army ants tunneling, the trajectory simulation of phenol photodissociation dynamics based on accurate full-dimensional anchor-points reactive potential surfaces and state couplings successfully reproduces the experimentally observed bimodal total kinetic energy release spectra. Analysis of the trajectories uncovers an unexpected dissociation pathway. The new method for including tunneling in full-dimensional molecular dynamics simulations is general, and it can also be used for electronically adiabatic processes. My coauthors in this work are Xuefei Xu, Jingjing Zheng, and Ke R. Yang. This work was supported in part by U.S. Department of Energy, Office of Basic Energy Sciences, under SciDAC Grant No. DE-SC0008666.

  20. Worldwide trend of atmospheric mercury since 1995

    Directory of Open Access Journals (Sweden)

    F. Slemr

    2011-05-01

    Full Text Available Concern about the adverse effects of mercury on human health and ecosystems has led to tightening emission controls since the mid 1980s. But the resulting mercury emissions reductions in many parts of the world are believed to be offset or even surpassed by the increasing emissions in rapidly industrializing countries. Consequently, concentrations of atmospheric mercury are expected to remain roughly constant. Here we show that the worldwide atmospheric mercury concentrations have decreased by about 20 to 38 % since 1996 as indicated by long-term monitoring at stations in the Southern and Northern Hemispheres combined with intermittent measurements of latitudinal distribution over the Atlantic Ocean. The total reduction of the atmospheric mercury burden of this magnitude within 14 years is unusually large among most atmospheric trace gases and is at odds with the current mercury emission inventories with nearly constant anthropogenic emissions over this period. This suggests a major shift in the biogeochemical cycle of mercury including oceans and soil reservoirs. Decreasing reemissions from the legacy of historical mercury emissions are the most likely explanation for this decline since the hypothesis of an accelerated oxidation rate of elemental mercury in the atmosphere is not supported by the observed trends of other trace gases. Acidification of oceans, climate change, excess nutrient input and pollution may also contribute by their impact on the biogeochemistry of ocean and soils. Consequently, models of the atmospheric mercury cycle have to include soil and ocean mercury pools and their dynamics to be able to make projections of future trends.

  1. Atmospheric Composition Instrumentation.

    Science.gov (United States)

    1977-12-26

    9fI urpAt .~~~ — 7. A THOR(a) 9. CON I RACT OR GRANT HUM BER(.) ! ~~~~~~~~ /otis 7 ~~ ~~F 1962~~~ 4~~~~~~ 1 H 9. FoRMING ORGANIZATION NAN NO...objective of the Upper Atmosphere Re- search Program is the acquisition of 1- nowledge of the ohysica] and chemica ) properties and phenomena of the vitally

  2. Atmospheric gas phase reactions

    Science.gov (United States)

    Platt, Ulrich

    This chapter introduces the underlying physicochemical principles and the relevance of atmospheric gas phase reactions. In particular, reaction orders, the concept of elementary reactions, definition of and factors determining reaction rates (kinetic theory of chemical reactions), and photochemical reactions are discussed. Sample applications of the pertinent reaction pathways in tropospheric chemistry are presented, particularly reactions involving free radicals (OH, NO3, halogen oxides) and their roles in the self-cleaning of the troposphere. The cycles of nitrogen and sulfur species as well as the principles of tropospheric ozone formation are introduced. Finally, the processes governing the stratospheric ozone layer (Chapman Cycle and extensions) are discussed.

  3. MOBILE ATMOSPHERIC SENSING

    Directory of Open Access Journals (Sweden)

    L. Wang

    2017-11-01

    Full Text Available Atmospheric quality dramatically deteriorates over the past decades around themetropolitan areas of China. Due to the coal combustion, industrial air pollution, vehicle waste emission, etc., the public health suffers from exposure to such air pollution as fine particles of particulates, sulfur and carbon dioxide, etc. Many meteorological stations have been built to monitor the condition of air quality over the city. However, they are installed at fixed sites and cover quite a small region. The monitoring results of these stations usually do NOT coincide with the public perception of the air quality. This paper is motivated to mimic the human breathing along the citys transportation network by the mobile sensing vehicle of atmospheric quality. To obtain the quantitative perception of air quality, the Environmental Monitoring Vehicle of Wuhan University (EMV-WHU has been developed to automatically collect the data of air pollutants. The EMV-WHU is equipped with GPS/IMU, sensors of PM2.5, carbon dioxide, anemometer, temperature, humidity, noise, and illumination, as well as the visual and infrared camera. All the devices and sensors are well collaborated with the customized synchronization mechanism. Each sort of atmospheric data is accompanied with the uniform spatial and temporal label of high precision. Different spatial and data-mining techniques, such as spatial correlation analysis, logistic regression, spatial clustering, are employed to provide the periodic report of the roadside air quality. With the EMV-WHU, constant collection of the atmospheric data along the Luoyu Road of Wuhan city has been conducted at the daily peak and non-peak time for half a year. Experimental results demonstrated that the EMV is very efficient and accurate for the perception of air quality. Comparative findings with the meteorological stations also show the intelligence of big data analysis and mining of all sorts of EMV measurement of air quality. It is

  4. Rectenna related atmospheric effects

    Science.gov (United States)

    Lee, J.

    1980-01-01

    Possible meteorological effects arising from the existence and operations of a solar power satellite (SPS) system rectenna are examined. Analysis and model simulations in some chosen site situations and meteorological conditions indicate that the meteorological effects of the construction and operation of a rectenna are small, particularly outside the boundary of the structure. From weather and climate points of view, installation of an SPS rectenna seems likely to have effects comparable with those due to other nonindustrial land use changes covering the same area. The absorption and scattering of microwave radiation in the troposphere would have negligible atmospheric effects.

  5. 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 ...

  6. Peroxy radical chemistry and the control of ozone photochemistry at Mace Head, Ireland during the summer of 2002

    Directory of Open Access Journals (Sweden)

    Z. L. Fleming

    2006-01-01

    Full Text Available Peroxy radical (HO2+ΣRO2 measurements, using the PEroxy Radical Chemical Amplification (PERCA technique at the North Atlantic Marine Boundary Layer EXperiment (NAMBLEX at Mace Head in summer 2002, are presented and put into the context of marine, boundary-layer chemistry. A suite of other chemical parameters (NO, NO2, NO3, CO, CH4, O3, VOCs, peroxides, photolysis frequencies and meteorological measurements, are used to present a detailed analysis of the role of peroxy radicals in tropospheric oxidation cycles and ozone formation. Under the range of conditions encountered the peroxy radical daily maxima varied from 10 to 40 pptv. The diurnal cycles showed an asymmetric shape typically shifted to the afternoon. Using a box model based on the master chemical mechanism the average model measurement agreement was 2.5 across the campaign. The addition of halogen oxides to the model increases the level of model/measurement agreement, apparently by respeciation of HOx. A good correlation exists between j(HCHO.[HCHO] and the peroxy radicals indicative of the importance of HCHO in the remote atmosphere as a HOx source, particularly in the afternoon. The peroxy radicals showed a strong dependence on [NO2] with a break point at 0.1 ppbv, where the radicals increased concomitantly with the reactive VOC loading, this is a lower value than seen at representative urban campaigns. The HO2/(HO2+ΣRO2 ratios are dependent on [NOx] ranging between 0.2 and 0.6, with the ratio increasing linearly with NOx. Significant night-time levels of peroxy radicals were measured up to 25 pptv. The contribution of ozone-alkenes and NO3-alkene chemistry to night-time peroxy radical production was shown to be on average 59 and 41%. The campaign mean net ozone production rate was 0.11±0.3 ppbv h-1. The ozone production rate was strongly dependent on [NO] having linear sensitivity (dln(P(O3/dln(NO=1.0. The results imply that the N(O3 (the in-situ net photochemical rate of ozone

  7. Ozone photochemistry in an oil and natural gas extraction region during winter: simulations of a snow-free season in the Uintah Basin, Utah

    Science.gov (United States)

    Edwards, P. M.; Young, C. J.; Aikin, K.; deGouw, J.; Dubé, W. P.; Geiger, F.; Gilman, J.; Helmig, D.; Holloway, J. S.; Kercher, J.; Lerner, B.; Martin, R.; McLaren, R.; Parrish, D. D.; Peischl, J.; Roberts, J. M.; Ryerson, T. B.; Thornton, J.; Warneke, C.; Williams, E. J.; Brown, S. S.

