WorldWideScience

Sample records for stratospheric bromine photochemistry

  1. Vertical sounding balloons for stratospheric photochemistry

    Science.gov (United States)

    Pommereau, J. P.

    The use of vertical sounding balloons for stratospheric photochemistry studies is illustrated by the use of a vertical piloted gas balloon for the search of NO2 diurnal variations. It is shown that the use of montgolfieres (hot air balloons) can enhance the vertical sounding technique. Particular attention is given to a sun-heated montgolfiere and to the more sophisticated infrared montgolfiere that is able to perform three to four vertical excursions per day and to remain aloft for weeks or months.

  2. 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).

  3. Molecular beam studies of stratospheric photochemistry

    Science.gov (United States)

    Moore, Teresa Anne

    1998-12-01

    Photochemistry of chlorine oxide containing species plays a major role in stratospheric ozone depletion. This thesis discusses two photodissociation studies of the key molecules ClONO2 and ClOOCl which were previously thought to only produce Cl-atom (ozone depleting) products at wavelengths relevant to the stratosphere. The development of a molecular beam source of ClOOCl and the photodissociation dynamics of the model system Cl2O are also discussed. In the first chapter, the photochemistry of ClONO2 is examined at 308 nm using the technique of photofragment translational spectroscopy. Two primary decomposition pathways, leading to Cl + NO3 and ClO + NO2, were observed, with a lower limit of 0.33 for the relative yield of ClO. The angular distributions for both channels were anisotropic, indicating that the dissociation occurs within a rotational period. Chapter two revisits the photodissociation dynamics of Cl2O at 248 and 308 nm, on which we had previously reported preliminary findings. At 248 nm, three distinct dissociation pathways leading to Cl + ClO products were resolved. At 308 nm, the angular distribution was slightly more isotropic that previously reported, leaving open the possibility that Cl2O excited at 308 nm lives longer than a rotational period. Chapter three describes the development and optimization of a molecular beam source of ClOOCl. We utilized pulsed laser photolysis of ClA2O to generate ClO radicals, and cooled the cell to promote three body recombination to form ClOOCl. The principal components in the beam were Cl2, Cl2O, and ClOOCl. In the fourth chapter, the photodissociation dynamics of ClOOCl are investigated at 248 and 308 nm. We observed multiple dissociation pathways which produced ClO + ClO and 2Cl + O2 products. The relative Cl:ClO product yields are 1.0:0.13 and 1.0:0.20 for ClOOCl photolysis at 248 and 308 nm, respectively. The upper limit for the relative yield of the ClO + ClO channel was 0.19 at 248 nm and 0.31 at 308 nm

  4. 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.

  5. Photochemistry, mixing and transport in Jupiter's stratosphere constrained by Cassini

    Science.gov (United States)

    Hue, V.; Hersant, F.; Cavalié, T.; Dobrijevic, M.; Sinclair, J. A.

    2018-06-01

    In this work, we aim at constraining the diffusive and advective transport processes in Jupiter's stratosphere, using Cassini/CIRS observations published by Nixon et al. (2007,2010). The Cassini-Huygens flyby of Jupiter on December 2000 provided the highest spatially resolved IR observations of Jupiter so far, with the CIRS instrument. The IR spectrum contains the fingerprints of several atmospheric constituents and allows probing the tropospheric and stratospheric composition. In particular, the abundances of C2H2 and C2H6, the main compounds produced by methane photochemistry, can be retrieved as a function of latitude in the pressure range at which CIRS is sensitive to. CIRS observations suggest a very different meridional distribution for these two species. This is difficult to reconcile with their photochemical histories, which are thought to be tightly coupled to the methane photolysis. While the overall abundance of C2H2 decreases with latitude, C2H6 becomes more abundant at high latitudes. In this work, a new 2D (latitude-altitude) seasonal photochemical model of Jupiter is developed. The model is used to investigate whether the addition of stratospheric transport processes, such as meridional diffusion and advection, are able to explain the latitudinal behavior of C2H2 and C2H6. We find that the C2H2 observations are fairly well reproduced without meridional diffusion. Adding meridional diffusion to the model provides an improved agreement with the C2H6 observations by flattening its meridional distribution, at the cost of a degradation of the fit to the C2H2 distribution. However, meridional diffusion alone cannot produce the observed increase with latitude of the C2H6 abundance. When adding 2D advective transport between roughly 30 mbar and 0.01 mbar, with upwelling winds at the equator and downwelling winds at high latitudes, we can, for the first time, reproduce the C2H6 abundance increase with latitude. In parallel, the fit to the C2H2 distribution is

  6. Evaluation of linear ozone photochemistry parametrizations in a stratosphere-troposphere data assimilation system

    Directory of Open Access Journals (Sweden)

    A. J. Geer

    2007-01-01

    Full Text Available This paper evaluates the performance of various linear ozone photochemistry parametrizations using the stratosphere-troposphere data assimilation system of the Met Office. A set of experiments were run for the period 23 September 2003 to 5 November 2003 using the Cariolle (v1.0 and v2.1, LINOZ and Chem2D-OPP (v0.1 and v2.1 parametrizations. All operational meteorological observations were assimilated, together with ozone retrievals from the Michelson Interferometer for Passive Atmospheric Sounding (MIPAS. Experiments were validated against independent data from the Halogen Occultation Experiment (HALOE and ozonesondes. Additionally, a simple offline method for comparing the parametrizations is introduced. It is shown that in the upper stratosphere and mesosphere, outside the polar night, ozone analyses are controlled by the photochemistry parametrizations and not by the assimilated observations. The most important factor in getting good results at these levels is to pay attention to the ozone and temperature climatologies in the parametrizations. There should be no discrepancies between the climatologies and the assimilated observations or the model, but there is also a competing demand that the climatologies be objectively accurate in themselves. Conversely, in the lower stratosphere outside regions of heterogeneous ozone depletion, the ozone analyses are dominated by observational increments and the photochemistry parametrizations have little influence. We investigate a number of known problems in LINOZ and Cariolle v1.0 in more detail than previously, and we find discrepancies in Cariolle v2.1 and Chem2D-OPP v2.1, which are demonstrated to have been removed in the latest available versions (v2.8 and v2.6 respectively. In general, however, all the parametrizations work well through much of the stratosphere, helped by the presence of good quality assimilated MIPAS observations.

  7. Solid-State Photochemistry as a Formation Mechanism for Titan's Stratospheric C4N2 Ice Clouds

    Science.gov (United States)

    Anderson, C. M.; Samuelson, R. E.; Yung, Y. L.; McLain, J. L.

    2016-01-01

    We propose that C4N2 ice clouds observed in Titan's springtime polar stratosphere arise due to solid-state photochemistry occurring within extant ice cloud particles of HCN-HC3N mixtures. This formation process resembles the halogen-induced ice particle surface chemistry that leads to condensed nitric acid trihydrate (NAT) particles and ozone depletion in Earth's polar stratosphere. As our analysis of the Cassini Composite Infrared Spectrometer 478 per centimeter ice emission feature demonstrates, this solid-state photochemistry mechanism eliminates the need for the relatively high C4N2 saturation vapor pressures required (even though they are not observed) when the ice is produced through the usual procedure of direct condensation from the vapor.

  8. Laboratory Studies of Stratospheric Bromine Chemistry: Kinetics of the Reactions of Bromine Monoxide with Nitrogen Dioxide and Atomic Oxygen.

    Science.gov (United States)

    Thorn, Robert Peyton, Jr.

    interferences from production of vibrationally or electronically excited O_2 are discussed. The effect of the faster reaction rate coefficients that are reported for the rm BrO + NO_2 + M and BrO + O(^3P) reactions upon bromine partitioning and ozone depletion in the stratosphere is discussed.

  9. 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.

  10. The photochemistry and kinetics of chlorine compounds important to stratospheric mid-latitude ozone destruction

    Science.gov (United States)

    Goldfarb, Leah

    1997-09-01

    The catalytic destruction of stratospheric ozone via chlorinated species was first proposed in the 1970's. Since that time a decline in column ozone abundance in the polar regions as well as at mid-latitudes has been observed. Much of this reduction has been attributed to the increases in anthropogenic chlorine compounds such as CFCs. This study summarizes experimental results obtained using pulsed-photolysis resonance fluorescence and pulsed- photolysis long-path absorption methods to study processes important to chlorine-catalyzed ozone destruction: the quantum yields of the products in the dissociation of ClONO2 and the reactions of free radicals with ClONO2 and ClO. The quantum yields for the production of O, Cl and ClO from ClONO2 were studied at specific laser wavelengths (193, 222, 248, and 308 nm). Cl and ClO yields were comparable at nearly all the wavelengths, expect for 193 nm, where the O atom yield was appreciable. The yields at 308 nm (a wavelength available in the stratosphere) were 0.64 ± 0.17 for Cl, 0.37 ± 0.18 for ClO and product yield for the former reaction, previously unreported, was determined to be ~1. The kinetics of the reaction of O atoms with ClO were measured using a new experimental system built specifically to investigate such radical-radical reactions. A slight negative temperature dependence (E/B = -90 ± 30) was observed over the temperature range (227-363 K). From the measured Arrhenius equation the rate constant at 240 K is 4.1 × 10-11 cm3molecule-1s-1 which is in excellent agreement (l.4% greater) with the currently recommended value. This observation is significant, since this reaction is the rate limiting the dominate chlorine catalytic cycle that destroys O3 near 40 km. To analyze the implications of the kinetic and photochemical information from this work, a box model was constructed. The vertical profile of ozone concentrations and loss rates calculated by this simple model compare well with atmospheric measurements and

  11. The Sensitivity of Arctic Ozone Loss to Polar Stratospheric Cloud Volume and Chlorine and Bromine Loading in a Chemistry and Transport Model

    Science.gov (United States)

    Douglass, A. R.; Stolarski, R. S.; Strahan, S. E.; Polansky, B. C.

    2006-01-01

    The sensitivity of Arctic ozone loss to polar stratospheric cloud volume (V(sub PSC)) and chlorine and bromine loading is explored using chemistry and transport models (CTMs). A simulation using multi-decadal output from a general circulation model (GCM) in the Goddard Space Flight Center (GSFC) CTM complements one recycling a single year s GCM output in the Global Modeling Initiative (GMI) CTM. Winter polar ozone loss in the GSFC CTM depends on equivalent effective stratospheric chlorine (EESC) and polar vortex characteristics (temperatures, descent, isolation, polar stratospheric cloud amount). Polar ozone loss in the GMI CTM depends only on changes in EESC as the dynamics repeat annually. The GSFC CTM simulation reproduces a linear relationship between ozone loss and Vpsc derived from observations for 1992 - 2003 which holds for EESC within approx.85% of its maximum (approx.1990 - 2020). The GMI simulation shows that ozone loss varies linearly with EESC for constant, high V(sub PSC).

  12. Ozone Formation Induced by the Impact of Reactive Bromine and Iodine Species on Photochemistry in a Polluted Marine Environment.

    Science.gov (United States)

    Shechner, M; Tas, E

    2017-12-19

    Reactive iodine and bromine species (RIS and RBS, respectively) are known for altering atmospheric chemistry and causing sharp tropospheric ozone (O 3 ) depletion in polar regions and significant O 3 reduction in the marine boundary layer (MBL). Here we use measurement-based modeling to show that, unexpectedly, both RIS and RBS can lead to enhanced O 3 formation in a polluted marine environment under volatile organic compound (VOC)-limited conditions associated with high nitrogen oxide (NO X = [NO] + [NO 2 ]) concentrations. Under these conditions, the daily average O 3 mixing ratio increased to ∼44 and ∼28% for BrO and IO mixing ratios of up to ∼6.8 and 4.7 ppt, respectively. The increase in the level of O 3 was partially induced by enhanced ClNO 3 formation for higher Br 2 and I 2 emission flux. The increase in the level of O 3 was associated with an increased mixing ratio of hydroperoxyl radical to hydroxyl radical ([HO 2 ]/[OH]) and increased [NO 2 ]/[NO] with higher levels of RBS and/or RIS. NO X -rich conditions are typical of the polluted MBL, near coastlines and ship plumes. Considering that O 3 is toxic to humans, plants, and animals and is a greenhouse gas, our findings call for adequate updating of local and regional air-quality models with the effects of activities of RBS and RIS on O 3 mixing ratios in the polluted MBL.

  13. The chemistry of bromine in the stratosphere: Influence of a new rate constant for the reaction BrO + HO2

    Science.gov (United States)

    Pirre, Michel; Marceau, Francois J.; Lebras, Georges; Maguin, Francoise; Poulet, Gille; Ramaroson, Radiela

    1994-01-01

    The impact of new laboratory data for the reaction BrO + HO2 yields HOBr + O2 in the depletion of global stratospheric ozone has been estimated using a one-dimensional photochemical model taking into account the heterogeneous reaction on sulphate aerosols which converts N2O5 into HNO3. Assuring an aerosol loading 2 times as large as the 'background' and a reaction probability of 0.1 for the above heterogeneous reaction, the 6 fold increase in the measured rate constant for the reaction of BrO with HO2 increases the computed depletion of global ozone produced by 20 ppt of total bromine from 2.01 percent to 2.36 percent. The use of the higher rate constant increases the HOBr mixing ratio and makes the bromine partitioning and the ozone depletion very sensitive to the branching ratio of the potential channel forming HBr in the BrO + HO2 reaction.

  14. A multi-model intercomparison of halogenated very short-lived substances (TransCom-VSLS: linking oceanic emissions and tropospheric transport for a reconciled estimate of the stratospheric source gas injection of bromine

    Directory of Open Access Journals (Sweden)

    R. Hossaini

    2016-07-01

    Full Text Available The first concerted multi-model intercomparison of halogenated very short-lived substances (VSLS has been performed, within the framework of the ongoing Atmospheric Tracer Transport Model Intercomparison Project (TransCom. Eleven global models or model variants participated (nine chemical transport models and two chemistry–climate models by simulating the major natural bromine VSLS, bromoform (CHBr3 and dibromomethane (CH2Br2, over a 20-year period (1993–2012. Except for three model simulations, all others were driven offline by (or nudged to reanalysed meteorology. The overarching goal of TransCom-VSLS was to provide a reconciled model estimate of the stratospheric source gas injection (SGI of bromine from these gases, to constrain the current measurement-derived range, and to investigate inter-model differences due to emissions and transport processes. Models ran with standardised idealised chemistry, to isolate differences due to transport, and we investigated the sensitivity of results to a range of VSLS emission inventories. Models were tested in their ability to reproduce the observed seasonal and spatial distribution of VSLS at the surface, using measurements from NOAA's long-term global monitoring network, and in the tropical troposphere, using recent aircraft measurements – including high-altitude observations from the NASA Global Hawk platform. The models generally capture the observed seasonal cycle of surface CHBr3 and CH2Br2 well, with a strong model–measurement correlation (r  ≥  0.7 at most sites. In a given model, the absolute model–measurement agreement at the surface is highly sensitive to the choice of emissions. Large inter-model differences are apparent when using the same emission inventory, highlighting the challenges faced in evaluating such inventories at the global scale. Across the ensemble, most consistency is found within the tropics where most of the models (8 out of 11 achieve best agreement to

  15. Inorganic bromine in the marine boundary layer: a critical review

    Directory of Open Access Journals (Sweden)

    R. Sander

    2003-01-01

    Full Text Available The cycling of inorganic bromine in the marine boundary layer (mbl has received increased attention in recent years. Bromide, a constituent of sea water, is injected into the atmosphere in association with sea-salt aerosol by breaking waves on the ocean surface. Measurements reveal that supermicrometer sea-salt aerosol is substantially depleted in bromine (often exceeding 50% relative to conservative tracers, whereas marine submicrometer aerosol is often enriched in bromine. Model calculations, laboratory studies, and field observations strongly suggest that the supermicrometer depletions reflect the chemical transformation of particulate bromide to reactive inorganic gases that influence the processing of ozone and other important constituents of marine air. Mechanisms for the submicrometer enrichments are not well understood. Currently available techniques cannot reliably quantify many Br containing compounds at ambient concentrations and, consequently, our understanding of inorganic Br cycling over the oceans and its global significance are uncertain. To provide a more coherent framework for future research, we have reviewed measurements in marine aerosol, the gas phase, and in rain. We also summarize sources and sinks, as well as model and laboratory studies of chemical transformations. The focus is on inorganic bromine over the open oceans outside the polar regions. The generation of sea-salt aerosol at the ocean surface is the major tropospheric source producing about 6.2 Tg/a of bromide. The transport of Br from continents (as mineral aerosol, and as products from biomass-burning and fossil-fuel combustion can be of local importance. Transport of degradation products of long-lived Br containing compounds from the stratosphere and other sources contribute lesser amounts. Available evidence suggests that, following aerosol acidification, sea-salt bromide reacts to form Br2 and BrCl that volatilize to the gas phase and photolyze in daylight

  16. Atmospheric Photochemistry

    Science.gov (United States)

    Massey, Harrie; Potter, A. E.

    1961-01-01

    The upper atmosphere offers a vast photochemical laboratory free from solid surfaces, so all reactions take place in the gaseous phase. At 30 km altitude the pressure has fallen to about one-hundredth of that at ground level, and we shall, rather arbitrarily, regard the upper atmosphere as beginning at that height. By a little less than 100 km the pressure has fallen to 10(exp -3) mm Hg and is decreasing by a power of ten for every 15 km increase in altitude. Essentially we are concerned then with the photochemistry of a nitrogen-oxygen mixture under low-pressure conditions in which photo-ionization, as well as photodissociation, plays an important part. Account must also be taken of the presence of rare constituents, such as water vapour and its decomposition products, including particularly hydroxyl, oxides of carbon, methane and, strangely enough, sodium, lithium and calcium. Many curious and unfamiliar reactions occur in the upper atmosphere. Some of them are luminescent, causing the atmosphere to emit a dim light called the airglow. Others, between gaseous ions and neutral molecules, are almost a complete mystery at this time. Similar interesting phenomena must occur in other planetary atmospheres, and they might be predicted if sufficient chemical information were available.

  17. Stratospheric BrONO2 observed by MIPAS

    Directory of Open Access Journals (Sweden)

    H. Fischer

    2009-03-01

    Full Text Available The first measurements of stratospheric bromine nitrate (BrONO2 are reported. Bromine nitrate has been clearly identified in atmospheric infrared emission spectra recorded with the Michelson Interferometer for Passive Atmospheric Sounding (MIPAS aboard the European Envisat satellite, and stratospheric concentration profiles have been determined for different conditions (day and night, different latitudes. The BrONO2 concentrations show strong day/night variations, with much lower concentrations during the day. Maximum volume mixing ratios observed during night are 20 to 25 pptv. The observed concentration profiles are in agreement with estimations from photochemical models and show that the current understanding of stratospheric bromine chemistry is generally correct.

  18. Bromination of Phenol

    Science.gov (United States)

    Talbot, Christopher

    2013-01-01

    This "Science note" examines the bromination of phenol, a reaction that is commonly taught at A-level and IB (International Baccalaureate) as an example of electrophilic substitution. Phenol undergoes bromination with bromine or bromine water at room temperature. A white precipitate of 2,4,6-tribromophenol is rapidly formed. This…

  19. 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

  20. Preparation of bromine fluoride

    International Nuclear Information System (INIS)

    Domange, Pr; Duflo, J.

    1958-05-01

    This note addresses the preparation of bromine fluoride. It indicates the implemented process for the reaction, used products (fluorine and bromine), and column characteristics. It describes the operating mode. Apparatus drawing is provided

  1. Laboratory Investigations of Stratospheric Halogen Chemistry

    Science.gov (United States)

    Wine, Paul H.; Nicovich, J. Michael; Stickel, Robert E.; Hynes, Anthony J.

    1997-01-01

    A final report for the NASA-supported project on laboratory investigations of stratospheric halogen chemistry is presented. In recent years, this project has focused on three areas of research: (1) kinetic, mechanistic, and thermochemical studies of reactions which produce weakly bound chemical species of atmospheric interest; (2) development of flash photolysis schemes for studying radical-radical reactions of stratospheric interest; and (3) photochemistry studies of interest for understanding stratospheric chemistry. The first section of this paper contains a discussion of work which has not yet been published. All subsequent chapters contain reprints of published papers that acknowledge support from this grant.

  2. Photochemistry of Planetary Atmospheres

    Science.gov (United States)

    Yung, Y. L.

    2005-12-01

    The Space Age started half a century ago. Today, with the completion of a fairly detailed study of the planets of the Solar System, we have begun studying exoplanets (or extrasolar planets). The overriding question in is to ask whether an exoplanet is habitable and harbors life, and if so, what the biosignatures ought to be. This forces us to confront the fundamental question of what controls the composition of an atmosphere. The composition of a planetary atmosphere reflects a balance between thermodynamic equilibrium chemistry (as in the interior of giant planets) and photochemistry (as in the atmosphere of Mars). The terrestrial atmosphere has additional influence from life (biochemistry). The bulk of photochemistry in planetary atmospheres is driven by UV radiation. Photosynthesis may be considered an extension of photochemistry by inventing a molecule (chlorophyll) that can harvest visible light. Perhaps the most remarkable feature of photochemistry is catalytic chemistry, the ability of trace amounts of gases to profoundly affect the composition of the atmosphere. Notable examples include HOx (H, OH and HO2) chemistry on Mars and chlorine chemistry on Earth and Venus. Another remarkable feature of photochemistry is organic synthesis in the outer solar system. The best example is the atmosphere of Titan. Photolysis of methane results in the synthesis of more complex hydrocarbons. The hydrocarbon chemistry inevitably leads to the formation of high molecular weight products, giving rise to aerosols when the ambient atmosphere is cool enough for them to condense. These results are supported by the findings of the recent Cassini mission. Lastly, photochemistry leaves a distinctive isotopic signature that can be used to trace back the evolutionary history of the atmosphere. Examples include nitrogen isotopes on Mars and sulfur isotopes on Earth. Returning to the question of biosignatures on an exoplanet, our Solar System experience tells us to look for speciation

  3. Deriving an atmospheric budget of total organic bromine using airborne in-situ measurements of brominated hydrocarbons in the Western Pacific during SHIVA

    Science.gov (United States)

    Sala, Stephan; Bönisch, Harald; Keber, Timo; Oram, Dave; Mills, Graham; Engel, Andreas

    2014-05-01

    Halogenated hydrocarbons play a major role as precursors for stratospheric ozone depletion. Released from the surface in the troposphere, the halocarbons reach the stratosphere via transport through the tropical tropopause layer. The contribution of the so called very short lived species (VSLS), having atmospheric lifetimes of less than half a year as sources gases for stratospheric bromine is significant. Source gas observations of long-lived bromine compounds and VSLS have so far not been able to explain the amount of bromine derived in the stratosphere from observations of BrO and modeling of the ratio of BrO to total bromine. Due to the short lifetimes and the high atmospheric variability, the representativeness of the available observations of VSLS source gases remains unclear, as these may vary with region and display seasonal variability. During the SHIVA (Stratospheric Ozone: Halogen Impacts in a Varying Atmosphere) project an extensive dataset with over 700 samples of ambient air of all halogen species relevant for the atmospheric budget of total organic bromine (long lived halocarbons: H-1301, H-1211, H-1202, H-2402 and CH3Br, very short lived substances: CHBr3, CH2Br2, CHBr2Cl, CHBrCl2 and CHBrCl) have been collected from onboard the FALCON aircraft in the West Pacific region. Measurements were performed with the newly developed fully-automated in-situ instrument GHOST-MS (Gas chromatograph for the Observation of Tracers - coupled with a Mass Spectrometer) by the Goethe University of Frankfurt and with the onboard whole-air sampler WASP with subsequent ground based state-of-the-art GC/MS analysis by the University of East Anglia. We will present the datasets, compare these to other observation, derive a bromine budget for the West Pacific and derive an estimate of the amount of bromine from VSLS reaching the stratosphere. Using the mean mixing ratios in the upper troposphere of the halocarbons mentioned above, the calculated budget of the total organic

  4. 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.

  5. A multi-model intercomparison of halogenated very short-lived substances (TransCom-VSLS): linking oceanic emissions and tropospheric transport for a reconciled estimate of the stratospheric source gas injection of bromine

    OpenAIRE

    Hossaini, R.; Patra, P. K.; Leeson, A. A.; Krysztofiak, G.; Abraham, N. L.; Andrews, S. J.; Archibald, A. T.; Aschmann, J.; Atlas, E. L.; Belikov, D. A.; Bonisch, H.; Carpenter, L. J.; Dhomse, S.; Dorf, M.; Engel, A.

    2016-01-01

    The first concerted multi-model intercomparison of halogenated very short-lived substances (VSLS) has been performed, within the framework of the ongoing Atmospheric Tracer Transport Model Intercomparison Project (TransCom). Eleven global models or model variants participated (nine chemical transport models and two chemistry–climate models) by simulating the major natural bromine VSLS, bromoform (CHBr3) and dibromomethane (CH2Br2), over a 20-year period (1993–2012). Except f...

  6. Bromine intercalated graphite for lightweight composite conductors

    KAUST Repository

    Amassian, Aram; Patole, Archana

    2017-01-01

    A method of fabricating a bromine-graphite/metal composite includes intercalating bromine within layers of graphite via liquid-phase bromination to create brominated-graphite and consolidating the brominated-graphite with a metal nanopowder via a

  7. Photochemistry of the actinides

    International Nuclear Information System (INIS)

    Toth, L.M.; Bell, J.T.; Friedman, H.A.

    1979-01-01

    It has been found that all three major actinides have a useful variety of photochemical reactions which could be used to achieve a separations process that requires fewer reagents. Several features merit enumerating: (1) Laser photochemistry is not now as uniquely important in fuel reprocessing as it is in isotopic enrichment. The photochemistry can be successfully accomplished with conventional light sources. (2) The easiest place to apply photo-reprocessing is on the three actinides U, Pu, and Np. The solutions are potentially cleaner and more amenable to photoreactions. (3) Organic-phase photoreactions are probably not worth much attention because of the troublesome solvent redox chemistry associated with the photochemical reaction. (4) Upstream process treatment on the raffinate (dissolver solution) may never be too attractive since the radiation intensity precludes the usage of many optical materials and the nature of the solution is such that light transmission into it might be totally impossible

  8. Horizontal and vertical structure of reactive bromine events probed by bromine monoxide MAX-DOAS

    Directory of Open Access Journals (Sweden)

    W. R. Simpson

    2017-08-01

    Full Text Available Heterogeneous photochemistry converts bromide (Br− to reactive bromine species (Br atoms and bromine monoxide, BrO that dominate Arctic springtime chemistry. This phenomenon has many impacts such as boundary-layer ozone depletion, mercury oxidation and deposition, and modification of the fate of hydrocarbon species. To study environmental controls on reactive bromine events, the BRomine, Ozone, and Mercury EXperiment (BROMEX was carried out from early March to mid-April 2012 near Barrow (Utqiaġvik, Alaska. We measured horizontal and vertical gradients in BrO with multiple-axis differential optical absorption spectroscopy (MAX-DOAS instrumentation at three sites, two mobile and one fixed. During the campaign, a large crack in the sea ice (an open lead formed pushing one instrument package ∼ 250 km downwind from Barrow (Utqiaġvik. Convection associated with the open lead converted the BrO vertical structure from a surface-based event to a lofted event downwind of the lead influence. The column abundance of BrO downwind of the re-freezing lead was comparable to upwind amounts, indicating direct reactions on frost flowers or open seawater was not a major reactive bromine source. When these three sites were separated by ∼ 30 km length scales of unbroken sea ice, the BrO amount and vertical distributions were highly correlated for most of the time, indicating the horizontal length scales of BrO events were typically larger than ∼ 30 km in the absence of sea ice features. Although BrO amount and vertical distribution were similar between sites most of the time, rapid changes in BrO with edges significantly smaller than this ∼ 30 km length scale episodically transported between the sites, indicating BrO events were large but with sharp edge contrasts. BrO was often found in shallow layers that recycled reactive bromine via heterogeneous reactions on snowpack. Episodically, these surface-based events propagated aloft when

  9. Stratospheric aerosols

    International Nuclear Information System (INIS)

    Rosen, J.; Ivanov, V.A.

    1993-01-01

    Stratospheric aerosol measurements can provide both spatial and temporal data of sufficient resolution to be of use in climate models. Relatively recent results from a wide range of instrument techniques for measuring stratospheric aerosol parameters are described. Such techniques include impactor sampling, lidar system sensing, filter sampling, photoelectric particle counting, satellite extinction-sensing using the sun as a source, and optical depth probing, at sites mainly removed from tropospheric aerosol sources. Some of these techniques have also had correlative and intercomparison studies. The main methods for determining the vertical profiles of stratospheric aerosols are outlined: lidar extinction measurements from satellites; impactor measurements from balloons and aircraft; and photoelectric particle counter measurements from balloons, aircraft, and rockets. The conversion of the lidar backscatter to stratospheric aerosol mass loading is referred to. Absolute measurements of total solar extinction from satellite orbits can be used to extract the aerosol extinction, and several examples of vertical profiles of extinction obtained with the SAGE satellite are given. Stratospheric mass loading can be inferred from extinction using approximate linear relationships but under restrictive conditions. Impactor sampling is essentially the only method in which the physical nature of the stratospheric aerosol is observed visually. Vertical profiles of stratospheric aerosol number concentration using impactor data are presented. Typical profiles using a dual-size-range photoelectric dustsonde particle counter are given for volcanically disturbed and inactive periods. Some measurements of the global distribution of stratospheric aerosols are also presented. Volatility measurements are described, indicating that stratospheric aerosols are composed primarily of about 75% sulfuric acid and 25% water

  10. Radiation and photochemistry section

    International Nuclear Information System (INIS)

    1991-01-01

    The highlights of this past year in the Radiation and Photochemistry Section at Argonne include: (1) picosecond optical studies of radical cations and excited states produced in hydrocarbon radiolysis provided the first kinetic measurements of ion transformation and production of triplet and singlet excited states by ion recombination. (2) studies of radical cations of alkyl-substituted amines and sulfides provided insights into ion-molecule reactions of radical cations in the condensed phase. (3) studies of the behavior of strained alkane radical cations, such as cubane + ·, revealed new rearrangements and remarkable, medium-dependent differences in their structures. (4) H·atom reactions yielding e aq - provided the first reliable measurements of hydrated-electron enthalpy and entropy and forced the revision of some previous thinking about the driving force in aq - reactions

  11. Bromine intercalated graphite for lightweight composite conductors

    KAUST Repository

    Amassian, Aram

    2017-07-20

    A method of fabricating a bromine-graphite/metal composite includes intercalating bromine within layers of graphite via liquid-phase bromination to create brominated-graphite and consolidating the brominated-graphite with a metal nanopowder via a mechanical pressing operation to generate a bromine-graphite/metal composite material.

  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 (I 2 ) 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 I 2 and snowpack iodide (I - ) measurements, which were conducted near Utqiaġvik, AK, in February 2014. Using chemical ionization mass spectrometry, I 2 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 I 2 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 I 2 is likely a dominant source of iodine atoms in the Arctic.

  13. Atmospheric Bromine in the Arctic

    International Nuclear Information System (INIS)

    Berg, W.W.; Sperry, P.D.; Rahn, K.A.; Gladney, E.S.

    1983-01-01

    We report the first measurements of both particulate and gas phase bromine in the Arctic troposphere. Data from continuous sampling of the Arctic aerosol over a period of 4 years (1976--1980) indicate that the bromine content in the aerosol averages 6 +- 4 ngBr/SCM (5 +- 3 pptm Br) for 9 months of every year. During the 3-month period between February 15 and May 15, however, we observed an annual sharp maximum in particulate bromine with levels exceeding 100 ngBr/SCM (82 pptm Br). The Arctic aerosol showed no bromine enrichment relative to seawater except for this 3 month peak period. During the bromine maximum, enrichment factors reached 40 with average values near 10. Calculations of the amount of excess bromine in the Arctic aerosol showed that over 90% of the peak bromine had an origin other than from direct bulk seawater injection. Total levels of gas phase bromine in the Arctic troposphere found during the peak aerosol period averaged 422 +- 48 ngBr/SCM (118 +- 14 pptv). Total bromine content during this period averaged 474 +- 49 ngBr/SCM with gas-to-particle ratios ranging from 7 to 18. A measurement under nonpeak conditions showed total bromine levels at <25 ngBr/SCM. The possibility that local contamination contributed to the seasonal development of the 3-month bromine peak was carefully considered and ruled out. Elevated particualte bromine levels, with peak values ranging from 22 to 30 ngBr/SCM, were also found at Ny-Alesund, Spitsbergen (Norway). The apparent seasonal nature of this bromine peak suggests that the large bromine maximum observed at Barrow is not an isolated or unique phenomenon characteristic of that sampling location

  14. Microwave Photochemistry II. Photochemistry of 2-tert-butylphenol

    Czech Academy of Sciences Publication Activity Database

    Církva, Vladimír; Kurfürstová, Jana; Karban, Jindřich; Hájek, Milan

    2004-01-01

    Roč. 168, č. 3 (2004), s. 197-204 ISSN 1010-6030 R&D Projects: GA ČR GA203/02/0879 Institutional research plan: CEZ:AV0Z4072921 Keywords : microwave photochemistry * electrodeless discharge lamp * 2-tert-Butylphenol Subject RIV: CC - Organic Chemistry Impact factor: 2.235, year: 2004

  15. 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.

  16. The natural stratosphere of 1974. CIAP monograph 1. Final report

    International Nuclear Information System (INIS)

    1975-09-01

    The Climatic Impact Assessment Program (CIAP) of the U.S. Department of Transportation is charged with the 'assessment' of the impact of future aircraft fleets and other vehicles operating in, or transiting through, the stratosphere. CIAP monograph 1 gives a survey, largely from an experimental standpoint, of what is known in 1974 about the unperturbed stratosphere with respect to an application to stratospheric flight. It reviews the overall structure of the stratosphere, its origin in terms of ozone photochemistry, solar irradiance and overall radiative energy balance, other chemically reactive minor species, and atmospheric motions on a variety of scales of time and distance. The limitations of our understanding are emphasized in the presentation. Also, the monograph examines briefly what is known about the effect of massive injections of nitrogen oxides (from atmospheric nuclear explosions) and sulfur oxides (from major volcanic eruptions)

  17. Sudden Stratospheric Warming Compendium

    Data.gov (United States)

    National Oceanic and Atmospheric Administration, Department of Commerce — Sudden Stratospheric Warming Compendium (SSWC) data set documents the stratospheric, tropospheric, and surface climate impacts of sudden stratospheric warmings. This...

  18. Uranium hexafluoride. Bromine spectrophotometric determination

    International Nuclear Information System (INIS)

    Anon.

    Bromine determination in hydrolized uranium hexafluoride by reduction of bromates by ferrous sulfate, oxidation of bromides by potassium permanganate to give bromine which is extracted into carbon tetrachloride and transformed in eosine for spectrophotometry at 510 nm. The method is suitable for determining 5 to 150 ppm with respect to uranium [fr

  19. Microwave Photochemistry III. Photochemistry of 4-tert-Butylphenol

    Czech Academy of Sciences Publication Activity Database

    Církva, Vladimír; Kurfürstová, J.; Karban, Jindřich; Hájek, Milan

    2005-01-01

    Roč. 174, č. 1 (2005), s. 38-44 ISSN 1010-6030 R&D Projects: GA ČR(CZ) GA203/02/0879; GA AV ČR(CZ) KSK4040110 Institutional research plan: CEZ:AV0Z40720504 Keywords : microwave photochemistry * electrodeless discharge lamp * 4-tert-Butylphenol Subject RIV: CC - Organic Chemistry Impact factor: 2.286, year: 2005

  20. Flow photochemistry: Old light through new windows

    Directory of Open Access Journals (Sweden)

    Jonathan P. Knowles

    2012-11-01

    Full Text Available Synthetic photochemistry carried out in classic batch reactors has, for over half a century, proved to be a powerful but under-utilised technique in general organic synthesis. Recent developments in flow photochemistry have the potential to allow this technique to be applied in a more mainstream setting. This review highlights the use of flow reactors in organic photochemistry, allowing a comparison of the various reactor types to be made.

  1. The Effect of Representing Bromine from VSLS on the Simulation and Evolution of Antarctic Ozone

    Science.gov (United States)

    Oman, Luke D.; Douglass, Anne R.; Salawitch, Ross J.; Canty, Timothy P.; Ziemke, Jerald R.; Manyin, Michael

    2016-01-01

    We use the Goddard Earth Observing System Chemistry Climate Model (GEOSCCM), a contributor to both the 2010 and 2014 WMO Ozone Assessment Reports, to show that inclusion of 5 parts per trillion (ppt) of stratospheric bromine(Br(sub y)) from very short lived substances (VSLS) is responsible for about a decade delay in ozone hole recovery. These results partially explain the significantly later recovery of Antarctic ozone noted in the 2014 report, as bromine from VSLS was not included in the 2010 Assessment. We show multiple lines of evidence that simulations that account for VSLS Br(sub y) are in better agreement with both total column BrO and the seasonal evolution of Antarctic ozone reported by the Ozone Monitoring Instrument (OMI) on NASAs Aura satellite. In addition, the near zero ozone levels observed in the deep Antarctic lower stratospheric polar vortex are only reproduced in a simulation that includes this Br(sub y) source from VSLS.