    2013-09-01

    The Uintah Basin in northeastern Utah, a region of intense oil and gas extraction, experienced ozone (O3) concentrations above levels harmful to human health for multiple days during the winters of 2009-2010 and 2010-2011. These wintertime O3 pollution episodes occur during cold, stable periods when the ground is snow-covered, and have been linked to emissions from the oil and gas extraction process. The Uintah Basin Winter Ozone Study (UBWOS) was a field intensive in early 2012, whose goal was to address current uncertainties in the chemical and physical processes that drive wintertime O3 production in regions of oil and gas development. Although elevated O3 concentrations were not observed during the winter of 2011-2012, the comprehensive set of observations tests our understanding of O3 photochemistry in this unusual emissions environment. A box model, constrained to the observations and using the near-explicit Master Chemical Mechanism (MCM) v3.2 chemistry scheme, has been used to investigate the sensitivities of O3 production during UBWOS 2012. Simulations identify the O3 production photochemistry to be highly radical limited (with a radical production rate significantly smaller than the NOx emission rate). Production of OH from O3 photolysis (through reaction of O(1D) with water vapor) contributed only 170 pptv day-1, 8% of the total primary radical source on average (primary radicals being those produced from non-radical precursors). Other radical sources, including the photolysis of formaldehyde (HCHO, 52%), nitrous acid (HONO, 26%), and nitryl chloride (ClNO2, 13%) were larger. O3 production was also found to be highly sensitive to aromatic volatile organic compound (VOC) concentrations, due to radical amplification reactions in the oxidation scheme of these species. Radical production was shown to be small in comparison to the emissions of nitrogen oxides (NOx), such that NOx acted as the primary radical sink. Consequently, the system was highly VOC

  8. Ozone photochemistry in an oil and natural gas extraction region during winter: simulations of a snow-free season in the Uintah Basin, Utah

    Directory of Open Access Journals (Sweden)

    P. M. Edwards

    2013-09-01

    Full Text Available The Uintah Basin in northeastern Utah, a region of intense oil and gas extraction, experienced ozone (O3 concentrations above levels harmful to human health for multiple days during the winters of 2009–2010 and 2010–2011. These wintertime O3 pollution episodes occur during cold, stable periods when the ground is snow-covered, and have been linked to emissions from the oil and gas extraction process. The Uintah Basin Winter Ozone Study (UBWOS was a field intensive in early 2012, whose goal was to address current uncertainties in the chemical and physical processes that drive wintertime O3 production in regions of oil and gas development. Although elevated O3 concentrations were not observed during the winter of 2011–2012, the comprehensive set of observations tests our understanding of O3 photochemistry in this unusual emissions environment. A box model, constrained to the observations and using the near-explicit Master Chemical Mechanism (MCM v3.2 chemistry scheme, has been used to investigate the sensitivities of O3 production during UBWOS 2012. Simulations identify the O3 production photochemistry to be highly radical limited (with a radical production rate significantly smaller than the NOx emission rate. Production of OH from O3 photolysis (through reaction of O(1D with water vapor contributed only 170 pptv day−1, 8% of the total primary radical source on average (primary radicals being those produced from non-radical precursors. Other radical sources, including the photolysis of formaldehyde (HCHO, 52%, nitrous acid (HONO, 26%, and nitryl chloride (ClNO2, 13% were larger. O3 production was also found to be highly sensitive to aromatic volatile organic compound (VOC concentrations, due to radical amplification reactions in the oxidation scheme of these species. Radical production was shown to be small in comparison to the emissions of nitrogen oxides (NOx, such that NOx acted as the primary radical sink. Consequently, the system was

  9. Aerosol optical extinction during the Front Range Air Pollution and Photochemistry Éxperiment (FRAPPÉ) 2014 summertime field campaign, Colorado, USA

    Science.gov (United States)

    Dingle, Justin H.; Vu, Kennedy; Bahreini, Roya; Apel, Eric C.; Campos, Teresa L.; Flocke, Frank; Fried, Alan; Herndon, Scott; Hills, Alan J.; Hornbrook, Rebecca S.; Huey, Greg; Kaser, Lisa; Montzka, Denise D.; Nowak, John B.; Reeves, Mike; Richter, Dirk; Roscioli, Joseph R.; Shertz, Stephen; Stell, Meghan; Tanner, David; Tyndall, Geoff; Walega, James; Weibring, Petter; Weinheimer, Andrew

    2016-09-01

    Summertime aerosol optical extinction (βext) was measured in the Colorado Front Range and Denver metropolitan area as part of the Front Range Air Pollution and Photochemistry Éxperiment (FRAPPÉ) campaign during July-August 2014. An Aerodyne cavity attenuated phase shift particle light extinction monitor (CAPS-PMex) was deployed to measure βext (at average relative humidity of 20 ± 7 %) of submicron aerosols at λ = 632 nm at 1 Hz. Data from a suite of gas-phase instrumentation were used to interpret βext behavior in various categories of air masses and sources. Extinction enhancement ratios relative to CO (Δβext / ΔCO) were higher in aged urban air masses compared to fresh air masses by ˜ 50 %. The resulting increase in Δβext / ΔCO for highly aged air masses was accompanied by formation of secondary organic aerosols (SOAs). In addition, the impacts of aerosol composition on βext in air masses under the influence of urban, natural oil and gas operations (O&G), and agriculture and livestock operations were evaluated. Estimated non-refractory mass extinction efficiency (MEE) values for different air mass types ranged from 1.51 to 2.27 m2 g-1, with the minimum and maximum values observed in urban and agriculture-influenced air masses, respectively. The mass distribution for organic, nitrate, and sulfate aerosols presented distinct profiles in different air mass types. During 11-12 August, regional influence of a biomass burning event was observed, increasing the background βext and estimated MEE values in the Front Range.

  10. Aerosol optical extinction during the Front Range Air Pollution and Photochemistry Éxperiment (FRAPPÉ 2014 summertime field campaign, Colorado, USA

    Directory of Open Access Journals (Sweden)

    J. H. Dingle

    2016-09-01

    Full Text Available Summertime aerosol optical extinction (βext was measured in the Colorado Front Range and Denver metropolitan area as part of the Front Range Air Pollution and Photochemistry Éxperiment (FRAPPÉ campaign during July–August 2014. An Aerodyne cavity attenuated phase shift particle light extinction monitor (CAPS-PMex was deployed to measure βext (at average relative humidity of 20 ± 7 % of submicron aerosols at λ = 632 nm at 1 Hz. Data from a suite of gas-phase instrumentation were used to interpret βext behavior in various categories of air masses and sources. Extinction enhancement ratios relative to CO (Δβext ∕ ΔCO were higher in aged urban air masses compared to fresh air masses by  ∼  50 %. The resulting increase in Δβext ∕ ΔCO for highly aged air masses was accompanied by formation of secondary organic aerosols (SOAs. In addition, the impacts of aerosol composition on βext in air masses under the influence of urban, natural oil and gas operations (O&G, and agriculture and livestock operations were evaluated. Estimated non-refractory mass extinction efficiency (MEE values for different air mass types ranged from 1.51 to 2.27 m2 g−1, with the minimum and maximum values observed in urban and agriculture-influenced air masses, respectively. The mass distribution for organic, nitrate, and sulfate aerosols presented distinct profiles in different air mass types. During 11–12 August, regional influence of a biomass burning event was observed, increasing the background βext and estimated MEE values in the Front Range.

  11. Aqueous Photochemistry of Secondary Organic Aerosol of α-Pinene and α-Humulene Oxidized with Ozone, Hydroxyl Radical, and Nitrate Radical

    Energy Technology Data Exchange (ETDEWEB)

    Romonosky, Dian E.; Li, Ying; Shiraiwa, Manabu; Laskin, Alexander; Laskin, Julia; Nizkorodov, Sergey

    2017-01-18

    Formation of secondary organic aerosols (SOA) from biogenic volatile organic compounds 13 (BVOC) occurs via O3- and OH-initiated reactions during the day and reactions with NO3 during the 14 night. We explored the effect of these three oxidation conditions on the molecular composition and 15 aqueous photochemistry of model SOA prepared from two common BVOC. A common monoterpene, α- 16 pinene, and sesquiterpene, α-humulene, were used to form SOA in a smog chamber via BVOC + O3, 17 BVOC + NO3, and BVOC + OH + NOx oxidation. Samples of SOA were collected, extracted in water, 18 and photolyzed in an aqueous solution in order to simulate the photochemical cloud processing of SOA. 19 The extent of change in the molecular level composition of SOA over 4 hours of photolysis (roughly 20 equivalent to 64 hours of photolysis under ambient conditions) was assessed with high-resolution 21 electrospray ionization mass spectrometry. The analysis revealed significant differences in the molecular 22 composition between monoterpene and sesquiterpene SOA formed by the different oxidation pathways. 23 The composition further evolved during photolysis with the most notable change corresponding to the 24 nearly-complete removal of nitrogen-containing organic compounds. Hydrolysis of SOA compounds also 25 occurred in parallel with photolysis. The preferential loss of larger SOA compounds during photolysis 26 and hydrolysis made the SOA compounds more volatile on average. This study suggests that cloud- and 27 fog-processing may under certain conditions lead to a reduction in the SOA loading as opposed to an 28 increase in SOA loading commonly assumed in the literature.

  12. Regarding the use and misuse of retinal protonated Schiff base photochemistry as a test case for time-dependent density-functional theory

    Energy Technology Data Exchange (ETDEWEB)

    Valsson, Omar [Department of Chemistry and Applied Biosciences, ETH Zurich and Facoltà di Informatica, Instituto di Scienze Computationali, Università della Svizzera italiana, Via Giuseppe Buffi 13, CH-6900 Lugano (Switzerland); Filippi, Claudia, E-mail: c.filippi@utwente.nl [MESA+ Institute for Nanotechnology, University of Twente, P.O. Box 217, 7500 AE Enschede (Netherlands); Casida, Mark E., E-mail: mark.casida@ujf-grenoble.fr [Laboratoire de Chimie Théorique, Département de Chimie Moléculaire (DCM), Institut de Chimie Moléculaire de Grenoble (ICMG), Université Joseph Fourier, Grenoble I, F-3801 Grenoble (France)

    2015-04-14

    The excited-state relaxation of retinal protonated Schiff bases (PSBs) is an important test case for biological applications of time-dependent (TD) density-functional theory (DFT). While well-known shortcomings of approximate TD-DFT might seem discouraging for application to PSB relaxation, progress continues to be made in the development of new functionals and of criteria allowing problematic excitations to be identified within the framework of TD-DFT itself. Furthermore, experimental and theoretical ab initio advances have recently lead to a revised understanding of retinal PSB photochemistry, calling for a reappraisal of the performance of TD-DFT in describing this prototypical photoactive system. Here, we re-investigate the performance of functionals in (TD-)DFT calculations in light of these new benchmark results, which we extend to larger PSB models. We focus on the ability of the functionals to describe primarily the early skeletal relaxation of the chromophore and investigate how far along the out-of-plane pathways these functionals are able to describe the subsequent rotation around formal single and double bonds. Conventional global hybrid and range-separated hybrid functionals are investigated as the presence of Hartree-Fock exchange reduces problems with charge-transfer excitations as determined by the Peach-Benfield-Helgaker-Tozer Λ criterion and by comparison with multi-reference perturbation theory results. While we confirm that most functionals cannot render the complex photobehavior of the retinal PSB, do we also observe that LC-BLYP gives the best description of the initial part of the photoreaction.

  13. VULCAN: An Open-source, Validated Chemical Kinetics Python Code for Exoplanetary Atmospheres

    Science.gov (United States)

    Tsai, Shang-Min; Lyons, James R.; Grosheintz, Luc; Rimmer, Paul B.; Kitzmann, Daniel; Heng, Kevin

    2017-02-01

    We present an open-source and validated chemical kinetics code for studying hot exoplanetary atmospheres, which we name VULCAN. It is constructed for gaseous chemistry from 500 to 2500 K, using a reduced C-H-O chemical network with about 300 reactions. It uses eddy diffusion to mimic atmospheric dynamics and excludes photochemistry. We have provided a full description of the rate coefficients and thermodynamic data used. We validate VULCAN by reproducing chemical equilibrium and by comparing its output versus the disequilibrium-chemistry calculations of Moses et al. and Rimmer & Helling. It reproduces the models of HD 189733b and HD 209458b by Moses et al., which employ a network with nearly 1600 reactions. We also use VULCAN to examine the theoretical trends produced when the temperature-pressure profile and carbon-to-oxygen ratio are varied. Assisted by a sensitivity test designed to identify the key reactions responsible for producing a specific molecule, we revisit the quenching approximation and find that it is accurate for methane but breaks down for acetylene, because the disequilibrium abundance of acetylene is not directly determined by transport-induced quenching, but is rather indirectly controlled by the disequilibrium abundance of methane. Therefore we suggest that the quenching approximation should be used with caution and must always be checked against a chemical kinetics calculation. A one-dimensional model atmosphere with 100 layers, computed using VULCAN, typically takes several minutes to complete. VULCAN is part of the Exoclimes Simulation Platform (ESP; exoclime.net) and publicly available at https://github.com/exoclime/VULCAN.

  14. Atmospheric mercury—An overview

    Science.gov (United States)

    Schroeder, William H.; Munthe, John

    This paper presents a broad overview and synthesis of current knowledge and understanding pertaining to all major aspects of mercury in the atmosphere. The significant physical, chemical, and toxicological properties of this element and its environmentally relebant species encountered in the atmosphere are examined. Atmospheric pathways and processes considered herein include anthropogenic as well as natural sources of Hg emissions to the atmosphere, aerial transport and dispersion (including spatial and temporal variability), atmospheric transformations (both physical and chemical types), wet and dry removal/deposition processes to Earth's surface. In addition, inter-compartmental (air-water/soil/vegetation) transfer and biogeochemical cycling of mercury are considered and discussed. The section on numerical modelling deals with atmospheric transport models as well as process-oriented models. Important gaps in our current knowledge of mercury in the atmospheric environment are identified, and suggestions for future areas of research are offered.

  15. Coupled atmosphere-wildland fire modelling

    Directory of Open Access Journals (Sweden)

    Jacques Henri Balbi

    2009-10-01

    Full Text Available Simulating the interaction between fire and atmosphere is critical to the estimation of the rate of spread of the fire. Wildfire’s convection (i.e., entire plume can modify the local meteorology throughout the atmospheric boundary layer and consequently affect the fire propagation speed and behaviour. In this study, we use for the first time the Méso-NH meso-scale numerical model coupled to the point functional ForeFire simplified physical front-tracking wildfire model to investigate the differences introduced by the atmospheric feedback in propagation speed and behaviour. Both numerical models have been developed as research tools for operational models and are currently used to forecast localized extreme events. These models have been selected because they can be run coupled and support decisions in wildfire management in France and Europe. The main originalities of this combination reside in the fact that Méso-NH is run in a Large Eddy Simulation (LES configuration and that the rate of spread model used in ForeFire provides a physical formulation to take into account the effect of wind and slope. Simulations of typical experimental configurations show that the numerical atmospheric model is able to reproduce plausible convective effects of the heat produced by the fire. Numerical results are comparable to estimated values for fire-induced winds and present behaviour similar to other existing numerical approaches.

  16. The use of experimental data and their uncertainty for assessing ozone photochemistry in the Eastern Iberian Peninsula.

    Science.gov (United States)

    Miñarro, Marta Doval; Castell-Balaguer, Nuria; Téllez, Laura; Mantilla, Enrique

    2012-10-01

    Observation-based methods are useful tools to explore the sensitivity of ozone concentrations to precursor controls. With the aim of assessing the ozone precursor sensitivity in two locations: Paterna (suburban) and Villar del Arzobispo (rural) of the Turia river basin in the east of Spain, the photochemical indicator O(3)/NO(y) and the Extent-of-Reaction (EOR) parameter have been calculated from field measurements. In Paterna, the O(3)/NO(y) ratio varied from 0 to 13 with an average value of 5.1 (SD 3.2), whereas the averaged value for the EOR was 0.43 (SD 0.14). In Villar del Arzobispo, the O(3)/NO(y) ratio changed from 5 to 30 with a mean value of 13.6 (SD 4.7) and the EOR gave an averaged value of 0.72 (SD 0.11). The results show two different patterns of ozone production as a function of the location. The suburban area shows a VOC-sensitive regime whereas the rural one shows a transition regime close to NO(x)-sensitive conditions. No seasonal differences in these regimes are observed along the monitoring campaigns. Finally, an analysis of the influence of the measurement quality of NO(y), NO(x) and O(3) on the uncertainty of the O(3)/NO(y) ratio and the EOR was performed showing that the uncertainty of O(3)/NO(y) is not dependent on either its value or the individual values of O(3) and NO(y) but just on the quality of O(3) and NO(y) measurements. The maximum uncertainty is 26% as long as the combined uncertainties of O(3) and NO(y) remain below the 7.5%. The case of the EOR is different and its uncertainty depends on both the value of the EOR parameter and the individual concentration values of NO(y) and NO(x). The uncertainty of the EOR estimation can be very high (>200%) if the combined uncertainties of both NO(y) and NO(x) are high (>7.5%), or especially, if u(NO(y)) and u(NO(x)) differ considerably from each other (>3.5%). Copyright © 2012 Elsevier Ltd. All rights reserved.