  2. Balloon-borne stratospheric BrO measurements: comparison with Envisat/SCIAMACHY BrO limb profiles

    Directory of Open Access Journals (Sweden)

    M. Dorf

    2006-01-01

    Full Text Available For the first time, results of four stratospheric BrO profiling instruments, are presented and compared with reference to the SLIMCAT 3-dimensional chemical transport model (3-D CTM. Model calculations are used to infer a BrO profile validation set, measured by 3 different balloon sensors, for the new Envisat/SCIAMACHY (ENVIronment SATellite/SCanning Imaging Absorption spectroMeter for Atmospheric CHartographY satellite instrument. The balloon observations include (a balloon-borne in situ resonance fluorescence detection of BrO (Triple, (b balloon-borne solar occultation DOAS measurements (Differential Optical Absorption Spectroscopy of BrO in the UV, and (c BrO profiling from the solar occultation SAOZ (Systeme d'Analyse par Observation Zenithale balloon instrument. Since stratospheric BrO is subject to considerable diurnal variation and none of the measurements are performed close enough in time and space for a direct comparison, all balloon observations are considered with reference to outputs from the 3-D CTM. The referencing is performed by forward and backward air mass trajectory calculations to match the balloon with the satellite observations. The diurnal variation of BrO is considered by 1-D photochemical model calculation along the trajectories. The 1-D photochemical model is initialised with output data of the 3-D model with additional constraints on the vertical transport, the total amount and photochemistry of stratospheric bromine as given by the various balloon observations. Total [Bry]=(20.1±2.5 pptv obtained from DOAS BrO observations at mid-latitudes in 2003, serves as an upper limit of the comparison. Most of the balloon observations agree with the photochemical model predictions within their given error estimates. First retrieval exercises of BrO limb profiling from the SCIAMACHY satellite instrument on average agree to around 20% with the photochemically-corrected balloon observations of the remote sensing instruments (SAOZ

  3. Vacuum ultraviolet photochemistry of polymers

    International Nuclear Information System (INIS)

    Skurat, Vladimir

    2003-01-01

    The interaction of vacuum UV radiation (wavelength range from 1 to 200 nm) with polymers is interesting for fundamental and applied sciences. This interest is stimulated by various reasons: - Wide applications of polymeric materials in semiconductor technology, where they are used as photoresist materials in combination with VUV light sources (lasers, excimer lamps, synchrotron radiation and others). - Polymers are widely used as spacecraft materials in the last 20 years. On near-Earth orbits, the polymeric materials of spacecraft surfaces are destroyed by solar radiation. - VUV radiation is one of the components of gas discharge plasmas, which are used for treatment of polymer, with the aim of modifying their surface properties. The main features of interaction of VUV radiation with polymers are discussed. The spectra of intrinsic absorption of saturated polymers (polyethylene, polypropylene, polytetrafluoroethylene and others) are situated mainly in the VUV region. The photochemistry of polymers in the VUV region is very different from their photochemistry at wavelengths longer than 200 nm, where the absorption spectra belong to impurities and polymer defects. The polymer photochemistry in the VUV region is wavelength-dependent. At wavelengths longer than about 140 nm, the main role is played by transformations of primary-formed singlet excited molecules. At shorter wavelengths the role of photoionization increases progressively and the main features of VUV photolysis become similar to the picture of radiolysis, with significant contributions of charge pairs and triplet excited molecules. Very important features of VUV light absorption in polymers are high absorption coefficients. Because of this, the surface layers absorb large doses of energy. This leads to very profound transformation of material on the polymer surface. In particular for polymers which are considered destroyed by radiation (for example, perfluoropolymers), this leads to VUV-induced erosion

  4. Convective Transport of Very-short-lived Bromocarbons to the Stratosphere

    Science.gov (United States)

    Liang, Qing; Atlas, Elliot Leonard; Blake, Donald Ray; Dorf, Marcel; Pfeilsticker, Klaus August; Schauffler, Sue Myhre

    2014-01-01

    We use the NASA GEOS Chemistry Climate Model (GEOSCCM) to quantify the contribution of two most important brominated very short-lived substances (VSLS), bromoform (CHBr3) and dibromomethane (CH2Br2), to stratospheric bromine and its sensitivity to convection strength. Model simulations suggest that the most active transport of VSLS from the marine boundary layer through the tropopause occurs over the tropical Indian Ocean, the Western Pacific warm pool, and off the Pacific coast of Mexico. Together, convective lofting of CHBr3 and CH2Br2 and their degradation products supplies 8 ppt total bromine to the base of the Tropical Tropopause Layer (TTL, 150 hPa), similar to the amount of VSLS organic bromine available in the marine boundary layer (7.8-8.4 ppt) in the above active convective lofting regions. Of the total 8 ppt VSLS-originated bromine that enters the base of TTL at 150 hPa, half is in the form of source gas injection (SGI) and half as product gas injection (PGI). Only a small portion (Br2, together, contribute 7.7 pptv to the present-day inorganic bromine in the stratosphere. However, varying model deep convection strength between maximum and minimum convection conditions can introduce a 2.6 pptv uncertainty in the contribution of VSLS to inorganic bromine in the stratosphere (BryVSLS). Contrary to the conventional wisdom, minimum convection condition leads to a larger BryVSLS as the reduced scavenging in soluble product gases, thus a significant increase in PGI (2-3 ppt), greatly exceeds the relative minor decrease in SGI (a few 10ths ppt.

  5. 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.

  6. An exemplary case of a bromine explosion event linked to cyclone development in the Arctic

    Directory of Open Access Journals (Sweden)

    A.-M. Blechschmidt

    2016-02-01

    Full Text Available Intense, cyclone-like shaped plumes of tropospheric bromine monoxide (BrO are regularly observed by GOME-2 on board the MetOp-A satellite over Arctic sea ice in polar spring. These plumes are often transported by high-latitude cyclones, sometimes over several days despite the short atmospheric lifetime of BrO. However, only few studies have focused on the role of polar weather systems in the development, duration and transport of tropospheric BrO plumes during bromine explosion events. The latter are caused by an autocatalytic chemical chain reaction associated with tropospheric ozone depletion and initiated by the release of bromine from cold brine-covered ice or snow to the atmosphere. In this manuscript, a case study investigating a comma-shaped BrO plume which developed over the Beaufort Sea and was observed by GOME-2 for several days is presented. By making combined use of satellite data and numerical models, it is shown that the occurrence of the plume was closely linked to frontal lifting in a polar cyclone and that it most likely resided in the lowest 3 km of the troposphere. In contrast to previous case studies, we demonstrate that the dry conveyor belt, a potentially bromine-rich stratospheric air stream which can complicate interpretation of satellite retrieved tropospheric BrO, is spatially separated from the observed BrO plume. It is concluded that weather conditions associated with the polar cyclone favoured the bromine activation cycle and blowing snow production, which may have acted as a bromine source during the bromine explosion event.

  7. A refined method for calculating equivalent effective stratospheric chlorine

    Science.gov (United States)

    Engel, Andreas; Bönisch, Harald; Ostermöller, Jennifer; Chipperfield, Martyn P.; Dhomse, Sandip; Jöckel, Patrick

    2018-01-01

    Chlorine and bromine atoms lead to catalytic depletion of ozone in the stratosphere. Therefore the use and production of ozone-depleting substances (ODSs) containing chlorine and bromine is regulated by the Montreal Protocol to protect the ozone layer. Equivalent effective stratospheric chlorine (EESC) has been adopted as an appropriate metric to describe the combined effects of chlorine and bromine released from halocarbons on stratospheric ozone. Here we revisit the concept of calculating EESC. We derive a refined formulation of EESC based on an advanced concept of ODS propagation into the stratosphere and reactive halogen release. A new transit time distribution is introduced in which the age spectrum for an inert tracer is weighted with the release function for inorganic halogen from the source gases. This distribution is termed the release time distribution. We show that a much better agreement with inorganic halogen loading from the chemistry transport model TOMCAT is achieved compared with using the current formulation. The refined formulation shows EESC levels in the year 1980 for the mid-latitude lower stratosphere, which are significantly lower than previously calculated. The year 1980 is commonly used as a benchmark to which EESC must return in order to reach significant progress towards halogen and ozone recovery. Assuming that - under otherwise unchanged conditions - the EESC value must return to the same level in order for ozone to fully recover, we show that it will take more than 10 years longer than estimated in this region of the stratosphere with the current method for calculation of EESC. We also present a range of sensitivity studies to investigate the effect of changes and uncertainties in the fractional release factors and in the assumptions on the shape of the release time distributions. We further discuss the value of EESC as a proxy for future evolution of inorganic halogen loading under changing atmospheric dynamics using simulations from

  8. Millimeter wave spectroscopic measurements of stratospheric and mesospheric constituents over the Italian Alps: stratospheric ozone

    Directory of Open Access Journals (Sweden)

    V. Romaniello

    2007-06-01

    altitude ozone photochemistry dominates over transport processes. The correlation of lower stratospheric ozone concentrations with potential vorticity as an indicator of transport is instead not as clear-cut, due to very complex mixing processes that characterize stratospheric air at mid-latitudes. Correlations of O3 over Testa Grigia with stratospheric tracers such as N2O and HCN, also observed by means of the GBMS, are planned for the future, in order to better characterize lower stratospheric dynamics and therefore lower stratospheric ozone concentrations at mid-latitudes.

  9. Airborne Arctic Stratospheric Expedition II: An overview

    Science.gov (United States)

    Anderson, James G.; Toon, Owen B.

    1993-11-01

    The sudden onset of ozone depletion in the antarctic vortex set a precedent for both the time scale and the severity of global change. The Airborne Antarctic Ozone Experiment (AAOE), staged from Punta Arenas, Chile, in 1987, established that CFCs, halons, and methyl bromide, the dominant sources of chlorine and bromine radicals in the stratosphere, control the rate of ozone destruction over the Antarctic; that the vortex is depleted in reactive nitrogen and water vapor; and that diabatic cooling during the Antarctic winter leads to subsidence within the vortex core, importing air from higher altitudes and lower latitudes. This last conclusion is based on observed dramatic distortion in the tracer fields, most notably N2O.In 1989, the first Airborne Arctic Stratospheric Expedition (AASE-I), staged from Stavanger, Norway, and using the same aircraft employed for AAOE (the NASA ER-2 and the NASA DC-8), discovered that while NOx and to some degree NOy were perturbed within the arctic vortex, there was little evidence for desiccation. Under these (in contrast to the antarctic) marginally perturbed conditions, however, ClO was found to be dramatically enhanced such that a large fraction of the available (inorganic) chlorine resided in the form of ClO and its dimer ClOOCl.This leaves two abiding issues for the northern hemisphere and the mission of the second Airborne Arctic Stratospheric Expedition (AASE-II): (1) Will significant ozone erosion occur within the arctic vortex in the next ten years as chlorine loading in the stratosphere exceeds four parts per billion by volume? (2) Which mechanisms are responsible for the observed ozone erosion poleward of 30°N in the winter/spring northern hemisphere reported in satellite observations?

  10. The photochemistry of the paleoatmosphere

    Science.gov (United States)

    Levine, J. S.

    1982-01-01

    Recent progress in the understanding of the chemistry and photochemistry of the paleoatmosphere is reviewed with emphasis on the application of photochemical models to the investigation of the evolution of the atmosphere. Photochemical calculations are presented which show that a primordial highly reducing atmosphere composed of methane and ammonia, if it formed at all, would be short-lived in the presence of solar ultraviolet radiation, giving way rapidly to a more mildly reducing atmosphere of carbon dioxide and nitrogen. Estimations of O2 produced from the photolysis of water vapor prior to the emergence of photosynthesis range from less than 10 to the -14th to 0.1 times the present atmospheric level, indicating the need for further research. A series of photochemical models of increasing complexity has been developed to study the evolution of atmospheric ozone taking into account reactions with O atoms, hydrogen oxides, nitrogen oxides, and chlorine as well as vertical transport, temperature and tropospheric chemistry so that the total content and vertical distribution of O3 may be determined for a specified level of paleoatmospheric O2.

  11. A New Formulation of Equivalent Effective Stratospheric Chlorine (EESC)

    Science.gov (United States)

    Newman, P. A.; Daniel, J. S.; Waugh, D. W.; Nash, E. R.

    2007-01-01

    Equivalent effective stratospheric chlorine (EESC) is a convenient parameter to quantify the effects of halogens (chlorine and bromine) on ozone depletion in the stratosphere. We show and discuss a new formulation of EESC that now includes the effects of age-of-air dependent fractional release values and an age-of-air spectrum. This new formulation provides quantitative estimates of EESC that can be directly related to inorganic chlorine and bromine throughout the stratosphere. Using this EESC formulation, we estimate that human-produced ozone depleting substances will recover to 1980 levels in 2041 in the midlatitudes, and 2067 over Antarctica. These recovery dates are based upon the assumption that the international agreements for regulating ozone-depleting substances are adhered to. In addition to recovery dates, we also estimate the uncertainties in the estimated time of recovery. The midlatitude recovery of 2041 has a 95% confidence uncertainty from 2028 to 2049, while the 2067 Antarctic recovery has a 95% confidence uncertainty from 2056 to 2078. The principal uncertainties are from the estimated mean age-of-air, and the assumption that the mean age-of-air and fractional release values are time independent. Using other model estimates of age decrease due to climate change, we estimate that midlatitude recovery may be accelerated from 2041 to 2031.

  12. Electronic properties of bromine-doped carbon nanotubes

    CERN Document Server

    Jhi, S H; Cohen, M L

    2002-01-01

    Intercalation of bromine molecules (Br2) into single-wall carbon nanotube (SWNT) ropes is studied using the ab initio pseudopotential density functional method. Electronic and vibrational properties of the SWNT and Br2 are studied for various bromine concentrations. A drastic change in the charge transfer, bromine stretching-mode, and bromine bond-length is observed when the bromine-bromine distance decreases. Calculated electronic structures show that, at high bromine concentrations, the bromine ppsigma level broadens due to the interbromine interaction. These states overlap with the electronic bands of the SWNT near the Fermi level which results in a substantial charge transfer from carbon to bromine.

  13. Stratospheric ethane on Neptune - Comparison of groundbased and Voyager IRIS retrievals

    Science.gov (United States)

    Kostiuk, Theodor; Romani, Paul; Espenak, Fred; Bezard, Bruno

    1992-01-01

    Near-simultaneous ground and spacecraft measurements of 12-micron ethane emission spectra during the Voyager encounter with Neptune have furnished bases for the determination of stratospheric ethane abundance and the testing and constraining of Neptune methane-photochemistry models. The ethane retrievals were sensitive to the thermal profile used. Contribution functions for warm thermal profiles peaked at higher altitudes, as expected, with the heterodyne functions covering lower-pressure regions. Both constant- and nonconstant-with-height profiles remain candidate distributions for Neptune's stratospheric ethane.

  14. Finding the Missing Stratospheric Br(sub y): A Global Modeling Study of CHBr3 and CH2Br2

    Science.gov (United States)

    Liang, Q.; Stolarski, R. S.; Kawa, S. R.; Nielsen, J. E.; Douglass, A. R.; Rodriguez, J. M.; Blake, D. R.; Atlas, E. L.; Ott, L. E.

    2010-01-01

    Recent in situ and satellite measurements suggest a contribution of 5 pptv to stratospheric inorganic bromine from short-lived bromocarbons. We conduct a modeling study of the two most important short-lived bromocarbons, bromoform (CHBr3) and dibromomethane (CH2Br2), with the Goddard Earth Observing System Chemistry Climate Model (GEOS CCM) to account for this missing stratospheric bromine. We derive a "top-down" emission estimate of CHBr3 and CH2Br2 using airborne measurements in the Pacific and North American troposphere and lower stratosphere obtained during previous NASA aircraft campaigns. Our emission estimate suggests that to reproduce the observed concentrations in the free troposphere, a global oceanic emission of 425 Gg Br yr(exp -1) for CHBr3 and 57 Gg Br yr(exp -l) for CH2Br2 is needed, with 60% of emissions from open ocean and 40% from coastal regions. Although our simple emission scheme assumes no seasonal variations, the model reproduces the observed seasonal variations of the short-lived bromocarbons with high concentrations in winter and low concentrations in summer. This indicates that the seasonality of short-lived bromocarbons is largely due to seasonality in their chemical loss and transport. The inclusion of CHBr3 and CH2Br2 contributes 5 pptv bromine throughout the stratosphere. Both the source gases and inorganic bromine produced from source gas degradation (BrSLS) in the troposphere are transported into the stratosphere, and are equally important. Inorganic bromine accounts for half (2.5 pptv) of the bromine from the inclusion of CHBr3 and CHzBr2 near the tropical tropopause and its contribution rapidly increases to 100% as altitude increases. More than 85% of the wet scavenging of Br(sub y)(sup VSLS) occurs in large-scale precipitation below 500 hPa. Our sensitivity study with wet scavenging in convective updrafts switched off suggests that Br(sub y)(sup SLS) in the stratosphere is not sensitive to convection. Convective scavenging only

  15. Enhanced photochemistry on metal surfaces

    International Nuclear Information System (INIS)

    Goncher, G.M.; Parsons, C.A.; Harris, C.B.

    1984-01-01

    Due to the fast relaxation of molecular excited states in the vicinity of a metal or semiconductor surface, few observations of surface photochemistry have been reported. The following work concerns the surface-enhanced photo-reactions of a variety of physisorbed molecules on roughened Ag surfaces. In summary, photodecomposition leads to a graphitic surface carbon product which is monitored via surface-enhanced Raman scattering. In most cases an initial two-photon molecular absorption step followed by further absorption and fragmentation is thought to occur. Enhancement of the incident fields occurs through roughness-mediated surface plasmon resonances. This mechanism provides the amplified electromagnetic surface fields responsible for the observed photodecomposition. The photodecomposition experiments are performed under ultra-high vacuum. Surface characterization of the roughened surfaces was done by Scanning Electron Microscopy (SEM), and electron-stimulated emission. The SEM revealed morphology on the order of 300-400 A. This size of roughness feature, when modelled as isolated spheres should exhibit the well-known Mie resonances for light of the correct wavelengths. For protrusions existing on a surface these Mie resonances can be thought of as a coupling of the light with the surface plasmon. Experimental verification of these resonances was provided by the electron-stimulated light emission results. These showed that a polished Ag surface emitted only the expected transition radiation at the frequency of the Ag bulk plasmon. Upon roughening, however, a broad range of lower frequencies extending well into the visible are seen from electron irradiation of the surface. Large enhancements are expected for those frequencies which are able to couple into the surface modes

  16. 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

  17. Surface-Plasmon-Driven Hot Electron Photochemistry.

    Science.gov (United States)

    Zhang, Yuchao; He, Shuai; Guo, Wenxiao; Hu, Yue; Huang, Jiawei; Mulcahy, Justin R; Wei, Wei David

    2017-11-30

    Visible-light-driven photochemistry has continued to attract heightened interest due to its capacity to efficiently harvest solar energy and its potential to solve the global energy crisis. Plasmonic nanostructures boast broadly tunable optical properties coupled with catalytically active surfaces that offer a unique opportunity for solar photochemistry. Resonant optical excitation of surface plasmons produces energetic hot electrons that can be collected to facilitate chemical reactions. This review sums up recent theoretical and experimental approaches for understanding the underlying photophysical processes in hot electron generation and discusses various electron-transfer models on both plasmonic metal nanostructures and plasmonic metal/semiconductor heterostructures. Following that are highlights of recent examples of plasmon-driven hot electron photochemical reactions within the context of both cases. The review concludes with a discussion about the remaining challenges in the field and future opportunities for addressing the low reaction efficiencies in hot-electron-induced photochemistry.

  18. Refractory concentrate gold leaching: Cyanide vs. bromine

    Science.gov (United States)

    Dadgar, Ahmad

    1989-12-01

    Gold extraction, recovery and economics for two refractory concentrates were investigated using cyanide and bromine reagents. Gold extractions for cyanide leaching (24-48 hours) and bromine leaching (six hours) were the same and ranged from 94 to 96%. Gold recoveries from bromine pregnant solutions using carbon adsorption, ion exchange, solvent extraction, and zinc and aluminum precipitation methods were better than 99.9%. A preliminary economic analysis indicates that chemical costs for cyanidation and bromine process are 11.70 and 11.60 respectively, per tonne of calcine processed.

  19. A Lagrangian View of Stratospheric Trace Gas Distributions

    Science.gov (United States)

    Schoeberl, M. R.; Sparling, L.; Dessler, A.; Jackman, C. H.; Fleming, E. L.

    1998-01-01

    As a result of photochemistry, some relationship between the stratospheric age-of-air and the amount of tracer contained within an air sample is expected. The existence of such a relationship allows inferences about transport history to be made from observations of chemical tracers. This paper lays down the conceptual foundations for the relationship between age and tracer amount, developed within a Lagrangian framework. In general, the photochemical loss depends not only on the age of the parcel but also on its path. We show that under the "average path approximation" that the path variations are less important than parcel age. The average path approximation then allows us to develop a formal relationship between the age spectrum and the tracer spectrum. Using the relation between the tracer and age spectra, tracer-tracer correlations can be interpreted as resulting from mixing which connects parts of the single path photochemistry curve, which is formed purely from the action of photochemistry on an irreducible parcel. This geometric interpretation of mixing gives rise to constraints on trace gas correlations, and explains why some observations are do not fall on rapid mixing curves. This effect is seen in the ATMOS observations.

  20. A new formulation of equivalent effective stratospheric chlorine (EESC

    Directory of Open Access Journals (Sweden)

    P. A. Newman

    2007-09-01

    Full Text Available Equivalent effective stratospheric chlorine (EESC is a convenient parameter to quantify the effects of halogens (chlorine and bromine on ozone depletion in the stratosphere. We show, discuss, and analyze a new formulation of EESC that now includes the effects of age-of-air dependent fractional release values and an age-of-air spectrum. This EESC can be more appropriately applied to various parts of the stratosphere because of this dependence on mean age-of-air. This new formulation provides quantitative estimates of EESC that can be directly related to inorganic chlorine and bromine throughout the stratosphere. In this paper, we first provide a detailed description of the EESC calculation. We then use this EESC formulation to estimate that human-produced ozone depleting substances will recover to 1980 levels in 2041 in the midlatitudes, and 2067 over Antarctica. These recovery dates are based upon the assumption that the international agreements for regulating ozone-depleting substances are adhered to. In addition to recovery dates, we also estimate the uncertainties and possible problems in the estimated times of recovery. The midlatitude recovery of 2041 has a 95% confidence uncertainty from 2028 to 2049, while the 2067 Antarctic recovery has a 95% confidence uncertainty from 2056 to 2078. The principal uncertainties are from the estimated mean age-of-air and fractional release values, and the assumption that these quantities are time independent. Using other model estimates of age decrease due to climate change, we estimate that midlatitude recovery may be significantly accelerated.

  1. Synthesis, characterization and photochemistry of a new ...

    Indian Academy of Sciences (India)

    The synthesis, crystal structure, redox characteristics and photochemistry of a new heptamolyb- ... The ability of [Mo7O24]−6 to function as a pure “inor- .... Abbreviations used: bpp = 1,3-bis(4-pyridyl)propane; 2-amp = 2-aminopyridine; DMSO ...

  2. 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)

  3. Interactive Photochemistry in Earth System Models to Assess Uncertainty in Ozone and Greenhouse Gases. Final report

    Energy Technology Data Exchange (ETDEWEB)

    Prather, Michael J. [Univ. of California, Irvine, CA (United States); Hsu, Juno [Univ. of California, Irvine, CA (United States); Nicolau, Alex [Univ. of California, Irvine, CA (United States); Veidenbaum, Alex [Univ. of California, Irvine, CA (United States); Smith, Philip Cameron [Lawrence Livermore National Lab. (LLNL), Livermore, CA (United States); Bergmann, Dan [Lawrence Livermore National Lab. (LLNL), Livermore, CA (United States)

    2014-11-07

    Atmospheric chemistry controls the abundances and hence climate forcing of important greenhouse gases including N2O, CH4, HFCs, CFCs, and O3. Attributing climate change to human activities requires, at a minimum, accurate models of the chemistry and circulation of the atmosphere that relate emissions to abundances. This DOE-funded research provided realistic, yet computationally optimized and affordable, photochemical modules to the Community Earth System Model (CESM) that augment the CESM capability to explore the uncertainty in future stratospheric-tropospheric ozone, stratospheric circulation, and thus the lifetimes of chemically controlled greenhouse gases from climate simulations. To this end, we have successfully implemented Fast-J (radiation algorithm determining key chemical photolysis rates) and Linoz v3.0 (linearized photochemistry for interactive O3, N2O, NOy and CH4) packages in LLNL-CESM and for the first time demonstrated how change in O2 photolysis rate within its uncertainty range can significantly impact on the stratospheric climate and ozone abundances. From the UCI side, this proposal also helped LLNL develop a CAM-Superfast Chemistry model that was implemented for the IPCC AR5 and contributed chemical-climate simulations to CMIP5.

  4. Bromine pretreated chitosan for adsorption of lead

    Indian Academy of Sciences (India)

    Pollution by heavy metals like lead (II) is responsible for health hazards and environmental degradation. Adsorption is a prevalent method applied for removal of heavy metal pollutants from water. This study explored adsorption performances of 30% bromine pretreated chitosan for lead (II) abatement from water. Bromine ...

  5. Chlorine in the stratosphere

    OpenAIRE

    VON CLARMANN, T.

    2013-01-01

    This paper reviews the various aspects of chlorine compounds in the stratosphere, both their roles as reactants and as tracers of dynamical processes. In the stratosphere, reactive chlorine is released from chlorofluorocarbons and other chlorine-containing organic source gases. To a large extent reactive chlorine is then sequestered in reservoir species ClONO2 and HCl. Re-activation of chlorine happens predominantly in polar winter vortices by heterogeneous reaction in combination with sunlig...

  6. Combining Eosin Y with Selectfluor: A Regioselective Brominating System for Para-Bromination of Aniline Derivatives.

    Science.gov (United States)

    Huang, Binbin; Zhao, Yating; Yang, Chao; Gao, Yuan; Xia, Wujiong

    2017-07-21

    A mild, metal-free, and absolutely para-selective bromination of aniline derivatives has been developed in excellent yields, wherein the organic dye Eosin Y is employed as the bromine source in company with Selectfluor. Neither air nor moisture sensitive, this facile reaction proceeds smoothly at room temperature and completes within a short time. Mechanistic studies indicate a radical pathway; therefore, the existence of an in situ generated brominating reagent, "Selectbrom", is postulated, which may reasonably account for the unique regioselectivity for the para-bromination of N-acyl- as well as N-sulfonylanilines.

  7. Stratospheric Aerosol Measurements

    Science.gov (United States)

    Pueschel, Rudolf, F.; Gore, Warren J. (Technical Monitor)

    1998-01-01

    Stratospheric aerosols affect the atmospheric energy balance by scattering and absorbing solar and terrestrial radiation. They also can alter stratospheric chemical cycles by catalyzing heterogeneous reactions which markedly perturb odd nitrogen, chlorine and ozone levels. Aerosol measurements by satellites began in NASA in 1975 with the Stratospheric Aerosol Measurement (SAM) program, to be followed by the Stratospheric Aerosol and Gas Experiment (SAGE) starting in 1979. Both programs employ the solar occultation, or Earth limb extinction, techniques. Major results of these activities include the discovery of polar stratospheric clouds (PSCs) in both hemispheres in winter, illustrations of the impacts of major (El Chichon 1982 and Pinatubo 1991) eruptions, and detection of a negative global trend in lower stratospheric/upper tropospheric aerosol extinction. This latter result can be considered a triumph of successful worldwide sulfur emission controls. The SAGE record will be continued and improved by SAGE III, currently scheduled for multiple launches beginning in 2000 as part of the Earth Observing System (EOS). The satellite program has been supplemented by in situ measurements aboard the ER-2 (20 km ceiling) since 1974, and from the DC-8 (13 km ceiling) aircraft beginning in 1989. Collection by wire impactors and subsequent electron microscopic and X-ray energy-dispersive analyses, and optical particle spectrometry have been the principle techniques. Major findings are: (1) The stratospheric background aerosol consists of dilute sulfuric acid droplets of around 0.1 micrometer modal diameter at concentration of tens to hundreds of monograms per cubic meter; (2) Soot from aircraft amounts to a fraction of one percent of the background total aerosol; (3) Volcanic eruptions perturb the sulfuric acid, but not the soot, aerosol abundance by several orders of magnitude; (4) PSCs contain nitric acid at temperatures below 195K, supporting chemical hypotheses

  8. short communication polyvinylpyrrolidone-bromine complex

    African Journals Online (AJOL)

    Preferred Customer

    Benzylic bromides were conveniently obtained in high yields via the reaction of the corresponding alcohols with crosslinked polyvinylpyrrolidone-bromine ... The traditional methods include highly toxic reagent such as HBr gas [3], BBr3 [4, ...

  9. Systematic vibration thermodynamic properties of bromine

    Science.gov (United States)

    Liu, G. Y.; Sun, W. G.; Liao, B. T.

    2015-11-01

    Based on the analysis of the maturity and finiteness of vibrational levels of bromine molecule in ground state and evaluating the effect on statistical computation, according to the elementary principles of quantum statistical theorem, using the full set of bromine molecular vibrational levels determined with algebra method, the statistical contribution for bromine systematical macroscopic thermodynamic properties is discussed. Thermodynamic state functions Helmholtz free energy, entropy and observable vibration heat capacity are calculated. The results show that the determination of full set of vibrational levels and maximum vibrational quantum number is the key in the correct statistical analysis of bromine systematical thermodynamic property. Algebra method results are clearly different from data of simple harmonic oscillator and the related algebra method results are no longer analytical but numerical and are superior to simple harmonic oscillator results. Compared with simple harmonic oscillator's heat capacities, the algebra method's heat capacities are more consistent with the experimental data in the given temperature range of 600-2100 K.

  10. Bromine accumulation in acidic black colluvial soils

    Science.gov (United States)

    Martínez Cortizas, Antonio; Ferro Vázquez, Cruz; Kaal, Joeri; Biester, Harald; Costa Casais, Manuela; Taboada Rodríguez, Teresa; Rodríguez Lado, Luis

    2016-02-01

    Recent investigations showed that bromine is incorporated to soil organic matter (SOM), its content increasing with humification. But few research was done on its long-term accumulation and the role played by pedogenetic processes, as those involved in organic matter stabilization. We investigated bromine content and distribution in four deep, acidic, organic-rich, Holocene soils from an oceanic area of Western Europe. Bromine concentrations (93-778 μg g-1) in the silt + clay (stabilized as aluminium-OM associations, and to a lesser extent on soil acidity (pH) and iron-OM associations. Thus, at scales of thousands of years, bromine accumulation in acidic soils is linked to the pool of metal-clay-stabilized organic matter.

  11. 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.

  12. Modeling the inorganic bromine partitioning in the tropical tropopause layer over the eastern and western Pacific Ocean

    Directory of Open Access Journals (Sweden)

    M. A. Navarro

    2017-08-01

    Full Text Available The stratospheric inorganic bromine (Bry burden arising from the degradation of brominated very short-lived organic substances (VSLorg and its partitioning between reactive and reservoir species is needed for a comprehensive assessment of the ozone depletion potential of brominated trace gases. Here we present modeled inorganic bromine abundances over the Pacific tropical tropopause based on aircraft observations of VSLorg from two campaigns of the Airborne Tropical TRopopause EXperiment (ATTREX 2013, carried out over the eastern Pacific, and ATTREX 2014, carried out over the western Pacific and chemistry-climate simulations (along ATTREX flight tracks using the specific meteorology prevailing. Using the Community Atmosphere Model with Chemistry (CAM-Chem we model that BrO and Br are the daytime dominant species. Integrated across all ATTREX flights, BrO represents ∼ 43 and 48 % of daytime Bry abundance at 17 km over the western and eastern Pacific, respectively. The results also show zones where Br / BrO > 1 depending on the solar zenith angle (SZA, ozone concentration, and temperature. On the other hand, BrCl and BrONO2 were found to be the dominant nighttime species with ∼  61 and 56 % of abundance at 17 km over the western and eastern Pacific, respectively. The western-to-eastern differences in the partitioning of inorganic bromine are explained by different abundances of ozone (O3, nitrogen dioxide (NO2, total inorganic chlorine (Cly, and the efficiency of heterogeneous reactions of bromine reservoirs (mostly BrONO2 and HBr occurring on ice crystals.

  13. Stratospheric H2O

    International Nuclear Information System (INIS)

    Ellsaesser, H.W.

    1979-01-01

    Documentation of the extreme aridity (approx. 3% relative humidity) of the lower stratosphere and the rapid decrease of mixing ratio with height just above the polar tropopause (20-fold in the 1st km) was begun by Dobson et al., (1946) in 1943. They recognized that this extreme and persistent aridity must be dynamically maintained else it would have been wiped out by turbulent diffusion. This led Brewer (1949) to hypothesize a stratospheric circulation in which all air enters through the tropical tropopause where it is freeze dried to a mass mixing ratio of 2 to 3 ppM. This dry air then spreads poleward and descends through the polar tropopauses overpowering upward transport of water vapor by diffusion which would otherwise be permitted by the much warmer temperatures of the polar tropopauses. Questions can indeed be raised as to the absolute magnitudes of stratospheric mixing ratios, the effective temperature of the tropical tropopause cold trap, the reality of winter pole freeze-dry sinks and the representativeness of the available observations suggesting an H 2 O mixing ratio maximum just above the tropical tropopause and a constant mixing ratio from the tropopause to 30 to 35 km. However, no model that better fits all of the available data is available, than does the Brewer (1949) hypothesis coupled with a lower stratosphere winter pole, freeze-dry sink, at least over Antarctica

  14. Solid state photochemistry. Subpanel A-2(c): Challenges and opportunities in photochemistry

    Energy Technology Data Exchange (ETDEWEB)

    Czanderna, A.W. [National Renewable Energy Laboratory, Golden, CO (United States)

    1996-09-01

    In contrast with the prior two subsections, the topics in solid state photochemistry range from photo(thermal)-induced degradation to synthesizing new compounds with desirable functions or properties. We will therefore discuss the importance of each relative to existing technological barriers, recent progress, potential applications, and the advantages expected from new information from basic science, especially, as it relates to the DOE mission.

  15. The Electrodeless Discharge Lamp: A Prospective Tool for Photochemistry Part 3. The Microwave Photochemistry Reactor

    Czech Academy of Sciences Publication Activity Database

    Klán, P.; Hájek, Milan; Církva, Vladimír

    2001-01-01

    Roč. 140, č. 3 (2001), s. 185-189 ISSN 1010-6030 Institutional research plan: CEZ:AV0Z4072921 Keywords : photochemistry * electrodeless discharge lamp * microwave Subject RIV: CH - Nuclear ; Quantum Chemistry Impact factor: 1.038, year: 2001

  16. A personal perspective on the future of flow photochemistry

    NARCIS (Netherlands)

    Noël, Timothy

    2017-01-01

    Photochemistry and photoredox catalysis have witnessed a remarkable comeback in the last decade. Flow chemistry has been of pivotal importance to alleviate some of the classical obstacles associated with photochemistry. Herein, we analyze some of the most exciting features provided by photo flow

  17. 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.

  18. Tunable lasers for waste management photochemistry applications

    International Nuclear Information System (INIS)

    Finch, F.T.

    1978-09-01

    A review of lasers with potential photochemical applications in waste management indicates that dye lasers, as a class, can provide tunable laser output through the visible and near-uv regions of the spectrum of most interest to photochemistry. Many variables can affect the performance of a specific dye laser, and the interactions of these variables, at the current state of the art, are complex. The recent literature on dye-laser characteristics has been reviewed and summarized, with emphasis on those parameters that most likely will affect the scaling of dye lasers in photochemical applications. Current costs are reviewed and correlated with output power. A new class of efficient uv lasers that appear to be scalable in both energy output and pulse rate, based on rare-gas halide excimers and similar molecules, is certain to find major applications in photochemistry. Because the most important developments are too recent to be adequately described in the literature or are the likely outcome of current experiments, the basic physics underlying the class of excimer lasers is described. Specific cost data are unavailable, but these new gas lasers should reflect costs similar to those of existing gas lasers, in particular, the pulsed CO 2 lasers. To complete the survey of tunable-laser characteristics, the technical characteristics of the various classes of lasers in the ir are summarized. Important developments in ir laser technology are being accelerated by isotope-separation research, but, initially at least, this portion of the spectrum is least likely to receive emphasis in waste-management-oriented photochemistry

  19. 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

  20. A, a Brominated Flame Retardant

    Directory of Open Access Journals (Sweden)

    Tomomi Takeshita

    2013-01-01

    Full Text Available Tetrabromobisphenol A (TBBPA, a brominated flame retardant, has been found to exacerbate pneumonia in respiratory syncytial virus- (RSV- infected mice. We examined the effect of Brazilian propolis (AF-08 on the exacerbation of RSV infection by TBBPA exposure in mice. Mice were fed a powdered diet mixed with 1% TBBPA alone, 0.02% AF-08 alone, or 1% TBBPA and 0.02% AF-08 for four weeks and then intranasally infected with RSV. TBBPA exposure increased the pulmonary virus titer and level of IFN-γ, a representative marker of pneumonia due to RSV infection, in the lungs of infected mice without toxicity. AF-08 was significantly effective in reducing the virus titers and IFN-γ level increased by TBBPA exposure. Also, AF-08 significantly reduced proinflammatory cytokine (TNF-α and IL-6 levels in the lungs of RSV-infected mice with TBBPA exposure, but Th2 cytokine (IL-4 and IL-10 levels were not evidently increased. Neither TBBPA exposure nor AF-08 treatment affected the anti-RSV antibody production in RSV-infected mice. In flow cytometry analysis, AF-08 seemed to be effective in reducing the ratio of pulmonary CD8a+ cells in RSV-infected mice with TBBPA exposure. TBBPA and AF-08 did not exhibit anti-RSV activity in vitro. Thus, AF-08 probably ameliorated pneumonia exacerbated by TBBPA exposure in RSV-infected mice by limiting excess cellular immune responses.

  1. Preparation of bromine fluoride; Preparation du fluorure de brome

    Energy Technology Data Exchange (ETDEWEB)

    Domange, Pr; Duflo, J.

    1958-05-15

    This note addresses the preparation of bromine fluoride. It indicates the implemented process for the reaction, used products (fluorine and bromine), and column characteristics. It describes the operating mode. Apparatus drawing is provided.

  2. Potential For Stratospheric Ozone Depletion During Carboniferous

    Science.gov (United States)

    Bill, M.; Goldstein, A. H.