  17. The Photochemistry of Pyrimidine in Pure H2O Ice Subjected to Different Radiation Environments and the Formation of Uracil

    Science.gov (United States)

    Nuevo, M.; Chen, Y.-J.; Materese. C. K..; Hu, W.-J.; Qiu, J.-M.; Wu, S.-R.; Fung, H.-S.; Sandford, S. A.; Chu, C.-C.; Yih, T.-S.; hide

    2013-01-01

    Nucleobases are N-heterocycles which are the informational subunits of DNA and RNA. They include pyrimidine bases (uracil, cytosine, and thymine) and purine bases (adenine and guanine). Nucleobases have been detected in several meteorites, although no Nheterocycles have been observed in space to data. Laboratory experiments showed that the ultraviolet (UV) irradiation of pyrimidine in pure H2O ice at low temperature (<=20 K) leads to the formation of pyrimidine derivatives including the nucleobase uracil and its precursor 4(3H)-pyrimidone. These results were confirmed by quantum chemical calculations. When pyrimidine is mixed with combinations of H2O, NH3, CH3OH, and CH4 ices under similar conditions, uracil and cytosine are formed. In the present work we study the formation of 4(3H)-pyrimidone and uracil from the irradiation of pyrimidine in H2O ice with high-energy UV photons (Lyman , He I, and He II lines) provided by a synchrotron source. The photo-destruction of pyrimidine in these H2O ices as well as the formation yields for 4(3H)-pyrimidone and uracil are compared with our previous results in order to study the photo-stability of pyrimidine and the production efficiency of uracil as a function of the photon energy.

  18. Ectopic expression of ultraviolet-rhodopsins in the blue photoreceptor cells of Drosophila: visual physiology and photochemistry of transgenic animals.

    Science.gov (United States)

    Feiler, R; Bjornson, R; Kirschfeld, K; Mismer, D; Rubin, G M; Smith, D P; Socolich, M; Zuker, C S

    1992-10-01

    We have generated transgenic flies expressing R7 cell-specific opsins in the major class of photoreceptor cells of the Drosophila retina and characterized their spectral properties using high-resolution microspectrophotometry and sensitivity recordings. We show that the Rh3 and Rh4 opsin genes encode UV-sensitive opsins with similar spectral properties (lambda max = 345 nm and 375 nm), and that Rh3 corresponds to the R7p and R7marg class of visual pigments. We have also generated Rh3 and Rh4 isoform-specific antibodies and present an R7 cell map of the Drosophila retina. In a related set of experiments, we show that it is possible to coexpress two different visual pigments functionally in the same cell and produce photoreceptors that display the summed spectral response of the individual pigments. These findings open up the possibility of tuning an animal's visual behavior by targeted expression of combinations of opsin genes to selective types of photoreceptors.

  19. Sunscreen synthesis and their immobilisation on polymethylmethacrylate: an integrated project in organic chemistry, polymer chemistry and photochemistry; Sintese de fotoprotetores e sua imobilizacao em poli(metacrilato de metilo): um projeto integrado de quimica organica, quimica de polimeros e fotoquimica

    Energy Technology Data Exchange (ETDEWEB)

    Murtinho, Dina Maria B.; Serra, Maria Elisa S.; Pineiro, Marta, E-mail: dmurtinho@ci.uc.p [Universidade de Coimbra (Portugal). Faculdade de Ciencias e Tecnologia. Dept. de Quimica

    2010-07-01

    Dibenzalacetone and other aldol condensation products are known sunscreens commonly used in cosmetics. This type of compounds can easily be prepared in an Organic Chemistry Lab by reaction of aldehydes with ketones in basic medium. These compounds can be incorporated in poly(methyl methacrylate) and used as UV light absorbers, for example in sunglasses. This project has the advantage of using inexpensive reagents which are readily available in Chemistry Laboratories. This experiment can also be a base starting point for discussions of organic, polymer and photochemistry topics. (author)

  20. Air emissions in France. Metropolitan area substances implied in acidification, eutrophication and photochemistry; Emissions dans l'air en France. Metropole substances impliquees dans les phenomenes d'acidification, d'eutrophisation et de photochimie

    Energy Technology Data Exchange (ETDEWEB)

    NONE

    2002-04-01

    Acidification, eutrophication and photochemistry: SO{sub 2}, NO{sub x}, NH{sub 3}, NMVOCs (total and speciation relating to more than 200 different compounds), CO, acid equivalent index (Aeq) and photochemical ozone creation potential (POCP) are presented. Density ratios relating to population, area, gross product, primary energy consumption, etc. Emissions are presented by the mean of charts for each substance and the main source categories with a five years step until 1990 then yearly beyond. Dates corresponding to the maximum and minimum values are also included. (author)

  1. Caustics of atmospheric waves

    Science.gov (United States)

    Godin, Oleg A.

    2015-04-01

    Much like light and sound, acoustic-gravity waves in inhomogeneous atmosphere often have a caustic or caustics, where the ray theory predicts unphysical, divergent values of the wave amplitude and needs to be modified. Increase of the wave magnitude in the vicinity of a caustic makes such vicinities of primary interest in a number of problems, where a signal needs to be separated from a background noise. The value of wave focusing near caustics should be carefully quantified in order to evaluate possible nonlinearities promoted by the focusing. Physical understanding of the wave field in the vicinity of a caustic is also important for understanding of the wave reflection from and transmission (tunneling) through the caustic. To our knowledge, in contrast to caustics of acoustic, electromagnetic, and seismic waves as well as gravity waves in incompressible fluids, asymptotics of acoustic-gravity waves in the vicinity of a caustic have never been studied systematically. In this paper, we fill this gap. Atmospheric waves are considered as linear acoustic-gravity waves in a neutral, horizontally stratified, moving ideal gas of variable composition. Air temperature and wind velocity are assumed to be gradually varying functions of height, and slowness of these variations determines the large parameter of the problem. The scale height of the atmosphere can be large or small compared to the vertical wavelength. It is found that the uniform asymptotics of the wave field in the presence of a simple caustic can be expressed in terms of the Airy function and its derivative. As for the acoustic waves, the argument of the Airy function is expressed in terms of the eikonal calculated in the ray, or WKB, approximation. The geometrical, or Berry, phase, which arises in the consistent WKB approximation for acoustic-gravity waves, plays an important role in the caustic asymptotics. In the uniform asymptotics, the terms with the Airy function and its derivative are weighted by cosine

  2. Complementary roles of microwave and infrared instruments in atmospheric sounding

    Science.gov (United States)

    McMillin, L.; Fleming, H.; Gray, D.; Grody, N.; Reale, A.

    1987-02-01

    Radiance measurements in the infrared and microwave regions respond differently to changes in the atmosphere. These differences in response lead to differences in the ability to derive profiles of atmospheric parameters such as temperature and moisture. A summary of the characteristics of each region is presented, followed by an evaluation of the results of simulation studies and extrapolations from existing instruments, both of which were designed to assess the relative advantages of the two wavelength regions. The studies show that the combination of the information from the two spectral regions leads to more accurate retrievals than can be obtained from either spectral region alone at all levels of the atmosphere.

  3. Introducing a dark reaction to photochemistry: photocatalytic hydrogen from [FeFe] hydrogenase active site model complexes.

    Science.gov (United States)

    Lomoth, Reiner; Ott, Sascha

    2009-12-07

    The light-driven splitting of water into its constituting elements gives access to a valuable fuel from an abundant substrate, using sunlight as the only energy source. Synthetic diiron complexes as functional models of the [FeFe] hydrogenase H2ase enzyme active site have moved into the centre of focus as potentially viable catalysts for the reductive side of this process, i.e. the reduction of protons to molecular hydrogen. The active site of the enzyme, as well as its mimics in an artificial system, are required to accumulate two electrons from single electron transfer events and to combine them with two protons to form hydrogen. Whereas in biology this reaction is not coupled to photosynthesis and thus proceeds in the dark, additional aspects need to be considered when designing a functional artificial system for the light-driven reduction of protons. Suitable photosensitizers have to be chosen that not only provide sufficient driving force for the reduction of the synthetic diiron catalyst, but also allow for selective excitation to minimize photodegradation. Electron transfer efficiencies have to be optimized for all steps and the sequential nature of the catalyst reduction requires a sufficient stability of potentially labile intermediates of the catalytic cycle. In this perspective, systems for the light-driven conversion of protons to molecular hydrogen are discussed where the catalyst is based on model complexes of the [FeFe] H2ase active site. Covalently linked dyads, supramolecular assemblies and multi-component systems will be examined with an emphasis on mechanistic electron transfer schemes, the properties of the individual components, their scope and their potential limitations.

  4. Future Atmospheric Neutrino Detectors

    CERN Document Server

    Geiser, A

    2000-01-01

    Future experiments focusing on atmospheric neutrino detection are reviewed. One of the main goals of these experiments is the detection of an unambiguous oscillation pattern (nu_mu reappearance) to prove the oscillation hypothesis. Further goals include the discrimination of nu_mu - nu_tau and nu_mu - nu_sterile oscillations, and the detection of a potential small nu_mu - nu_e contribution. The search for matter effects in three or more flavour oscillations can be used to constrain hybrid oscillation models and potentially measure the sign of delta m^2. The detectors and measurement techniques proposed to achieve these goals are described, and their physics reach is discussed.

  5. Phytoremediation of Atmospheric Methane

    Science.gov (United States)

    2013-04-15

    photosynthetically fixing it into their tissues.  To calculate the atmospheric conductance or mass transfer  coefficient in vegetated fields of  maize  we used...uptake through aerodynamic and leaf boundary layers and the stomata of  maize  at  field scale as determined by continuous stable isotope measurements... digestion  with specific homing endonucleases (Figure 4).  Completion of the triple vector construction of mmoX, Y and Z in E. coli was confirmed by PCR

  6. Archean Earth Atmosphere Fractal Haze Aggregates: Light Scattering Calculations and the Faint Young Sun Paradox

    Science.gov (United States)

    Boness, D. A.; Terrell-Martinez, B.

    2010-12-01

    As part of an ongoing undergraduate research project of light scattering calculations involving fractal carbonaceous soot aggregates relevant to current anthropogenic and natural sources in Earth's atmosphere, we have read with interest a recent paper [E.T. Wolf and O.B Toon,Science 328, 1266 (2010)] claiming that the Faint Young Sun paradox discussed four decades ago by Carl Sagan and others can be resolved without invoking heavy CO2 concentrations as a greenhouse gas warming the early Earth enough to sustain liquid water and hence allow the origin of life. Wolf and Toon report that a Titan-like Archean Earth haze, with a fractal haze aggregate nature due to nitrogen-methane photochemistry at high altitudes, should block enough UV light to protect the warming greenhouse gas NH3 while allowing enough visible light to reach the surface of the Earth. To test this hypothesis, we have employed a rigorous T-Matrix arbitrary-particle light scattering technique, to avoid the simplifications inherent in Mie-sphere scattering, on haze fractal aggregates at UV and visible wavelenths of incident light. We generate these model aggregates using diffusion-limited cluster aggregation (DLCA) algorithms, which much more closely fit actual haze fractal aggregates than do diffusion-limited aggregation (DLA) algorithms.

  7. Formation of aqueous-phase α-hydroxyhydroperoxides (α-HHP: potential atmospheric impacts

    Directory of Open Access Journals (Sweden)

    R. Zhao

    2013-06-01

    Full Text Available The focus of this work is on quantifying the degree of the aqueous-phase formation of α-hydroxyhydroperoxides (α-HHPs via reversible nucleophilic addition of H2O2 to aldehydes. Formation of this class of highly oxygenated organic hydroperoxides represents a poorly characterized aqueous-phase processing pathway that may lead to enhanced SOA formation and aerosol toxicity. Specifically, the equilibrium constants of α-HHP formation have been determined using proton nuclear-magnetic-resonance (1H NMR spectroscopy and proton-transfer-reaction mass spectrometry (PTR-MS. Significant α-HHP formation was observed from formaldehyde, acetaldehyde, propionaldehyde, glycolaldehyde, glyoxylic acid, and methylglyoxal, but not from methacrolein and ketones. Low temperatures enhanced the formation of α-HHPs but slowed their formation rates. High inorganic salt concentrations shifted the equilibria toward the hydrated form of the aldehydes and slightly suppressed α-HHP formation. Using the experimental equilibrium constants, we predict the equilibrium concentration of α-HHPs to be in the μM level in cloud water, but it may also be present in the mM level in aerosol liquid water (ALW, where the concentrations of H2O2 and aldehydes can be high. Formation of α-HHPs in ALW may significantly affect the effective Henry's law constants of H2O2 and aldehydes but may not affect their gas-phase levels. The photochemistry and reactivity of this class of atmospheric species have not been studied.

  8. A Chemical Kinetics Network for Lightning and Life in Planetary Atmospheres

    Science.gov (United States)

    Rimmer, P. B.; Helling, Ch

    2016-05-01

    There are many open questions about prebiotic chemistry in both planetary and exoplanetary environments. The increasing number of known exoplanets and other ultra-cool, substellar objects has propelled the desire to detect life and prebiotic chemistry outside the solar system. We present an ion-neutral chemical network constructed from scratch, Stand2015, that treats hydrogen, nitrogen, carbon, and oxygen chemistry accurately within a temperature range between 100 and 30,000 K. Formation pathways for glycine and other organic molecules are included. The network is complete up to H6C2N2O3. Stand2015 is successfully tested against atmospheric chemistry models for HD 209458b, Jupiter, and the present-day Earth using a simple one-dimensional photochemistry/diffusion code. Our results for the early Earth agree with those of Kasting for CO2, H2, CO, and O2, but do not agree for water and atomic oxygen. We use the network to simulate an experiment where varied chemical initial conditions are irradiated by UV light. The result from our simulation is that more glycine is produced when more ammonia and methane is present. Very little glycine is produced in the absence of any molecular nitrogen and oxygen. This suggests that the production of glycine is inhibited if a gas is too strongly reducing. Possible applications and limitations of the chemical kinetics network are also discussed.

  9. Formation of aqueous-phase α-hydroxyhydroperoxides (α-HHP): potential atmospheric impacts

    Science.gov (United States)

    Zhao, R.; Lee, A. K. Y.; Soong, R.; Simpson, A. J.; Abbatt, J. P. D.

    2013-06-01

    The focus of this work is on quantifying the degree of the aqueous-phase formation of α-hydroxyhydroperoxides (α-HHPs) via reversible nucleophilic addition of H2O2 to aldehydes. Formation of this class of highly oxygenated organic hydroperoxides represents a poorly characterized aqueous-phase processing pathway that may lead to enhanced SOA formation and aerosol toxicity. Specifically, the equilibrium constants of α-HHP formation have been determined using proton nuclear-magnetic-resonance (1H NMR) spectroscopy and proton-transfer-reaction mass spectrometry (PTR-MS). Significant α-HHP formation was observed from formaldehyde, acetaldehyde, propionaldehyde, glycolaldehyde, glyoxylic acid, and methylglyoxal, but not from methacrolein and ketones. Low temperatures enhanced the formation of α-HHPs but slowed their formation rates. High inorganic salt concentrations shifted the equilibria toward the hydrated form of the aldehydes and slightly suppressed α-HHP formation. Using the experimental equilibrium constants, we predict the equilibrium concentration of α-HHPs to be in the μM level in cloud water, but it may also be present in the mM level in aerosol liquid water (ALW), where the concentrations of H2O2 and aldehydes can be high. Formation of α-HHPs in ALW may significantly affect the effective Henry's law constants of H2O2 and aldehydes but may not affect their gas-phase levels. The photochemistry and reactivity of this class of atmospheric species have not been studied.

  10. On the role of the simplest S-nitrosothiol, HSNO, in atmospheric and biological processes

    Energy Technology Data Exchange (ETDEWEB)

    Hochlaf, Majdi, E-mail: hochlaf@univ-mlv.fr; Linguerri, Roberto [Université Paris-Est, Laboratoire Modélisation et Simulation Multi Echelle, MSME UMR 8208 CNRS, 5 bd Descartes, 77454 Marne-la-Vallée (France); Francisco, Joseph S. [Department of Chemistry and Department of Earth and Atmospheric Sciences, Purdue University, West Lafayette, Indiana 47906 (United States)

    2013-12-21

    Using state-of-the-art theoretical methods, we investigate the lowest electronic states of singlet and triplet spin multiplicities of HSNO. These computations are done using configuration interaction ab initio methods and the aug-cc-pV5Z basis set. One-dimensional cuts of the six-dimensional potential energy surfaces of these electronic states along the HS, SN stretches and HSN, SNO bending and torsion coordinates are calculated. Several avoided crossings and conical intersections are found. We computed also radiative lifetimes and spin-orbit couplings of these electronic states. Our work shows that the dynamics on these excited states is very complex, and suggest that multi-step mechanisms will populate the ground state via radiationless processes or lead to predissociation or intramolecular isomerization. For instance, these potentials are used to propose mechanisms for the IR, Vis, and UV light-induced cis-trans interconversions of HSNO and reactivity towards HS + NO and H + SNO products. Our findings are in good agreement with previous experimental studies on the photochemistry of HSNO. The atmospheric implication of HSNO is also discussed.

  11. In Situ Single Particle Measurement of Atmospheric Aging of Carbonaceous Aerosols During CARES

    Science.gov (United States)

    Cahill, J. F.; Suski, K.; Hubbe, J.; Shilling, J.; Zaveri, R. A.; Springston, S. R.; Prather, K. A.