    Methyl bromide (CH3Br) constitutes the largest source of bromine atoms to the strato- sphere whereas methyl chloride (CH3Cl) is the most abundant halocarbon in the tro- posphere. Both gases play an important role in stratospheric ozone depletion. For in- stance, Br coupled reactions are responsible for 30 to 50 % of total ozone loss in the polar vortex. Currently, the largest natural sources of CH3Br and CH3Cl appear to be biological production in the oceans, inorganic production during biomass burning and plant production in salt marsh ecosystems. Variations of paleofluxes of CH3Br and CH3Cl can be estimated by analyses of oceanic paleoproductivity, stratigraphic analyses of frequency and distribution of fossil charcoal indicating the occurrence of wildfires, and/or by paleoreconstruction indicating the extent of salt marshes. Dur- ing the lower Carboniferous time (Tournaisian-Visean), the southern margin of the Laurasian continent was characterized by charcoal deposits. Estimation on frequency of charcoal layers indicates that wildfires occur in a range of 3-35 years (Falcon-Lang 2000). This suggests that biomass burning could be an important source of CH3Br and CH3Cl during Tournaisian-Viesan time. During Tounaisian and until Merame- cian carbon and oxygen isotope records have short term oscillations (Bruckschen et al. 1999, Mii et al. 1999). Chesterian time (mid- Carboniferous) is marked by an in- crease in delta18O values ( ~ 2 permil) and an increase of glacial deposit frequency suggesting lower temperatures. The occurrence of glacial deposits over the paleopole suggests polar conditions and the associated special features of polar mete- orology such as strong circumpolar wind in the stratosphere (polar vortex) and polar stratospheric clouds. Thus, conditions leading to polar statospheric ozone depletion can be found. Simultaneously an increase in delta13C values is documented. We interpret the positive shift in delta13C as a result of higher bioproductivity

  3. Stratospheric minor species vertical distributions during polar winter by balloon borne UV-Vis spectrometry

    Science.gov (United States)

    Pommereau, J. P.; Piquard, J.

    1994-01-01

    A light, relatively cheap and easy to operate balloonborne UV-visible spectrometer was designed for investigating ozone photochemistry in the Arctic winter. The instrument was flown 11 times during the European Arctic Stratospheric Ozone Experiment (EASOE) in winter 1991-92 in Northern Scandinavia. The first simultaneous measurements of vertical distributions of aerosols, PSC's, O3, NO2 and OClO inside the vortex during flight no. 6 on 16 January, in cold conditions are reported, which show that nitrogen oxides were almost absent (lower than 100 ppt) in the stratosphere below 22 km, while a layer of relatively large OClO concentration (15 ppt) was present at the altitude of the minimum temperature.

  4. Microwave Photochemistry. Applications in Organic Synthesis

    Czech Academy of Sciences Publication Activity Database

    Církva, Vladimír; Relich, Stanislav

    2011-01-01

    Roč. 8, č. 3 (2011), s. 282-293 ISSN 1570-193X Institutional research plan: CEZ:AV0Z40720504 Keywords : microwave * photochemistry * electrodeless discharge lamp Subject RIV: CH - Nuclear ; Quantum Chemistry Impact factor: 2.406, year: 2011 http://www.scopus.com/record/display.url?eid=2-s2.0-79960013317&origin=resultslist&sort=plf-f&src=s&st1=cirkva%2cv&sid=95rFucNho6qr5iGwVeMnh_W%3a150&sot=b&sdt=b&sl=21&s=AUTHOR-NAME%28cirkva%2cv%29&relpos=0&relpos=0&searchTerm=AUTHOR-NAME(cirkva,v)

  5. A stratospheric aerosol increase

    Science.gov (United States)

    Rosen, J. M.; Hofmann, D. J.

    1980-01-01

    Large disturbances were noted in the stratospheric aerosol content in the midlatitude Northern Hemisphere commencing about 7 months after the eruption of La Soufriere and less than 1 month after the eruption of Sierra Negra. The aerosol was characterized by a very steep size distribution in the 0.15 to 0.25 micron radius range and contained a volatile component. Measurements near the equator and at the South Pole indicate that the disturbance was widespread. These observations were made before the May 18 eruption of Mt. St. Helens.

  6. Brominated flame retardants and endocrine disruption

    NARCIS (Netherlands)

    Vos, J.G.; Becher, G.; Berg, van den M.; Boer, de J.; Leonards, P.E.G.

    2003-01-01

    From an environmental point of view, an increasing important group of organohalogen compounds are the brominated flame retardants (BFRs), which are widely used in polymers and textiles and applied in construction materials, furniture, and electronic equipment. BFRs with the highest production volume

  7. Brominated flame retardants and endocrine disruption

    NARCIS (Netherlands)

    Vos, Joseph G.; Becher, Georg; Van Den Berg, Martin; Leonards, Pim E G

    2003-01-01

    From an environmental point of view, an increasing important group of organo-halogen compounds are the brominated flame retardants (BFRs), which are widely used in polymers and textiles and applied in construction materials, furniture, and electronic equipment. BFRs with the highest production

  8. Structure and functionality of bromine doped graphite.

    Science.gov (United States)

    Hamdan, Rashid; Kemper, A F; Cao, Chao; Cheng, H P

    2013-04-28

    First-principles calculations are used to study the enhanced in-plane conductivity observed experimentally in Br-doped graphite, and to study the effect of external stress on the structure and functionality of such systems. The model used in the numerical calculations is that of stage two doped graphite. The band structure near the Fermi surface of the doped systems with different bromine concentrations is compared to that of pure graphite, and the charge transfer between carbon and bromine atoms is analyzed to understand the conductivity change along different high symmetry directions. Our calculations show that, for large interlayer separation between doped graphite layers, bromine is stable in the molecular form (Br2). However, with increased compression (decreased layer-layer separation) Br2 molecules tend to dissociate. While in both forms, bromine is an electron acceptor. The charge exchange between the graphite layers and Br atoms is higher than that with Br2 molecules. Electron transfer to the Br atoms increases the number of hole carriers in the graphite sheets, resulting in an increase of conductivity.

  9. short communication polyvinylpyrrolidone-bromine complex

    African Journals Online (AJOL)

    Preferred Customer

    2011-06-15

    2Department of Organic-Polymer Chemistry, Mazandaran University, Babolsar, Iran. (Received June 15, 2011; revised January 11, 2012). ABSTRACT. Benzylic bromides were conveniently obtained in high yields via the reaction of the corresponding alcohols with crosslinked polyvinylpyrrolidone-bromine complex ...

  10. 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. .

  11. Proceedings of the Fourteenth DOE solar photochemistry research conference

    International Nuclear Information System (INIS)

    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

  12. Modeling the interaction of ozone with chloroform and bromoform under conditions close to stratospheric

    Science.gov (United States)

    Strokova, N. E.; Yagodovskaya, T. V.; Savilov, S. V.; Lukhovitskaya, E. E.; Vasil'ev, E. S.; Morozov, I. I.; Lunin, V. V.

    2013-02-01

    The reactions of ozone with chloroform and bromoform are studied using a flow gas discharge vacuum unit under conditions close to stratospheric (temperature range, 77-250 K; pressure, 10-3-0.1 Torr in the presence of nitrate ice). It is shown that the reaction with bromoform begins at 160 K; the reaction with chloroform, at 190 K. The reaction products are chlorine and bromine oxides of different composition, identified by low-temperature FTIR spectroscopy. The presence of nitrate ice raises the temperature of reaction onset to 210 K.

  13. Stable bromine isotopic composition of methyl bromide released from plant matter

    Science.gov (United States)

    Horst, Axel; Holmstrand, Henry; Andersson, Per; Thornton, Brett F.; Wishkerman, Asher; Keppler, Frank; Gustafsson, Örjan

    2014-01-01

    Methyl bromide (CH3Br) emitted from plants constitutes a natural source of bromine to the atmosphere, and is a component in the currently unbalanced global CH3Br budget. In the stratosphere, CH3Br contributes to ozone loss processes. Studies of stable isotope composition may reduce uncertainties in the atmospheric CH3Br budget, but require well-constrained isotope fingerprints of the source end members. Here we report the first measurements of stable bromine isotopes (δ81Br) in CH3Br from abiotic plant emissions. Incubations of both KBr-fortified pectin, a ubiquitous cell-stabilizing macromolecule, and of a natural halophyte (Salicornia fruticosa), yielded an enrichment factor (ε) of -2.00 ± 0.23‰ (1σ, n = 8) for pectin and -1.82 ± 0.02‰ (1σ, n = 4) for Salicornia (the relative amount of the heavier 81Br was decreased in CH3Br compared to the substrate salt). For short incubations, and up to 10% consumption of the salt substrate, this isotope effect was similar for temperatures from 30 up to 300 °C. For longer incubations of up to 90 h at 180 °C the δ81Br values increased from -2‰ to 0‰ for pectin and to -1‰ for Salicornia. These δ81Br source signatures of CH3Br formation from plant matter combine with similar data for carbon isotopes to facilitate multidimensional isotope diagnostics of the CH3Br budget.

  14. Tropospheric Bromine Chemistry: Implications for Present and Pre-industrial Ozone and Mercury

    Science.gov (United States)

    Parella, J. P.; Jacob, D. J.; Liang, Q.; Zhang, Y.; Mickley, L. J.; Miller, B.; Evans, M. J.; Yang, X.; Pyle, J. A.; Theys, N.; hide

    2012-01-01

    We present a new model for the global tropospheric chemistry of inorganic bromine (Bry) coupled to oxidant-aerosol chemistry in the GEOS-Chem chemical transport model (CTM). Sources of tropospheric Bry include debromination of sea-salt aerosol, photolysis and oxidation of short-lived bromocarbons, and transport from the stratosphere. Comparison to a GOME-2 satellite climatology of tropospheric BrO columns shows that the model can reproduce the observed increase of BrO with latitude, the northern mid-latitudes maximum in winter, and the Arctic maximum in spring. This successful simulation is contingent on the HOBr + HBr reaction taking place in aqueous aerosols and ice clouds. Bromine chemistry in the model decreases tropospheric ozone mixing ratios by mercury against oxidation by Br. This suggests that historical anthropogenic mercury emissions may have mostly deposited to northern mid-latitudes, enriching the corresponding surface reservoirs. The persistent rise in background surface ozone at northern mid-latitudes during the past decades could possibly contribute to the observations of elevated mercury in subsurface waters of the North Atlantic.

  15. Stratospheric aerosol geoengineering

    Energy Technology Data Exchange (ETDEWEB)

    Robock, Alan [Department of Environmental Sciences, Rutgers University, 14 College Farm Road, New Brunswick, NJ 08901 (United States)

    2015-03-30

    The Geoengineering Model Intercomparison Project, conducting climate model experiments with standard stratospheric aerosol injection scenarios, has found that insolation reduction could keep the global average temperature constant, but global average precipitation would reduce, particularly in summer monsoon regions around the world. Temperature changes would also not be uniform; the tropics would cool, but high latitudes would warm, with continuing, but reduced sea ice and ice sheet melting. Temperature extremes would still increase, but not as much as without geoengineering. If geoengineering were halted all at once, there would be rapid temperature and precipitation increases at 5–10 times the rates from gradual global warming. The prospect of geoengineering working may reduce the current drive toward reducing greenhouse gas emissions, and there are concerns about commercial or military control. Because geoengineering cannot safely address climate change, global efforts to reduce greenhouse gas emissions and to adapt are crucial to address anthropogenic global warming.

  16. Stratospheric aerosol geoengineering

    International Nuclear Information System (INIS)

    Robock, Alan

    2015-01-01

    The Geoengineering Model Intercomparison Project, conducting climate model experiments with standard stratospheric aerosol injection scenarios, has found that insolation reduction could keep the global average temperature constant, but global average precipitation would reduce, particularly in summer monsoon regions around the world. Temperature changes would also not be uniform; the tropics would cool, but high latitudes would warm, with continuing, but reduced sea ice and ice sheet melting. Temperature extremes would still increase, but not as much as without geoengineering. If geoengineering were halted all at once, there would be rapid temperature and precipitation increases at 5–10 times the rates from gradual global warming. The prospect of geoengineering working may reduce the current drive toward reducing greenhouse gas emissions, and there are concerns about commercial or military control. Because geoengineering cannot safely address climate change, global efforts to reduce greenhouse gas emissions and to adapt are crucial to address anthropogenic global warming

  17. Mousse photochemistry formation; Formacao fotoquimica de mousse

    Energy Technology Data Exchange (ETDEWEB)

    Rangel, George W.M.; Nicodem, David E. [Universidade Federal, Rio de Janeiro, RJ (Brazil). Inst. de Quimica]. E-mail: gwallace_iq@yahoo.com.br; nicodem@iq.ufrj.br

    2003-07-01

    The petroleum, when spilled in the sea it forms an emulsion of water in oil could contain up to 90% of water. This emulsion, called Mousse of Chocolate, it can be very stable, taking to the increase of the environmental impact and impeding the microbiological degradation. It was observed that the petroleum, when irradiated with solar light, it forms Mousse more easily. However, same being known about the importance of the action of the light in the formation of Mousse, little it is known regarding the processes and conditions involved in the formation of Mousse. This project proposes the study of the process of formation of Mousse, in function of the suffered transformations for petroleum after solar irradiation. We will study the relationship between the stability and formation of Mousse and the present amount of asphaltenes in the petroleum as a result of the irradiation. We will develop a methodology for analysis of emulsions of water in petroleum, in way we know her/it the stability of the emulsion in function of the time and the amount of water in the same. We will study the behavior of a sample of Brazilian petroleum of Campos' Basin, already used in other photochemistry studies. We will analyze the effect of the time of irradiation in the asphaltenes formation and Mousse. We will also analyze other types of petroleum, for us to compare results with obtained them in the Brazilian petroleum. (author)

  18. Radiation Chemistry and Photochemistry of Ionic Liquids

    International Nuclear Information System (INIS)

    Wishart, J.F.; Takahaski, K.

    2010-01-01

    As our understanding of ionic liquids and their tunable properties has grown, it is possible to see many opportunities for ionic liquids to contribute to the sustainable use of energy. The potential safety and environmental benefits of ionic liquids, as compared to conventional solvents, have attracted interest in their use as processing media for the nuclear fuel cycle. Therefore, an understanding of the interactions of ionizing radiation and photons with ionic liquids is strongly needed. However, the radiation chemistry of ionic liquids is still a relatively unexplored topic although there has been a significant increase in the number of researchers in the field recently. This article provides a brief introduction to ionic liquids and their interesting properties, and recent advances in the radiation chemistry and photochemistry of ionic liquids. In this article, we will mainly focus on excess electron dynamics and radical reaction dynamics. Because solvation dynamics processes in ionic liquids are much slower than in molecular solvents, one of the distinguishing characteristics is that pre-solvated electrons play an important role in ionic liquid radiolysis. It will be also shown that the reaction dynamics of radical ions is significantly different from that observed in molecular solvents because of the Coulombic screening effects and electrostatic interactions in ionic liquids.

  19. Deriving an atmospheric budget of total organic bromine using airborne in-situ measurements from the Western Pacific during SHIVA

    Science.gov (United States)

    Sala, S.; Bönisch, H.; Keber, T.; Oram, D. E.; Mills, G.; Engel, A.

    2014-02-01

    During the SHIVA (Stratospheric Ozone: Halogen Impacts in a Varying Atmosphere) project an extensive dataset of all halogen species relevant for the atmospheric budget of total organic bromine has been collected in the West Pacific region using the FALCON aircraft operated by the German Aerospace agency DLR (Deutsches Zentrum für Luft- und Raumfahrt) covering a vertical range from the planetary boundary layer up to the ceiling altitude of the aircraft of 13 km. In total, more than 700 measurements were performed with the newly developed fully-automated in-situ instrument GHOST-MS (Gas cHromatograph for the Observation of Tracers - coupled with a Mass Spectrometer) by the Goethe University of Frankfurt (GUF) and with the onboard whole-air sampler WASP with subsequent ground based state-of-the-art GC/MS analysis by the University of East Anglia (UEA). Both instruments yield good agreement for all major (CHBr3 and CH2Br2) and minor (CHBrCl, CHBrCl2 and CHBr2Cl) VSLS (very short-lived substances), at least at the level of their 2 σ measurement uncertainties. In contrast to the suggestion that the Western Pacific could be a major source region for VSLS (Pyle et al., 2011), we found only slightly enhanced mixing ratios of brominated halogen source gases relative to the levels reported in Montzka et al. (2011) for other tropical regions. A budget for total organic bromine, including all four halons,CH3Br and the VSLS, is derived for the upper troposphere, the input region for the TTL and thus also for the stratosphere, compiled from the SHIVA dataset. With exception of the two minor VSLS CHBrCl2 and CHBr2Cl, excellent agreement with the values reported in Montzka et al. (2011) is found, while being slightly higher than previous studies from our group based on balloon-borne measurements.

  20. Membrane-less hydrogen bromine flow battery

    Science.gov (United States)

    Braff, William A.; Bazant, Martin Z.; Buie, Cullen R.

    2013-08-01

    In order for the widely discussed benefits of flow batteries for electrochemical energy storage to be applied at large scale, the cost of the electrochemical stack must come down substantially. One promising avenue for reducing stack cost is to increase the system power density while maintaining efficiency, enabling smaller stacks. Here we report on a membrane-less hydrogen bromine laminar flow battery as a potential high-power density solution. The membrane-less design enables power densities of 0.795 W cm-2 at room temperature and atmospheric pressure, with a round-trip voltage efficiency of 92% at 25% of peak power. Theoretical solutions are also presented to guide the design of future laminar flow batteries. The high-power density achieved by the hydrogen bromine laminar flow battery, along with the potential for rechargeable operation, will translate into smaller, inexpensive systems that could revolutionize the fields of large-scale energy storage and portable power systems.

  1. Symproportionation versus Disproportionation in Bromine Redox Systems

    International Nuclear Information System (INIS)

    Toporek, Marcin; Michałowska-Kaczmarczyk, Anna M.; Michałowski, Tadeusz

    2015-01-01

    Graphical abstract: Display Omitted -- Highlights: • The disproportionation and symproportionation of bromine in different media is presented. • All the redox systems are elaborated according to the principles of the generalized approach to electrolytic redox systems (GATES/GEB). • All physicochemical knowledge is involved in the algorithm applied for this purpose. • The graphical representation of the systems is the basis of gaining the detailed physicochemical knowledge on the systems in question. -- Abstract: The paper refers to dynamic (titration) redox systems where symproportionation or disproportionation of bromine species occur. The related systems are modeled according to principles assumed in the Generalized Approach to Electrolytic Redox Systems (GATES), with Generalized Electron Balance (GEB) concept involved in the GATES/GEB software. The results obtained from calculations made with use of iterative computer programs prepared according to MATLAB computational software, are presented graphically, as 2D and 3D graphs

  2. Membrane-less hydrogen bromine flow battery

    OpenAIRE

    Braff, W. A.; Bazant, M. Z.; Buie, C. R.

    2014-01-01

    In order for the widely discussed benefits of flow batteries for electrochemical energy storage to be applied at large scale, the cost of the electrochemical stack must come down substantially. One promising avenue for reducing stack cost is to increase the system power density while maintaining efficiency, enabling smaller stacks. Here we report on a membrane-less, hydrogen bromine laminar flow battery as a potential high power density solution. The membrane-less design enables power densiti...

  3. Bromine release during Plinian eruptions along the Central American Volcanic Arc

    Science.gov (United States)

    Hansteen, T. H.; Kutterolf, S.; Appel, K.; Freundt, A.; Perez-Fernandez, W.; Wehrmann, H.

    2010-12-01

    Volcanoes of the Central American Volcanic Arc (CAVA) have produced at least 72 highly explosive eruptions within the last 200 ka. The eruption columns of all these “Plinian” eruptions reached well into the stratosphere such that their released volatiles may have influenced atmospheric chemistry and climate. While previous research has focussed on the sulfur and chlorine emissions during such large eruptions, we here present measurements of the heavy halogen bromine by means of synchrotron radiation induced micro-XRF microanalysis (SR-XRF) with typical detection limits at 0.3 ppm (in Fe rich standard basalt ML3B glass). Spot analyses of pre-eruptive glass inclusions trapped in minerals formed in magma reservoirs were compared with those in matrix glasses of the tephras, which represent the post-eruptive, degassed concentrations. The concentration difference between inclusions and matrix glasses, multiplied by erupted magma mass determined by extensive field mapping, yields estimates of the degassed mass of bromine. Br is probably hundreds of times more effective in destroying ozone than Cl, and can accumulate in the stratosphere over significant time scales. Melt inclusions representing deposits of 22 large eruptions along the CAVA have Br contents between 0.5 and 13 ppm. Br concentrations in matrix glasses are nearly constant at 0.4 to 1.5 ppm. However, Br concentrations and Cl/Br ratios vary along the CAVA. The highest values of Br contents (>8 ppm) and lowest Cl/Br ratios (170 to 600) in melt inclusions occur across central Nicaragua and southern El Salvador, and correlate with bulk-rock compositions of high Ba/La > 85 as well as low La/Yb discharged 700 kilotons of Br. On average, each of the remaining 21 CAVA eruptions studied have discharged c.100 kilotons of bromine. During the past 200 ka, CAVA volcanoes have emitted a cumulative mass of 3.2 Mt of Br through highly explosive eruptions. There are six periods in the past (c. 2ka, 6ka, 25ka, 40ka, 60ka, 75

  4. Hydrogen-bromine fuel cell advance component development

    Science.gov (United States)

    Charleston, Joann; Reed, James

    1988-01-01

    Advanced cell component development is performed by NASA Lewis to achieve improved performance and longer life for the hydrogen-bromine fuel cells system. The state-of-the-art hydrogen-bromine system utilizes the solid polymer electrolyte (SPE) technology, similar to the SPE technology developed for the hydrogen-oxygen fuel cell system. These studies are directed at exploring the potential for this system by assessing and evaluating various types of materials for cell parts and electrode materials for Bromine-hydrogen bromine environment and fabricating experimental membrane/electrode-catalysts by chemical deposition.

  5. 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.

    2016-01-01

    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. PMID:27185928

  6. LOW POWER UPCONVERSION FOR SOLAR FUELS PHOTOCHEMISTRY

    Energy Technology Data Exchange (ETDEWEB)

    Castellano, Felix N. [Bowling Green State University

    2013-08-05

    chromophores poised for upconversion photochemistry are also presented.

  7. Photochemistry of modified proteins benzophenone-containing bovine serum albumin

    International Nuclear Information System (INIS)

    Mariano, P.S.; Glover, G.I.; Wilkinson, T.J.

    1976-01-01

    The results of exploratory and mechanistic studies of the photochemistry of poly-p-benzoyl-acetimido-bovine serum albumin, a modified protein containing photoreactive and photosensitizing groups, are reported. Specifically described are recent findings concerning (1) the synthesis and characterization of a modified bovine serum albumin that contains benzophenone-like moieties, (2) the photochemistry of this modified protein which appeared to involve photoreductive coupling of the benzophenone chromophores to the protein backbone, and (3) triplet energy transfer from modified bovine serum albumin to small molecule acceptors resulting in quenching of the photoreaction. (author)

  8. Ultrafast measurements of chlorine dioxide photochemistry

    Energy Technology Data Exchange (ETDEWEB)

    Ludowise, P.D.

    1997-08-01

    Time-resolved mass spectrometry and time-resolved photoelectron spectroscopy are used to study the ultrafast photodissociation dynamics of chlorine dioxide, an important constituent in stratospheric ozone depletion. Chapter 1 introduces these pump/probe techniques, in which a femtosecond pump pulse excites a molecule to a dissociative state. At a later time, a second femtosecond probe pulse ionizes the molecule. The resulting mass and photoelectron spectra are acquired as a function of the delay between the pump and probe pulses, which follows the evolution of the molecule on the excited state. A comparison to other techniques used to study reaction dynamics is discussed. Chapter 2 includes a detailed description of the design and construction of the experimental apparatus, which consists of a femtosecond laser system, a molecular beam time-of-flight spectrometer, and a data acquisition system. The time-of-flight spectrometer is specifically designed to have a short flight distance to maximize the photoelectron collection efficiency without degrading the resolution, which is limited by the bandwidth of the femtosecond laser system. Typical performance of the apparatus is demonstrated in a study of the time-resolved photoelectron spectroscopy of nitric oxide. The results of the time-resolved mass spectrometry experiments of chlorine dioxide are presented in Chapter 3. Upon excitation to the A {sup 2}A{sub 2} state near 3.2 eV, the molecule dissociates through an indirect two-step mechanism. The direct dissociation channel has been predicted to be open, but is not observed. A quantum beat is observed in the OClO{sup +} species, which is described as a vibrational coherence of the optically prepared A {sup 2}A{sub 2} state. Chapter 4 presents the results of the time-resolved photoelectron experiments of chlorine dioxide. At short delay time, the quantum beat of the OClO{sup +} species is observed in the X {sup 1}A{sub 1} state of the ion. At infinite delay, the signal

  9. Stratospheric BrO abundance measured by a balloon-borne submillimeterwave radiometer

    Directory of Open Access Journals (Sweden)

    R. A. Stachnik

    2013-03-01

    Full Text Available Measurements of mixing ratio profiles of stratospheric bromine monoxide (BrO were made using observations of BrO rotational line emission at 650.179 GHz by a balloon-borne SIS (superconductor-insulator-superconductor submillimeterwave heterodyne limb sounder (SLS. The balloon was launched from Ft. Sumner, New Mexico (34° N on 22 September 2011. Peak mid-day BrO abundance varied from 16 ± 2 ppt at 34 km to 6 ± 4 ppt at 16 km. Corresponding estimates of total inorganic bromine (Bry, derived from BrO vmr (volume mixing ratio using a photochemical box model, were 21 ± 3 ppt and 11 ± 5 ppt, respectively. Inferred Bry abundance exceeds that attributable solely to decomposition of long-lived methyl bromide and other halons, and is consistent with a contribution from bromine-containing very short lived substances, BryVSLS, of 4 ppt to 8 ppt. These results for BrO and Bry were compared with, and found to be in good agreement with, those of other recent balloon-borne and satellite instruments.

  10. Aerosol-associated changes in tropical stratospheric ozone following the eruption of Mount Pinatubo

    Science.gov (United States)

    Grant, William B.; Browell, Edward V.; Fishman, Jack; Brackett, Vincent G.; Veiga, Robert E.; Nganga, Dominique; Minga, A.; Cros, Bernard; Butler, Carolyn F.; Fenn, Marta A.

    1994-01-01

    The large amount of sulfuric acid aerosol formed in the stratosphere by conversion of sulfur dioxide emitted by the eruption of Mount Pinatubo (15.14 deg N, 120.35 deg E) in the Philippines around June 15, 1991, has had a pronounced effect on lower stratospheric ozone in the tropics. Measurements of stratospheric ozone in the tropics using electrochemical concentration cell (ECC) sondes before and after the eruption and the airborne UV differential absorption lidar (DIAL) system after the eruption are compared with Stratospheric Aerosol and Gas Experiment II (SAGE II) measurements from several years before the eruption and ECC sonde measurements from the year prior to the eruption to determine the resulting changes. Ozone decreases of up to 33 % compared with SAGE II climatological values were found to be directly correlated with altitude regions of enhanced aerosol loading in the 16- to 28-km range. A maximum partial-column decrease of 29 +/- Dobson units (DU) was found over the 16- to 28-km range in September 1991 along with small increases (to 5.9 +/- 2 DU) from 28 to 31.5 km. A large decrease of ozone was also found at 4 deg to 8 deg S from May to August 1992, with a maximum decrease of 33 +/- 7 DU found above Brazzaville in July. Aerosol data form the visible channel of the advanced very high resolution radiometer (AVHRR) and the visible wavelength of the UV DIAL system were used to examine the relationship between aerosol (surface area) densities and ozone changes. The tropical stratospheric ozone changes we observed in 1991 and 1992 are likely be explained by a combination of dynamical (vertical transport) perturbations, radiative perturbations on ozone photochemistry, and heterogeneous chemistry.

  11. Uranium hexafluoride and uranyl nitrate. Ionometric determination of bromine

    International Nuclear Information System (INIS)

    Anon.

    Bromine was determined in uranium hexafluoride. The method is suitable for determining 2 to 20 ppm with respect to uranium. Bromides are oxidized by potassium permanganate to give bromine which is extracted into carbon tetrachloride, reduced by ascorbic acid and determined by ionometry [fr

  12. Brominated flame retardants: occurrence, dietary intake and risk assessment

    NARCIS (Netherlands)

    Winter-Sorkina R de; Bakker MI; Wolterink G; Zeijlmaker MJ; SIR

    2006-01-01

    Brominated flame retardants have entered the human food chain. For the time being the occurrence of these chemicals in Dutch food does not pose a human health risk. However, this might easily change at increasing contents of flame retardants in Dutch food. The monitoring of brominated flame

  13. Peroxometal-mediated oxidation of bromine leading to ...

    Indian Academy of Sciences (India)

    Administrator

    Peroxometal-mediated oxidation of bromine leading to environmentally favourable protocol for selective bromination of organic substrates: Implications for vanadium bromo peroxidase (VBrPO). SIDDHARTHA D DHAR and MIHIR K CHAUDHURI. Department of Chemistry, Indian Institute of Technology,. Guwahati 781 001 ...

  14. Condensed Acids In Antartic Stratospheric Clouds

    Science.gov (United States)

    Pueschel, R. F.; Snetsinger, K. G.; Toon, O. B.; Ferry, G. V.; Starr, W. L.; Oberbeck, V. R.; Chan, K. R.; Goodman, J. K.; Livingston, J. M.; Verma, S.; hide

    1992-01-01

    Report dicusses nitrate, sulfate, and chloride contents of stratospheric aerosols during 1987 Airborne Antarctic Ozone Experiment. Emphasizes growth of HNO3*3H2O particles in polar stratospheric clouds. Important in testing theories concerning Antarctic "ozone hole".

  15. Cassini/CIRS Observations of Water Vapor in Titan's Stratosphere

    Science.gov (United States)

    Bjoraker, Gordon L.; Achterberg, R. K.; Anderson, C. M.; Samuelson, R. E.; Carlson, R. C.; Jennings, D. E.

    2008-01-01

    The Composite Infrared Spectrometer (CIRS) on the Cassini spacecraft has obtained spectra of Titan during most of the 44 flybys of the Cassini prime mission. Water vapor on Titan was first detected using whole-disk observations from the Infrared Space Observatory (Coustenis et al 1998, Astron. Astrophys. 336, L85-L89). CIRS data permlt the retrieval of the latitudinal variation of water on Titan and some limited information on its vertical profile. Emission lines of H2O on Titan are very weak in the CIRS data. Thus, large spectral averages as well as improvements in calibration are necessary to detect water vapor. Water abundances were retrieved in nadir spectra at 55 South, the Equator, and at 19 North. Limb spectra of the Equator were also modeled to constrain the vertical distribution of water. Stratospheric temperatures in the 0.5 - 4.0 mbar range were obtained by inverting spectra of CH4 in the v4 band centered at 1304/cm. The temperature in the lower stratosphere (4 - 20 mbar) was derived from fitting pure rotation lines of CH4 between 80 and 160/cm. The origin of H2O and CO2 is believed to be from the ablation of micrometeorites containing water ice, followed by photochemistry. This external source of water originates either within the Saturn system or from the interplanetary medium. Recently, Horst et al (J. Geophys. Res. 2008, in press) developed a photochemical model of Titan in which there are two external sources of oxygen. Oxygen ions (probably from Enceladus) precipitate into Titan's atmosphere to form CO at very high altitudes (1100 km). Water ice ablation at lower altitudes (700 km) forms H2O and subsequent chemistry produces CO2. CIRS measurements of CO, CO2, and now of H2O will provide valuable constraints to these photochemical models and - improve our understanding of oxygen chemistry on Titan.

  16. Stratospheric Platforms for Monitoring Purposes

    International Nuclear Information System (INIS)

    Konigorski, D.; Gratzel, U.; Obersteiner, M.; Schneidereit, M.

    2010-01-01

    Stratospheric platforms are emerging systems based on challenging technology. Goal is to create a platform, payload, and mission design which is able to complement satellite services on a local scale. Applications are close to traditional satellite business in telecommunication, navigation, science, and earth observation and include for example mobile telecommunications, navigation augmentation, atmospheric research, or border control. Stratospheric platforms could potentially support monitoring activities related to safeguards, e.g. by imagery of surfaces, operational conditions of nuclear facilities, and search for undeclared nuclear activities. Stratospheric platforms are intended to be flown in an altitude band between 16 and 30 km, above 16-20 km to take advantage of usually lower winds facilitating station keeping, below 30 km to limit the challenges to achieve a reasonable payload at acceptable platform sizes. Stratospheric platforms could substitute satellites which are expensive and lack upgrade capabilities for new equipment. Furthermore they have practically an unlimited time over an area of interest. It is intended to keep the platforms operational and maintenance free on a 24/7 basis with an average deployment time of 3 years. Geostationary satellites lack resolution. Potential customers like Armed Forces, National Agencies and commercial customers have indicated interest in the use of stratospheric platforms. Governmental entities are looking for cheaper alternatives to communications and surveillance satellites and stratospheric platforms could offer the following potential advantages: Lower operational cost than satellite or UAV (Unmanned Aerial Vehicles) constellation (fleet required); Faster deployment than satellite constellation; Repositioning capability and ability to loiter as required; Persistent long-term real-time services over a fairly large regional spot; Surge capability: Able to extend capability (either monitoring or communications

  17. PHOTOCHEMISTRY IN TERRESTRIAL EXOPLANET ATMOSPHERES. I. PHOTOCHEMISTRY MODEL AND BENCHMARK CASES

    Energy Technology Data Exchange (ETDEWEB)

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

    2012-12-20

    We present a comprehensive photochemistry model for exploration of the chemical composition of terrestrial exoplanet atmospheres. The photochemistry model is designed from the ground up to have the capacity to treat all types of terrestrial planet atmospheres, ranging from oxidizing through reducing, which makes the code suitable for applications for the wide range of anticipated terrestrial exoplanet compositions. The one-dimensional chemical transport model treats up to 800 chemical reactions, photochemical processes, dry and wet deposition, surface emission, and thermal escape of O, H, C, N, and S bearing species, as well as formation and deposition of elemental sulfur and sulfuric acid aerosols. We validate the model by computing the atmospheric composition of current Earth and Mars and find agreement with observations of major trace gases in Earth's and Mars' atmospheres. We simulate several plausible atmospheric scenarios of terrestrial exoplanets and choose three benchmark cases for atmospheres from reducing to oxidizing. The most interesting finding is that atomic hydrogen is always a more abundant reactive radical than the hydroxyl radical in anoxic atmospheres. Whether atomic hydrogen is the most important removal path for a molecule of interest also depends on the relevant reaction rates. We also find that volcanic carbon compounds (i.e., CH{sub 4} and CO{sub 2}) are chemically long-lived and tend to be well mixed in both reducing and oxidizing atmospheres, and their dry deposition velocities to the surface control the atmospheric oxidation states. Furthermore, we revisit whether photochemically produced oxygen can cause false positives for detecting oxygenic photosynthesis, and find that in 1 bar CO{sub 2}-rich atmospheres oxygen and ozone may build up to levels that have conventionally been accepted as signatures of life, if there is no surface emission of reducing gases. The atmospheric scenarios presented in this paper can serve as the

  18. Direct Vapor-Phase Bromination of Multiwall Carbon Nanotubes

    Directory of Open Access Journals (Sweden)

    Ilya Mazov

    2012-01-01

    Full Text Available We present the simple procedure of the vapor-phase bromination of multiwall carbon nanotubes (MWNTs at moderate temperatures. MWNTs with average diameter 9±3 nm were treated with Br2 vapors at 250°C to produce Br-functionalized product. Transmission electron microscopy analysis was used to prove low damage of MWNT walls during bromination. X-ray photoelectron spectroscopy (XPS and differential thermal analysis (DTA were used to investigate chemical composition of the surface of initial and brominated nanotubes. The experimental results show that the structure of MWNTs is not affected by the bromination process and the total amount of Br-containing surface functions reaches 2.5 wt. %. Electrophysical properties of initial and brominated MWNTs were investigated showing decrease of conductivity for functionalized sample. Possible mechanism of the vapor-phase bromination via surface defects and oxygen-containing functional groups was proposed according to data obtained. Additional experiments with bromination of annealed low-defected MWNTs were performed giving Br content a low as 0.75 wt. % proving this hypothesis.

  19. Stratospheric aerosols and precursor gases

    Science.gov (United States)

    1982-01-01

    Measurements were made of the aerosol size, height and geographical distribution, their composition and optical properties, and their temporal variation with season and following large volcanic eruptions. Sulfur-bearing gases were measured in situ in the stratosphere, and studied of the chemical and physical processes which control gas-to-particle conversion were carried out in the laboratory.

  20. Hydrogen-Bromine Flow Battery: Hydrogen Bromine Flow Batteries for Grid Scale Energy Storage

    Energy Technology Data Exchange (ETDEWEB)

    None

    2010-10-01

    GRIDS Project: LBNL is designing a flow battery for grid storage that relies on a hydrogen-bromine chemistry which could be more efficient, last longer and cost less than today’s lead-acid batteries. Flow batteries are fundamentally different from traditional lead-acid batteries because the chemical reactants that provide their energy are stored in external tanks instead of inside the battery. A flow battery can provide more energy because all that is required to increase its storage capacity is to increase the size of the external tanks. The hydrogen-bromine reactants used by LBNL in its flow battery are inexpensive, long lasting, and provide power quickly. The cost of the design could be well below $100 per kilowatt hour, which would rival conventional grid-scale battery technologies.

  1. One-dimensional numerical modeling of Blue Jet and its impact on stratospheric chemistry

    Science.gov (United States)

    Duruisseau, F.; Thiéblemont, R.; Huret, N.

    2011-12-01

    In the stratosphere the ozone layer is very sensitive to the NOx abundance. The ionisation of N2 and O2 molecules by TLE's (Transient Luminous Events) is a source of NOx which is currently not well quantified and could act as a loss of ozone. In this study a one dimensional explicit parameterization of a Blue-Jet propagation based on that proposed by Raizer et al. (2006 and 2007) has been developed. This parameterization considers Blue-Jet as a streamer initiated by a bidirectional leader discharge, emerging from the anvil and sustained by moderate cloud charge. The streamer growth varies with the electrical field induced by initial cloud charge and the initial altitude. This electrical parameterization and the chemical mechanisms associated with the discharge have been implemented into a detailed chemical model of stratospheric ozone including evolution of nitrogen, chlorine and bromine species. We will present several tests performed to validate the electrical code and evaluate the propagation velocity and the maximum altitude attains by the blue jet as a function of electrical parameters. The results obtained giving the spatiotemporal evolution of the electron density are then used to initiate the specific chemistry associated with the Blue Jet. Preliminary results on the impact of such discharge on the ozone content and the whole stratospheric system will be presented.

  2. Chlorine and bromine contents in tobacco and tobacco smoke

    International Nuclear Information System (INIS)

    Haesaenen, E.; Manninen, P.K.G.; Himberg, K.; Vaeaetaeinen, V.

    1990-01-01

    The chlorine and bromine contents in tobacco and tobacco smoke in both the particulate and gaseous phases were studied by neutron activation analysis. Eleven popular brands of western filter cigarettes were tested. Methyl chloride and methyl bromide concentrations were measured in the gaseous phase in two leading brands in Finland. The results suggest that the mainstream smoke from one cigarette conveys into the lungs about 150 μg chlorine and about 5 μg bromine. Probably most of the chlorine and bromine is in the form of organic compounds and the main components are methyl chloride and methyl bromide. (author) 14 refs.; 1 tab

  3. (Development of Bromine-77 from the LAMPF facility)

    Energy Technology Data Exchange (ETDEWEB)

    1989-01-01

    The objective of the work was to conduct the necessary studies required to evaluate the efficacy, potential benefit and role of bromine-77 labeled steroids in the detection and evaluation of treatment for hormone-dependent tumors. This report presents progress on the following tasks: An initial investigation concentrating on the radiobromination at carbon-6 or carbon-7 in selected simple steroids utilizing the nuclides, bromine-82 and bromine-77, analytical spectroscopy of radiolabeled compounds, and investigating the biodistribution, toxicology and tumor affinity of labeled agents.

  4. Magnetic trapping of cold bromine atoms.

    Science.gov (United States)

    Rennick, C J; Lam, J; Doherty, W G; Softley, T P

    2014-01-17

    Magnetic trapping of bromine atoms at temperatures in the millikelvin regime is demonstrated for the first time. The atoms are produced by photodissociation of Br2 molecules in a molecular beam. The lab-frame velocity of Br atoms is controlled by the wavelength and polarization of the photodissociation laser. Careful selection of the wavelength results in one of the pair of atoms having sufficient velocity to exactly cancel that of the parent molecule, and it remains stationary in the lab frame. A trap is formed at the null point between two opposing neodymium permanent magnets. Dissociation of molecules at the field minimum results in the slowest fraction of photofragments remaining trapped. After the ballistic escape of the fastest atoms, the trapped slow atoms are lost only by elastic collisions with the chamber background gas. The measured loss rate is consistent with estimates of the total cross section for only those collisions transferring sufficient kinetic energy to overcome the trapping potential.

  5. Photochemistry Saturn's Atmosphere. 2; Effects of an Influx of External Oxygen

    Science.gov (United States)

    Moses, Julianne I.; Lellouch, Emmanuel; Bezard, Bruno; Gladstone, G. Randall; Allen, Mark

    2000-01-01

    We use a one-dimensional diurnally averaged model of photochemistry and diffusion in Saturn's stratosphere to investigate the influence of extraplanetary debris on atmospheric chemistry. In particular, we consider the effects of an influx of oxygen from micrometeoroid ablation or from ring-particle diffusion; the contribution from cometary impacts, satellite debris, or ring vapor is deemed to be less important. The photochemical model results are compared directly with Infrared Space Observatory (ISO) observations to constrain the influx of extraplanetary oxygen to Saturn. From the ISO observations, we determine that the column densities of CO2 and H2O above 10 mbar in Saturn's atmosphere are (6.3 +/- 1) x 10(exp 14) and (1.4 +/- 0.4) x 10(exp 15)/ square cm, respectively; our models indicate that a globally averaged oxygen influx of (4+/-2) x 10(exp 6) O atoms /sq cm/s is required to explain these observations. Models with a locally enhanced influx of H20 operating over a small fraction of the projected area do not provide as good a fit to the ISO H2O observations. If volatile oxygen compounds comprise one-third to one-half of the exogenic source by mass, then Saturn is currently being bombarded with (3 +/- 2) x 10(exp -16) g/square cm/s of extraplanetary material. To reproduce the observed CO2/H2O ratio in Saturn's stratosphere, some of the exogenic oxygen must arrive in the form of a carbon-oxygen bonded species such as CO or CO2. An influx consistent with the composition of cometary ices fails to reproduce the high observed CO2/H2O ratio, suggesting that (i) the material has ices that are slightly more carbon-rich than is typical for comets, (ii) a contribution from an organic-rich component is required, or (iii) some of the hydrogen-oxygen bonded material is converted to carbon-oxygen bonded material without photochemistry (e.g., during the ablation process). We have also reanalyzed the 5-micron CO observations of Noll and Larson and determine that the CO

  6. Radiation and Photochemistry Section annual report, October 1990--September 1991

    International Nuclear Information System (INIS)

    1991-12-01

    This report describes the radiation chemistry and photochemistry of reactive intermediates in the condensed phase. The section on the chemistry of ions treats condensed-phase reactions of radical cations, radical cations in zeolite matrices, high energy chemistry, ions and excited states in radiolysis, and photochemistry of the polymer imaging systems. The section on the role of solvent in chemical reactivity describes a study of atomic hydrogen and deuterium in water radiolysis, solvated electron thermodynamics and transport properties, solvent relaxation dynamics, and solvation of an excess electron in an aqueous solution of LiCl. A separate section outlines activities at the 20-MeV linac and the 3-MeV Van de Graaff accelerator

  7. Tetrameric DABCO™-Bromine: an Efficient and Versatile Reagent ...

    African Journals Online (AJOL)

    NJD

    Reagent for Bromination of Various Organic Compounds. Majid M. Heravi,a* ... aDepartment of Chemistry, School of Sciences, Azzahra University, Vanak, Tehran, Iran. bChemistry ... Synthesis of "-bromo ketones and nitriles has also been ...

  8. Bromine pretreated chitosan for adsorption of lead (II) from water

    Indian Academy of Sciences (India)

    isotherm and maximum sorption capacity of 30% bromine pretreated chitosan sorbent was 1·755 g/kg with 85–. 90% lead .... C by applying Lagergren first ... Lead (II) ions concentrations were determined by using an .... following equation.

  9. The bromine content of some Dutch crops and fruits

    International Nuclear Information System (INIS)

    Admiraal, P.; Kok, H.A.; Das, H.A.; Hoede, D.; Zonderhuis, J.

    1975-09-01

    The natural bromine-content of Dutch potatoes, vegetables and fruits was determined by instrumental neutron activation analysis. Results are given for 348 samples divided over 20 crops and fruits. The data are compared to values published in the literature

  10. The nature of light. A brief introduction to photochemistry

    OpenAIRE

    Font, Josep

    2017-01-01

    The first lecture of the seminar on Light, Darkness and Living Beings, held in Mataró in March 2015, was devoted to explaining the dual nature of light and the interaction of this electromagnetic radiation with matter, considering mainly the photochemical aspects. This article summarizes the lecture, offering a brief description of the basis of photochemistry and giving some examples of reactions that need light in order to occur. Examples related to biological systems (e.g. plant photosynthe...

  11. How stratospheric are deep stratospheric intrusions? LUAMI 2008

    Directory of Open Access Journals (Sweden)

    T. Trickl

    2016-07-01

    Full Text Available A large-scale comparison of water-vapour vertical-sounding instruments took place over central Europe on 17 October 2008, during a rather homogeneous deep stratospheric intrusion event (LUAMI, Lindenberg Upper-Air Methods Intercomparison. The measurements were carried out at four observational sites: Payerne (Switzerland, Bilthoven (the Netherlands, Lindenberg (north-eastern Germany, and the Zugspitze mountain (Garmisch-Partenkichen, German Alps, and by an airborne water-vapour lidar system creating a transect of humidity profiles between all four stations. A high data quality was verified that strongly underlines the scientific findings. The intrusion layer was very dry with a minimum mixing ratios of 0 to 35 ppm on its lower west side, but did not drop below 120 ppm on the higher-lying east side (Lindenberg. The dryness hardens the findings of a preceding study (“Part 1”, Trickl et al., 2014 that, e.g., 73 % of deep intrusions reaching the German Alps and travelling 6 days or less exhibit minimum mixing ratios of 50 ppm and less. These low values reflect values found in the lowermost stratosphere and indicate very slow mixing with tropospheric air during the downward transport to the lower troposphere. The peak ozone values were around 70 ppb, confirming the idea that intrusion layers depart from the lowermost edge of the stratosphere. The data suggest an increase of ozone from the lower to the higher edge of the intrusion layer. This behaviour is also confirmed by stratospheric aerosol caught in the layer. Both observations are in agreement with the idea that sections of the vertical distributions of these constituents in the source region were transferred to central Europe without major change. LAGRANTO trajectory calculations demonstrated a rather shallow outflow from the stratosphere just above the dynamical tropopause, for the first time confirming the conclusions in “Part 1” from the Zugspitze CO observations. The

  12. Laboratory chemistry and stratospheric clouds

    Science.gov (United States)

    Molina, Mario J.

    1989-01-01

    Results are presented from laboratory experiments on the chemistry of ice particles to study the role of HCl and ClONO2 from CFCs in stratospheric ozone depletion over Antarctica. It is found that gaseous HCl is scavenged with high efficiency by the ice and the gas phase chlorine nitrate may react with the HCL-containing ice to produce Cl2. Also, consideration is given ot the behavior of solid nitric acid trihydrate and sulfuric acid aerosols.

  13. 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

    Energy Technology Data Exchange (ETDEWEB)

    Broennimann, S.; Siegrist, F.C.; Eugster, W.; Cattin, R.; Sidle, C.; Wanner, H. [Inst. of Geography, Univ. of Bern (Switzerland); Hirschberg, M.M. [Lehrstuhl fuer Bioklimatologie und Immissionsforschung, TU Muenchen, Freising-Weihenstephan (Germany); Schneiter, D. [MeteoSwiss, Station Aerologique, Payerne (Switzerland); Perego, S. [IBM Switzerland, Zuerich (Switzerland)

    2001-04-01

    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. (orig.)

  14. 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

  15. In-situ BrO measurements in the upper troposphere / lower stratosphere. Validation of the ENVISAT satellite measurements and photochemical model studies

    Energy Technology Data Exchange (ETDEWEB)

    Hrechanyy, S.

    2007-04-15

    Inorganic bromine species form the second most important halogen family affecting stratospheric ozone (WMO, 2003). Although the stratospheric bromine mixing ratio is about two orders of magnitude lower than the chlorine one, bromine has much higher ozone depleting potential (factor of about 45) compared to chlorine. This study reports and discusses atmospheric bromine monoxide, BrO, measurements in the altitude range 15-30 km performed by the balloon-borne instrument TRIPLE and aircraft instrument HALOX employing the chemical conversion resonance fluorescence technique, which is the only proven in-situ technique for the measurements of BrO. 57 HALOX flights have been performed in the frame of five field campaigns ranging from the Arctic to tropics. Three TRIPLE flights were carried out at high and mid latitudes in the frame of the SCIAMACHY (SCanning Imaging Absorption spectroMeter for Atmospheric CHartographY) validation. Calibration, consistency checks, data analysis, and error assessment for the in-situ measurements are described. The balloon measurements have yielded vertical profiles of BrO between 15 and 30 km altitude at northern mid- and at arctic latitudes. From the aircraft measurements a meridional BrO distribution from tropical to the arctic latitudes between 15 and 20 km altitude was obtained. In order to check the reliability of the bromine chemistry in the CLaMS model the BrO profile measured by TRIPLE on June 9, 2003 in Arctic spring/summer conditions was compared to a simulated BrO profile. For the simulation the model was initialized with appropriate satellite and balloon measurements and with a total stratospheric bromine of 18.4 pptv. Very good agreement between the TRIPLE measurements and model results was found. Measurements of BrO in the tropical tropopause layer (TTL) are well suited to investigate the contribution of very short-lived bromine species (VSLS) to the inorganic bromine, Bry. Since tropical HALOX BrO measurements from TROCCINOX

  16. Deriving an atmospheric budget of total organic bromine using airborne in situ measurements from the western Pacific area during SHIVA

    Science.gov (United States)

    Sala, S.; Bönisch, H.; Keber, T.; Oram, D. E.; Mills, G.; Engel, A.

    2014-07-01

    During the recent SHIVA (Stratospheric Ozone: Halogen Impacts in a Varying Atmosphere) project an extensive data set of all halogen species relevant for the atmospheric budget of total organic bromine was collected in the western Pacific region using the Falcon aircraft operated by the German Aerospace agency DLR (Deutsches Zentrum für Luft- und Raumfahrt) covering a vertical range from the planetary boundary layer up to the ceiling altitude of the aircraft of 13 km. In total, more than 700 measurements were performed with the newly developed fully automated in situ instrument GHOST-MS (Gas chromatograph for the Observation of Tracers - coupled with a Mass Spectrometer) by the Goethe University of Frankfurt (GUF) and with the onboard whole-air sampler WASP with subsequent ground-based state-of-the-art GC / MS analysis by the University of East Anglia (UEA). Both instruments yield good agreement for all major (CHBr3 and CH2Br2) and minor (CH2BrCl, CHBrCl2 and CHBr2Cl) VSLS (very short-lived substances), at least at the level of their 2σ measurement uncertainties. In contrast to the suggestion that the western Pacific could be a region of strongly increased atmospheric VSLS abundance (Pyle et al., 2011), we found only in the upper troposphere a slightly enhanced amount of total organic bromine from VSLS relative to the levels reported in Montzka and Reimann et al. (2011) for other tropical regions. From the SHIVA observations in the upper troposphere, a budget for total organic bromine, including four halons (H-1301, H-1211, H-1202, H-2402), CH3Br and the VSLS, is derived for the level of zero radiative heating (LZRH), the input region for the tropical tropopause layer (TTL) and thus also for the stratosphere. With the exception of the two minor VSLS CHBrCl2 and CHBr2Cl, excellent agreement with the values reported in Montzka and Reimann et al. (2011) is found, while being slightly higher than previous studies from our group based on balloon-borne measurements.

  17. Dissolved organic matter composition drives the marine production of brominated very short-lived substances.

    Science.gov (United States)

    Liu, Yina; Thornton, Daniel C O; Bianchi, Thomas S; Arnold, William A; Shields, Michael R; Chen, Jie; Yvon-Lewis, Shari A

    2015-03-17

    Brominated very short-lived substances (BrVSLS), such as bromoform, are important trace gases for stratospheric ozone chemistry. These naturally derived trace gases are formed via bromoperoxidase-mediated halogenation of dissolved organic matter (DOM) in seawater. Information on DOM type in relation to the observed BrVSLS concentrations in seawater, however, is scarce. We examined the sensitivity of BrVSLS production in relation to the presence of specific DOM moieties. A total of 28 model DOM compounds in artificial seawater were treated with vanadium bromoperoxidase (V-BrPO). Our results show a clear dependence of BrVSLS production on DOM type. In general, molecules that comprise a large fraction of the bulk DOM pool did not noticeably affect BrVSLS production. Only specific cell metabolites and humic acid appeared to significantly enhance BrVSLS production. Amino acids and lignin phenols suppressed enzyme-mediated BrVSLS production and may instead have formed halogenated nonvolatile molecules. Dibromomethane production was not observed in any experiments, suggesting it is not produced by the same pathway as the other BrVSLS. Our results suggest that regional differences in DOM composition may explain the observed BrVSLS concentration variability in the global ocean. Ultimately, BrVSLS production and concentrations are likely affected by DOM composition, reactivity, and cycling in the ocean.

  18. Global atmospheric model for mercury including oxidation by bromine atoms

    Directory of Open Access Journals (Sweden)

    C. D. Holmes

    2010-12-01

    Full Text Available Global models of atmospheric mercury generally assume that gas-phase OH and ozone are the main oxidants converting Hg0 to HgII and thus driving mercury deposition to ecosystems. However, thermodynamic considerations argue against the importance of these reactions. We demonstrate here the viability of atomic bromine (Br as an alternative Hg0 oxidant. We conduct a global 3-D simulation with the GEOS-Chem model assuming gas-phase Br to be the sole Hg0 oxidant (Hg + Br model and compare to the previous version of the model with OH and ozone as the sole oxidants (Hg + OH/O3 model. We specify global 3-D Br concentration fields based on our best understanding of tropospheric and stratospheric Br chemistry. In both the Hg + Br and Hg + OH/O3 models, we add an aqueous photochemical reduction of HgII in cloud to impose a tropospheric lifetime for mercury of 6.5 months against deposition, as needed to reconcile observed total gaseous mercury (TGM concentrations with current estimates of anthropogenic emissions. This added reduction would not be necessary in the Hg + Br model if we adjusted the Br oxidation kinetics downward within their range of uncertainty. We find that the Hg + Br and Hg + OH/O3 models are equally capable of reproducing the spatial distribution of TGM and its seasonal cycle at northern mid-latitudes. The Hg + Br model shows a steeper decline of TGM concentrations from the tropics to southern mid-latitudes. Only the Hg + Br model can reproduce the springtime depletion and summer rebound of TGM observed at polar sites; the snowpack component of GEOS-Chem suggests that 40% of HgII deposited to snow in the Arctic is transferred to the ocean and land reservoirs, amounting to a net deposition flux to the Arctic of 60 Mg a−1. Summertime events of depleted Hg0 at Antarctic sites due to subsidence are much better simulated by

  19. Tunable Far Infrared Studies in Support of Stratospheric Measurements

    Science.gov (United States)

    Chance, Kelly V.; Park, K.; Nolt, I. G.; Evenson, K. M.

    2001-01-01

    This report summarizes research done under NASA Grant NAG5-4653. The research performed under this grant has been a collaboration between institutions including the Smithsonian Astrophysical Observatory, the National Institute of Standards and Technology, the University of Oregon, and the NASA Langley Research Center. The program has included fully line-resolved measurements of submillimeter and far infrared spectroscopic line parameters (pressure broadening coefficients and their temperature dependences, and line positions) for the analysis of field measurements of stratospheric constituents, far infrared database improvements, and studies for improved satellite measurements of the Earth's atmosphere. This research program is designed to enable the full utilization of spectra obtained in far infrared/submillimeter field measurements, such as FIRS-2, FILOS, IBEX, SLS, EosMLS, and proposed European Space Agency measurements of OH (e.g., PIRAMHYD and SFINX) for the retrieval of accurate stratospheric altitude profiles of key trace gases involved in ozone layer photochemistry. For the analysis of the spectra obtained in the stratosphere from far infrared measurements it is necessary to have accurate values of the molecular parameters (line positions, strengths, and pressure broadening coefficients) for the measured molecules and for possible interfering species. Knowledge of line positions is in increasingly good shape, with some notable exceptions. The increase in position information includes research that has been performed in the present program of research on HO2, H2O, H2O2, O3, HCl, HF, HBr, HI, CO, OH, and ClO. Examples where further line position studies are necessary include hot band and minor isotopomer lines of some of the major trace species (H2O, O3) and normal lines of some triatomic and larger molecules (NO2). Knowledge of strengths is in generally good shape, since most of the lines are from electric dipole transitions whose intensities are well

  20. Stratospheric HTO perturbations 1980-1983

    Science.gov (United States)

    Mason, A. S.

    1985-02-01

    Three perturbations of the stratospheric tritiated water burden have occurred. An atmospheric nuclear detonation in 1980 injected about 2.1 MCi. The massive eruptions of the volcano El Chichon may have contributed to a doubling of the removal rate in 1982. An unusually large wintertime exchange with the upper stratosphere may have occurred between 1982 and 1983.

  1. Fate of higher brominated PBDEs in lactating cows.

    Science.gov (United States)

    Kierkegaard, Amelie; Asplund, Lillemor; de Wit, Cynthia A; McLachlan, Michael S; Thomas, Gareth O; Sweetman, Andrew J; Jones, Kevin C

    2007-01-15

    Dietary intake studies of lower brominated diphenyl ethers (BDEs) have shown that fish and animal products are important vectors of human exposure, but almost no data exist for higher brominated BDEs. Therefore, the fate of hepta- to decaBDEs was studied in lactating cows exposed to a naturally contaminated diet by analyzing feed, feces, and milk samples from a previous mass balance study of PCB. Tissue distribution was studied in one cow slaughtered after the experiment. BDE-209 was the dominant congener in feed, organs, adipose tissues, and feces, but not in milk. In contrast to PCBs and lower brominated BDEs, concentrations of hepta- to decaBDEs in adipose tissue were 9-80 times higher than in milk fat and the difference increased with degree of bromination/log K(OW). The congener profiles in adipose tissue and feed differed; BDE-207, BDE-196, BDE-197, and BDE-182 accumulated to a surprisingly greater extent in the fat compared to their isomers, suggesting metabolic debromination of BDE-209 to these BDEs. The results indicate that meat rather than dairy product consumption may be an important human exposure route to higher brominated BDEs.

  2. What Controls the Arctic Lower Stratosphere Temperature?

    Science.gov (United States)

    Newman, Paul A.; Nash, Eric R.; Einaudi, Franco (Technical Monitor)

    2001-01-01

    The temperature of the Arctic lower stratosphere is critical for understanding polar ozone levels. As temperatures drop below about 195 K, polar stratospheric clouds form, which then convert HCl and ClONO2 into reactive forms that are catalysts for ozone loss reactions. Hence, the lower stratospheric temperature during the March period is a key parameter for understanding polar ozone losses. The temperature is basically understood to be a result of planetary waves which drive the polar temperature away from a cold "radiative equilibrium" state. This is demonstrated using NCEP/NCAR reanalysis calculations of the heat flux and the mean polar temperature. The temperature during the March period is fundamentally driven by the integrated impact of large scale waves moving from the troposphere to the stratosphere during the January through February period. We will further show that the recent cold years in the northern polar vortex are a result of this weakened wave driving of the stratosphere.

  3. Mercury oxidation from bromine chemistry in the free troposphere over the southeastern US

    Directory of Open Access Journals (Sweden)

    S. Coburn

    2016-03-01

    Full Text Available The elevated deposition of atmospheric mercury over the southeastern United States is currently not well understood. Here we measure partial columns and vertical profiles of bromine monoxide (BrO radicals, a key component of mercury oxidation chemistry, to better understand the processes and altitudes at which mercury is being oxidized in the atmosphere. We use data from a ground-based MAX-DOAS instrument located at a coastal site ∼  1 km from the Gulf of Mexico in Gulf Breeze, FL, where we had previously detected tropospheric BrO (Coburn et al., 2011. Our profile retrieval assimilates information about stratospheric BrO from the WACCM chemical transport model (CTM, and uses only measurements at moderately low solar zenith angles (SZAs to estimate the BrO slant column density contained in the reference spectrum (SCDRef. The approach has 2.6 degrees of freedom, and avoids spectroscopic complications that arise at high SZA; knowledge about SCDRef further helps to maximize sensitivity in the free troposphere (FT. A cloud-free case study day with low aerosol load (9 April 2010 provided optimal conditions for distinguishing marine boundary layer (MBL: 0–1 km and free-tropospheric (FT: 1–15 km BrO from the ground. The average daytime tropospheric BrO vertical column density (VCD of ∼  2.3  ×  1013 molec cm−2 (SZA  <  70° is consistent with our earlier reports on other days. The vertical profile locates essentially all tropospheric BrO above 4 km, and shows no evidence for BrO inside the MBL (detection limit  <  0.5 pptv. BrO increases to  ∼  3.5 pptv at 10–15 km altitude, consistent with recent aircraft observations. Our case study day is consistent with recent aircraft studies, in that the oxidation of gaseous elemental mercury (GEM by bromine radicals to form gaseous oxidized mercury (GOM is the dominant pathway for GEM oxidation throughout the troposphere above Gulf

  4. The geochemistry of stable chlorine and bromine isotopes

    Energy Technology Data Exchange (ETDEWEB)

    Eggenkamp, Hans [Onderzock and Beleving, Bussum (Netherlands)

    2014-11-01

    First book solely dedicated to the geochemistry of chlorine and bromine isotopes. Detailed description of analytical techniques, including their advantages and disadvantages. Indication of research fields where measurement of these isotopes is especially useful. This book provides detailed information on the history, analysis and applications of chlorine and bromine isotope geochemistry. Chlorine and bromine are geochemically unique as they prefer to exist as single charged negative ions. For this reason isotope fractionation reflects mostly processes that are not related to changes in the redox state and this fractionation is generally modest. The book will describe the processes that are most easily detected using these isotopes. Also isotope variations, and processes that cause them, measured in oxidised species such as perchlorates and in organic molecules will be described in this book.

  5. Sodium, Iodine and Bromine in Polar Ice Cores

    DEFF Research Database (Denmark)

    Maffezzoli, Niccolo

    Abstract: This research focuses on sodium, bromine and iodine in polar ice cores, with the aim of reviewing and advancing their current understanding with additional measurements and records, and investigating the connections of these tracers with sea ice and their feasibility as sea ice indicators...... with a description of the main analytic al techniques used to measure ionic and elemental species in ice cores. Chapter 4 introduces sodium, bromine and iodine with a theoretical perspective and a particular focus on their connections with sea ice. Some of the physical and chemical properties that are believed...... back trajectory analyses of the past 17 years. The results identify the aerosol source area influencing the Renland ice cap, a result necessary for the interpretation of impurity records obtained from the ice core. Chapter 6 reviews the published ice/snow measurements of bromine and iodine at polar...

  6. An Efficient and Facile Methodology for Bromination of Pyrimidine and Purine Nucleosides with Sodium Monobromoisocyanurate (SMBI

    Directory of Open Access Journals (Sweden)

    Roger Stromberg

    2013-10-01

    Full Text Available An efficient and facile strategy has been developed for bromination of nucleosides using sodium monobromoisocyanurate (SMBI. Our methodology demonstrates bromination at the C-5 position of pyrimidine nucleosides and the C-8 position of purine nucleosides. Unprotected and also several protected nucleosides were brominated in moderate to high yields following this procedure.

  7. A closer look at Arctic ozone loss and polar stratospheric clouds

    Directory of Open Access Journals (Sweden)

    N. R. P. Harris

    2010-09-01

    Full Text Available The empirical relationship found between column-integrated Arctic ozone loss and the potential volume of polar stratospheric clouds inferred from meteorological analyses is recalculated in a self-consistent manner using the ERA Interim reanalyses. The relationship is found to hold at different altitudes as well as in the column. The use of a PSC formation threshold based on temperature dependent cold aerosol formation makes little difference to the original, empirical relationship. Analysis of the photochemistry leading to the ozone loss shows that activation is limited by the photolysis of nitric acid. This step produces nitrogen dioxide which is converted to chlorine nitrate which in turn reacts with hydrogen chloride on any polar stratospheric clouds to form active chlorine. The rate-limiting step is the photolysis of nitric acid: this occurs at the same rate every year and so the interannual variation in the ozone loss is caused by the extent and persistence of the polar stratospheric clouds. In early spring the ozone loss rate increases as the solar insolation increases the photolysis of the chlorine monoxide dimer in the near ultraviolet. However the length of the ozone loss period is determined by the photolysis of nitric acid which also occurs in the near ultraviolet. As a result of these compensating effects, the amount of the ozone loss is principally limited by the extent of original activation rather than its timing. In addition a number of factors, including the vertical changes in pressure and total inorganic chlorine as well as denitrification and renitrification, offset each other. As a result the extent of original activation is the most important factor influencing ozone loss. These results indicate that relatively simple parameterisations of Arctic ozone loss could be developed for use in coupled chemistry climate models.

  8. ATMOS Stratospheric Deuterated Water and Implications for Tropospheric-Stratospheric Transport

    Science.gov (United States)

    Moyer, Elisabeth J.; Irion, Fredrick W.; Yung, Yuk L.; Gunson, Michael R.

    1996-01-01

    Measurements of the isotopic composition of stratospheric water by the ATMOS instrument are used to infer the convective history of stratospheric air. The average water vapor entering the stratosphere is found to be highly depleted of deuterium, with delta-D(sub w) of -670 +/- 80 (67% deuterium loss). Model calculations predict, however, that under conditions of thermodynamic equilibrium, dehydration to stratospheric mixing ratios should produce stronger depletion to delta-D(sub w) of -800 to 900 (80-90% deuterium loss). Deuterium enrichment of water vapor in ascending parcels can occur only in conditions of rapid convection; enrichments persisting into the stratosphere require that those conditions continue to near-tropopause altitudes. We conclude that either the predominant source of water vapor to the uppermost troposphere is enriched convective water, most likely evaporated cloud ice, or troposphere-stratosphere transport occurs closely associated with tropical deep convection.

  9. 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.

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

    International Nuclear Information System (INIS)

    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

  11. Solar research with stratospheric balloons

    Science.gov (United States)

    Vázquez, Manuel; Wittmann, Axel D.

    Balloons, driven by hot air or some gas lighter than air, were the first artificial machines able to lift payloads (including humans) from the ground. After some pioneering flights the study of the physical properties of the terrestrial atmosphere constituted the first scientific target. A bit later astronomers realized that the turbulence of the atmospheric layers above their ground-based telescopes deteriorated the image quality, and that balloons were an appropriate means to overcome, total or partially, this problem. Some of the most highly-resolved photographs and spectrograms of the sun during the 20th century were actually obtained by balloon-borne telescopes from the stratosphere. Some more recent projects of solar balloon astronomy will also be described.

  12. Quantifying the contributions to stratospheric ozone changes from ozone depleting substances and greenhouse gases

    Directory of Open Access Journals (Sweden)

    D. A. Plummer

    2010-09-01

    Full Text Available A state-of-the-art chemistry climate model coupled to a three-dimensional ocean model is used to produce three experiments, all seamlessly covering the period 1950–2100, forced by different combinations of long-lived Greenhouse Gases (GHGs and Ozone Depleting Substances (ODSs. The experiments are designed to quantify the separate effects of GHGs and ODSs on the evolution of ozone, as well as the extent to which these effects are independent of each other, by alternately holding one set of these two forcings constant in combination with a third experiment where both ODSs and GHGs vary. We estimate that up to the year 2000 the net decrease in the column amount of ozone above 20 hPa is approximately 75% of the decrease that can be attributed to ODSs due to the offsetting effects of cooling by increased CO2. Over the 21st century, as ODSs decrease, continued cooling from CO2 is projected to account for more than 50% of the projected increase in ozone above 20 hPa. Changes in ozone below 20 hPa show a redistribution of ozone from tropical to extra-tropical latitudes with an increase in the Brewer-Dobson circulation. In addition to a latitudinal redistribution of ozone, we find that the globally averaged column amount of ozone below 20 hPa decreases over the 21st century, which significantly mitigates the effect of upper stratospheric cooling on total column ozone. Analysis by linear regression shows that the recovery of ozone from the effects of ODSs generally follows the decline in reactive chlorine and bromine levels, with the exception of the lower polar stratosphere where recovery of ozone in the second half of the 21st century is slower than would be indicated by the decline in reactive chlorine and bromine concentrations. These results also reveal the degree to which GHG-related effects mute the chemical effects of N2O on ozone in the standard future scenario used for the WMO Ozone Assessment. Increases in the

  13. Brominated Dioxins: Little-Known New Health Hazards - A Review

    Directory of Open Access Journals (Sweden)

    Piskorska-Pliszczyńska Jadwiga

    2014-10-01

    Full Text Available This article reviews the present state of the science concerning the polybrominated dibenzo-p-dioxins (PBDDs and dibenzofurans (PBDFs. Everywhere in the world people are exposed to anthropogenic origin chemicals. Some of them are long-lived organic compounds, which persist over the years in the environment. Persistent organic pollutants, such as organohalogen compounds, accumulate in environmental and biological compartments and have adverse effects on the health of humans and animals. Little is known about the brominated and mixed chloro/bromo dioxin and furans. Existing literature suggests that brominated dioxins and furans have similar toxicity profiles to their chlorinated analogues. The exposure data are extremely limited, showing a major data gap in estimating the potential environmental and health risk of these chemicals. The rapid increase in the use of brominated flame retardants (the main source of these pollutants has raised the level of concern over environmental and health damage from brominated dioxins and furans. It is likely that human as well as wildlife exposure to these contaminants will increase with their greater use. The findings reported here present strong evidence of the PBDDs and PBDFs as an emerging new class of contaminants.

  14. Ecotoxicity and biodegradability of new brominated flame retardants: A review

    Czech Academy of Sciences Publication Activity Database

    Ezechiáš, Martin; Covino, Stefano; Cajthaml, Tomáš

    2014-01-01

    Roč. 110, č. 2 (2014), s. 153-167 ISSN 0147-6513 R&D Projects: GA MŠk(CZ) EE2.3.30.0003; GA TA ČR TE01020218 Institutional support: RVO:61388971 Keywords : Ecotoxicity * brominated flame retardants * biodegradation * review Subject RIV: EE - Microbiology, Virology Impact factor: 2.762, year: 2014

  15. Novel and simple synthesis of brominated 1,10-phenanthrolines

    Czech Academy of Sciences Publication Activity Database

    Výprachtický, Drahomír; Kaňková, Dana; Pokorná, Veronika; Kmínek, Ivan; Dzhabarov, Vagif; Cimrová, Věra

    2014-01-01

    Roč. 67, č. 6 (2014), s. 915-921 ISSN 0004-9425 R&D Projects: GA ČR GAP106/12/0827; GA ČR(CZ) GA13-26542S Institutional support: RVO:61389013 Keywords : 1,10-phenanthroline * electrophilic aromatic substitution * bromination Subject RIV: CD - Macromolecular Chemistry Impact factor: 1.558, year: 2014

  16. Self-assembled growth of nanostructural Ge islands on bromine ...

    Indian Academy of Sciences (India)

    bromine-passivated Si(111) surfaces at room temperature. AMAL K DAS1 ... Both the islands and the layer are nanocrystalline. This appears ..... coworkers estimated an activation energy of 0.59 ±0.1 eV for Ge diffusion on Si(100) and 0.45 eV ...

  17. Estimation of the residual bromine concentration after disinfection of cooling water by statistical evaluation.

    Science.gov (United States)

    Megalopoulos, Fivos A; Ochsenkuehn-Petropoulou, Maria T

    2015-01-01

    A statistical model based on multiple linear regression is developed, to estimate the bromine residual that can be expected after the bromination of cooling water. Make-up water sampled from a power plant in the Greek territory was used for the creation of the various cooling water matrices under investigation. The amount of bromine fed to the circuit, as well as other important operational parameters such as concentration at the cooling tower, temperature, organic load and contact time are taken as the independent variables. It is found that the highest contribution to the model's predictive ability comes from cooling water's organic load concentration, followed by the amount of bromine fed to the circuit, the water's mean temperature, the duration of the bromination period and finally its conductivity. Comparison of the model results with the experimental data confirms its ability to predict residual bromine given specific bromination conditions.

  18. Laboratory studies of stratospheric aerosol chemistry

    Science.gov (United States)

    Molina, Mario J.

    1996-01-01

    In this report we summarize the results of the two sets of projects funded by the NASA grant NAG2-632, namely investigations of various thermodynamic and nucleation properties of the aqueous acid system which makes up stratospheric aerosols, and measurements of reaction probabilities directly on ice aerosols with sizes corresponding to those of polar stratospheric cloud particles. The results of these investigations are of importance for the assessment of the potential stratospheric effects of future fleets of supersonic aircraft. In particular, the results permit to better estimate the effects of increased amounts of water vapor and nitric acid (which forms from nitrogen oxides) on polar stratospheric clouds and on the chemistry induced by these clouds.

  19. Trajectory tracking control for underactuated stratospheric airship

    Science.gov (United States)

    Zheng, Zewei; Huo, Wei; Wu, Zhe

    2012-10-01

    Stratospheric airship is a new kind of aerospace system which has attracted worldwide developing interests for its broad application prospects. Based on the trajectory linearization control (TLC) theory, a novel trajectory tracking control method for an underactuated stratospheric airship is presented in this paper. Firstly, the TLC theory is described sketchily, and the dynamic model of the stratospheric airship is introduced with kinematics and dynamics equations. Then, the trajectory tracking control strategy is deduced in detail. The designed control system possesses a cascaded structure which consists of desired attitude calculation, position control loop and attitude control loop. Two sub-loops are designed for the position and attitude control loops, respectively, including the kinematics control loop and dynamics control loop. Stability analysis shows that the controlled closed-loop system is exponentially stable. Finally, simulation results for the stratospheric airship to track typical trajectories are illustrated to verify effectiveness of the proposed approach.

  20. Benefits, risks, and costs of stratospheric geoengineering

    KAUST Repository

    Robock, Alan; Marquardt, Allison; Kravitz, Ben; Stenchikov, Georgiy L.