    2011-12-01

    Atmospheric aging of aerosols through photochemistry, heterogeneous reactions and aqueous processing can change their physical and chemical properties, impacting their gas uptake, radiative forcing, and activation of cloud nuclei. Understanding the timescale and magnitude of this aging process is essential for accurate aerosol-climate modeling and predictions. An aircraft aerosol time-of-flight mass spectrometer (A-ATOFMS) measured single particle mixing state during the Carbonaceous Aerosols and Radiative Effects Study (CARES) in the summer of 2010 over Sacramento, CA. On 6/23/10, flights in the morning and afternoon performed pseudo-Lagrangian sampling of the Sacramento urban plume. Carbonaceous particles from these flights were classified into 'aged' and 'fresh' classes based on their mixing state, with aged particles having more secondary species, such as nitrate and sulfate. In the morning flight, a clear decreasing trend in the ratio of fresh/aged particle types was seen as the flight progressed, whereas in the afternoon flight, the ratio was essentially constant. These data show that in the morning carbonaceous aerosols can become heavily oxidized in a few hours. Further analysis of particle mixing state and the timescale of carbonaceous aerosol aging will be presented

  12. Wind Power Prediction Considering Nonlinear Atmospheric Disturbances

    Directory of Open Access Journals (Sweden)

    Yagang Zhang

    2015-01-01

    Full Text Available This paper considers the effect of nonlinear atmospheric disturbances on wind power prediction. A Lorenz system is introduced as an atmospheric disturbance model. Three new improved wind forecasting models combined with a Lorenz comprehensive disturbance are put forward in this study. Firstly, we define the form of the Lorenz disturbance variable and the wind speed perturbation formula. Then, different artificial neural network models are used to verify the new idea and obtain better wind speed predictions. Finally we separately use the original and improved wind speed series to predict the related wind power. This proves that the corrected wind speed provides higher precision wind power predictions. This research presents a totally new direction in the wind prediction field and has profound theoretical research value and practical guiding significance.

  13. Improved reference models for middle atmosphere ozone

    Science.gov (United States)

    Keating, G. M.; Pitts, M. C.; Chen, C.

    1990-01-01

    This paper describes the improvements introduced into the original version of ozone reference model of Keating and Young (1985, 1987) which is to be incorporated in the next COSPAR International Reference Atmosphere (CIRA). The ozone reference model will provide information on the global ozone distribution (including the ozone vertical structure as a function of month and latitude from 25 to 90 km) combining data from five recent satellite experiments: the Nimbus 7 LIMS, Nimbus 7 SBUV, AE-2 Stratospheric Aerosol Gas Experiment (SAGE), Solar Mesosphere Explorer (SME) UV Spectrometer, and SME 1.27 Micron Airglow. The improved version of the reference model uses reprocessed AE-2 SAGE data (sunset) and extends the use of SAGE data from 1981 to the 1981-1983 time period. Comparisons are presented between the results of this ozone model and various nonsatellite measurements at different levels in the middle atmosphere.

  14. Color Shaded-Relief GeoTIFF Image Showing the Combined 2-m and Interpolated 10-m Bathymetry Generated from National Oceanic and Atmospheric Administration (NOAA) Survey H12013 Off the Entrance to the Connecticut River in Northeastern Long Island Sound (H12013_INT2M_GEO.TIF, Geographic, WGS84)

    Data.gov (United States)

    U.S. Geological Survey, Department of the Interior — The U.S. Geological Survey (USGS), in cooperation with the National Oceanic and Atmospheric Administration (NOAA) and the Connecticut Department of Energy and...

  15. Atmospheric propagation of THz radiation.

    Energy Technology Data Exchange (ETDEWEB)

    Wanke, Michael Clement; Mangan, Michael A.; Foltynowicz, Robert J.

    2005-11-01

    In this investigation, we conduct a literature study of the best experimental and theoretical data available for thin and thick atmospheres on THz radiation propagation from 0.1 to 10 THz. We determined that for thick atmospheres no data exists beyond 450 GHz. For thin atmospheres data exists from 0.35 to 1.2 THz. We were successful in using FASE code with the HITRAN database to simulate the THz transmission spectrum for Mauna Kea from 0.1 to 2 THz. Lastly, we successfully measured the THz transmission spectra of laboratory atmospheres at relative humidities of 18 and 27%. In general, we found that an increase in the water content of the atmosphere led to a decrease in the THz transmission. We identified two potential windows in an Albuquerque atmosphere for THz propagation which were the regions from 1.2 to 1.4 THz and 1.4 to 1.6 THz.

  16. Combination N-Way Power Divider/Combiner and Noninvasive Reflected Power Detection

    Data.gov (United States)

    National Oceanic and Atmospheric Administration, Department of Commerce — An N-way RF/microwave power divider/combiner utilizes one input and N outputs, or conversely N inputs and one output to divide (or combine) RF/microwave power while...

  17. Formation of Polar Stratospheric Clouds in the Atmosphere

    Science.gov (United States)

    Aloyan, Artash; Yermakov, Alex; Arutyunyan, Vardan; Larin, Igor

    2014-05-01

    A new mathematical model of the global transport of gaseous species and aerosols in the atmosphere and the formation of polar stratospheric clouds (PSCs) in both hemispheres was constructed. PSCs play a significant role in ozone chemistry since heterogeneous reactions proceed on their particle surfaces and in the bulk, affecting the gas composition of the atmosphere, specifically, the content of chlorine and nitrogen compounds, which are actively involved in the destruction of ozone. Stratospheric clouds are generated by co-condensation of water vapor and nitric acid on sulfate particles and in some cases during the freezing of supercooled water as well as when nitric acid vapors are dissolved in sulfate aerosol particles [1]. These clouds differ in their chemical composition and microphysics [2]. In this study, we propose new kinetic equations describing the variability of species in the gas and condensed phases to simulate the formation of PSCs. Most models for the formation of PSCs use constant background values of sulfate aerosols in the lower stratosphere. This approach is too simplistic since sulfate aerosols in the stratosphere are characterized by considerably nonuniform spatial and temporal variations. Two PSC types are considered: Type 1 refers to the formation of nitric acid trihydrate (NAT) and Type 2 refers to the formation of particles composed of different proportions of H2SO4/HNO3/H2O. Their formation is coupled with the spatial problem of sulfate aerosol generation in the upper troposphere and lower stratosphere incorporating the chemical and kinetic transformation processes (photochemistry, nucleation, condensation/evaporation, and coagulation) and using a non-equilibrium particle-size distribution [3]. In this formulation, the system of equations is closed and allows an adequate description of the PSC dynamics in the stratosphere. Using the model developed, numerical experiments were performed to reproduce the spatial and temporal variability of

  18. The groundwater-land-surface-atmosphere connection: soil moisture effects on the atmospheric boundary layer in fully-coupled simulations

    Energy Technology Data Exchange (ETDEWEB)

    Maxwell, R M; Chow, F K; Kollet, S J

    2007-02-02

    This study combines a variably-saturated groundwater flow model and a mesoscale atmospheric model to examine the effects of soil moisture heterogeneity on atmospheric boundary layer processes. This parallel, integrated model can represent spatial variations in land-surface forcing driven by three-dimensional (3D) atmospheric and subsurface components. The development of atmospheric flow is studied in a series of idealized test cases with different initial soil moisture distributions generated by an offline spin-up procedure or interpolated from a coarse-resolution dataset. These test cases are performed with both the fully-coupled model (which includes 3D groundwater flow and surface water routing) and the uncoupled atmospheric model. The effects of the different soil moisture initializations and lateral subsurface and surface water flow are seen in the differences in atmospheric evolution over a 36-hour period. The fully-coupled model maintains a realistic topographically-driven soil moisture distribution, while the uncoupled atmospheric model does not. Furthermore, the coupled model shows spatial and temporal correlations between surface and lower atmospheric variables and water table depth. These correlations are particularly strong during times when the land surface temperatures trigger shifts in wind behavior, such as during early morning surface heating.

  19. Cloud system resolving model study of the roles of deep convection for photo-chemistry in the TOGA COARE/CEPEX region

    Directory of Open Access Journals (Sweden)

    M. Salzmann

    2008-05-01

    Full Text Available A cloud system resolving model including photo-chemistry (CSRMC has been developed based on a prototype version of the Weather Research and Forecasting (WRF model and is used to study influences of deep convection on chemistry in the TOGA COARE/CEPEX region. Lateral boundary conditions for trace gases are prescribed from global chemistry-transport simulations, and the vertical advection of trace gases by large scale dynamics, which is not reproduced in a limited area cloud system resolving model, is taken into account. The influences of deep convective transport and of lightning on NOx, O3, and HOx(=HO2+OH, in the vicinity of the deep convective systems are investigated in a 7-day 3-D 248×248 km2 horizontal domain simulation and several 2-D sensitivity runs with a 500 km horizontal domain. Mid-tropospheric entrainment is more important on average for the upward transport of O3 in the 3-D run than in the 2-D runs, but at the same time undiluted O3-poor air from the marine boundary layer reaches the upper troposphere more frequently in the 3-D run than in the 2-D runs, indicating the presence of undiluted convective cores. In all runs, in situ lightning is found to have only minor impacts on the local O3 budget. Near zero O3 volume mixing ratios due to the reaction with lightning-produced NO are only simulated in a 2-D sensitivity run with an extremely high number of NO molecules per flash, which is outside the range of current estimates. The fraction of NOx chemically lost within the domain varies between 20 and 24% in the 2-D runs, but is negligible in the 3-D run, in agreement with a lower average NOx concentration in the 3-D run despite a greater number of flashes. Stratosphere to troposphere transport of O3 is simulated to occur episodically in thin filaments in the 2-D runs, but on average net upward transport

  20. 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.