    2009-01-01

    Injecting sulfate aerosol precursors into the stratosphere has been suggested as a means of geoengineering to cool the planet and reduce global warming. The decision to implement such a scheme would require a comparison of its benefits, dangers

  1. Bromine measurements in ozone depleted air over the Arctic Ocean

    Directory of Open Access Journals (Sweden)

    J. A. Neuman

    2010-07-01

    Full Text Available In situ measurements of ozone, photochemically active bromine compounds, and other trace gases over the Arctic Ocean in April 2008 are used to examine the chemistry and geographical extent of ozone depletion in the arctic marine boundary layer (MBL. Data were obtained from the NOAA WP-3D aircraft during the Aerosol, Radiation, and Cloud Processes affecting Arctic Climate (ARCPAC study and the NASA DC-8 aircraft during the Arctic Research of the Composition of the Troposphere from Aircraft and Satellites (ARCTAS study. Fast (1 s and sensitive (detection limits at the low pptv level measurements of BrCl and BrO were obtained from three different chemical ionization mass spectrometer (CIMS instruments, and soluble bromide was measured with a mist chamber. The CIMS instruments also detected Br2. Subsequent laboratory studies showed that HOBr rapidly converts to Br2 on the Teflon instrument inlets. This detected Br2 is identified as active bromine and represents a lower limit of the sum HOBr + Br2. The measured active bromine is shown to likely be HOBr during daytime flights in the arctic. In the MBL over the Arctic Ocean, soluble bromide and active bromine were consistently elevated and ozone was depleted. Ozone depletion and active bromine enhancement were confined to the MBL that was capped by a temperature inversion at 200–500 m altitude. In ozone-depleted air, BrO rarely exceeded 10 pptv and was always substantially lower than soluble bromide that was as high as 40 pptv. BrCl was rarely enhanced above the 2 pptv detection limit, either in the MBL, over Alaska, or in the arctic free troposphere.

  2. 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.

  3. Formation of reactive nitrogen oxides from urban grime photochemistry

    Science.gov (United States)

    Baergen, Alyson M.; Donaldson, D. James

    2016-05-01

    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 evidence that surface-associated nitrate undergoes further reaction. Here, we examine the gas phase products of the photochemistry of real, field-collected urban grime using incoherent broadband cavity-enhanced absorption spectroscopy (IBBCEAS). Gas phase nitrogen oxides are emitted upon illumination of grime samples and their production increases with ambient relative humidity (RH) up to 35 % after which the production becomes independent of RH. These results are discussed in the context of water uptake onto and evaporation from grime films.

  4. Fluorescence Spectroscopy, Exciton Dynamics and Photochemistry of Single Allophycocyanin Trimers

    International Nuclear Information System (INIS)

    Ying, Liming; Xie, Xiaoliang

    1998-01-01

    We report a study of the spectroscopy and exciton dynamics of the allophycocyanin trimer (APC), a light harvesting protein complex from cyanobacteria, by room-temperature single-molecule measurements of fluorescence spectra, lifetimes, intensity trajectories and polarization modulation. Emission spectra of individual APC trimers are found to be homogeneous on the time scale of seconds. In contrast, their emission lifetimes are found to be widely distributed, because of generation of exciton traps during the course of measurements. The intensity trajectories and polarization modulation experiments indicate reversible ixciton trap formation within the three quasi-independent pairs of strong interacting a84 and B84 chromophores in APC, as well a photobleaching of individual chromophores. Comparison experiments under continuous wave and pulsed excitation reveal a two-photon mechanism for generating exciton traps and/or photobleaching, which involves exciton-exciton annihilation. These single-molecule experiments provide new insights into exciton dynamics and photochemistry of light-harvesting complexes

  5. Atmospheric chemistry of carboxylic acids: microbial implication versus photochemistry

    Science.gov (United States)

    Vaïtilingom, M.; Charbouillot, T.; Deguillaume, L.; Maisonobe, R.; Parazols, M.; Amato, P.; Sancelme, M.; Delort, A.-M.

    2011-08-01

    The objective of this work was to compare experimentally the contribution of photochemistry vs. microbial activity to the degradation of carboxylic acids present in cloud water. For this, we selected 17 strains representative of the microflora existing in real clouds and worked on two distinct artificial cloud media that reproduce marine and continental cloud chemical composition. Photodegradation experiments with hydrogen peroxide (H2O2) as a source of hydroxyl radicals were performed under the same microcosm conditions using two irradiation systems. Biodegradation and photodegradation rates of acetate, formate, oxalate and succinate were measured on both media at 5 °C and 17 °C and were shown to be on the same order of magnitude (around 10-10-10-11 M s-1). The chemical composition (marine or continental origin) had little influence on photodegradation and biodegradation rates while the temperature shift from 17 °C to 5 °C decreased biodegradation rates of a factor 2 to 5. In order to test other photochemical scenarios, theoretical photodegradation rates were calculated considering hydroxyl (OH) radical concentration values in cloud water estimated by cloud chemistry modelling studies and available reaction rate constants of carboxylic compounds with both hydroxyl and nitrate radicals. Considering high OH concentration ([OH] = 1 × 10-12 M) led to no significant contribution of microbial activity in the destruction of carboxylic acids. On the contrary, for lower OH concentration (at noon, [OH] = 1 × 10-14 M), microorganisms could efficiently compete with photochemistry and in similar contributions than the ones estimated by our experimental approach. Combining these two approaches (experimental and theoretical), our results led to the following conclusions: oxalate was only photodegraded; the photodegradation of formate was usually more efficient than its biodegradation; the biodegradation of acetate and succinate seemed to exceed their photodegradation.

  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. Issues in Stratospheric Ozone Depletion.

    Science.gov (United States)

    Lloyd, Steven Andrew

    Following the announcement of the discovery of the Antarctic ozone hole in 1985 there have arisen a multitude of questions pertaining to the nature and consequences of polar ozone depletion. This thesis addresses several of these specific questions, using both computer models of chemical kinetics and the Earth's radiation field as well as laboratory kinetic experiments. A coupled chemical kinetic-radiative numerical model was developed to assist in the analysis of in situ field measurements of several radical and neutral species in the polar and mid-latitude lower stratosphere. Modeling was used in the analysis of enhanced polar ClO, mid-latitude diurnal variation of ClO, and simultaneous measurements of OH, HO_2, H_2 O and O_3. Most importantly, such modeling was instrumental in establishing the link between the observed ClO and BrO concentrations in the Antarctic polar vortex and the observed rate of ozone depletion. The principal medical concern of stratospheric ozone depletion is that ozone loss will lead to the enhancement of ground-level UV-B radiation. Global ozone climatology (40^circS to 50^ circN latitude) was incorporated into a radiation field model to calculate the biologically accumulated dosage (BAD) of UV-B radiation, integrated over days, months, and years. The slope of the annual BAD as a function of latitude was found to correspond to epidemiological data for non-melanoma skin cancers for 30^circ -50^circN. Various ozone loss scenarios were investigated. It was found that a small ozone loss in the tropics can provide as much additional biologically effective UV-B as a much larger ozone loss at higher latitudes. Also, for ozone depletions of > 5%, the BAD of UV-B increases exponentially with decreasing ozone levels. An important key player in determining whether polar ozone depletion can propagate into the populated mid-latitudes is chlorine nitrate, ClONO_2 . As yet this molecule is only indirectly accounted for in computer models and field

  8. Occurrence of bromine in fluidised bed combustion of solid recovered fuel

    Energy Technology Data Exchange (ETDEWEB)

    Vainikka, P.

    2011-12-15

    Corrosive ash species are the single most important factor limiting the electric efficiency of steam boiler plants fired with waste or biomass. Chlorine has been found to have a central role in the chemistry involved as it reduces the melting temperature of ash, forms corrosive vapour and gas species in the furnace and halogenated deposits on boiler heat transfer surfaces. In this context chlorine has been extensively researched. At the time of writing this thesis there was hardly any published data available on the occurrence of bromine (Br) in the aforementioned context. The objective of this work was to review the occurrence of bromine in solid fuels and characterise the behaviour of bromine in full-scale fluidised bed combustion. The review on the occurrence of bromine in solid fuels revealed that in anthropogenic wastes bromine is mainly found in connection to flame retarded substances. Several weight percentages of bromine can be found in plastics treated with brominated flame retardants (BFRs). Bromine is typically found some 100-200 mg kg-1 in mixed municipal solid wastes (MSW). Bromine may be enriched in fuels with high share of plastics, such as solid recovered fuel (SRF) or refuse derived fuel (RDF). Up to 2000 mg kg-1 was found as a monthly average in SRF, typical levels being 20-200 mg kg-1. Wastewater sludge from paper mills may contain bromine 20-100 mg kg-1 due the use of bromine based biocides. In other fuels bromine may be found in significant amounts in marine influenced coal deposits and peat as well as in biomass treated with brominated pesticides. In the experimental part SRF, spruce bark and wastewater sludge from a paper mill were co-fired in a full- scale bubbling fluidised bed (BFB) boiler, and the collected fuels, aerosols and waterwall deposits were analysed with the focus on the fate of bromine. Bromine was mainly found to form water soluble high vapour pressure alkali metal halides in the furnace - in the form of KBr(g) and NaBr(g) as

  9. Applications of continuous-flow photochemistry in organic synthesis, material science, and water treatment

    NARCIS (Netherlands)

    Cambié, D.; Bottecchia, C.; Straathof, N.J.W.; Hessel, V.; Noël, T.

    2016-01-01

    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

  10. 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

  11. Measurements to understand the role of the sub Arctic environment on boundary layer ozone, gaseous mercury and bromine oxide concentrations

    Science.gov (United States)

    Netcheva, S.; Bottenheim, J.; Staebler, R.; Steffen, A.; Bobrowski, N.; Moores, J.

    2009-04-01

    Marine Boundary Layer spring time ozone (O3) and Gaseous Elemental Mercury (GEM) depletion episodes in Polar Regions and the role played by reactive halogen species have been studied for several years. Understanding of the photochemistry involved has improved significantly in the last few years, but many questions remain. The key in filling many gaps of information is in conducting systematic measurements over freezing and thawing surfaces of big water basins in Polar Regions where depletion episodes are thought to originate. Regardless of extensive research in the field, data sets collected over the ice are limited due to logistics and engineering challenges. The fast changing Arctic environment with its potential implications for climate change and human and ecosystem health demand urgent development of a predictive capability that could only be achieved by complete quantitative understanding of these phenomena. The Out On The Ice (OOTI) mini atmospheric chemistry laboratory was developed in 2004 specifically to permit collecting data at remote locations in an autonomous way. The system is battery powered, easily transported by snowmobile and quickly deployed at a target location. The equipment has undergone multiple engineering and instrumentation improvements. In its current version, it conducts fully automated measurements of O3, GEM and carbon dioxide (CO2) simultaneously at two levels: right above a surface of interest and at 2.5 meters. This is accomplished by utilizing two identical sets of instruments (2B for O3 and Gardis for GEM), or by continuous valve switching (CO2). A vertical profile of bromine oxide is determined by scanning the collecting optics of a Differential Optical Absorption Spectrometer through different elevation angles. Furthermore a full set of meteorological data is acquired in parallel with the chemical measurements in order to evaluate environmental and air mass transport contributions. We will present results from data collected

  12. Bromine and water quality – Selected aspects and future perspectives

    International Nuclear Information System (INIS)

    Winid, Bogumiła

    2015-01-01

    Bromine is a microelement present in waters, both in inorganic and in a wide range of organic compounds, though at lower concentrations. Typically, concentrations of organobromine compounds in waters are several orders of magnitude lower than of bromides. Two issues are addressed in the paper: the influence of bromides on the quality of treated waters and organobromines as contaminants of natural waters. Bromide presence in treated water gives rise to formation of potentially mutagenic disinfection by-products (DBPs). Registered amounts of DBPs in potable waters, exceeding the admissible levels, and the published data on DBPs in waters used for leisure and recreation activities, clearly indicate the health risk. Major sources are identified and registered concentrations of EDB, DBCB, methyl bromide, bromacil and PBDEs in the aquatic environment are summarized. The effects of bromide on DBPs formation and numerous examples of organobromine contamination of the aquatic environment indicate that the presence of bromides and organobromine compounds in the aquatic environment will have to be given more consideration, for several reasons. Firstly, larger amounts of bromide are present in saline and contaminated waters and the proportion of such waters being handled is increasing. Similarly, the processes of water purification, treatment and disinfection are now playing a major role. Secondly, emissions from manufacturing of bromine-containing materials growing, due to, inter alia, intensive development of the electronic industry and the plastic manufacturing sector. Thirdly, bromine compounds are also used as medicine ingredients. There is now a growing awareness of the presence of pharmaceuticals in the aquatic environment. Fourth, low bromide concentrations in hypergene zones may be modified in the future, partly because of the climate changes, which may give rise to difficulties with water treatment systems. Water quality standards having relevance to water used for

  13. Stratospheric dryness: model simulations and satellite observations

    Directory of Open Access Journals (Sweden)

    J. Lelieveld

    2007-01-01

    Full Text Available The mechanisms responsible for the extreme dryness of the stratosphere have been debated for decades. A key difficulty has been the lack of comprehensive models which are able to reproduce the observations. Here we examine results from the coupled lower-middle atmosphere chemistry general circulation model ECHAM5/MESSy1 together with satellite observations. Our model results match observed temperatures in the tropical lower stratosphere and realistically represent the seasonal and inter-annual variability of water vapor. The model reproduces the very low water vapor mixing ratios (below 2 ppmv periodically observed at the tropical tropopause near 100 hPa, as well as the characteristic tape recorder signal up to about 10 hPa, providing evidence that the dehydration mechanism is well-captured. Our results confirm that the entry of tropospheric air into the tropical stratosphere is forced by large-scale wave dynamics, whereas radiative cooling regionally decelerates upwelling and can even cause downwelling. Thin cirrus forms in the cold air above cumulonimbus clouds, and the associated sedimentation of ice particles between 100 and 200 hPa reduces water mass fluxes by nearly two orders of magnitude compared to air mass fluxes. Transport into the stratosphere is supported by regional net radiative heating, to a large extent in the outer tropics. During summer very deep monsoon convection over Southeast Asia, centered over Tibet, moistens the stratosphere.

  14. Competition between Halogen, Hydrogen and Dihydrogen Bonding in Brominated Carboranes

    Czech Academy of Sciences Publication Activity Database

    Fanfrlík, Jindřich; Holub, Josef; Růžičková, Z.; Řezáč, Jan; Lane, P. D.; Wann, D. A.; Hnyk, Drahomír; Růžička, A.; Hobza, Pavel

    2016-01-01

    Roč. 17, č. 21 (2016), s. 3373-3376 ISSN 1439-4235 R&D Projects: GA ČR(CZ) GBP208/12/G016; GA ČR(CZ) GA15-05677S Institutional support: RVO:61388963 ; RVO:61388980 Keywords : bromine * carboranes * halogen bonds * sigma holes * X-ray crystal structure Subject RIV: CF - Physical ; Theoretical Chemistry; CA - Inorganic Chemistry (UACH-T) Impact factor: 3.075, year: 2016

  15. Stratospheric Aerosol and Gas Experiment (SAGE) IV Pathfinder

    Data.gov (United States)

    National Aeronautics and Space Administration — The Clean Air Act mandates NASA to monitor stratospheric ozone, and stratospheric aerosol measurements are vital to our understanding of climate.  Maintaining...

  16. Atmospheric chemistry of carboxylic acids: microbial implication versus photochemistry

    Directory of Open Access Journals (Sweden)

    M. Vaïtilingom

    2011-08-01

    Full Text Available The objective of this work was to compare experimentally the contribution of photochemistry vs. microbial activity to the degradation of carboxylic acids present in cloud water. For this, we selected 17 strains representative of the microflora existing in real clouds and worked on two distinct artificial cloud media that reproduce marine and continental cloud chemical composition. Photodegradation experiments with hydrogen peroxide (H2O2 as a source of hydroxyl radicals were performed under the same microcosm conditions using two irradiation systems. Biodegradation and photodegradation rates of acetate, formate, oxalate and succinate were measured on both media at 5 °C and 17 °C and were shown to be on the same order of magnitude (around 10−10–10−11 M s−1. The chemical composition (marine or continental origin had little influence on photodegradation and biodegradation rates while the temperature shift from 17 °C to 5 °C decreased biodegradation rates of a factor 2 to 5.

    In order to test other photochemical scenarios, theoretical photodegradation rates were calculated considering hydroxyl (OH radical concentration values in cloud water estimated by cloud chemistry modelling studies and available reaction rate constants of carboxylic compounds with both hydroxyl and nitrate radicals. Considering high OH concentration ([OH] = 1 × 10−12 M led to no significant contribution of microbial activity in the destruction of carboxylic acids. On the contrary, for lower OH concentration (at noon, [OH] = 1 × 10−14 M, microorganisms could efficiently compete with photochemistry and in similar contributions than the ones estimated by our experimental approach.

    Combining these two approaches (experimental and theoretical, our results led to the following conclusions: oxalate was only photodegraded; the photodegradation of formate was usually more

  17. Sources and sinks of stratospheric water vapor

    International Nuclear Information System (INIS)

    Ellsaesser, H.W.

    1979-11-01

    A tutorial review of the understanding of stratospheric H 2 O and the processes controlling it is presented. Paradoxes posed by currently available observational data are cited and suggestions made as to how they might be resolved. Such resolution appears to require: that the bulk of our current data provides unrepresentative and misleading vertical and latitudinal H 2 O gradients immediately downstream from the tropical tropopause; and, that there exists within the troposphere a mechanism different from or in addition to the tropical tropopause cold trap for drying air to the mixing ratios found in the lower stratosphere. Satisfaction of these requirements will reconcile much heretofore puzzling observational data and will obviate the necessity for a stratospheric sink for H 2 O

  18. The Distribution of Hydrogen, Nitrogen, and Chlorine Radicals in the Lower Stratosphere: Implications for Changes in O3 due to Emission of NO(y) from Supersonic Aircraft

    Science.gov (United States)

    Salawitch, R. J.; Wofsy, S. C.; Wennberg, P. O.; Cohen, R. C.; Anderson, J. G.; Fahey, D. W.; Gao, R. S.; Keim, E. R.; Woodbridge, E. L.; Stimpfle, R. M.; hide

    1994-01-01

    In situ measurements of hydrogen, nitrogen, and chlorine radicals obtained in the lower stratosphere during the Stratospheric Photochemistry, Aerosols and Dynamics Expedition (SPADE) are compared to results from a photochemical model that assimilates measurements of radical precursors and environmental conditions. Models allowing for heterogeneous hydrolysis of N2O5 agree well with measured concentrations of NO and ClO, but concentrations of HO2 and OH are underestimated by 10 to 25%, concentrations of NO2 are overestimated by 10 to 30%, and concentrations of HCl are overestimated by a factor of 2. Discrepancies for [OH] and [HO2] are reduced if we allow for higher yields of O(sup 1)D) from 03 photolysis and for heterogeneous production of HNO2. The data suggest more efficient catalytic removal of O3 by hydrogen and halogen radicals relative to nitrogen oxide radicals than predicted by models using recommended rates and cross sections. Increases in [O3] in the lower stratosphere may be larger in response to inputs of NO(sub y) from supersonic aircraft than estimated by current assessment models.

  19. High-Resolution Spectroscopy of Stratospheric Ethane Following the Jupiter Impact of 2009

    Science.gov (United States)

    Fast, Kelly; Kostiuk, Theodor; Livengood, Timothy A.; Hewagama, Tilak; Amen, John

    2010-01-01

    We report on high-resolution infrared spectroscopy of ethane (C2H6) performed at the latitude of an impact site on Jupiter discovered on 19 July 2009 by A. Wesley from a location in Murrumbateman, Australia. The observations used the NASA Goddard Space Flight Center's Heterodyne Instrument for Planetary Wind and Composition (HIPWAC) at the NASA Infrared Telescope Facility (IRTF) on Mauna Kea, Hawaii. HIPWAC is a mid-infrared (9-12 microns) heterodyne spectrometer operating at the highest limit of spectral resolving power (lambda\\Delta\\lambda > l06), providing information on atmospheric constituent abundance and temperature through fully resolved tine shapes. Ethane is a stable trace product of methane photochemistry that is nearly uniformly mixed in Jupiter's stratosphere, providing an effective probe of that altitude region. Ethane emission line profiles near 11,74 microns in the Ug band were measured in Jupiter's stratosphere at 25 MHz (11.00083/cm) resolution. A sequence of spectra of ethane acquired over a range of longitude at the impact latitude (56S planetocentric) probes constituent abundance and temperature profile, both on and off the impact region. Near the site of the impact, ethane emission increased above levels measured well outside the impact region. Radiative transfer analysis indicates increased ethane mole fraction (30% greater). Variation in the measured continuum level and line intensities within 75deg of the impact longitude indicate the presence of an opacity source (haze) at altitudes near and above the tropopause and as high as the 10-mbar level near the impact site. The indication of possible haze opacity up to the 10-mbar level in the atmosphere is consistent with measurements made by HIPWAC's predecessor as part of the IRTF Shoemaker Levy-9 campaign in 1994.

  20. Observations of Inland Snowpack-driven Bromine Chemistry near the Brooks Range, Alaska

    Science.gov (United States)

    Peterson, P.; Pöhler, D.; Sihler, H.; Zielcke, J.; S., General; Friess, U.; Platt, U.; Simpson, W. R.; Nghiem, S. V.; Shepson, P. B.; Stirm, B. H.; Pratt, K.

    2017-12-01

    The snowpack produces high amounts of reactive bromine in the polar regions during spring. The resulting atmospheric bromine chemistry depletes boundary layer ozone to near-zero levels and alters oxidation of atmospheric pollutants, particularly elemental mercury. To improve our understanding of the spatial extent of this bromine chemistry in Arctic coastal regions, the Purdue Airborne Laboratory for Atmospheric Research (ALAR), equipped with the Heidelberg Imaging differential optical absorption spectroscopy (DOAS) instrument, measured the spatial distribution of BrO, an indicator of active bromine chemistry, over northern Alaska during the March 2012 BRomine Ozone Mercury Experiment (BROMEX). Here we show that this bromine chemistry, commonly associated with snow-covered sea ice regions in the Arctic Ocean, is active 200 km inland in the foothills of the Brooks Range. Profiles retrieved from limb-viewing measurements show this event was located near the snowpack surface, with measured BrO mole ratios of 20 pmol mol-1 in a 500 m thick layer. This observed bromine chemistry is likely enabled by deposition of transported sea salt aerosol or gas phase bromine species from prior activation events to the snowpack. These observations of halogen activation hundreds of km from the coast suggest the impacts of this springtime bromine chemistry are not restricted to sea ice regions and directly adjacent coastal regions.

  1. 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.

  2. 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.

  3. The photochemistry of ring-substituted cinnamyl acetates

    International Nuclear Information System (INIS)

    Fleming, S.A.; Renault, L.; Grundy, E.C.; Pincock, J.A.

    2006-01-01

    The photochemistry of the (E)-cinnamyl acetates ((E)-1-aryl-3-propenyl acetates, 8a-8e) with substituents H, 4-CH 3 O, 3-CH 3 O, 4-CF 3 , and 3-CF 3 , respectively, was examined in both cyclohexane and methanol solvents. Alkene isomerization (E to Z) occurred more efficiently than other reactions and evidence is presented that this process occurs from the excited triplet state. In a slower process, 1,3-migration of the acetoxy group led to the rearranged 3-aryl-3-propenyl acetate isomers (9a-9e) as the major pathway, particularly in cylohexane. In methanol, the isomeric ethers 3-aryl-3-methoxypropene (14) and 1-aryl-3-methoxypropene (15) were formed by reaction of methanol with the photochemically generated cation. The combined yield of 14 and 15 (95% and 5%, respectively) was quantitative for the 4-methoxyphenyl compound (8b). Independent irradiations of the isomers 9a-9c demonstrated that the ethers 14 and 15 were primary photoproducts from 8 and not secondary photoproducts from 9. Fluorescence quantum yields and excited singlet state lifetimes indicated that the reactions, other than the E to Z isomerization, are from the excited singlet state. (author)

  4. 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.

  5. The photochemistry of neptunium in aqueous perchloric acid solutions

    International Nuclear Information System (INIS)

    Friedman, H.A.; Toth, L.M.; Osborne, M.M.

    1979-01-01

    The photochemistry of neptunium ions in aqueous perchloric acid has been investigated using 254 and 300 nm UV radiation. In the absence of other reagents, Np(IV) and (V) oxidized to Np(VI), in a stepwise fashion, with individual quantum efficiencies for each step that vary from 0.02 to 0.004. Decreasing acid concentration favors the Np(IV) → Np(V) reaction whereas it hinders the Np(V) → Np(VI) photo-oxidation. When ethanol, acetaldehyde and other mild reducing agents are added to neptunium-perchloric acid solutions which are then photolyzed, the Np species are reduced to Np(III) in a stepwise fashion with individual quantum efficiencies that vary from 0.07 to 0.006. The overall photoredox reactions of neptunium are subject to competing secondary product reactions that become significant as the photolysis products accumulate. Absorption spectrophotometry was used to monitor the changes in Np oxidation states and reference spectra of the various Np oxidation states are given for 1.0 N HClO 4 . The Np species have absorption bands in the 300 to 1320 nm region that obey Beer's law only when they were properly resolved. (author)

  6. Soft x-ray photochemistry in solid surfaces

    International Nuclear Information System (INIS)

    Sekiguchi, Tetsuhiro; Baba, Yuji

    2000-01-01

    Resent studies on photochemistry using synchrotron soft x-rays in solid surfaces are reviewed. A type of site-selective chemical reaction induced by inner-shell excitation is classified into two model systems that are referred to as 'Element-specific fragmentation' and 'Bonding-site-specific dissociation.' The former system uses difference of core-binding-energies in different elements and the latter is based on the existence of plural unoccupied molecular orbitals with different antibonding character. The selectivity of the reaction in respective systems is discussed in terms of mass-patterns of desorbed fragment-ions and photon-energy dependence of the ion yields. Also discussed are the fragmentation and desorption mechanisms which include intrinsic direct photofragmentation and indirect channels induced by secondary electrons. The latter process reduces the selectivity of the reaction. Furthermore, two experimental approaches, which have recently been performed to estimate the relative magnitude of contribution in the direct and indirect processes to the total yields, are described: (1) the layer-thickness dependence and (2) polarization-angle dependence in the photofragmentation. (author)

  7. Photochemistry in the Atmospheres of Denver and Mexico City

    Science.gov (United States)

    Cantrell, C. A.

    2016-12-01

    The composition of atmospheres in and downwind of urban centers has been the subject of study for decades. While early campaigns involved measurements exclusively from the ground, more recent studies have included airborne-based observations. Improved understanding has hinged critically on the development of instrumentation for better qualitifcation of pollutants, and measurement of previously unobserved species in the gas and particulate phases. Comprehensive, well-planned studies have, over time, led to more detailed understanding of chemical transformations and thus improved model representations and directions for further research. This presentation focuses on findings from two case studies of urban atmospheres, namely the MILAGRO study in the Mexico City metropolitan area and the FRAPPE study in the Denver metropolitan region. Both studies made use of extensive ground-based networks and multiple aircraft platforms. The data collected during these studies have been combined with numerical models to derive assessments of the evolution of atmospheric composition due to photochemistry, mixing, and surface processes. Here, analysis of MILAGRO data focuses on the evolution of outflow downwind of the urban region. In FRAPPE, the focus is the possible role of oil and gas exploration on urban air quality. These findings are used to assess the accuracy of current numerical models to reproduce observations, and to point toward areas possibly needing further study.

  8. 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.

  9. New stratospheric UV/visible radiance measurements

    Directory of Open Access Journals (Sweden)

    F. J. Marceau

    1994-01-01

    Full Text Available A stratospheric balloon was launched on 12 October 1986 from the "CNES" base at Aire sur l'Adour (France to record twilight radiance in the stratosphere. The near-UV and visible radiances were continuously monitored by a photometer during sunrise. Some observations are presented for different viewing azimuthal planes and viewing elevation angles. They show the influence of aerosols layers and clouds which can be also seen on related photographs. The results as a whole may be used for testing some radiative models, especially for twilight conditions.

  10. Equatorial waves in the stratosphere of Uranus

    Science.gov (United States)

    Hinson, David P.; Magalhaes, Julio A.

    1991-01-01

    Analyses of radio occultation data from Voyager 2 have led to the discovery and characterization of an equatorial wave in the Uranus stratosphere. The observed quasi-periodic vertical atmospheric density variations are in close agreement with theoretical predictions for a wave that propagates vertically through the observed background structure of the stratosphere. Quantitative comparisons between measurements obtained at immersion and at emersion yielded constraints on the meridional and zonal structure of the wave; the fact that the two sets of measurements are correlated suggests a wave of planetary scale. Two equatorial wave models are proposed for the wave.

  11. Ozone-Temperature Diurnal and Longer Term Correlations, in the Lower Thermosphere, Mesosphere and Stratosphere, Based on Measurements from SABER on TIMED

    Science.gov (United States)

    Huang, Frank T.; Mayr, Hans G.; Russell, James M., III; Mlynczak, Martin G.

    2012-01-01

    The analysis of mutual ozone-temperature variations can provide useful information on their interdependencies relative to the photochemistry and dynamics governing their behavior. Previous studies have mostly been based on satellite measurements taken at a fixed local time in the stratosphere and lower mesosphere. For these data, it is shown that the zonal mean ozone amounts and temperatures in the lower stratosphere are mostly positively correlated, while they are mostly negatively correlated in the upper stratosphere and in the lower mesosphere. The negative correlation, due to the dependence of photochemical reaction rates on temperature, indicates that ozone photochemistry is more important than dynamics in determining the ozone amounts. In this study, we provide new results by extending the analysis to include diurnal variations over 24 hrs of local time, and to larger spatial regimes, to include the upper mesosphere and lower thermosphere (MLT). The results are based on measurements by the SABER instrument on the TIMED satellite. For mean variations (i.e., averages over local time and longitude) in the MLT, our results show that there is a sharp reversal in the correlation near 80 km altitude, above which the ozone mixing ratio and temperature are mostly positively correlated, while they are mostly negatively correlated below 80 km. This is consistent with the view that above -80 km, effects due to dynamics are more important compared to photochemistry. For diurnal variations, both the ozone and temperature show phase progressions in local time, as a function of altitude and latitude. For temperature, the phase progression is as expected, as they represent migrating tides. For day time ozone, we also find regular phase progression in local time over the whole altitude range of our analysis, 25 to 105 km, at least for low latitudes. This was not previously known, although phase progressions had been noted by us and by others at lower altitudes. For diurnal

  12. Photochemistry and aerosol in alpine region: mixing and transport

    International Nuclear Information System (INIS)

    Chaxel, E.

    2006-11-01

    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)

  13. Composite Materials With Uncured Epoxy Matrix Exposed in Stratosphere During NASA Stratospheric Balloon Flight

    Science.gov (United States)

    Kondyurin, Alexey; Kondyurina, Irina; Bilek, Marcela; de Groh, Kim K.

    2013-01-01

    A cassette of uncured composite materials with epoxy resin matrixes was exposed in the stratosphere (40 km altitude) over three days. Temperature variations of -76 to 32.5C and pressure up to 2.1 torr were recorded during flight. An analysis of the chemical structure of the composites showed, that the polymer matrix exposed in the stratosphere becomes crosslinked, while the ground control materials react by way of polymerization reaction of epoxy groups. The space irradiations are considered to be responsible for crosslinking of the uncured polymers exposed in the stratosphere. The composites were cured on Earth after landing. Analysis of the cured composites showed that the polymer matrix remains active under stratospheric conditions. The results can be used for predicting curing processes of polymer composites in a free space environment during an orbital space flight.

  14. Reactive Nitrogen, Ozone and Ozone Production in the Arctic Troposphere and the Impact of Stratosphere-Troposphere Exchange

    Science.gov (United States)

    Liang, Q.; Rodriquez, J. M.; Douglass, A. R.; Crawford, J. H.; Apel, E.; Bian, H.; Blake, D. R.; Brune, W.; Chin, M.; Colarco, P. R.; hide

    2011-01-01

    We analyze the aircraft observations obtained during the Arctic Research of the Composition of the Troposphere from Aircraft and Satellite (ARCTAS) mission together with the GEOS-5 CO simulation to examine O3 and NOy in the Arctic and sub-Arctic region and their source attribution. Using a number of marker tracers and their probability density distributions, we distinguish various air masses from the background troposphere and examine their contribution to NOx, O3, and O3 production in the Arctic troposphere. The background Arctic troposphere has mean O3 of approximately 60 ppbv and NOx of approximately 25 pptv throughout spring and summer with CO decreases from approximately 145 ppbv in spring to approximately 100 ppbv in summer. These observed CO, NOx and O3 mixing ratios are not notably different from the values measured during the 1988 ABLE-3A and the 2002 TOPSE field campaigns despite the significant changes in the past two decades in processes that could have changed the Arctic tropospheric composition. Air masses associated with stratosphere-troposphere exchange are present throughout the mid and upper troposphere during spring and summer. These air masses with mean O3 concentration of 140-160 ppbv are the most important direct sources of O3 in the Arctic troposphere. In addition, air of stratospheric origin is the only notable driver of net O3 formation in the Arctic due to its sustainable high NOx (75 pptv in spring and 110 pptv in summer) and NOy (approximately 800 pptv in spring and approximately 1100 pptv in summer) levels. The ARCTAS measurements present observational evidence suggesting significant conversion of nitrogen from HNO3 to NOx and then to PAN (a net formation of approximately 120 pptv PAN) in summer when air of stratospheric origin is mixed with tropospheric background during stratosphere-to-troposphere transport. These findings imply that an adequate representation of stratospheric O3 and NOy input are essential in accurately simulating O3

  15. New insight into photo-bromination processes in saline surface waters: The case of salicylic acid

    International Nuclear Information System (INIS)

    Tamtam, Fatima; Chiron, Serge

    2012-01-01

    It was shown, through a combination of field and laboratory observations, that salicylic acid can undergo photo-bromination reactions in sunlit saline surface waters. Laboratory-scale experiments revealed that the photochemical yields of 5-bromosalicylic acid and 3,5-dibromosalicylic acid from salicylic acid were always low (in the 4% range at most). However, this might be of concern since these compounds are potential inhibitors of the 20α-hydroxysteroid dehydrogenase enzyme, with potential implications in endocrine disruption processes. At least two mechanisms were involved simultaneously to account for the photo-generation of brominated substances. The first one might involve the formation of reactive brominated radical species (Br·, Br 2 · − ) through hydroxyl radical mediated oxidation of bromide ions. These ions reacted more selectively than hydroxyl radicals with electron-rich organic pollutants such as salicylic acid. The second one might involve the formation of hypobromous acid, through a two electron oxidation of bromine ions by peroxynitrite. This reaction was catalyzed by nitrite, since these ions play a crucial role in the formation of nitric oxide upon photolysis. This nitric oxide further reacts with superoxide radical anions to yield peroxynitrite and by ammonium through the formation of N-bromoamines, probably due to the ability of N-bromoamines to promote the aromatic bromination of phenolic compounds. Field measurements revealed the presence of salicylic acid together with 5-bromosalicylic and 3,5-dibromosalicylic acid in a brackish coastal lagoon, thus confirming the environmental significance of the proposed photochemically induced bromination pathways. -- Highlights: ► Brominated derivatives of salicylic acid were detected in a brackish lagoon. ► A photochemical pathway was hypothesized to account for bromination of salicylic acid. ► Radical bromine species are partly responsible for the bromination process. ► Hypobromous acid

  16. Effects of model chemistry and data biases on stratospheric ozone assimilation

    Directory of Open Access Journals (Sweden)

    L. Coy

    2007-06-01

    Full Text Available The innovations or observation minus forecast (O–F residuals produced by a data assimilation system provide a convenient metric of evaluating global analyses. In this study, O–F statistics from the Global Ozone Assimilation Testing System (GOATS are used to examine how ozone assimilation products and their associated O–F statistics depend on input data biases and ozone photochemistry parameterizations (OPP. All the GOATS results shown are based on a 6-h forecast and analysis cycle using observations from SBUV/2 (Solar Backscatter UltraViolet instrument-2 during September–October 2002. Results show that zonal mean ozone analyses are more independent of observation biases and drifts when using an OPP, while the mean ozone O–Fs are more sensitive to observation drifts when using an OPP. In addition, SD O–Fs (standard deviations are reduced in the upper stratosphere when using an OPP due to a reduction of forecast model noise and to increased covariance between the forecast model and the observations. Experiments that changed the OPP reference state to match the observations by using an "adaptive" OPP scheme reduced the mean ozone O–Fs at the expense of zonal mean ozone analyses being more susceptible to data biases and drifts. Additional experiments showed that the upper boundary of the ozone DAS can affect the quality of the ozone analysis and therefore should be placed well above (at least a scale height the region of interest.

  17. Quantitative structure-activity relationship modeling on in vitro endocrine effects and metabolic stability involving 26 selected brominated flame retardants

    NARCIS (Netherlands)

    Harju, M.; Hamers, T.; Kamstra, J.H.; Sonneveld, E.; Boon, J.P.

    2007-01-01

    In this work, quantitative structure-activity relationships (QSARs) were developed to aid human and environmental risk assessment processes for brominated flame retardants (BFRs). Brominated flame retardants, such as the high-production-volume chemicals polybrominated diphenyl ethers (PBDEs),

  18. Benefits, risks, and costs of stratospheric geoengineering

    KAUST Repository

    Robock, Alan

    2009-10-02

    Injecting sulfate aerosol precursors into the stratosphere has been suggested as a means of geoengineering to cool the planet and reduce global warming. The decision to implement such a scheme would require a comparison of its benefits, dangers, and costs to those of other responses to global warming, including doing nothing. Here we evaluate those factors for stratospheric geoengineering with sulfate aerosols. Using existing U.S. military fighter and tanker planes, the annual costs of injecting aerosol precursors into the lower stratosphere would be several billion dollars. Using artillery or balloons to loft the gas would be much more expensive. We do not have enough information to evaluate more exotic techniques, such as pumping the gas up through a hose attached to a tower or balloon system. Anthropogenic stratospheric aerosol injection would cool the planet, stop the melting of sea ice and land-based glaciers, slow sea level rise, and increase the terrestrial carbon sink, but produce regional drought, ozone depletion, less sunlight for solar power, and make skies less blue. Furthermore it would hamper Earth-based optical astronomy, do nothing to stop ocean acidification, and present many ethical and moral issues. Further work is needed to quantify many of these factors to allow informed decision-making.