  1. Remote measurement of atmospheric pollutants

    Science.gov (United States)

    Allario, F.; Hoell, J.; Seals, R. K.

    1979-01-01

    The concentration and vertical distribution of atmospheric ammonia and ozone are remotely sensed, using dual-C02-laser multichannel infrared Heterodyne Spectrometer (1HS). Innovation makes atmospheric pollution measurements possible with nearly-quantum-noise-limited sensitivity and ultrafine spectral resolution.

  2. Atmospheres of hot alien Worlds

    NARCIS (Netherlands)

    Brogi, Matteo

    2014-01-01

    This thesis presents observations of exoplanets orbiting very close to their parent star, with a particular focus on a novel technique for characterizing their atmospheres. This is based on the use of high-resolution spectroscopy from the ground. The first detection of the atmosphere of a

  3. atmospheric transparency under harmattan conditions

    African Journals Online (AJOL)

    2006-05-20

    May 20, 2006 ... air, the transparency of the atmosphere is also strongly dependent on the elevation angle of the sun. Hence, to contrast the atmospheric transmission characteristics in the two harmattan conditions, measurements made at the same solar elevation (42. °) and optical air mass (m, = 1.5) have been used.

  4. Chemical pathway analysis of the Martian atmosphere: The formation and destruction of ozone

    Science.gov (United States)

    Boxe, C.; Stock, J.; Lehmann, R.; Grenfell, L.; Patzer, A.; Rauer, H.; Yung, Y. L.

    2014-12-01

    Ozone is a species of major importance in the Martian atmosphere e.g. since it is involved in the stabilization of Mars' major atmospheric constituent carbon dioxide. Below XX km altitude, ozone acts as an atomic oxygen source, which is produced by photolysis and oxidizes carbon monoxide via catalytic cycles involving odd hydrogen (HOx=H+OH+HO2). Originating mainly from H2O photolysis, odd hydrogen destroys ozone resulting in the observed anti-correlation between water vapor and ozone. Compared with species from the HOx-family, ozone is relatively easy to detect by e.g. UV spectroscopy or IR heterodyne spectroscopy. Similar to carbon dioxide, the concentration of ozone can be critically influenced by chemical trace species acting as catalysts in chemical pathways. The identification of such chemical pathways in complex reaction networks and the quantification of their contribution is in general challenging. Therefore, we use an automated computer algorithm (PAP - Pathway Analysis Program), which is specifically designed to address such problems. In this work, we apply the PAP-algorithm to the results of the newly updated JPL/Caltech photochemical column model of the Martian atmosphere in order to investigate the Martian atmospheric ozone photochemistry. The efficiencies of individual ozone formation and destruction pathways are calculated for different atmospheric heights, by applying the algorithm to each vertical layer of the column model in turn. The results of our investigations suggest that ozone is primarily produced by a Chapman-like mechanism, whereby atomic oxygen is produced by carbon dioxide photolysis instead of molecular oxygen photolysis. In the ozone layer at approximately 40 km altitude, ozone formation is chiefly dominated by a chemical pathway where atomic oxygen is supplied by vertical transport. Ozone consumption pathways involving ozone photolysis are most efficient except for a layer around 40 km altitude where the reaction between ozone and

  5. Atmospheric Processing of European Air Masses: Evidences from the Modelling of HOx Measurements over Cyprus

    Science.gov (United States)

    Mallik, C.; Martinez, M.; Novelli, A.; Reiffs, A.; Derstroff, B.; Sauvage, C.; Bourtsoukidis, E.; Phillips, G. J.; Fischer, H.; Meusel, H.; Su, H.; Crowley, J.; Schuladen, J.; Williams, J.; Tomsche, L.; Hafermann, S.; Javed, M. U.; Lelieveld, J.; Harder, H.

    2016-12-01

    Atmospheric concentrations of the hydroxyl radical (OH) and the hydroperoxyl radical (HO2), were measured in Cyprus along with a suite of other trace gases during the CYPHEX (CYprus PHotochemistry EXperiment) field campaign, in the summer of 2014. Cyprus is a remote island in the Eastern Mediterranean located downwind of the mainland Europe emissions. The lowest HOx production was observed in aged air masses with the lowest O3 and CO levels and processed for an extended period in the marine boundary layer. To study the contributions of various photochemical precursors to the HOx budget, OH and HO2 were simulated with a photochemical box model (CAABA) constrained with measurements. The model could simulate the observed HOx levels reasonably well, but it failed to reproduce the HOx partitioning, and OH levels were overestimated by about 50% when biogenic hydrocarbons were not included. When isoprene, emitted from the local vegetation, was included in the model, the gap between modelled and measured OH reduced, with the modelled OH being only about 20% too high. The remaining discrepancy vanished by including measured pinene (α and β) reactivity (concentration x rate constant w.r.t. OH) into the model. However, pinene chemistry caused the model to underestimate HO2 by about 20%. Since biogenic emissions account for a major fraction of the global hydrocarbon budget, we tested the performance of a global model EMAC, with the same chemical scheme as CAABA, in simulating the measured OH and HO2 in Cyprus. We found that EMAC is able to simulate the HO2 concentrations, but severely overestimated OH (as well as NO levels), which influences the lifetime of many gaseous species in the atmosphere.

  6. 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.

  7. Geologic signatures of atmospheric effects on impact cratering on Venus

    Science.gov (United States)

    1996-01-01

    Highlights of the research include geologic signatures of impact energy and atmospheric response to crater formation. Laboratory experiments were performed at the NASA Ames Vertical Gun Range (AVGR) to assess the interaction between disrupted impactor and atmosphere during entry, and to assess the energy coupling between impacts and the surrounding atmosphere. The Schlieren imaging at the AVGR was used in combination with Magellan imaging and theoretical studies to study the evolution of the impactor following impact. The Schlieren imaging documented the downrange blast front created by vaporization during oblique impacts. Laboratory experiments allowed assessing the effect of impact angle on coupling efficiency with an atmosphere. And the impact angle's effect on surface blasts and run-out flows allowed the distinction of crater clusters created by simultaneous impacts from those created by isolated regions of older age.

  8. The Heating of the Solar Atmosphere: from the Bottom Up?

    Science.gov (United States)

    Winebarger, Amy

    2014-01-01

    The heating of the solar atmosphere remains a mystery. Over the past several decades, scientists have examined the observational properties of structures in the solar atmosphere, notably their temperature, density, lifetime, and geometry, to determine the location, frequency, and duration of heating. In this talk, I will review these observational results, focusing on the wealth of information stored in the light curve of structures in different spectral lines or channels available in the Solar Dynamic Observatory's Atmospheric Imaging Assembly, Hinode's X-ray Telescope and Extreme-ultraviolet Imaging Spectrometer, and the Interface Region Imaging Spectrograph. I will discuss some recent results from combined data sets that support the heating of the solar atmosphere may be dominated by low, near-constant heating events.

  9. Exposure of lambs to atmospheric ammonia

    Energy Technology Data Exchange (ETDEWEB)

    Drummond, J.G.; Curtis, S.E.; Lewis, J.M.; Hinds, F.C.; Simon, J.

    1976-01-01

    Two trials were conducted to determine the effects of chronic exposure to atmospheric ammonia at a concentration of 75 ppm on weight gain and efficiency of feed conversion by lambs. Lambs were weighed and then randomly allotted to four dynamic air-pollutant exposure chambers. Initial weights (mean +/- SE) of lambs were 22.1 +/- .46 kg and 27.5 +/- 1.54 kg for trials 1 and 2, respectively (n=12 in both trials). Lambs in two chambers (controls) were maintained in an atmosphere of filtered room air. Lambs in the other two chambers (NH/sub 3/ -exposed) were exposed to an atmosphere of filtered air plus atmospheric ammonia at a concentration of 75 ppm. Exposure period was 28 days in both trials. Feed and water were available at all times. Lamb weight gain and feed disappearance were determined weekly. Upon termination of each trial, one lamb was randomly selected from each chamber, sacrificed, and gross and histopathologic structural changes noted. Weight gain and efficiency of feed conversion data for the two trials were combined for statistical analysis. Control lambs gained on the average .09 kg/day (.28 vs .19) more (P<.01) and consumed on the average .68 kg of feed (4.53 vs 5.21) less per kilogram of weight gain (P<.10) than did NH/sub 3/-exposed lambs. Ammonia-exposed lambs in both trials showed profuse lacrimation, severe coughing and sneezing, and profuse nasal discharge, which was bloody in some instances. Gross and histopathologic findings appeared to be qualitatively similar between treatments, but more pronounced in NH/sub 3/-exposed lambs.

  10. PV Perspectives On The Titan Atmospheric Circulation

    Science.gov (United States)

    Allison, M.

    Potential vorticity (or PV) has become an important tool for the conceptual model- ing of atmospheric/oceanic circulations and promises to be an important element of the diagnostic study of Titan. Recent applications of PV thinking to numerical simu- lations and observations of several extraterrestrial atmospheres have encouraged the prospects for a unified understanding of planetary circulations encompassing a wide range of rotation and stratification parameters. The accumulated evidence suggests that zonal-mean winds and temperatures at the jet levels approximate a state of zero potential vorticity within the bounding low-latitudes of anticyclonic flow, with the ex- terior cyclonic regions conforming to a PV state that is well mixed with respect to its polar limit [e.g. Allison et al., 1994; Allison, 2000]. The forthcoming reconnais- sance of Titan's atmosphere by the Cassini-Huygens mission will likely represent the greatest leap in the science of planetary meteorology for the coming decade, and pro- vide a unique test of the application of PV thinking to a global cyclostrophic regime, possibly in combination with a geostrophic sub-layer. The visualization of potential vorticity maps of the eight scale-height depth of atmosphere between Titan's surface and its visually opaque haze layer may be facilitated with an appropriately modeified but informationally equivalent formulation of the Ertel PV which removes the expo- nential variation with altitude of its inverse density factor [cf. Lait, 1994]. Specific examples of these kinds of maps and sections will be presented, as constrained by available observations, with a view to their eventual definition by anticipated in situ vertical profiles and orbital global maps from Cassini-Huygens.

  11. High Altitude Jet Fuel Photochemistry.

    Science.gov (United States)

    1982-10-01

    aroma - +0.07 +0.06 tic hydrocarbons, with values of 0.1600 (Reference 75) and 0.0400 (Reference 76) for toluene, while Kenley, et al. (Reference 74...the individual elementary reactions is needed before any J conclusions can be drawn as to the reactions responsible for any effects of

  12. Photochemistry and enzymology of photosynthesis

    Energy Technology Data Exchange (ETDEWEB)

    Radmer, R.

    1979-07-30

    In the first task, a specially designed mass spectrometer system monitors the gas exchange occurring in response to single short flashes of light. This apparatus will be primarily used to study photosystem II donor reactions, such as the photooxidation of hydroxylamine, hydrazine, and hydrogen peroxide. This technique will also be used to study the light-induced exchange of O/sub 2/ and CO/sub 2/ in algae. The second task, biochemical studies, will focus on the role of chloroplast copper in photosynthesis. We propose to isolate, purify, and characterize the chloroplast copper enzyme polyphenol oxidase, and attempt to elucidate its role in photosynthesis. These studies will be integrated with a new program devoted to the biochemical response of the photosynthetic membrane to stress. The third task is a series of studies on the light-harvesting and electron-transport mechanisms of C/sub 4/ plants. This program will address three basic problems: (1) the effect of different preparative procedures on various photosynthetic reactions, with particular emphasis on photosystem II reactions in corn bundle sheath chloroplasts; (2) the development and testing of photosystem II assays; and (3) studies of the stoichiometry of electron carriers in bundle sheath chloroplasts, and whether cyclic phosphorylation could be a major pathway in this tissue.

  13. Photochemistry of alkyl halide dimers

    Science.gov (United States)

    Fan, Y. B.; Randall, K. L.; Donaldson, D. J.

    1993-03-01

    Dimers and other small clusters of CH3I, C2H5I, i- and n-C3H7I, HI, CF3I, CH3Br, and C2H5Br formed in a supersonic expansion are irradiated at 248 and 193 nm and the halogen molecule product probed via laser induced fluorescence spectroscopy. Both dimers and larger clusters of RI (R=H, alkyl) excited at each wavelength yield I2 in its ground electronic state with very little internal energy. Clusters of CF3I and those containing alkyl bromides do not give halogen molecule products after excitation at either wavelength. A model for the dynamics in the dimer excited state which explains these results is presented.

  14. Saturn: atmosphere, ionosphere, and magnetosphere.

    Science.gov (United States)

    Gombosi, Tamas I; Ingersoll, Andrew P

    2010-03-19

    The Cassini spacecraft has been in orbit around Saturn since 30 June 2004, yielding a wealth of data about the Saturn system. This review focuses on the atmosphere and magnetosphere and briefly outlines the state of our knowledge after the Cassini prime mission. The mission has addressed a host of fundamental questions: What processes control the physics, chemistry, and dynamics of the atmosphere? Where does the magnetospheric plasma come from? What are the physical processes coupling the ionosphere and magnetosphere? And, what are the rotation rates of Saturn's atmosphere and magnetosphere?

  15. Hydrodynamics of oceans and atmospheres

    CERN Document Server

    Eckart, Carl

    1960-01-01

    Hydrodynamics of Oceans and Atmospheres is a systematic account of the hydrodynamics of oceans and atmospheres. Topics covered range from the thermodynamic functions of an ideal gas and the thermodynamic coefficients for water to steady motions, the isothermal atmosphere, the thermocline, and the thermosphere. Perturbation equations, field equations, residual equations, and a general theory of rays are also presented. This book is comprised of 17 chapters and begins with an introduction to the basic equations and their solutions, with the aim of illustrating the laws of dynamics. The nonlinear

  16. Mars Atmospheric History Derived from Upper-Atmospheric Structure of 38Ar/36Ar Measured From MAVEN

    Science.gov (United States)

    Jakosky, Bruce; Slipski, Marek; Benna, Mehdi; Mahaffy, Paul; Elrod, Meredith K.; Yelle, Roger; Stone, Shane; Alsaeed, Noora

    2016-10-01

    Measurements of the structure of the Martian upper atmosphere made from MAVEN observations allow us to derive homopause and exobase altitudes in the Mars upper atmosphere and to determine the isotopic fractionation that occurs between them. Fractionation in the ratio of 38Ar/36Ar occurs between the homopause and exobase due to diffusive separation. This fractionation, combined with measurements of the bulk atmospheric ratio, is used to determine the total amount of argon lost to space by pick-up-ion sputtering. Our analysis is based on Rayleigh distillation, modified by replenishment of gas to the atmosphere by outgassing, impact, and crustal weathering. Approximately 80 % of the 36Ar that was ever in the atmosphere has been removed through time. This high value requires that a major fraction of Mars atmospheric gas has been lost to space. It points strongly to loss to space as having been the dominant mechanism driving the transition in Martian climate from an early, warm, wet environment to today's cold, dry, thin atmosphere.

  17. State of the art incubator for controlled atmosphere studies

    DEFF Research Database (Denmark)

    Nielsen, Per Væggemose

    1998-01-01

    A state of the art incubator for studies of the biological effect of controlled atmosphere was designed. Working conditions are all combinations of: Temperature (5 to 40°C), Humidity (25 to 98%), oxygen (0.1 to 30%) and nitrogen (0.1 to 50%). Several points were given specific considerations...

  18. Information Flow in an Atmospheric Model and Data Assimilation

    Science.gov (United States)

    Yoon, Young-noh

    2011-01-01

    Weather forecasting consists of two processes, model integration and analysis (data assimilation). During the model integration, the state estimate produced by the analysis evolves to the next cycle time according to the atmospheric model to become the background estimate. The analysis then produces a new state estimate by combining the background…

  19. Formation of oxygen complexes in controlled atmosphere at surface ...

    Indian Academy of Sciences (India)

    cleaned under vacuum up to 1273 K. Specific functional groups, subsequently formed under dry CO2 or O2 atmosphere on the surface of boron-doped and phosphorus-doped glassy carbon samples, were examined using the temperature-programmed desorption method combined with mass spectrometric analysis.

  20. On the construction of a regional atmospheric climate model

    DEFF Research Database (Denmark)

    Christensen, J. H.; Van Meijgaard, E.

    1992-01-01

    A Regional Atmospheric Climate Model which combines the physical parameterization package of the General Circulation or Climate Model (ECHAM) used at the Max Planck Institute for Meteorology in Hamburg, and the dynamics package of the Nordic - Dutch - Irish Limited Area Model (HIRLAM), has been...... developed. The necessary changes applied to both model packages in order to obtain a working code are described. -from Authors...