  19. Triton - Stratospheric molecules and organic sediments

    Science.gov (United States)

    Thompson, W. Reid; Singh, Sushil K.; Khare, B. N.; Sagan, Carl

    1989-01-01

    Continuous-flow plasma discharge techniques show production rates of hydrocarbons and nitriles in N2 + CH4 atmospheres appropriate to the stratosphere of Titan, and indicate that a simple eddy diffusion model together with the observed electron flux quantitatively matches the Voyager IRIS observations for all the hydrocarbons, except for the simplest ones. Charged particle chemistry is very important in Triton's stratosphere. In the more CH4-rich case of Titan, many hydrocarbons and nitriles are produced in high yield. If N2 is present, the CH4 fraction is low, but hydrocarbons and nitriles are produced in fair yield, abundances of HCN and C2H2 in Triton's stratosphere exceed 10 to the 19th molecules/sq cm per sec, and NCCN, C3H4, and other species are predicted to be present. These molecules may be detected by IRIS if the stratosphere is as warm as expected. Both organic haze and condensed gases will provide a substantial UV and visible opacity in Triton's atmosphere.

  20. Stratospheric tritium sampling. Final progress report

    International Nuclear Information System (INIS)

    Mason, A.S.; Oestlund, H.G.

    1985-09-01

    Stratospheric tritium sampling was part of Project Airstream (sponsored by the US Department of Energy) between 1975 and 1983. Data from the final deployment in November 1983 are reported here, and the results of the 9 years of effort are summarized. 9 refs., 2 figs., 2 tabs

  1. Stratospheric General Circulation with Chemistry Model (SGCCM)

    Science.gov (United States)

    Rood, Richard B.; Douglass, Anne R.; Geller, Marvin A.; Kaye, Jack A.; Nielsen, J. Eric; Rosenfield, Joan E.; Stolarski, Richard S.

    1990-01-01

    In the past two years constituent transport and chemistry experiments have been performed using both simple single constituent models and more complex reservoir species models. Winds for these experiments have been taken from the data assimilation effort, Stratospheric Data Analysis System (STRATAN).

  2. Stratospheric Impact of Varying Sea Surface Temperatures

    Science.gov (United States)

    Newman, Paul A.; Nash, Eric R.; Nielsen, Jon E.; Waugh, Darryn; Pawson, Steven

    2004-01-01

    The Finite-Volume General Circulation Model (FVGCM) has been run in 50 year simulations with the: 1) 1949-1999 Hadley Centre sea surface temperatures (SST), and 2) a fixed annual cycle of SSTs. In this presentation we first show that the 1949-1999 FVGCM simulation produces a very credible stratosphere in comparison to an NCEP/NCAR reanalysis climatology. In particular, the northern hemisphere has numerous major and minor stratospheric warming, while the southern hemisphere has only a few over the 50-year simulation. During the northern hemisphere winter, temperatures are both warmer in the lower stratosphere and the polar vortex is weaker than is found in the mid-winter southern hemisphere. Mean temperature differences in the lower stratosphere are shown to be small (less than 2 K), and planetary wave forcing is found to be very consistent with the climatology. We then will show the differences between our varying SST simulation and the fixed SST simulation in both the dynamics and in two parameterized trace gases (ozone and methane). In general, differences are found to be small, with subtle changes in planetary wave forcing that lead to reduced temperatures in the SH and increased temperatures in the NH.

  3. Synchronous volcanic eruptions and abrupt climate change ∼17.7 ka plausibly linked by stratospheric ozone depletion.

    Science.gov (United States)

    McConnell, Joseph R; Burke, Andrea; Dunbar, Nelia W; Köhler, Peter; Thomas, Jennie L; Arienzo, Monica M; Chellman, Nathan J; Maselli, Olivia J; Sigl, Michael; Adkins, Jess F; Baggenstos, Daniel; Burkhart, John F; Brook, Edward J; Buizert, Christo; Cole-Dai, Jihong; Fudge, T J; Knorr, Gregor; Graf, Hans-F; Grieman, Mackenzie M; Iverson, Nels; McGwire, Kenneth C; Mulvaney, Robert; Paris, Guillaume; Rhodes, Rachael H; Saltzman, Eric S; Severinghaus, Jeffrey P; Steffensen, Jørgen Peder; Taylor, Kendrick C; Winckler, Gisela

    2017-09-19

    Glacial-state greenhouse gas concentrations and Southern Hemisphere climate conditions persisted until ∼17.7 ka, when a nearly synchronous acceleration in deglaciation was recorded in paleoclimate proxies in large parts of the Southern Hemisphere, with many changes ascribed to a sudden poleward shift in the Southern Hemisphere westerlies and subsequent climate impacts. We used high-resolution chemical measurements in the West Antarctic Ice Sheet Divide, Byrd, and other ice cores to document a unique, ∼192-y series of halogen-rich volcanic eruptions exactly at the start of accelerated deglaciation, with tephra identifying the nearby Mount Takahe volcano as the source. Extensive fallout from these massive eruptions has been found >2,800 km from Mount Takahe. Sulfur isotope anomalies and marked decreases in ice core bromine consistent with increased surface UV radiation indicate that the eruptions led to stratospheric ozone depletion. Rather than a highly improbable coincidence, circulation and climate changes extending from the Antarctic Peninsula to the subtropics-similar to those associated with modern stratospheric ozone depletion over Antarctica-plausibly link the Mount Takahe eruptions to the onset of accelerated Southern Hemisphere deglaciation ∼17.7 ka.

  4. Adenine and 2-aminopurine: paradigms of modern theoretical photochemistry.

    Science.gov (United States)

    Serrano-Andrés, Luis; Merchán, Manuela; Borin, Antonio C

    2006-06-06

    Distinct photophysical behavior of nucleobase adenine and its constitutional isomer, 2-aminopurine, has been studied by using quantum chemical methods, in particular an accurate ab initio multiconfigurational second-order perturbation theory. After light irradiation, the efficient, ultrafast energy dissipation observed for nonfluorescent 9H-adenine is explained here by the nonradiative internal conversion process taking place along a barrierless reaction path from the initially populated 1(pipi* La) excited state toward a low-lying conical intersection (CI) connected with the ground state. In contrast, the strong fluorescence recorded for 2-aminopurine at 4.0 eV with large decay lifetime is interpreted by the presence of a minimum in the 1(pipi* La) hypersurface lying below the lowest CI and the subsequent potential energy barrier required to reach the funnel to the ground state. Secondary deactivation channels were found in the two systems related to additional CIs involving the 1(pipi* Lb) and 1(npi*) states. Although in 9H-adenine a population switch between both states is proposed, in 7H-adenine this may be perturbed by a relatively larger barrier to access the 1(npi*) state, and, therefore, the 1(pipi* Lb) state becomes responsible for the weak fluorescence measured in aqueous adenine at approximately 4.5 eV. In contrast to previous models that explained fluorescence quenching in adenine, unlike in 2-aminopurine, on the basis of the vibronic coupling of the nearby 1(pipi*) and 1(npi*) states, the present results indicate that the 1(npi*) state does not contribute to the leading photophysical event and establish the prevalence of a model based on the CI concept in modern photochemistry.

  5. Stratospheric experiments on curing of composite materials

    Science.gov (United States)

    Chudinov, Viacheslav; Kondyurin, Alexey; Svistkov, Alexander L.; Efremov, Denis; Demin, Anton; Terpugov, Viktor; Rusakov, Sergey

    2016-07-01

    Future space exploration requires a large light-weight structure for habitats, greenhouses, space bases, space factories and other constructions. A new approach enabling large-size constructions in space relies on the use of the technology of polymerization of fiber-filled composites with a curable polymer matrix applied in the free space environment on Erath orbit. In orbit, the material is exposed to high vacuum, dramatic temperature changes, plasma of free space due to cosmic rays, sun irradiation and atomic oxygen (in low Earth orbit), micrometeorite fluence, electric charging and microgravitation. The development of appropriate polymer matrix composites requires an understanding of the chemical processes of polymer matrix curing under the specific free space conditions to be encountered. The goal of the stratospheric flight experiment is an investigation of the effect of the stratospheric conditions on the uncured polymer matrix of the composite material. The unique combination of low residual pressure, high intensity UV radiation including short-wave UV component, cosmic rays and other aspects associated with solar irradiation strongly influences the chemical processes in polymeric materials. We have done the stratospheric flight experiments with uncured composites (prepreg). A balloon with payload equipped with heater, temperature/pressure/irradiation sensors, microprocessor, carrying the samples of uncured prepreg has been launched to stratosphere of 25-30 km altitude. After the flight, the samples have been tested with FTIR, gel-fraction, tensile test and DMA. The effect of cosmic radiation has been observed. The composite was successfully cured during the stratospheric flight. The study was supported by RFBR grants 12-08-00970 and 14-08-96011.

  6. Distribution of bromine in mixed iodide-bromide organolead perovskites and its impact on photovoltaic performance

    NARCIS (Netherlands)

    Zhou, Yang; Wang, Feng; Fang, Hong-Hua; Loi, Maria Antonietta; Xie, Fang-Yan; Zhao, Ni; Wong, Ching-Ping

    2016-01-01

    Mixed iodide-bromide (I-Br) organolead perovskites are of great interest for both single junction and tandem solar cells since the optical bandgap of the materials can be tuned by varying the bromine to iodine ratio. Yet, it remains unclear how bromine incorporation modifies the properties of the

  7. Control of fouling organisms in estuarine cooling water systems by chlorine and bromine chloride

    International Nuclear Information System (INIS)

    Burton, D.T.; Margrey, S.L.

    1979-01-01

    The study described was initiated to evaluate the antifouling effectiveness of chlorine and bromine chloride in low velocity flow areas where estuarine waters are used for cooling purposes. The relative antifouling effectiveness of chlorine and bromine chloride under intermittent and continuous modes of application in low velocity flow areas was evaluated at an estuarine power plant located on the Chesapeake Bay

  8. A Multistep Synthesis Incorporating a Green Bromination of an Aromatic Ring

    Science.gov (United States)

    Cardinal, Pascal; Greer, Brandon; Luong, Horace; Tyagunova, Yevgeniya

    2012-01-01

    Electrophilic aromatic substitution is a fundamental topic taught in the undergraduate organic chemistry curriculum. A multistep synthesis that includes a safer and greener method for the bromination of an aromatic ring than traditional bromination methods is described. This experiment is multifaceted and can be used to teach students about…

  9. Obtaining the Iodine Value of Various Oils via Bromination with Pyridinium Tribromide

    Science.gov (United States)

    Simurdiak, Michael; Olukoga, Olushola; Hedberg, Kirk

    2016-01-01

    A laboratory exercise was devised that allows students to rapidly and fairly accurately determine the iodine value of oleic acid. This method utilizes the addition of elemental bromine to the unsaturated bonds in oleic acid, due to bromine's relatively fast reaction rate compared to that of the traditional Wijs solution method. This method also…

  10. New fast organic scintillators using intramolecular bromine quenching

    International Nuclear Information System (INIS)

    Berlman, I.B.; Lutz, S.S.; Flournoy, J.M.; Ashford, C.B.; Franks, L.A.

    1984-01-01

    Organic scintillator solutions with decay times as fast as 500 ps and with relatively high conversion efficiencies have been developed. The intramolecular quenching was achieved through the novel approach of adding a bromine atom to the 3- or 4-position of para-oligophenylenes, the fluorescent solutes in these binary solutions. The bromine serves to enhance singlet-to-triplet intersystem crossing in the chromophore, causing a reduction in the scintillation yield and a concomitant reduction in the decay time. The very fast value given above probably also involves some intermolecular self-quenching at high concentration. In addition, the bromine reduces the symmetry of the molecules, thereby increasing their solubility. Finally, an alkyl chain on the opposite para position further increases the solubility and also increases the immunity of the chromophore to quenching. The decay times for binary liquid solutions in toluene (at the indicated concentrations) were 0.51 ns for 4-BHTP (0.14 M), 0.75 ns for 3-BHTP (0.14 M), 0.57 ns for 3-BTP (0.14 M), and 1.3 ns for 4-BHQP (0.06 M). Binary plastics with 4-BHTP as the solute in concentrations up to 0.14 M were cast in polystyrene. The shortest decay time, 0.40 ns, was measured for the 0.14 M concentration. A plastic scintillator containing 3-BTP (0.11 M in polystyrene) had a decay time of 0.85 ns. These results compare favorably with the plastic scintillator BC-422 whose decay time is about 1.4 ns. (orig./HSI)

  11. Levels of brominated diphenylether, dibenzo-P-dioxin, and dibenzofuran in flue gases of a municipal waste combustor

    Science.gov (United States)

    Due to the extensive use of brominated flame retardants (BFRs), including brominated diphenylether (BDE) formulations, for various domestic and industrial applications, the presence of brominated chemicals in the waste stream is to be expected for decades. As much as 40% to 50% o...

  12. Pollution of Lake Mjoesa by brominated flame retardants

    Energy Technology Data Exchange (ETDEWEB)

    Schlabach, M.; Gundersen, H.; Mariussen, E. [NILU, Kjeller (Norway); Fjeld, E.; Breivik, E. [NIVA, Oslo (Norway); Kjellberg, G. [NIVA, Hamar (Norway)

    2004-09-15

    The worldwide use of brominated flame retardants (BFRs) is extensive and there are significant release of these components to the environment. The last twenty years the levels of the polybrominated diphenyl ethers (PBDE) in biota have increased, and in some areas the levels are comparable or even higher to what is reported for the polychlorinated biphenyls (PCB). This study was focused on the pollution of PBDEs in Lake Mjoesa, where unusually high concentrations have been found in fish. The objective of this part of the survey was to make a broader documentation of the PBDE levels in sediments and fish, and to localize areas with point sources of PBDEs.

  13. Environmental analysis of higher brominated diphenyl ethers and decabromodiphenyl ethane.

    Science.gov (United States)

    Kierkegaard, Amelie; Sellström, Ulla; McLachlan, Michael S

    2009-01-16

    Methods for environmental analysis of higher brominated diphenyl ethers (PBDEs), in particular decabromodiphenyl ether (BDE209), and the recently discovered environmental contaminant decabromodiphenyl ethane (deBDethane) are reviewed. The extensive literature on analysis of BDE209 has identified several critical issues, including contamination of the sample, degradation of the analyte during sample preparation and GC analysis, and the selection of appropriate detection methods and surrogate standards. The limited experience with the analysis of deBDethane suggests that there are many commonalities with BDE209. The experience garnered from the analysis of BDE209 over the last 15 years will greatly facilitate progress in the analysis of deBDethane.

  14. Theoretical performance of hydrogen-bromine rechargeable SPE fuel cell

    Science.gov (United States)

    Savinell, Robert F.; Fritts, S. D.

    1987-01-01

    A mathematical model was formulated to describe the performance of a hydrogen-bromine fuel cell. Porous electrode theory was applied to the carbon felt flow-by electrode and was coupled to theory describing the solid polymer electrolyte (SPE) system. Parametric studies using the numerical solution to this model were performed to determine the effect of kinetic, mass transfer, and design parameters on the performance of the fuel cell. The results indicate that the cell performance is most sensitive to the transport properties of the SPE membrane. The model was also shown to be a useful tool for scale-up studies.

  15. Research on the phenomenon of graphitization. Crystallographic study - Study of bromine sorption

    International Nuclear Information System (INIS)

    Maire, Jacques

    1967-01-01

    This research thesis reports the study of the mechanism of graphitization of carbon by using X-ray diffraction analysis and the physical and chemical study of lamellar reactions between carbon and bromine. The author first presents generalities and results of preliminary studies (meaning of graphitization, presentation of the various carbon groups and classes), and then reports the study of the graphitization of compact carbons (soft carbons). More precisely, he reports the crystallographic study of partially graphitized carbons: methods and principles, experimental results and their analysis, discussion of the graphitization mechanism. In the next part, the author reports the study of bromine sorption on carbons: experimental method, isotherms of a natural graphite and of a graphitized carbon, structure of carbon-bromine complexes, isotherms of graphitizable carbons and of all other carbons, distribution of bromine layers in partially graphitized carbons, bromine sorption and Fermi level

  16. Effects of bromine on mitosis in root-tips of Allium cepa

    Energy Technology Data Exchange (ETDEWEB)

    Chury, J; Slouka, V

    1949-01-01

    The root-tips of Allium cepa, 1.5-2 cm. long, were exposed to pure bromine vapor for five minutes. The root-tips were then washed for ten minutes in water, and kept in fresh-water at a temperature of 20-24/sup 0/C. Squash preparations were made and stained according to the method of Darlington and La Cour. Bromine acting for five minutes on the root-tips of Allium has a specific effect on the cell nucleus in the resting stage. The effects induced are shown thirty-six hours after treatment by spindle abnormalities in metaphase and anaphase, and result in polyploidy in a large number of cells. Bromine produces chromosome and chromatid fragmentation; the latter may be followed by reunion. The effect of the bromine is cumulative and depends on the time which elapses between treatment and fixation. The cytological effects induced by bromine strongly suggest that it is another specific mutafacient chemical.

  17. Labeling of receptor ligands with bromine radionuclides. Progress report, March 1, 1981-February 28, 1982

    International Nuclear Information System (INIS)

    Welch, M.J.

    1981-10-01

    In recent years there has been an interest in the use of various radioisotopes of bromine as labels for radiopharmaceuticals. Although radioisotopes of iodine have been used extensively as radiopharmaceutical labels, there are several advantages associated with the use of radiobromine as a label, due primarily to increased stability of bonds to the radiohalide and smaller steric perturbation resulting from substitution of the radiohalide. Methods of attaching radiobromine to receptor ligands with the potential of mapping estrogen receptors in mammary tumors and uteri were studied. Two ligands were studied extensively in vitro and in animal models; preliminary studies were also carried out in humans. To date, the only radioisotope of bromine used was bromine-77. In addition, a series of model compounds were labeled with bromine-77 using a recently described method for rapid bromination; the scope and limitations of this new rapid radiobromination technique were evaluated

  18. Selected topics in photochemistry of nucleic acids. Recent results and perspectives

    International Nuclear Information System (INIS)

    Loeber, G.; Kittler, L.

    1977-01-01

    Recent results on the following photoreactions of nucleic acids are reported: photochemistry of aza-bases and minor bases, formation of photoproducts of the non-cyclobutane type, formations of furocoumarin-pyrimidine photoadducts, fluorescence of dye-nucleic acid complexes and their role in chromosomal fluorescence staining, and mechanisms of the photochemical reaction. Results are discussed with respect to: (i) photobiological relevance of light-induced defects in nucleic acids; (ii) possibilities of achieving higher selectivity of light-induced defects in nucleic acids; (iii) the use of nucleic acid photochemistry to analyze genetic material. An extensive bibliography is included. (author)

  19. 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.

  20. Algae form brominated organic compounds in surface waters

    Energy Technology Data Exchange (ETDEWEB)

    Huetteroth, A; Putschew, A; Jekel, M [Tech. Univ. Berlin (Germany)

    2004-09-15

    Monitoring of organic halogen compounds, measured as adsorbable organic bromine (AOBr) revealed seasonal high concentrations of organic bromine compounds in a surface water (Lake Tegel, Berlin, Germany). Usually, in late summer, concentrations are up to five times higher than during the rest of the year. The AOBr of the lake inflows (throughout the year less then 6 {mu}g/L) were always lower then those in the lake, which indicates a production of AOBr in the lake. A correlation of the AOBr and chlorophyll-a concentration (1) in the lake provides first evidence for the influence of phototrophic organisms. The knowledge of the natural production of organohalogens is relatively recent. Up to now there are more then 3800 identified natural organohalogen compounds that have been detected in marine plants, animals, and bacteria and also in terrestrial plants, fungi, lichen, bacteria, insects, some higher animals, and humans. Halogenated organic compounds are commonly considered to be of anthropogenic origin; derived from e.g. pharmaceuticals, herbicides, fungicides, insecticides, flame retardants, intermediates in organic synthesis and solvents. Additionally they are also produced as by-products during industrial processes and by waste water and drinking water disinfection. Organohalogen compounds may be toxic, persistent and/or carcinogenic. In order to understand the source and environmental relevance of naturally produced organobromine compounds in surface waters, the mechanism of the formation was investigated using batch tests with lake water and algae cultures.

  1. Improved electrolyte for zinc-bromine flow batteries

    Science.gov (United States)

    Wu, M. C.; Zhao, T. S.; Wei, L.; Jiang, H. R.; Zhang, R. H.

    2018-04-01

    Conventional zinc bromide electrolytes offer low ionic conductivity and often trigger severe zinc dendrite growth in zinc-bromine flow batteries. Here we report an improved electrolyte modified with methanesulfonic acid, which not only improves the electrolyte conductivity but also ameliorates zinc dendrite. Experimental results also reveal that the kinetics and reversibility of Zn2+/Zn and Br2/Br- are improved in this modified electrolyte. Moreover, the battery's internal resistance is significantly reduced from 4.9 to 2.0 Ω cm2 after adding 1 M methanesulfonic acid, thus leading to an improved energy efficiency from 64% to 75% at a current density of 40 mA cm-2. More impressively, the battery is capable of delivering an energy efficiency of about 78% at a current density of as high as 80 mA cm-2 when the electrode is replaced by a thermally treated one. Additionally, zinc dendrite growth is found to be effectively suppressed in methanesulfonic acid supported media, which, as a result, enables the battery to be operated for 50 cycles without degradation, whereas the one without methanesulfonic acid suffers from significant decay after only 40 cycles, primarily due to severe zinc dendrite growth. These superior results indicate methanesulfonic acid is a promising supporting electrolyte for zinc-bromine flow batteries.

  2. Comparative environmental analysis of waste brominated plastic thermal treatments

    International Nuclear Information System (INIS)

    Bientinesi, M.; Petarca, L.

    2009-01-01

    The aim of this research activity is to investigate the environmental impact of different thermal treatments of waste electric and electronic equipment (WEEE), applying a life cycle assessment methodology. Two scenarios were assessed, which both allow the recovery of bromine: (A) the co-combustion of WEEE and green waste in a municipal solid waste combustion plant, and (B) the staged-gasification of WEEE and combustion of produced syngas in gas turbines. Mass and energy balances on the two scenarios were set and the analysis of the life cycle inventory and the life cycle impact assessment were conducted. Two impact assessment methods (Ecoindicator 99 and Impact 2002+) were slightly modified and then used with both scenarios. The results showed that scenario B (staged-gasification) had a potentially smaller environmental impact than scenario A (co-combustion). In particular, the thermal treatment of staged-gasification was more energy efficient than co-combustion, and therefore scenario B performed better than scenario A, mainly in the impact categories of 'fossil fuels' and 'climate change'. Moreover, the results showed that scenario B allows a higher recovery of bromine than scenario A; however, Br recovery leads to environmental benefits for both the scenarios. Finally the study demonstrates that WEEE thermal treatment for energy and matter recovery is an eco-efficient way to dispose of this kind of waste

  3. Catalytic degradation of brominated flame retardants by copper oxide nanoparticles

    Science.gov (United States)

    Dror, I.; Yecheskel, Y.; Berkowitz, B.

    2013-12-01

    Brominated flame retardants (BFRs) have been added to various products like plastic, textile, electronics and synthetic polymers at growing rates. In spite of the clear advantages of reducing fire damages, many of these BFRs may be released to the environment after their beneficial use which may lead to contamination of water resources. In this work we present the catalytic degradation of two brominated flame retardants (BFRs), tribromoneopentyl alcohol (TBNPA) and 2,4 dibromophenol (2,4-DBP) by copper oxide nanoparticles (nCuO) in aqueous solution. The degradation kinetics, the debromination, and the formation of intermediates by nCuO catalysis are compared to Fenton oxidation and to reduction by nano zero-valent iron (nZVI). The two studied BFRs are shown to degrade fully by the nCuO system within hours to days. Shorter reaction times showed differences in reaction pathways and kinetics for the two compounds. The 2,4-DBP showed faster degradation than TBNPA, by nCuO catalysis. Relatively high resistance to degradation was recorded for 2,4-DBP with nZVI, yielding 20% degradation after 24 h, while the TBNPA was degraded by 85% within 12 hours. A catalytic mechanism for radical generation and BFR degradation by nCuO is proposed. It is further suggested that H2O2 plays an essential role in the activation of the catalyst.

  4. Bromine species fluxes from Lake Constance’s catchment, and a preliminary lake mass balance

    Science.gov (United States)

    Gilfedder, B. S.; Petri, M.; Wessels, M.; Biester, H.

    2011-06-01

    Bromine was historically termed a cyclic salt in terrestrial freshwater environments due to its perceived conservative cycling between the oceans and the continents. This basic assumption has been challenged recently, with evidence that bromine is involved in dynamic chemical cycles in soils and freshwaters. We present here a study on dissolved bromine species (bromide, organically bound bromine, DOBr) concentrations and fluxes as well as sediment trap bromine levels and fluxes in Lake Constance, a large lake in southern Germany. Water samples were obtained from all major and some minor inflows and outflows over one year, where-after dissolved bromine species were measured by a combination of ICP-MS and ion chromatography coupled to an ICP-MS (IC-ICP-MS). Sediment traps were deployed at two locations for two years with Br, Ti and Zr levels being measured by μ-XRF. 190 t yr -1 of total dissolved bromine (TDBr) was delivered to the lake via 14 rivers and precipitation, with the rivers Alpenrhein (84 t TDBr yr -1) and the Schussen (50 t TDBr yr -1) providing the largest sources. The estimated particulate bromine flux contributed an extra 24-26 t Br yr -1. In comparison, only 40 t TDBr yr -1 was deposited to the lake's catchment by precipitation, and thus ˜80% of the riverine TDBr flux came from soils and rocks. Bromide was the dominant species accounting for, on average, 78% of TDBr concentrations and 93% of TDBr flux to the lake. Despite some high concentrations in the smaller lowland rivers, DOBr was only a minor component of the total riverine bromine flux (˜12 t yr -1, 7%), most of which came from the rivers Schussen, Bregenzer Ach and Argen. In contrast, most of the bromine in the sediment traps was bound to organic matter, and showed a clear seasonal pattern in concentrations, with a maximum in winter and minimum in summer. The summer minimum is thought to be due to dilution of a high Br autochthonous component by low bromine mineral and organic material from

  5. Effects of Greenhouse Gas Increase and Stratospheric Ozone Depletion on Stratospheric Mean Age of Air in 1960-2010

    Science.gov (United States)

    Li, F.; Newman, P. A.; Pawson, S.; Perlwitz, J.

    2017-12-01

    The strength of the stratospheric Brewer-Dobson circulation (BDC) in a changing climate has been extensively studied, but the relative importance of greenhouse gas (GHG) increases and stratospheric ozone depletion in driving the BDC changes remains uncertain. This study separates the impacts of GHG and stratospheric ozone forcings on stratospheric mean age of air in the 1960-2010 period using the Goddard Earth Observing System Model (GEOS) Chemistry-Climate Model (CCM). The experiment compares a set of controlled simulations using a coupled atmosphere-ocean version of the GEOS CCM, in which either GHGs, or stratospheric ozone, or both factors evolve over time. The model results show that GHGs and stratospheric ozone have about equal contributions to the simulated mean age decrease. It is also found that GHG increases account for about two thirds of the enhanced strength of the lower stratospheric residual circulation. The results show that ozone depletion causes an increase in the mean age of air in the Antarctic summer lower stratosphere through two processes: 1) a seasonal delay in the Antarctic polar vortex breakup, that inhibits young mid-latitude air from mixing with the older air inside the vortex; and 2) enhanced Antarctic downwelling, that brings older air from middle and upper stratosphere into the lower stratosphere.

  6. The stratospheric ozone and the ozone layer

    International Nuclear Information System (INIS)

    Zea Mazo, Jorge Anibal; Leon Aristizabal Gloria Esperanza; Eslava Ramirez Jesus Antonio

    2000-01-01

    An overview is presented of the principal characteristics of the stratospheric ozone in the Earth's atmosphere, with particular emphasis on the tropics and the ozone hole over the poles. Some effects produced in the atmosphere as a consequence of the different human activities will be described, and some data on stratospheric ozone will be shown. We point out the existence of a nucleus of least ozone in the tropics, stretching from South America to central Africa, with annual mean values less than 240 DU, a value lower than in the middle latitudes and close to the mean values at the South Pole. The existence of such a minimum is confirmed by mean values from measurements made on satellites or with earthbound instruments, for different sectors in Colombia, like Medellin, Bogota and Leticia

  7. Effects of intense stratospheric ionisation events

    International Nuclear Information System (INIS)

    Reid, G.C.; McAfee, J.R.; Crutzen, P.J.

    1978-01-01

    High levels of ionising radiation in the Earth's stratosphere will lead to increased concentrations of nitrogen oxides and decreased concentrations of ozone. Changes in the surface environment will include an increased level, of biologically harmful UV radiation, caused by the ozone depletion, and a decreased level of visible solar radiation, due to the presence of major enhancements in the stratospheric concentration of nitrogen dioxide. These changes have been studied quantitatively, using the passage of the Solar System through a supernova remnant shell as an example. Some of the potential environmental changes are a substantial global cooling, abnormally dry conditions, a reduction in global photosynthesis and a large increase in the flux of atmospheric fixed nitrogen to the surface of the Earth. Such events might have been the cause of mass extinctions in the distant past. (Author)

  8. Stratospheric ozone: an introduction to its study

    International Nuclear Information System (INIS)

    Nicolet, M.

    1975-01-01

    An analysis is made of the various reactions in which ozone and atomic oxygen are involved in the stratosphere. At the present time, hydrogen, nitrogen, and chlorine compounds in the ranges parts per million, parts per billion, and parts per trillion may have significant chemical effects. In the upper stratosphere, above the ozone peak, where there is no strong departure from photochemical equilibrium conditions, the action of hydroxyl and hydroperoxyl radicals of nitrogen dioxide and chlorine monoxide on atomic oxygen and of atomic chlorine on ozone can be introduced. A precise determination of their exact effects requires knowledge of the vertical distribution of the H 2 O, CH 4 , and H 2 dissociation by reaction of these molecules with electronically excited oxygen atom O( 1 D); the ratio of the OH and HO 2 concentrations and their absolute values, which depend on insufficiently known rate coefficients; the various origins of nitric oxide production, with their vertical distributions related to latitude and season; and the various sources giving different chlorine compounds that may be dissociated in the stratosphere. In the lower stratosphere, below the ozone peak, there is no important photochemical production of O 3 , but there exist various possibilities of transport. The predictability of the action of chemical reactions depends strongly on important interactions between OH and HO 2 radicals with CO and NO, respectively, which affect the ratio n(OH)/n(HO 2 ) at the tropopause level; between OH and NO 2 , which lead to the formation of nitric acid with its downward transport toward the troposphere; between NO and HO 2 , which lead to NO 2 and its subsequent photodissociation; between ClO and NO, which also lead to NO 2 and become more important than the reaction of ClO with O; and between Cl and various molecules, such as CH 4 and H 2 , which lead to HCl with its downward transportation toward the troposphere

  9. Stratospheric chlorine: Blaming it on nature

    International Nuclear Information System (INIS)

    Taube, G.

    1993-01-01

    Much of the bitter public debate over ozone depletion has centered on the claim that chlorofluorocarbons (CFCs) pale into insignificance alongside natural sources of chlorine in the stratosphere. If so, goes the argument, chlorine could not be depleting ozone as atmospheric scientists claim, because the natural sources have been around since time immemorial, and the ozone layer is still there. The claim, put forward in a book by Rogelio Maduro and Ralf Schauerhammer, has since been touted by former Atomic Energy Commissioner Dixy Lee Ray and talk-show host Rush Limbaugh, and it forms the basis of much of the backlash now being felt by atmospheric scientists. The argument is simple: Maduro and Schauerhammer calculate that 600 million tons of chlorine enters the atmosphere annually from seawater, 36 million tons from volcanoes, 8.4 million tons from biomass burning, and 5 million tons from ocean biota. In contrast, CFCs account for a mere 750,000 tons of atmospheric chlorine a year. Besides disputing the numbers, scientists have both theoretical and observational bases for doubting that much of this chlorine is getting into the stratosphere, where it could affect the ozone layer. Linwood Callis of the National Aeronautics and Space Administration's (NASA) Langley Research Center points out one crucial problem with the argument: Chlorine from natural sources is soluble, and so it gets rained out of the lower atmosphere. CFCs, in contrast, are insoluble and inert and thus make it to the stratosphere to release their chlorine. What's more, observations of stratospheric chemistry don't support the idea that natural sources are contributing much to the chlorine there

  10. Pulse radiolysis studies of the reactions of bromine atoms and dimethyl sulfoxide bromine atom complexes with alcohols

    Science.gov (United States)

    Sumiyoshi, Takashi; Fujiyoshi, Ryoko; Katagiri, Miho; Sawamura, Sadashi

    2007-05-01

    Dimethylsulfoxide (DMSO)-Br complexes were generated by pulse radiolysis of DMSO/bromomethane mixtures and the formation mechanism and spectral characteristics of the formed complexes were investigated in detail. The rate constant for the reaction of bromine atoms with DMSO and the extinction coefficient of the complex were obtained to be 4.6×10 9 M -1 s -1 and 6300 M -1 cm -1 at the absorption maximum of 430 nm. Rate constants for the reaction of bromine atoms with a series of alcohols were determined in CBrCl 3 solutions applying a competitive kinetic method using the DMSO-Br complex as the reference system. The obtained rate constants were ˜10 8 M -1 s -1, one or two orders larger than those reported for highly polar solvents. Rate constants of DMSO-Br complexes with alcohols were determined to be ˜ 10 7 M -1 s -1. A comparison of the reactivities of Br atoms and DMSO-Br complexes with those of chlorine atoms and chlorine atom complexes which are ascribed to hydrogen abstracting reactants strongly indicates that hydrogen abstraction from alcohols is not the rate determining step in the case of Br atoms and DMSO-Br complexes.

  11. The 'surf zone' in the stratosphere

    Science.gov (United States)

    McIntyre, M. E.; Palmer, T. N.

    Synoptic, coarse-grain, isentropic maps of Ertel's potential vorticity Q for the northern middle stratosphere, estimated using a large-Richardson-number approximation, are presented for a number of days in January-February 1979, together with some related isentropic trajectory calculations The effects of substituting FGGE for NMC base data are noted, as well as some slight corrections to maps published earlier. The combined evidence from the observations and from dynamical models strongly indicates the existence of planetary-wave breaking, a process in which material contours are rapidly and irreversibly deformed. In the winter stratosphere this occurs most spectacularly in a gigantic 'nonlinear critical layer', or 'surf zone', which surrounds the main polar vortex, and which tends to erode the vortex when wave amplitudes become large. Some of the FGGE-based Q maps suggest that we may be seeing glimpses of local dynamical instabilities and vortex-rollup phenomena within breaking planetary waves. Related phenomena in the troposphere are discussed. An objective definition of the area A( t) of the main vortex, as it appears on isentropic Q maps, is proposed. A smoothed time series of daily values of A( t) should be a statistically powerful 'circulation index' for the state of the winter-time middle stratosphere, which avoids the loss of information incurred by Eulerian space and time averaging.

  12. 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…

  13. Photochemistry of Nitrophenol Molecules and Clusters: Intra- vs Intermolecular Hydrogen Bond Dynamics

    Czech Academy of Sciences Publication Activity Database

    Grygoryeva, Kateřina; Kubečka, J.; Pysanenko, Andriy; Lengyel, Jozef; Slavíček, Petr; Fárník, Michal

    2016-01-01

    Roč. 120, č. 24 (2016), s. 4139-4146 ISSN 1089-5639 R&D Projects: GA ČR(CZ) GA15-12386S Institutional support: RVO:61388955 Keywords : photochemistry * clusters * laser techniques Subject RIV: CF - Physical ; Theoretical Chemistry Impact factor: 2.847, year: 2016

  14. Selected Contributions of the 4th International Conference on Semiconductor Photochemistry (5P4) Introduction.

    Czech Academy of Sciences Publication Activity Database

    Krýsa, J.; Klusoň, Petr; Malato, S.

    2014-01-01

    Roč. 230, JUL 2014 (2014), s. 1 ISSN 0920-5861 Grant - others:SMEC(ES) CTQ2012-38754-C03-01 Institutional support: RVO:67985858 Keywords : semiconductor photochemistry * catalysis * scientific applications Subject RIV: CC - Organic Chemistry OBOR OECD: Organic chemistry Impact factor: 3.893, year: 2014

  15. On the involvement of single-bond rotation in the primary photochemistry of photoactive yellow protein

    NARCIS (Netherlands)

    Stahl, A.D.; Hospes, M.; Singhal, K.; van Stokkum, I.; van Grondelle, R.; Groot, M.L.; Hellingwerf, K.J.

    2011-01-01

    Prior experimental observations, as well as theoretical considerations, have led to the proposal that C4-C7 single-bond rotation may play an important role in the primary photochemistry of photoactive yellow protein (PYP). We therefore synthesized an analog of this protein's 4-hydroxy-cinnamic acid

  16. Stratospheric concentrations of N2O in July 1975

    International Nuclear Information System (INIS)

    Krey, P.W.; Lagomarsino, R.J.; Schonberg, M.

    1977-01-01

    The first measurement of the hemispheric distribution of N 2 O concentrations in the lower stratosphere of the Northern Hemisphere is reported for July 1975. This distribution is similar to those of CCl 3 F and SF 6 , although N 2 O is more stable in the stratosphere than either of the other trace gases. The inventory of N 2 O in the stratosphere of the Northern Hemisphere in July 1975 against which future observations can be compared is 136 Tg

  17. PHOTOCHEMISTRY IN TERRESTRIAL EXOPLANET ATMOSPHERES. II. H{sub 2}S AND SO{sub 2} PHOTOCHEMISTRY IN ANOXIC ATMOSPHERES

    Energy Technology Data Exchange (ETDEWEB)

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

    2013-05-20

    Sulfur gases are common components in the volcanic and biological emission on Earth, and are expected to be important input gases for atmospheres on terrestrial exoplanets. We study the atmospheric composition and the spectra of terrestrial exoplanets with sulfur compounds (i.e., H{sub 2}S and SO{sub 2}) emitted from their surfaces. We use a comprehensive one-dimensional photochemistry model and radiative transfer model to investigate the sulfur chemistry in atmospheres ranging from reducing to oxidizing. The most important finding is that both H{sub 2}S and SO{sub 2} are chemically short-lived in virtually all types of atmospheres on terrestrial exoplanets, based on models of H{sub 2}, N{sub 2}, and CO{sub 2} atmospheres. This implies that direct detection of surface sulfur emission is unlikely, as their surface emission rates need to be extremely high (>1000 times Earth's volcanic sulfur emission) for these gases to build up to a detectable level. We also find that sulfur compounds emitted from the surface lead to photochemical formation of elemental sulfur and sulfuric acid in the atmosphere, which would condense to form aerosols if saturated. For terrestrial exoplanets in the habitable zone of Sun-like stars or M stars, Earth-like sulfur emission rates result in optically thick haze composed of elemental sulfur in reducing H{sub 2}-dominated atmospheres for a wide range of particle diameters (0.1-1 {mu}m), which is assumed as a free parameter in our simulations. In oxidized atmospheres composed of N{sub 2} and CO{sub 2}, optically thick haze, composed of elemental sulfur aerosols (S{sub 8}) or sulfuric acid aerosols (H{sub 2}SO{sub 4}), will form if the surface sulfur emission is two orders of magnitude more than the volcanic sulfur emission of Earth. Although direct detection of H{sub 2}S and SO{sub 2} by their spectral features is unlikely, their emission might be inferred by observing aerosol-related features in reflected light with future generation

  18. 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

  19. Retrieval of stratospheric and tropospheric BrO profiles and columns using ground-based zenith-sky DOAS observations at Harestua, 60° N

    Directory of Open Access Journals (Sweden)

    J. A. Pyle

    2007-09-01

    Full Text Available A profiling algorithm based on the optimal estimation method is applied to ground-based zenith-sky UV-visible measurements from Harestua, Southern Norway (60° N, 11° E in order to retrieve BrO vertical profiles. The sensitivity of the zenith-sky observations to the tropospheric BrO detection is increased by using for the spectral analysis a fixed reference spectrum corresponding to clear-sky noon summer conditions. The information content and retrieval errors are characterized and it is shown that the retrieved stratospheric profiles and total columns are consistent with correlative balloon and satellite observations, respectively. Tropospheric BrO columns are derived from profiles retrieved at 80° solar zenith angle during sunrise and sunset for the 2000–2006 period. They show a marked seasonality with mean column value ranging from 1.52±0.62×1013 molec/cm² in late winter/early spring to 0.92±0.38×1013 molec/cm² in summer, which corresponds to 1.0±0.4 and 0.6±0.2 pptv, respectively, if we assume that BrO is uniformly mixed in the troposphere. These column values are also consistent with previous estimates made from balloon, satellite, and other ground-based observations. Daytime (10:30 LT tropospheric BrO columns are compared to the p-TOMCAT 3-D tropospheric chemical transport model (CTM for the 2002–2003 period. p-TOMCAT shows a good agreement with the retrieved columns except in late winter/early spring where an underestimation by the model is obtained. This finding could be explained by the non-inclusion of sea-ice bromine sources in the current version of p-TOMCAT. Therefore the model cannot reproduce the possible transport of air-masses with enhanced BrO concentration due to bromine explosion events from the polar region to Harestua. The daytime stratospheric BrO columns are compared to the SLIMCAT stratospheric 3-D-CTM. The model run used in this study, which assumes 21.2 pptv for the Bry loading (15 pptv for long

  20. Brominated methanes as photoresponsive molecular storage of elemental Br2.

    Science.gov (United States)

    Kawakami, Kazumitsu; Tsuda, Akihiko

    2012-10-01

    The photochemical generation of elemental Br(2) from brominated methanes is reported. Br(2) was generated by the vaporization of carbon oxides and HBr through oxidative photodecomposition of brominated methanes under a 20 W low-pressure mercury lamp, wherein the amount and situations of Br(2) generation were photochemically controllable. Liquid CH(2)Br(2) can be used not only as an organic solvent but also for the photoresponsive molecular storage of Br(2), which is of great technical benefit in a variety of organic syntheses and in materials science. By taking advantage of the in situ generation of Br(2) from the organic solvent itself, many organobromine compounds were synthesized in high practical yields with or without the addition of a catalyst. Herein, Br(2) that was generated by the photodecomposition of CH(2)Br(2) retained its reactivity in solution to undergo essentially the same reactions as those that were carried out with solutions of Br(2) dissolved in CH(2)Br(2) that were prepared without photoirradiation. Furthermore, HBr, which was generated during the course of the photodecomposition of CH(2)Br(2), was also available for the substitution of the OH group for the Br group and for the preparation of the HBr salts of amines. Furthermore, the photochemical generation of Br(2) from CH(2)Br(2) was available for the area-selective photochemical bleaching of natural colored plants, such as red rose petals, wherein Br(2) that was generated photochemically from CH(2)Br(2) was painted onto the petal to cause radical oxidations of the chromophoric anthocyanin molecules. Copyright © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  1. The third international interlaboratory study on brominated flame retardants

    Energy Technology Data Exchange (ETDEWEB)

    Boer, J. de [Netherlands Institute for Fisheries Research, IJmuiden (Netherlands); Wells, D. [FRS Marine Laboratory, Aberdeen (United Kingdom)

    2004-09-15

    Polybrominated diphenyl ethers (PBDEs) have been produced as brominated flame retardants (BFRs) since the early 1970s and have been found in the aquatic environment since the late 1970s. However, as a result of their detection in sperm whales from deeper Atlantic waters and in human milk, many laboratories are now measuring PBDEs in environmental samples. A first international interlaboratory study (ILS) on the analysis of PBDEs, organised by the Bromine Science and Environmental Forum (BSEF), Brussels, Belgium, in collaboration with the Netherlands Institute for Fisheries Research (RIVO) was conducted in 1999-2000. The results showed that the 18 participating laboratories produced comparable results for BDE 47 in various matrices but had analytical difficulties for other BDEs, in particular for the BDEs 99 and 209. A second study was organised in 2001-2002 by BSEF, QUASIMEME and RIVO. That study showed improvement in comparability of the participating laboratories for BDE99 and some other BDEs. However, there was no improvement for BDE209. Hexabromocyclododecane (HBCD), tetrabromobisphenol-A (TBBP-A) and the dimethyl derivative of TBBP-A (dimethyl TBBP-A) were included in the second study. However, it appeared that only two or three laboratories were able to analyse these determinands. Others laboratories were still in the development phase with their methods for these BFRs. This third study was organised as a development exercise by QUASIMEME, in collaboration with RIVO between September and December 2003. The BFRs selected were the same as in the second study. Two biota test materials, a harbor sediment, a sewage sludge, and two standard solutions were dispatched to the participants.

  2. Recycling of plastic waste: Screening for brominated flame retardants (BFRs).

    Science.gov (United States)

    Pivnenko, K; Granby, K; Eriksson, E; Astrup, T F

    2017-11-01

    Flame retardants are chemicals vital for reducing risks of fire and preventing human casualties and property losses. Due to the abundance, low cost and high performance of bromine, brominated flame retardants (BFRs) have had a significant share of the market for years. Physical stability on the other hand, has resulted in dispersion and accumulation of selected BFRs in the environment and receiving biota. A wide range of plastic products may contain BFRs. This affects the quality of waste plastics as secondary resource: material recycling may potentially reintroduce the BFRs into new plastic product cycles and lead to increased exposure levels, e.g. through use of plastic packaging materials. To provide quantitative and qualitative data on presence of BFRs in plastics, we analysed bromophenols (tetrabromobisphenol A (TBBPA), dibromophenols (2,4- and 2,6-DBP) and 2,4,6-tribromophenol (2,4,6-TBP)), hexabromocyclododecane stereoisomers (α-, β-, and γ-HBCD), as well as selected polybrominated diphenyl ethers (PBDEs) in samples of household waste plastics, virgin and recycled plastics. A considerable number of samples contained BFRs, with highest concentrations associated with acrylonitrile butadiene styrene (ABS, up to 26,000,000ngTBBPA/g) and polystyrene (PS, up to 330,000ng∑HBCD/g). Abundancy in low concentrations of some BFRs in plastic samples suggested either unintended addition in plastic products or degradation of higher molecular weight BFRs. The presence of currently restricted flame retardants (PBDEs and HBCD) identified in the plastic samples illustrates that circular material flows may be contaminated for extended periods. The screening clearly showed a need for improved documentation and monitoring of the presence of BFRs in plastic waste routed to recycling. Copyright © 2017 Elsevier Ltd. All rights reserved.

  3. Bromine-doped DWNTs: A Molecular Faraday Cage

    Science.gov (United States)

    Chen, Gugang; Margine, Roxana; Gupta, Rajeev; Crespi, Vincent; Eklund, Peter; Sumanasekera, Gamini; Bandow, Shunji; Iijima, S.

    2003-03-01

    Raman scattering is used to probe the charge transfer distribution in Bromine-doped double-walled carbon nanotubes (DWNT). Using 1064 nm and 514.5 nm laser excitation we are able to study the charge-transfer sensitive phonons in the inner ( (5,5)) and outer ( (10,10)) tubes of the double-walled pair. The experimental results are compared to our tight binding band structure calculations that include a self-consistent electrostatic term sensitive to the average net charge density on each tube. Upon doping, the nanotube tangential and radial Raman bands from the outer (primary) tubes were observed to shift dramatically to higher frequencies, consistent with a C-C bond contraction driven by the acceptor-doping. The peak intensities of these bands significantly decreased with increasing doping exposure, and they eventually vanished, consistent with a deep depression in the Fermi energy that extinguishes the resonant Raman effect. Interestingly, at the same time, we observed little or no change for the tangential and radial Raman features identified with the inner (secondary) tubes during the bromine doping. Our electronic structure calculations show that the charge distribution between the outer and inner tubes depends on doping level and also, to some extent, on specific tube chirality combinations. In general, in agreement with experiment, the calculations find a very small net charge on the inner tube, consistent with a "Molecular Faraday Effect", e.g., a DWNT of (10, 10)/ (5, 5) configuration that exhibits 0.5 holes/Å total charge transfer, has only 0.04 holes/Å on the inner (secondary) tube.

  4. Preparation of radioactive labelled compounds Pt.1. 82Br labelled organic bromine compounds

    International Nuclear Information System (INIS)

    Otto, R.

    1988-05-01

    A simple method allowing the preparation of 82 Br labelled organic bromine compounds from olefins with chemical and radiochemical yields between 75 and 95% and the specific activities required, is described [fr

  5. Theoretical study of the reaction kinetics of atomic bromine with tetrahydropyran

    KAUST Repository

    Giri, Binod; Lo, John M H; Roscoe, John M.; Alquaity, Awad; Farooq, Aamir

    2015-01-01

    A detailed theoretical analysis of the reaction of atomic bromine with tetrahydropyran (THP, C5H10O) was performed using several ab initio methods and statistical rate theory calculations. Initial geometries of all species involved in the potential

  6. Bromine determination by neutron activation analysis and its distribution in the atmosphere

    International Nuclear Information System (INIS)

    Iturbe Garcia, J.L.; Lopez Munoz, B.E.

    2002-01-01

    Bromine, one of the main participants in ozone layer destruction, is 10 to 100 times more effective than chlorine. There are two principal sources of methyl bromide emissions: the oceans and some pesticides that are used in farming. Bromine was detected in 'premium' and 'magna sin' gasolines (2.86±0.96 and 1.54±0.38 ppm, respectively) as well as in condensed water found in exhaust pipes of vehicles. In addition, samples of rainwater were also analyzed to determine atmospheric bromine concentration. In water samples Br concentrations ranging from 2.09 to 0.06 ppm were found. The techniques utilised were neutron activation analysis and high voltage electrophoresis, the latter to determine the chemical form of bromine in condensed water samples. Finally, suspended particles from rainwater were also analysed by scanning electron microscopy (SEM). (author)

  7. Dynamic dielectric properties and the γ transition of bromine doped polyacrylonitrile

    Directory of Open Access Journals (Sweden)

    2007-10-01

    Full Text Available Based on monitoring the γ process (the lowest temperature-relaxation in polyacrylonitrile (PAN by dynamic dielectric spectroscopy, new evidence for the formation of a charge transfer complex between bromine dopants and nitrile groups is presented. The experimental work is carried out on PAN and nitrile polymerized PAN with and without bromine doping and the effects of these factors on the γ process are measured. Nitrile polymerization results in diminishing of the γ process and in a 15% increase in its activation energy, whereas bromine doping produces splitting of the original γ process in PAN – coupled with a significant activation energy increase – and its complete disappearance in nitrile polymerized PAN. Both the splitting of the γ process and the higher activation energy reflect bromine-nitrile adduct formation..

  8. Bromine and iodine in Chinese medical herbs determined via epithermal neutron activation analysis

    International Nuclear Information System (INIS)

    Chien-Yi Chen; Yuan-Yaw Wei; Sheng-Pin ChangLai; Lung-Kwang Pan

    2003-01-01

    Nineteen natural herbs and two prescriptions prepared from mixed herbs were analyzed via epithermal neutron activation analysis (ENAA) to evaluate their bromine and iodine concentration. Traditional medical doctors prescribed the samples presented in this work to most Taiwanese children for strengthening their immune systems. Empirical results indicated a wide diversity of bromine in the samples. Yet, the iodine concentration was only around one to tenth or twentieth of the bromine. The maximum daily intake (MDI) for various medical herbs was also widely diversified from one to tenfold on the basis of various criteria. The minimum detectable concentration (MDC) of bromine and iodine found was 0.42±0.14 ppm and 0.067±0.016 ppm, respectively. Compared to that from conventional thermal neutron activation analysis (NAA) for a similar evaluation, the extremely low MDC obtained here was attributed to the large amount of thermal neutron absorption during sample irradiation. (author)

  9. Molecular dynamics simulations and thermochemistry of reactive ion etching of silicon by chlorine, chlorine dimer, bromine, and bromine dimer cations

    Energy Technology Data Exchange (ETDEWEB)

    Valone, S.M.; Hanson, D.E.; Kress, J.D.

    1998-05-08

    Simulations of Cl plasma etch of Si surfaces with MD techniques agree reasonably well with the available experimental information on yields and surface morphologies. This information has been supplied to a Monte Carlo etch profile resulting in substantial agreement with comparable inputs provided through controlled experiments. To the extent that more recent measurements of etch rates are more reliable than older ones, preliminary MD simulations using bond-order corrections to the atomic interactions between neighboring Si atoms on the surface improves agreement with experiment through an increase in etch rate and improved agreement with XPS measurements of surface stoichiometry. Thermochemical and geometric analysis of small Si-Br molecules is consistent with the current notions of the effects of including brominated species in etchant gases.

  10. New insight into photo-bromination processes in saline surface waters: The case of salicylic acid

    Energy Technology Data Exchange (ETDEWEB)

    Tamtam, Fatima; Chiron, Serge, E-mail: serge.chiron@msem.univ-montp2.fr

    2012-10-01

    It was shown, through a combination of field and laboratory observations, that salicylic acid can undergo photo-bromination reactions in sunlit saline surface waters. Laboratory-scale experiments revealed that the photochemical yields of 5-bromosalicylic acid and 3,5-dibromosalicylic acid from salicylic acid were always low (in the 4% range at most). However, this might be of concern since these compounds are potential inhibitors of the 20{alpha}-hydroxysteroid dehydrogenase enzyme, with potential implications in endocrine disruption processes. At least two mechanisms were involved simultaneously to account for the photo-generation of brominated substances. The first one might involve the formation of reactive brominated radical species (Br{center_dot}, Br{sub 2}{center_dot}{sup -}) through hydroxyl radical mediated oxidation of bromide ions. These ions reacted more selectively than hydroxyl radicals with electron-rich organic pollutants such as salicylic acid. The second one might involve the formation of hypobromous acid, through a two electron oxidation of bromine ions by peroxynitrite. This reaction was catalyzed by nitrite, since these ions play a crucial role in the formation of nitric oxide upon photolysis. This nitric oxide further reacts with superoxide radical anions to yield peroxynitrite and by ammonium through the formation of N-bromoamines, probably due to the ability of N-bromoamines to promote the aromatic bromination of phenolic compounds. Field measurements revealed the presence of salicylic acid together with 5-bromosalicylic and 3,5-dibromosalicylic acid in a brackish coastal lagoon, thus confirming the environmental significance of the proposed photochemically induced bromination pathways. -- Highlights: Black-Right-Pointing-Pointer Brominated derivatives of salicylic acid were detected in a brackish lagoon. Black-Right-Pointing-Pointer A photochemical pathway was hypothesized to account for bromination of salicylic acid. Black

  11. On particles in the Arctic stratosphere

    Directory of Open Access Journals (Sweden)

    T. S. Jørgensen

    2003-06-01

    Full Text Available Soon after the discovery of the Antarctic ozone hole it became clear that particles in the polar stratosphere had an infl uence on the destruction of the ozone layer. Two major types of particles, sulphate aerosols and Polar Stratospheric Clouds (PSCs, provide the surfaces where fast heterogeneous chemical reactions convert inactive halogen reservoir species into potentially ozone-destroying radicals. Lidar measurements have been used to classify the PSCs. Following the Mt. Pinatubo eruption in June 1991 it was found that the Arctic stratosphere was loaded with aerosols, and that aerosols observed with lidar and ozone observed with ozone sondes displayed a layered structure, and that the aerosol and ozone contents in the layers frequently appeared to be negatively correlated. The layered structure was probably due to modulation induced by the dynamics at the edge of the polar vortex. Lidar observations of the Mt. Pinatubo aerosols were in several cases accompanied by balloon-borne backscatter soundings, whereby backscatter measurements in three different wavelengths made it possible to obtain information about the particle sizes. An investigation of the infl uence of synoptic temperature histories on the physical properties of PSC particles has shown that most of the liquid type 1b particles were observed in the process of an ongoing, relatively fast, and continuous cooling from temperatures clearly above the nitric acid trihydrate condensation temperature (TNAT. On the other hand, it appeared that a relatively long period, with a duration of at least 1-2 days, at temperatures below TNAT provide the conditions which may lead to the production of solid type 1a PSCs.

  12. Determination of arsenic and bromine in hot spring waters by neutron activation analysis

    International Nuclear Information System (INIS)

    Kikawada, Y.; Kawai, S.; Oi, T.

    2004-01-01

    Concentrations of arsenic and bromine dissolved in hot spring waters have been determined by neutron activation analysis using 0.5 cm 3 of sample waters without any chemical pretreatment. The samples prepared for neutron irradiation were simply pieces of filter papers which were infiltrated with samples. With the results of satisfactorily high accuracy and precision, this analytical method was found to be very convenient for the determinations of arsenic and bromine dissolved in water at ppm to sub-ppm levels. (author)

  13. The Limb Infrared Monitor of the Stratosphere (LIMS) experiment

    Science.gov (United States)

    Russell, J. M.; Gille, J. C.

    1978-01-01

    The Limb Infrared Monitor of the Stratosphere is used to obtain vertical profiles and maps of temperature and the concentration of ozone, water vapor, nitrogen dioxide, and nitric acid for the region of the stratosphere bounded by the upper troposphere and the lower mesosphere.

  14. Correlative measurements of the stratospheric aerosols

    Science.gov (United States)

    Santer, R.; Brogniez, C.; Herman, M.; Diallo, S.; Ackerman, M.

    1992-12-01

    Joint experiments were organized or available during stratospheric flights of a photopolarimeter, referred to as RADIBAL (radiometer balloon). In May 1984, RADIBAL flew simultaneously with another balloonborne experiment conducted by the Institut d'Aeronomie Spatiale de Belgique (IASB), which provides multiwavelength vertical profiles of the aerosol scattering coefficient. At this time, the El Chichon layer was observable quite directly from mountain sites. A ground-based station set up at Pic du Midi allowed an extensive description of the aerosol optical properties. The IASB and the Pic du Midi observations are consistent with the aerosol properties derived from the RADIBAL measurement analysis.

  15. Stratospheric ozone, ultraviolet radiation and climate change

    International Nuclear Information System (INIS)

    Boucher, O.

    2008-01-01

    It is well known that an overexposure to ultraviolet radiation is associated with a number of health risks such as an increased risk of cataracts and skin cancers. At a time when climate change is often blamed for all our environmental problems, what is the latest news about the stratospheric ozone layer and other factors controlling ultraviolet radiation at the surface of the Earth? Will the expected changes in the chemical composition of the atmosphere and changes in our climate increase or decrease the risk for skin cancer? This article investigates the role of the various factors influencing ultraviolet radiation and presents the latest knowledge on the subject. (author)

  16. The boiling point of stratospheric aerosols.

    Science.gov (United States)

    Rosen, J. M.

    1971-01-01

    A photoelectric particle counter was used for the measurement of aerosol boiling points. The operational principle involves raising the temperature of the aerosol by vigorously heating a portion of the intake tube. At or above the boiling point, the particles disintegrate rather quickly, and a noticeable effect on the size distribution and concentration is observed. Stratospheric aerosols appear to have the same volatility as a solution of 75% sulfuric acid. Chemical analysis of the aerosols indicates that there are other substances present, but that the sulfate radical is apparently the major constituent.

  17. Studying Stratospheric Temperature Variation with Cosmic Ray Measurements

    Science.gov (United States)

    Zhang, Xiaohang; He, Xiaochun

    2015-04-01

    The long term stratospheric cooling in recent decades is believed to be equally important as surface warming as evidence of influences of human activities on the climate system. Un- fortunatly, there are some discrepancies among different measurements of stratospheric tem- peratures, which could be partially caused by the limitations of the measurement techniques. It has been known for decades that cosmic ray muon flux is sensitive to stratospheric temperature change. Dorman proposed that this effect could be used to probe the tempera- ture variations in the stratophere. In this talk, a method for reconstructing stratospheric temperature will be discussed. We verify this method by comparing the stratospheric tem- perature measured by radiosonde with the ones derived from cosmic ray measurement at multiple locations around the globe.

  18. Stratospheric Temperature Trends Observed by TIMED/SABER

    Science.gov (United States)

    Xian, T.; Tan, R.

    2017-12-01

    Trends in the stratospheric temperature are studied based on the temperature profile observation from the Sounding of the Atmosphere using Broadband Emission Radiometry (SABER). The spatially trends are evaluated in different time scales ranging from decadal to monthly resolved. The results indicate a signature of BDC acceleration. There are strong warming trends (up to 9 K/decade) in the middle to upper stratosphere in the high latitude spring, summer, and autumn seasons, accompanied by strong cooling trends in the lower stratosphere. Besides, strong warming trends occurs through the whole stratosphere over the Southern Hemisphere, which confirms Antarctic ozone layer healing since 2000. In addition, the results demonstrate a significant warming trends in the middle of tropical stratosphere, which becomes strongest during June-July-August.

  19. Contributions of BrCl, Br2, BrOCl, Br2O, and HOBr to regiospecific bromination rates of anisole and bromoanisoles in aqueous solution.

    Science.gov (United States)

    Sivey, John D; Bickley, Mark A; Victor, Daniel A

    2015-04-21

    When bromide-containing waters are chlorinated, conventional wisdom typically assumes HOBr is the only active brominating agent. Several additional and often-overlooked brominating agents (including BrCl, Br2, BrOCl, Br2O) can form in chlorinated waters, albeit at generally lower concentrations than HOBr. The extent to which these additional brominating agents influence bromination rates of disinfection byproduct precursors is, however, poorly understood. Herein, the influence of BrCl, Br2, BrOCl, Br2O, and HOBr toward rates of sequential bromination of anisole was quantified. Conditions affecting bromine speciation (e.g., pH, concentrations of chloride, bromide, and chlorine) were varied, and regiospecific second-order rate constants were calculated for reactions of each brominating agent with anisole, 2-bromoanisole, and 4-bromoanisole. The regioselectivity of anisole bromination changed with pH, consistent with the participation of more than one brominating agent. Under conditions representative of chlorinated drinking water, contributions to bromination rates decreased as BrCl > BrOCl > HOBr > Br2O (Br2 negligible). The second-order rate constant determined for net bromination of anisole by HOBr is up to 3000-times less than reported in previous studies (which assumed HOBr was the only active brominating agent). Accordingly, models that assume HOBr is the only kinetically relevant brominating agent in solutions of free bromine may be insufficient for reactions involving modestly nucleophilic organic compounds.

  20. Persistence of Antarctic polar stratospheric clouds

    Science.gov (United States)

    Mccormick, M. Patrick; Trepte, C. R.

    1988-01-01

    The persistence of Polar Stratospheric Clouds (PSCs) observed by the Stratospheric Aerosol Measurement (SAM) 2 satellite sensor over a 9-year period is compared and contrasted. Histograms of the SAM 2 1.0 micron extinction ratio data (aerosol extinction normalized by the molecular extinction) at an altitude of 18 km in the Antarctic have been generated for three 10-day periods in the month of September. Statistics for eight different years (1979 to 1982 and 1984 to 1987) are shown in separate panels for each figure. Since the SAM 2 system is a solar occultation experiment, observations are limited to the edge of the polar night and no measurements are made deep within the vortex where temperatures could be colder. For this reason, use is made of the NMC global gridded fields and the known temperature-extinction relationship to infer additional information on the occurrence and areal coverage of PSCs. Calculations of the daily areal coverage of the 195 K isotherm will be presented for this same period of data. This contour level lies in the range of the predicted temperature for onset of the Type 1 particle enhancement mode at 50 mb (Poole and McCormick, 1988b) and should indicate approximately when formation of the binary HNO3-H2O particles begins.

  1. Study of photolytic aerosols at stratospheric pressures

    International Nuclear Information System (INIS)

    Delattre, Patrick.

    1975-07-01

    An experimental study of photolytic aerosol formation at stratospheric pressure (60 Torr) and laboratory temperature, was carried out previous to the exact simulation of photolytic aerosol formation in real stratospheric conditions. An experimental simulation device, techniques of generation of known mixtures of inert gases with SO 2 and NOsub(x) traces at low concentration (below 1 ppm volume) and H 2 O traces (a few ppm), and techniques for the determination and counting of aerosol particles at low pressures were perfected. The following results were achieved: the rate of vapor condensation on nuclei was reduced when total pressure decreased. At low pressure the working of condensation nuclei counters and the formation of photolytic aerosols is influenced by this phenomenon. An explanation is proposed, as well as means to avoid this unpleasant effect on the working of nuclei counters at low pressure. No photolytic aerosol production was ascertained at 60 Torr when water concentration was below 100 ppm whatever the concentration of SO 2 or NOsub(x) traces. With water concentration below 1200ppm and SO 2 trace concentration below 1ppm, the aerosol particles produced could not consist of sulfuric acid drops but probably of nitrosyl sulfate acide crystals [fr

  2. Stratospheric ozone - Impact of human activity

    Science.gov (United States)

    Mcelroy, Michael B.; Salawitch, Ross J.

    1989-01-01

    The current knowledge of the chemistry of the stratosphere is reviewed, with particular consideration given to the measurements from the Atmospheric Trace Molecule Spectroscopy (ATMOS) experiment and from the Airborne Antarctic Ozone Experiment. Analysis of the ATMOS data at 30 deg N suggests that the current understanding of the contemporary-stratosphere chemistry at mid-latitudes is relatively complete, except for possible problems with the diurnal variations of N2O5 at low altitudes, and with ClNO3 at higher altitudes. Except for some difficulties with these two compounds, the data from ATMOS agree well with the gas phase models for nitrogen and chlorine species at 30 deg N in spring. It is emphasized that, in addition to the HOCl mechanism proposed by Solomon et al. (1986), the ClO-BrO scheme proposed by McElroy et al. (1986), and the ClO dimer mechanism introduced by Molina and Molina (1987), other processes exist that are responsible for ozone removal.

  3. Satellite studies of the stratospheric aerosol

    International Nuclear Information System (INIS)

    McCormick, M.P.; Hamill, P.; Pepin, T.J.; Chu, W.P.; Swissler, T.J.; McMaster, L.R.

    1979-01-01

    The potential climatological and environmental importance of the stratospheric aerosol layer has prompted great interest in measuring the properties of this aerosol. In this paper we report on two recently deployed NASA satellite systems (SAM II and SAGE) that are monitoring the stratospheric aerosol. The satellite orbits are such that nearly global coverage is obtained. The instruments mounted in the spacecraft are sun photometers that measure solar intensity at specific wavelengths as it is moderated by atmospheric particulates and gases during each sunrise and sunset encountered by the satellites. The data obtained are ''inverted'' to yield vertical aerosol and gaseous (primarily ozone) extinction profiles with 1 km vertical resolution. Thus, latitudinal, longitudinal, and temporal variations in the aerosol layer can be evaluated. The satellite systems are being validated by a series of ground truth experiments using airborne and ground lidar, balloon-borne dustsondes, aircraft-mounted impactors, and other correlative sensors. We describe the SAM II and SAGE satellite systems, instrument characteristics, and mode of operation; outline the methodology of the experiments; and describe the ground truth experiments. We present preliminary results from these measurements

  4. 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.

  5. 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.

  6. An overview of aquatic photochemistry as it relates to microbial production

    Energy Technology Data Exchange (ETDEWEB)

    Miller, W.L. [Dalhousie Univ., Halifax, NS (Canada). Inst. of Oceanography

    2000-07-01

    A review of fundamental photochemistry and its potential impact on microbial processes in natural waters was presented. It is a known fact that solar radiation alters chromophoric dissolved organic matter (CDOM) and results in the production of a complex mixture of reactive oxygen species, inorganic nutrients, and carbon photoproducts. In addition, it results in reduced average molecular weight and changes in water optical properties. The largest carbon product results from the direct photo-mineralization of dissolved organic carbon (DOC) to dissolved inorganic carbon (DIC), thereby bypassing the microbial web. Other studies demonstrated that growth was enhanced for heterotrophic bacteria in natural samples exposed to sunlight, that bacterial growth was absent when stimulated by photochemistry and that there was a marked reduction in the ability of DOC to support bacterial growth after exposure to ultraviolet radiation B (UV-B). 20 refs., 1 fig.

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

    OpenAIRE

    H?lz, K.; Lietard, J.; Somoza, M. M.

    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...

  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. Ultrafast Infrared and UV-vis Studies of the Photochemistry of Methoxycarbonylphenyl Azides in Solution

    OpenAIRE

    Xue, Jiadan; Luk, Hoi Ling; Eswaran, S. V.; Hadad, Christopher M.; Platz, Matthew S.

    2012-01-01

    The photochemistry of 4-methoxycarbonylphenyl azide (2a), 2-methoxycarbonylphenyl azide (3a) and 2-methoxy-6-methoxycarbonylphenyl azide (4a) were studied by ultrafast time-resolved infrared (IR) and UV-vis spectroscopies in solution. Singlet nitrenes and ketenimines were observed and characterized for all three azides. Isoxazole species 3g and 4g are generated after photolysis of 3a and 4a, respectively, in acetonitrile. Triplet nitrene 4e formation correlated with the decay of singlet nitre...

  10. 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.

  11. 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.

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

    OpenAIRE

    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

    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...

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

    International Nuclear Information System (INIS)

    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

  14. Separation and enrichment of isotopes using laser photochemistry - fundamentals and prospectives

    International Nuclear Information System (INIS)

    Guesten, H.

    1978-01-01

    Basic knowledge is summed up on isotope separation by laser photochemistry. The principal prerequisites are explained of the application of atomic and molecular spectroscopy for this purpose. Practical examples are given of isotope separation of uranium, nitrogen, chlorine, carbon, sulfur, and molybdenum showing the application of two basic techniques, i.e., of gradual atom photoionization or gradual molecule photodissociation and of selective photochemical reactions. (L.K.)

  15. Microwave Photochemistry IV: Preparation of the Electrodeless Discharge Lamps for Photochemical Applications

    Czech Academy of Sciences Publication Activity Database

    Církva, Vladimír; Vlková, Leona; Relich, Stanislav; Hájek, Milan

    2006-01-01

    Roč. 179, 1-2 (2006), s. 229-233 ISSN 1010-6030 R&D Projects: GA AV ČR KSK4040110; GA ČR GA203/02/0879 Institutional research plan: CEZ:AV0Z40720504 Keywords : microwave photochemistry * electrodeless discharge lamp * uv/vis source Subject RIV: CC - Organic Chemistry Impact factor: 2.098, year: 2006

  16. Application of non-aqueous solvents to batteries. I Physicochemical properties of propionitrile/water two-phase solvent relevant to zinc-bromine batteries

    Science.gov (United States)

    Singh, P.; White, K.; Parker, A. J.

    1983-11-01

    The properties of bromine/propionitrile solution are investigated with a view to its use as an electrolyte in zinc-bromine batteries which use circulating electrolyte. The solution, which forms a two-phase system with water, has higher conductivity than the oils formed by complexation of bromine with organic salts such as N,N-methoxymethyl methylpiperidinium bromide and N,N-ethyl methylmorpholinium bromide. The activity of bromine in the aqueous phase of the bromine-propionitrile/water, two-phase system is very low; thus, coulombic efficiencies greater than 85 percent are achieved. Zinc-bromine batteries containing this solvent system show good charge/discharge characteristics.

  17. Dynamical response of the Arctic winter stratosphere to global warming

    Science.gov (United States)

    Karpechko, A.; Manzini, E.

    2017-12-01

    Climate models often simulate dynamical warming of the Arctic stratosphere as a response to global warming in association with a strengthening of the deep branch of the Brewer-Dobson circulation; however until now, no satisfactory mechanism for such a response has been suggested. Here we investigate the role of stationary planetary waves in the dynamical response of the Arctic winter stratosphere circulation to global warming by analysing simulations performed with atmosphere-only Coupled Model Intercomparison Project Phase 5 (CMIP5) models driven by prescribed sea surface temperatures (SSTs). We focus on December-February (DJF) because this is the period when the troposphere and stratosphere are strongly coupled. When forced by increased SSTs, all the models analysed here simulate Arctic stratosphere dynamical warming, mostly due to increased upward propagation of quasi-stationary wave number 1, as diagnosed by the meridional eddy heat flux. By analysing intermodel spread in the response we show that the stratospheric warming and increased wave flux to the stratosphere correlate with the strengthening of the zonal winds in subtropics and mid-latitudes near the tropopause- a robust response to global warming. These results support previous studies of future Arctic stratosphere changes and suggest a dynamical warming of the Arctic wintertime polar vortex as the most likely response to global warming.

  18. Observations of bromine monoxide transport in the Arctic sustained on aerosol particles

    Directory of Open Access Journals (Sweden)

    P. K. Peterson

    2017-06-01

    Full Text Available The return of sunlight in the polar spring leads to the production of reactive halogen species from the surface snowpack, significantly altering the chemical composition of the Arctic near-surface atmosphere and the fate of long-range transported pollutants, including mercury. Recent work has shown the initial production of reactive bromine at the Arctic surface snowpack; however, we have limited knowledge of the vertical extent of this chemistry, as well as the lifetime and possible transport of reactive bromine aloft. Here, we present bromine monoxide (BrO and aerosol particle measurements obtained during the March 2012 BRomine Ozone Mercury EXperiment (BROMEX near Utqiaġvik (Barrow, AK. The airborne differential optical absorption spectroscopy (DOAS measurements provided an unprecedented level of spatial resolution, over 2 orders of magnitude greater than satellite observations and with vertical resolution unable to be achieved by satellite methods, for BrO in the Arctic. This novel method provided quantitative identification of a BrO plume, between 500 m and 1 km aloft, moving at the speed of the air mass. Concurrent aerosol particle measurements suggest that this lofted reactive bromine plume was transported and maintained at elevated levels through heterogeneous reactions on colocated supermicron aerosol particles, independent of surface snowpack bromine chemistry. This chemical transport mechanism explains the large spatial extents often observed for reactive bromine chemistry, which impacts atmospheric composition and pollutant fate across the Arctic region, beyond areas of initial snowpack halogen production. The possibility of BrO enhancements disconnected from the surface potentially contributes to sustaining BrO in the free troposphere and must also be considered in the interpretation of satellite BrO column observations, particularly in the context of the rapidly changing Arctic sea ice and snowpack.

  19. Formation of brominated pollutants during the pyrolysis and combustion of tetrabromobisphenol A at different temperatures

    International Nuclear Information System (INIS)

    Ortuño, Nuria; Moltó, Julia; Conesa, Juan A.; Font, Rafael

    2014-01-01

    Tetrabromobisphenol A (TBBPA) is the most widely used brominated flame retardant worldwide. A detailed examination of the degradation products emitted during thermal decomposition of TBBPA is presented in the study. Runs were performed in a laboratory furnace at different temperatures (650 and 800 °C) and in different atmospheres (nitrogen and air). More than one hundred semivolatile compounds have been identified by GC/MS, with special interest in brominated ones. Presence of HBr and brominated light hydrocarbons increased with temperature and in the presence of oxygen. Maximum formation of PAHs is observed at pyrolytic condition at the higher temperature. High levels of 2,4-, 2,6- and 2,4,6- bromophenols were found. The levels of polybrominated dibenzo-p-dioxins and furans have been detected in the ppm range. The most abundant isomers are 2,4,6,8-TeBDF in pyrolysis and 1,2,3,7,8-PeBDF in combustion. These results should be considered in the assessment of thermal treatment of materials containing brominated flame retardants. - Highlights: • Decomposition of a brominated flame retardant is performed in a laboratory furnace. • Both pyrolysis and combustion at two different temperatures are studied. • Brominated organic compounds such as Br-dioxins and furans are analysed. • Main product of decomposition is HBr, accounting for ca. 50%. • Very high and dangerous levels of PBDD/Fs and precursors (bromophenols) are detected. - TBBPA mainly decomposes to give HBr and brominated hydrocarbons at high temperature, but high levels of bromophenols and polybrominated dibenzo-p-dioxins and furans are also produced

  20. Evidence for Dynamical Coupling of Stratosphere-MLT during recent minor Stratospheric Warmings in Southern Hemisphere

    Science.gov (United States)

    Kim, Yongha; Sunkara, Eswaraiah; Hong, Junseok; Ratnam, Venkat; Chandran, Amal; Rao, Svb; Riggin, Dennis

    2015-04-01

    The mesosphere-lower thermosphere (MLT) response to extremely rare minor sudden stratospheric warming (SSW) events was observed for the first time in the southern hemisphere (SH) during 2010 and is investigated using the meteor radar located at King Sejong Station (62.22°S, 58.78°W), Antarctica. Three episodic SSWs were noticed from early August to late October 2010. The mesospheric wind field was found to significantly differ from normal years due to enhanced planetary wave (PW) activity before the SSWs and secondary PWs in the MLT afterwards. The zonal winds in the mesosphere reversed approximately a week before the SSW occurrence in the stratosphere as has been observed 2002 major SSW, suggesting the downward propagation of disturbance during minor SSWs as well. Signatures of mesospheric cooling (MC) in association with SSWs are found in the Microwave Limb Sounder (MLS) measurements. SD-WACCM simulations are able to produce these observed features.

  1. Role of heme in bromine-induced lung injury

    Science.gov (United States)

    Lam, Adam; Vetal, Nilam; Matalon, Sadis; Aggarwal, Saurabh

    2016-01-01

    Bromine (Br2) gas inhalation poses an environmental and occupational hazard resulting in high morbidity and mortality. In this review, we underline the acute lung pathology (within 24 hours of exposure) and potential therapeutic interventions that may be utilized to mitigate Br2-induced human toxicity. We will discuss our latest published data, which suggests that an increase in heme-dependent tissue injury underlies the pathogenesis of Br2 toxicity. Our study was based on previous findings that demonstrated that Br2 upregulates the heme-degrading enzyme heme oxygenase-1 (HO-1), which converts toxic heme into billiverdin. Interestingly, following Br2 inhalation, heme levels were indeed elevated in bronchoalveolar lavage fluid, plasma, and whole lung tissue in C57BL/6 mice. High heme levels correlated with increased lung oxidative stress, lung inflammation, respiratory acidosis, lung edema, higher airway resistance, and mortality. However, therapeutic reduction of heme levels, by either scavenging with hemopexin or degradation by HO-1, improved lung function and survival. Therefore, heme attenuation may prove a useful adjuvant therapy to treat patients after Br2 exposure. PMID:27244263

  2. Extended analysis of fifth spectrum of bromine: Br V

    Science.gov (United States)

    Riyaz, A.; Tauheed, A.; Rahimullah, K.

    2014-11-01

    The fifth spectrum of bromine (Br V) has been studied in the 200-2400 Å wavelength region. The spectrum was photographed on a 3-m normal incidence vacuum spectrograph at the St. Francis Xavier University, Antigonish (Canada) and 6.65-m grazing incidence spectrograph at the Zeeman laboratory (Amsterdam). The light sources used were a triggered spark and sliding spark. The ground configuration of Br V is 4s24p. The excited configurations 4s4p2+4s2(4d+5d+5s+6s+7s+5g+6g)+4s4p(5p+4f)+4p24d in the even parity system and the 4p3+4s2(5p+6p+7p+4f)+4s4p4d+4s4p5s configurations in the odd parity system have been studied. Relativistic Hartree-Fock (HFR) and least squares fitted (LSF) parametric calculations have been used to interpret the observed spectrum. 99 levels of Br V have now been established, 43 being new. Among 394 classified spectral lines, 181 are newly classified. The level 4s27s 2S1/2 is revised. We estimate the accuracy of our measured wavelengths for sharp and unblended lines to be±0.005 Å. The ionization limit is determined as 479,657±200 cm-1 (59.470±0.025 eV).

  3. Brominated flame retardants in Belgian little owl (Athene noctua) eggs

    Energy Technology Data Exchange (ETDEWEB)

    Jaspers, V.; Covaci, A.; Maervoet, J.; Dauwe, T.; Schepens, P.; Eens, M. [Antwerp Univ. (Belgium)

    2004-09-15

    Since the 1960s, polybrominated diphenylethers (PBDEs), a class of brominated flame retardants (BFRs), are widely used in textiles, plastics, electronic equipment and other materials. Their massive use has led to the ubiquitous presence of PBDEs in the environment and in biota in which the PBDE levels seem to increase rapidly. High concentrations of some congeners may cause adverse effects in both wildlife and in human populations1 and this has led to the growing concern of scientists over the last decade and to the need for more data on environmental levels of PBDEs. The little owl (Athene noctua) is a small sedentary predator, which makes it a very suitable biomonitoring species. This owl species feeds on a variety of preys, including small mammals and birds, reptiles, amphibians, earthworms and beetles, depending on the season and the local circumstances. Because very limited information is available about contamination levels in the little owl, a study was conducted to determine the concentrations of PBDEs, polybrominated biphenyls (PBBs), polychlorinated biphenyls (PCBs) and organochlorine pesticides (OCPs) in deserted or addled eggs of little owls in Belgium. Eggs have been used successfully as a monitoring tool for persistent organic pollutants (POPs) in several studies. Although the analysis of POPs in deserted or addled eggs has clear limitations, these can be partially avoided by analysing only highly persistent components, for which the original composition will not change due to 'posthatching' microbiological degradation.

  4. Brominated flame retardants in Canadian chicken egg yolks.

    Science.gov (United States)

    Rawn, D F K; Sadler, A; Quade, S C; Sun, W-F; Lau, B P-Y; Kosarac, I; Hayward, S; Ryan, J J

    2011-06-01

    Chicken eggs categorised as conventional, omega-3 enriched, free range and organic were collected at grading stations in three regions of Canada between 2005 and 2006. Free run eggs, which were only available for collection from two regions, were also sampled during this time frame. Egg yolks from each of these egg types (n = 162) were analysed to determine brominated flame retardant levels, specifically polybrominated diphenyl ethers (PBDEs) and hexabromocyclododecane (HBCD). PBDEs were detected in 100% of the 162 samples tested, while HBCD was observed in 85% of the egg yolks. Total PBDE concentrations in egg yolks ranged from 0.018 to 20.9 ng g(-1) lipid (median = 3.03 ng g(-1) lipid), with PBDE 209 identified as being the major contributor to ΣPBDE concentrations. In addition to PBDE 209, PBDE 99, 47, 100, 183 and 153 were important contributors to ΣPBDE concentrations. Total HBCD concentrations ranged from below the limit of detection to a maximum concentration of 71.9 ng g(-1) lipid (median = 0.053 ng g(-1) lipid). The α-isomer was the dominant contributor to ΣHBCD levels in Canadian egg yolks and was the most frequently detected HBCD isomer. ΣPBDE levels exhibited large differences in variability between combinations of region and type. ΣHBCD concentrations were not significantly different among regions, although differences were observed between the different types of egg yolks analysed in the present study.

  5. Measurement-based modeling of bromine chemistry in the boundary layer: 1. Bromine chemistry at the Dead Sea

    Science.gov (United States)

    Tas, E.; Peleg, M.; Pedersen, D. U.; Matveev, V.; Pour Biazar, A.; Luria, M.

    2006-12-01

    The Dead Sea is an excellent natural laboratory for the investigation of Reactive Bromine Species (RBS) chemistry, due to the high RBS levels observed in this area, combined with anthropogenic air pollutants up to several ppb. The present study investigated the basic chemical mechanism of RBS at the Dead Sea using a numerical one-dimensional chemical model. Simulations were based on data obtained from comprehensive measurements performed at sites along the Dead Sea. The simulations showed that the high BrO levels measured frequently at the Dead Sea could only partially be attributed to the highly concentrated Br- present in the Dead Sea water. Furthermore, the RBS activity at the Dead Sea cannot solely be explained by a pure gas phase mechanism. This paper presents a chemical mechanism which can account for the observed chemical activity at the Dead Sea, with the addition of only two heterogeneous processes: the "Bromine Explosion" mechanism and the heterogeneous decomposition of BrONO2. Ozone frequently dropped below a threshold value of ~1 to 2 ppbv at the Dead Sea evaporation ponds, and in such cases, O3 became a limiting factor for the production of BrOx (BrO+Br). The entrainment of O3 fluxes into the evaporation ponds was found to be essential for the continuation of RBS activity, and to be the main reason for the jagged diurnal pattern of BrO observed in the Dead Sea area, and for the positive correlation observed between BrO and O3 at low O3 concentrations. The present study has shown that the heterogeneous decomposition of BrONO2 has a great potential to affect the RBS activity in areas influenced by anthropogenic emissions, mainly due to the positive correlation between the rate of this process and the levels of NO2. Further investigation of the influence of the decomposition of BrONO2 may be especially important in understanding the RBS activity at mid-latitudes.

  6. Measurement-based modeling of bromine chemistry in the boundary layer: 1. Bromine chemistry at the Dead Sea

    Directory of Open Access Journals (Sweden)

    E. Tas

    2006-01-01

    Full Text Available The Dead Sea is an excellent natural laboratory for the investigation of Reactive Bromine Species (RBS chemistry, due to the high RBS levels observed in this area, combined with anthropogenic air pollutants up to several ppb. The present study investigated the basic chemical mechanism of RBS at the Dead Sea using a numerical one-dimensional chemical model. Simulations were based on data obtained from comprehensive measurements performed at sites along the Dead Sea. The simulations showed that the high BrO levels measured frequently at the Dead Sea could only partially be attributed to the highly concentrated Br− present in the Dead Sea water. Furthermore, the RBS activity at the Dead Sea cannot solely be explained by a pure gas phase mechanism. This paper presents a chemical mechanism which can account for the observed chemical activity at the Dead Sea, with the addition of only two heterogeneous processes: the "Bromine Explosion" mechanism and the heterogeneous decomposition of BrONO2. Ozone frequently dropped below a threshold value of ~1 to 2 ppbv at the Dead Sea evaporation ponds, and in such cases, O3 became a limiting factor for the production of BrOx (BrO+Br. The entrainment of O3 fluxes into the evaporation ponds was found to be essential for the continuation of RBS activity, and to be the main reason for the jagged diurnal pattern of BrO observed in the Dead Sea area, and for the positive correlation observed between BrO and O3 at low O3 concentrations. The present study has shown that the heterogeneous decomposition of BrONO2 has a great potential to affect the RBS activity in areas influenced by anthropogenic emissions, mainly due to the positive correlation between the rate of this process and the levels of NO2. Further investigation of the influence of the decomposition of BrONO2 may be especially important in understanding the RBS activity at mid-latitudes.

  7. CERN: Antiprotons probe the nuclear stratosphere

    International Nuclear Information System (INIS)

    Anon.

    1995-01-01

    The outer periphery of heavy stable nuclei is notoriously difficult to study experimentally. While the well understood electromagnetic interaction between electrons (or muons) and protons has given the nuclear charge (or proton) distribution with high precision for almost all stable nuclei, neutron distribution studies are much less precise. This is especially true for large nuclear distances, where the nuclear density is small. A few previous experiments probing the nuclear ''stratosphere'' suggested that far from the centre of the nucleus (of the order of 2 nuclear radii) this stratosphere may be composed predominantly of neutrons. At the end of the sixties the term ''neutron halo'' was introduced to describe this phenomenon, but experimental evidence was scarce or even controversial, and remained so for almost a quarter of a century. Recently, the Warsaw/Munich/Berlin collaboration working within the PS203 experiment at CERN's LEAR low energy antiproton ring, proposed a new method to study the nuclear periphery using stopped antiprotons. The halo now looks firmer. A 200 MeV/c beam of antiprotons was slowed down by interactions with atomic electrons. When antiproton kinetic energy drops well below 1 keV, the particles are captured in the outermost orbits of ''exotic atoms'', where the antiprotons take the place of the usual orbital electrons. With the lower orbits in this antiprotonic atom empty, the antiproton drops toward the nuclear surface, first emitting Auger electrons and later predominantly antiprotonic X-rays. Due to the strong interaction between antiprotons and nucleons, the antiproton succumbs to annihilation with a nucleon in the rarified nuclear stratosphere, far above the innermost Bohr orbit of the atom. The annihilation probability in heavy nuclei is maximal where the nuclear density is about 3% of its central value and extends to densities many orders of magnitude smaller

  8. CERN: Antiprotons probe the nuclear stratosphere

    Energy Technology Data Exchange (ETDEWEB)

    Anon.

    1995-06-15

    The outer periphery of heavy stable nuclei is notoriously difficult to study experimentally. While the well understood electromagnetic interaction between electrons (or muons) and protons has given the nuclear charge (or proton) distribution with high precision for almost all stable nuclei, neutron distribution studies are much less precise. This is especially true for large nuclear distances, where the nuclear density is small. A few previous experiments probing the nuclear ''stratosphere'' suggested that far from the centre of the nucleus (of the order of 2 nuclear radii) this stratosphere may be composed predominantly of neutrons. At the end of the sixties the term ''neutron halo'' was introduced to describe this phenomenon, but experimental evidence was scarce or even controversial, and remained so for almost a quarter of a century. Recently, the Warsaw/Munich/Berlin collaboration working within the PS203 experiment at CERN's LEAR low energy antiproton ring, proposed a new method to study the nuclear periphery using stopped antiprotons. The halo now looks firmer. A 200 MeV/c beam of antiprotons was slowed down by interactions with atomic electrons. When antiproton kinetic energy drops well below 1 keV, the particles are captured in the outermost orbits of ''exotic atoms'', where the antiprotons take the place of the usual orbital electrons. With the lower orbits in this antiprotonic atom empty, the antiproton drops toward the nuclear surface, first emitting Auger electrons and later predominantly antiprotonic X-rays. Due to the strong interaction between antiprotons and nucleons, the antiproton succumbs to annihilation with a nucleon in the rarified nuclear stratosphere, far above the innermost Bohr orbit of the atom. The annihilation probability in heavy nuclei is maximal where the nuclear density is about 3% of its central value and extends to densities many orders of magnitude smaller. Antiproton annihilation on a proton or on a neutron at the nuclear

  9. Photochemistry of Fe(Iii)-Carboxylates in Polysaccharide-Based Materials with Tunable Mechanical Properties

    Science.gov (United States)

    Giammanco, Giuseppe E.

    We present the formulation and study of light-responsive materials based on carboxylate-containing polysaccharides. The functional groups in these natural polymers allow for strong interactions with transition metal ions such as Fe(III). The known photochemistry of hydroxycarboxylic acids in natural waters inspired us in exploring the visible light induced photochemistry of the carboxylates in these polysaccharides when coordinated to Fe(III) ions. Described in this dissertation are the design and characterization of the Fe(III)-polysaccharide materials, specifically the mechanistic aspects of the photochemistry and the effects that these reactions have on the structure of the polymer materials. We present a study of the quantitative photochemistry of different polysaccharide systems, where the presence of uronic acids was important for the photoreaction to take place. Alginate (Alg), pectate (Pec), hyaluronic acid (Hya), xanthan gum (Xan), and a polysaccharide extracted from the Noni fruit (NoniPs), were among the natural uronic acid-containing polysaccharide (UCPS) systems we analyzed. Potato starch, lacking of uronate groups, did not present any photochemistry in the presence of Fe(III); however, we were able to induce a photochemical response in this polysaccharide upon chemical manipulation of its functional groups. Important structure-function relationships were drawn from this study. The uronate moiety present in these polysaccharides is then envisioned as a tool to induce response to light in a variety of materials. Following this approach, we report the formulation of materials for controlled drug release, able to encapsulate and release different drug models only upon illumination with visible light. Furthermore, hybrid hydrogels were prepared from UPCS and non-responsive polymers. Different properties of these materials could be tuned by controlling the irradiation time, intensity and location. These hybrid gels were evaluated as scaffolds for tissue

  10. Brominated flame retardants in end-of-life management not problematic regarding formation of brominated dioxins/furans (PBDD/F)

    Energy Technology Data Exchange (ETDEWEB)

    Drohmann, D. [Great Lakes Chemical, Bergisch Gladbach (Germany); Tange, L. [Eurobrom B.V., Rijswijk (Netherlands); Rothenbacher, K. [Bromine Science and Environmental Forum, Brussels (Belgium)

    2004-09-15

    Bromine is used as the building block for some of the most effective flame retarding agents available to the plastics industry today. They are used to protect against the risk of accidental fires in a wide range of products. Brominated flame retardants (BFRs), as all flame retardants, act to decrease the risk of fire by increasing the fire resistance of the materials in which they are applied. There is a perception that BFRs affect adversely the end-of-life management of plastics through formation of brominated dioxins and furans (PBDD/F). In fact, there exists a wide range of data and practical experience demonstrating that the end-of-life management of plastics containing BFRs are fully compliant with legislation setting the strictest limit values for PBDD/F and is fully compatible with an integrated waste management concept. Furthermore, all existing EU Risk Assessments on BFRs according to the European Existing Substance Regulations include an assessment of the potential formation of dioxins and furans. All assessments conclude that the risks along the life-cycle of the chemicals for human health and the environment associated with the potential formation of PBDD/F are negligible. Moreover, two recent Swedish studies found, that consumer products with BFRs emit less pollutants than the same products without any FRs. This paper summarises available studies and presents the latest results regarding potential formation of brominated dioxins and furans in end-of-life management of plastics containing brominated flame retardants. Additionally, before BFR products enter the market they are tested for PBDD/F according to the ''German Dioxin Ordinance''. Depending on the substitution pattern the limit values for PBDD/F are set at <1{mu}g/kg (ppb) respectively <5{mu}g/kg (ppb).

  11. Stratonauts pioneers venturing into the stratosphere

    CERN Document Server

    Ehrenfried, Manfred "Dutch"

    2014-01-01

    Stratonauts chronicles humankind’s quest for ever higher altitudes from ancient times to the present. It is based upon history, science and technology, and tells some interesting and fascinating stories along the way. It pays tribute to those killed while attempting to reach the stratosphere over the past several centuries.   “Dutch” von Ehrenfried uses his personal experience as a NASA sensor operator on the RB-57F, flying to an altitude of 70,000 feet, as well as the input and experience from other RB-57F, U-2, A-12, SR-71 and F-104 pilots. Although many of the aircraft and balloons are described, more emphasis is placed on the crews and what they went through. This book is intended for aviators of all kinds and flying enthusiasts in general.

  12. Influence of stratospheric aerosol on albedo

    Energy Technology Data Exchange (ETDEWEB)

    Gormatyuk, Yu K; Kaufman, Yu G; Kolomeev, M P

    1985-06-01

    The influence of stratospheric aerosol (SA) on the transfer of solar radiation in the atmosphere is the principal factor determining the effect of SA on climate. The change in the radiation balance under the influence of SA is computed most precisely in radiative-convective models. However, the complex method used in these models cannot be used for other types of climate models. The objective of the study was to obtain a quantitative evaluation of the influence of SA on albedo without the use of simplifying assumptions. In the approximation of single scattering an expression is derived for change in albedo under the influence of stratospheric aerosol taking into account the dependence of albedo of the atmosphere-earth's surface system on solar zenith distance. The authors give the results of computations of the response of mean annual albedo to sulfuric acid aerosol for 10/sup 0/ latitude zones in the Northern Hemisphere. Specifically, computations of the optical characteristics of aerosol were made using the Mie theory for 10 spectral intervals taking in the range of wavelengths of solar radiation from 0.29 to 4.0 ..mu.. m. The refractive index of aerosol was stipulated in accordance with Palmer and Williams. The angular dependence of albedo for cloudless and cloudy atmospheres given by Harshvardhan was used. The values of undisturbed albedo were assumed to be identical for all wavelengths due to lack of climatological data on the spectral dependence of albedo of the atmosphere-earth's surface system. The angular distribution of the intensity of solar radiation for each of the latitude zones was computed by the method described by I.M. Alekseyev, et al.

  13. Stratospheric sulfate geoengineering impacts on global agriculture

    Science.gov (United States)

    Xia, L.; Robock, A.; Lawrence, P.; Lombardozzi, D.

    2015-12-01

    Stratospheric sulfate geoengineering has been proposed to reduce the impacts of anthropogenic climate change. If it is ever used, it would change agricultural production, and so is one of the future climate scenarios for the third phase of the Global Gridded Crop Model Intercomparison. As an example of those impacts, we use the Community Land Model (CLM-crop 4.5) to simulate how climate changes from the G4 geoengineering scenario from the Geoengineering Modeling Intercomparison Project. The G4 geoengineering scenario specifies, in combination with RCP4.5 forcing, starting in 2020 daily injections of a constant amount of SO2 at a rate of 5 Tg SO2 per year at one point on the Equator into the lower stratosphere. Eight climate modeling groups have completed G4 simulations. We use the crop model to simulate the impacts of climate change (temperature, precipitation, and solar radiation) on the global agriculture system for five crops - rice, maize, soybeans, cotton, and sugarcane. In general, without irrigation, compared with the reference run (RCP4.5), global production of cotton, rice and sugarcane would increase significantly due to the cooling effect. Maize and soybeans show different regional responses. In tropical regions, maize and soybean have a higher yield in G4 compared with RCP4.5, while in the temperate regions they have a lower yield under a geoengineered climate. Impacts on specific countries in terms of different crop production depend on their locations. For example, the United States and Argentina show soybean production reduction of about 15% under G4 compared to RCP4.5, while Brazil increases soybean production by about 10%.

  14. Utilization of oxidation reactions for the spectrophotometric determination of captopril using brominating agents

    Science.gov (United States)

    El-Didamony, Akram M.; Erfan, Eman A. H.

    2010-03-01

    Three simple, accurate and sensitive methods (A-C) for the spectrophotometric assay of captopril (CPL) in bulk drug, in dosage forms and in the presence of its oxidative degradates have been described. The methods are based on the bromination of captopril with a solution of excess brominating mixture in hydrochloric acid medium. After bromination, the excess brominating mixture is followed by the estimation of surplus bromine by three different reaction schemes. In the first method (A), the determination of the residual bromine is based on its ability to bleach the indigo carmine dye and measuring the absorbance at 610 nm. Method B, involves treating the unreacted bromine with a measured excess of iron(II) and the remaining iron(II) is complexed with 1,10-phenanthroline and the increase in absorbance is measured at 510 nm. In method (C), the surplus bromine is treated with excess of iron(II) and the resulting iron(III) is complexed with thiocyanate and the absorbance is measured at 478 nm. In all the methods, the amount of bromine reacted corresponds to the drug content. The different experimental parameters affecting the development and stability of the color are carefully studied and optimized. Beer's law is valid within a concentration range of 0.4-6.0, 0.4-2.8 and 1.2-4.8 μg mL -1 for methods A, B and C, respectively. The calculated apparent molar absorptivity was found to be 5.16 × 10 4, 9.95 × 10 4 and 1.74 × 10 5 L mol -1 cm -1, for methods A, B and C, respectively. Sandell's sensitivity, correlation coefficients, detection and quantification limits are also reported. No interference was observed from common additives found in pharmaceutical preparations. The proposed methods are successfully applied to the determination of CPL in the tablet formulations with mean recoveries of 99.94-100.11% and the results were statistically compared with those of a reference method by applying Student's t- and F-test.

  15. Terminal elimination half-lives of the brominated flame retardants TBBPA, HBCD, and lower brominated PBDEs in humans

    Energy Technology Data Exchange (ETDEWEB)

    Geyer, H.J.; Schramm, K.W.; Feicht, E.A.; Fried, K.W.; Henkelmann, B.; Lenoir, D. [GSF-National Research Center, Institute of Ecological Chemistry, Neuherberg (Germany); Darnerud, P.O.; Aune, M. [Swedish National Food Administration, Uppsala (Sweden); Schmid, P. [Swiss Federal Laboratories for Materials Testing and Research, Laboratory of Organic Chemistry, EMPA Duebendorf (Switzerland); McDonald, T.A. [Office of Environmental Health Assessment, California EPA, Oakland, CA (United States)

    2004-09-15

    Brominated flame retardants (BFRs) are widely used in polymers and textiles and applied in electronic equipment, construction materials, and furniture for the purpose of fire prevention. BFRs with the highest production volume are tetrabromobisphenol A (TBBPA), 1,2,5,6,9,10- hexabromocyclododecanes (HBCDs: {alpha}-HBCD + {beta}-HBCD + {gamma}-HBCD), and polybrominated diphenyl ethers (PBDEs). Several BFRs are highly lipophilic persistent organic pollutants (POPs) which have been identified in the aquatic and terrestrial environment including wildlife and humans. In exposed organisms including humans toxic effects, bioaccumulation, metabolism, and pharmacokinetics (especially half-life t{sub 1/2}) are important criterions in the hazard assessment. The aim of the present study was to estimate the terminal elimination half-lives (t{sub 1/2H}) of the main BFRs from the whole body (also named body-burden half-life) and/or from the adipose tissue (fat) of adult humans. The t{sub 1/2H} data for the following BFRs were evaluated: TBBPA, HBCD, 2,2',4,4'- tetrabromodiphenyl ether (BDE-47), 2,2',4,4',5-pentaBDE (BDE-99), 2,2',4,4',6-pentaBDE (BDE- 100), 2,2',4,4',5,5'-hexaBDE (BDE-153), and 2,2',4,4',5,6-hexaBDE (BDE-154).

  16. Simulation of stratospheric water vapor trends: impact on stratospheric ozone chemistry

    Directory of Open Access Journals (Sweden)

    A. Stenke

    2005-01-01

    Full Text Available A transient model simulation of the 40-year time period 1960 to 1999 with the coupled climate-chemistry model (CCM ECHAM4.L39(DLR/CHEM shows a stratospheric water vapor increase over the last two decades of 0.7 ppmv and, additionally, a short-term increase after major volcanic eruptions. Furthermore, a long-term decrease in global total ozone as well as a short-term ozone decline in the tropics after volcanic eruptions are modeled. In order to understand the resulting effects of the water vapor changes on lower stratospheric ozone chemistry, different perturbation simulations were performed with the CCM ECHAM4.L39(DLR/CHEM feeding the water vapor perturbations only to the chemistry part. Two different long-term perturbations of lower stratospheric water vapor, +1 ppmv and +5 ppmv, and a short-term perturbation of +2 ppmv with an e-folding time of two months were applied. An additional stratospheric water vapor amount of 1 ppmv results in a 5–10% OH increase in the tropical lower stratosphere between 100 and 30 hPa. As a direct consequence of the OH increase the ozone destruction by the HOx cycle becomes 6.4% more effective. Coupling processes between the HOx-family and the NOx/ClOx-family also affect the ozone destruction by other catalytic reaction cycles. The NOx cycle becomes 1.6% less effective, whereas the effectiveness of the ClOx cycle is again slightly enhanced. A long-term water vapor increase does not only affect gas-phase chemistry, but also heterogeneous ozone chemistry in polar regions. The model results indicate an enhanced heterogeneous ozone depletion during antarctic spring due to a longer PSC existence period. In contrast, PSC formation in the northern hemisphere polar vortex and therefore heterogeneous ozone depletion during arctic spring are not affected by the water vapor increase, because of the less PSC activity. Finally, this study shows that 10% of the global total ozone decline in the transient model run

  17. Sea ice and pollution-modulated changes in Greenland ice core methanesulfonate and bromine

    Science.gov (United States)

    Maselli, Olivia J.; Chellman, Nathan J.; Grieman, Mackenzie; Layman, Lawrence; McConnell, Joseph R.; Pasteris, Daniel; Rhodes, Rachael H.; Saltzman, Eric; Sigl, Michael

    2017-01-01

    Reconstruction of past changes in Arctic sea ice extent may be critical for understanding its future evolution. Methanesulfonate (MSA) and bromine concentrations preserved in ice cores have both been proposed as indicators of past sea ice conditions. In this study, two ice cores from central and north-eastern Greenland were analysed at sub-annual resolution for MSA (CH3SO3H) and bromine, covering the time period 1750-2010. We examine correlations between ice core MSA and the HadISST1 ICE sea ice dataset and consult back trajectories to infer the likely source regions. A strong correlation between the low-frequency MSA and bromine records during pre-industrial times indicates that both chemical species are likely linked to processes occurring on or near sea ice in the same source regions. The positive correlation between ice core MSA and bromine persists until the mid-20th century, when the acidity of Greenland ice begins to increase markedly due to increased fossil fuel emissions. After that time, MSA levels decrease as a result of declining sea ice extent but bromine levels increase. We consider several possible explanations and ultimately suggest that increased acidity, specifically nitric acid, of snow on sea ice stimulates the release of reactive Br from sea ice, resulting in increased transport and deposition on the Greenland ice sheet.

  18. Brominated Skeletal Components of the Marine Demosponges, Aplysina cavernicola and Ianthella basta: Analytical and Biochemical Investigations

    Directory of Open Access Journals (Sweden)

    Eike Brunner

    2013-04-01

    Full Text Available Demosponges possess a skeleton made of a composite material with various organic constituents and/or siliceous spicules. Chitin is an integral part of the skeleton of different sponges of the order Verongida. Moreover, sponges of the order Verongida, such as Aplysina cavernicola or Ianthella basta, are well-known for the biosynthesis of brominated tyrosine derivates, characteristic bioactive natural products. It has been unknown so far whether these compounds are exclusively present in the cellular matrix or whether they may also be incorporated into the chitin-based skeletons. In the present study, we therefore examined the skeletons of A. cavernicola and I. basta with respect to the presence of bromotyrosine metabolites. The chitin-based-skeletons isolated from these sponges indeed contain significant amounts of brominated compounds, which are not easily extractable from the skeletons by common solvents, such as MeOH, as shown by HPLC analyses in combination with NMR and IR spectroscopic measurements. Quantitative potentiometric analyses confirm that the skeleton-associated bromine mainly withstands the MeOH-based extraction. This observation suggests that the respective, but yet unidentified, brominated compounds are strongly bound to the sponge skeletons, possibly by covalent bonding. Moreover, gene fragments of halogenases suggested to be responsible for the incorporation of bromine into organic molecules could be amplified from DNA isolated from sponge samples enriched for sponge-associated bacteria.

  19. Removal of brominated flame retardant from electrical and electronic waste plastic by solvothermal technique

    International Nuclear Information System (INIS)

    Zhang, Cong-Cong; Zhang, Fu-Shen

    2012-01-01

    Highlights: ► A process for brominated flame retardants (BFRs) removal in plastic was established. ► The plastic became bromine-free with the structure maintained after this treatment. ► BFRs transferred into alcohol solvent were easily debrominated by metallic copper. - Abstract: Brominated flame retardants (BFRs) in electrical and electronic (E and E) waste plastic are toxic, bioaccumulative and recalcitrant. In the present study, tetrabromobisphenol A (TBBPA) contained in this type of plastic was tentatively subjected to solvothermal treatment so as to obtain bromine-free plastic. Methanol, ethanol and isopropanol were examined as solvents for solvothermal treatment and it was found that methanol was the optimal solvent for TBBPA removal. The optimum temperature, time and liquid to solid ratio for solvothermal treatment to remove TBBPA were 90 °C, 2 h and 15:1, respectively. After the treatment with various alcohol solvents, it was found that TBBPA was finally transferred into the solvents and bromine in the extract was debrominated catalyzed by metallic copper. Bisphenol A and cuprous bromide were the main products after debromination. The morphology and FTIR properties of the plastic were generally unchanged after the solvothermal treatment indicating that the structure of the plastic maintained after the process. This work provides a clean and applicable process for BFRs-containing plastic disposal.

  20. Removal of brominated flame retardant from electrical and electronic waste plastic by solvothermal technique

    Energy Technology Data Exchange (ETDEWEB)

    Zhang, Cong-Cong [Research Center For Eco-Environmental Sciences, Chinese Academy of Sciences, 18 Shuangqing Road, Beijing 100085 (China); Zhang, Fu-Shen, E-mail: fszhang@rcees.ac.cn [Research Center For Eco-Environmental Sciences, Chinese Academy of Sciences, 18 Shuangqing Road, Beijing 100085 (China)

    2012-06-30

    Highlights: Black-Right-Pointing-Pointer A process for brominated flame retardants (BFRs) removal in plastic was established. Black-Right-Pointing-Pointer The plastic became bromine-free with the structure maintained after this treatment. Black-Right-Pointing-Pointer BFRs transferred into alcohol solvent were easily debrominated by metallic copper. - Abstract: Brominated flame retardants (BFRs) in electrical and electronic (E and E) waste plastic are toxic, bioaccumulative and recalcitrant. In the present study, tetrabromobisphenol A (TBBPA) contained in this type of plastic was tentatively subjected to solvothermal treatment so as to obtain bromine-free plastic. Methanol, ethanol and isopropanol were examined as solvents for solvothermal treatment and it was found that methanol was the optimal solvent for TBBPA removal. The optimum temperature, time and liquid to solid ratio for solvothermal treatment to remove TBBPA were 90 Degree-Sign C, 2 h and 15:1, respectively. After the treatment with various alcohol solvents, it was found that TBBPA was finally transferred into the solvents and bromine in the extract was debrominated catalyzed by metallic copper. Bisphenol A and cuprous bromide were the main products after debromination. The morphology and FTIR properties of the plastic were generally unchanged after the solvothermal treatment indicating that the structure of the plastic maintained after the process. This work provides a clean and applicable process for BFRs-containing plastic disposal.

  1. Laboratory investigation of nitrile ices of Titan's stratospheric clouds

    Science.gov (United States)

    Nna Mvondo, D.; Anderson, C. M.; McLain, J. L.; Samuelson, R. E.

    2017-09-01

    Titan's mid to lower stratosphere contains complex cloud systems of numerous organic ice particles comprised of both hydrocarbon and nitrile compounds. Most of these stratospheric ice clouds form as a result of vapor condensation formation processes. However, there are additional ice emission features such as dicyanoacetylene (C4N2) and the 220 cm-1 ice emission feature (the "Haystack") that are difficult to explain since there are no observed vapor emission features associated with these ices. In our laboratory, using a high-vacuum chamber coupled to a FTIR spectrometer, we are engaged in a dedicated investigation of Titan's stratospheric ices to interpret and constrain Cassini Composite InfraRed Spectrometer (CIRS) far-IR data. We will present laboratory transmittance spectra obtained for propionitrile (CH3CH2CN), cyanogen (C2N2) and hydrogen cyanide (HCN) ices, as well as various combinations of their mixtures, to better understand the cloud chemistry occurring in Titan's stratosphere.

  2. Exposing Microorganisms in the Stratosphere for Planetary Protection

    Data.gov (United States)

    National Aeronautics and Space Administration — Earth’s stratosphere is similar to the surface of Mars: rarified air which is dry, cold, and irradiated. E-MIST is a balloon payload that has 4 independently...

  3. Is there any chlorine monoxide in the stratosphere?

    Science.gov (United States)

    Mumma, M. J.; Rogers, J. D.; Kostiuk, T.; Deming, D.; Hillman, J. J.; Zipoy, D.

    1983-01-01

    A ground-based search for stratospheric 35-ClO was carried out using an infrared heterodyne spectrometer in the solar absorption mode. Lines due to stratospheric HNO3 and tropospheric OCS were detected at about 0.2 percent absorptance levels, but the expected 0.1 percent lines of ClO in this same region were not seen. We find that stratospheric ClO is at least a factor of seven less abundant than is indicated by in situ measurements, and we set an upper limit of 2.3 x 10 to the 13th molecules/sq cm at the 95 percent confidence level for the integrated vertical column density of ClO. Our results imply that the release of chlorofluorocarbons may be significantly less important for the destruction of stratospheric ozone (O3) than is currently thought. Previously announced in STAR as N83-27518

  4. Possible effects of volcanic eruptions on stratospheric minor constituent chemistry

    Science.gov (United States)

    Stolarski, R. S.; Butler, D. M.

    1979-01-01

    Although stratosphere penetrating volcanic eruptions have been infrequent during the last half century, periods have existed in the last several hundred years when such eruptions were significantly more frequent. Several mechanisms exist for these injections to affect stratospheric minor constituent chemistry, both on the long-term average and for short-term perturbations. These mechanisms are reviewed and, because of the sensitivity of current models of stratospheric ozone to chlorine perturbations, quantitative estimates are made of chlorine injection rates. It is found that, if chlorine makes up as much as 0.5 to 1% of the gases released and if the total gases released are about the same magnitude as the fine ash, then a major stratosphere penetrating eruption could deplete the ozone column by several percent. The estimate for the Agung eruption of 1963 is just under 1% an amount not excluded by the ozone record but complicated by the peak in atmospheric nuclear explosions at about the same time.

  5. The Temperature of the Arctic and Antarctic Lower Stratosphere

    Science.gov (United States)

    Newman, Paul A.; Nash, Eric R.; Bhartia, P. K. (Technical Monitor)

    2002-01-01

    The temperature of the polar lower stratosphere during spring is the key factor in changing the magnitude of ozone loss in the polar vortices. In this talk, we will review the results of Newman et al. [2000] that quantitatively demonstrate that the polar lower stratospheric temperature is primarily controlled by planetary-scale waves. In particular, the tropospheric eddy heat flux in middle to late winter (January--February) is highly correlated with the mean polar stratospheric temperature during March. Strong midwinter planetary wave forcing leads to a warmer spring Arctic lower stratosphere in early spring, while weak midwinter forcing leads to cooler spring Arctic temperatures. In addition, this planetary wave driving also has a strong impact on the strength of the polar vortex. These results from the Northern Hemisphere will be contrasted with the Southern Hemisphere.

  6. Human health risk associated with brominated flame-retardants (BFRs).

    Science.gov (United States)

    Lyche, Jan L; Rosseland, Carola; Berge, Gunnar; Polder, Anuschka

    2015-01-01

    The purposes of this review are to assess the human exposure and human and experimental evidence for adverse effects of brominated flame-retardants (BFRs) with specific focus on intake from seafood. The leakage of BFRs from consumer products leads to exposure of humans from fetal life to adulthood. Fish and fish products contain the highest levels of BFRs and dominate the dietary intake of frequent fish eaters in Europe, while meat, followed by seafood and dairy products accounted for the highest US dietary intake. House dust is also reported as an important source of exposure for children as well as adults. The levels of BFRs in the general North American populations are higher than those in Europe and Japan and the highest levels are detected in infants and toddlers. The daily intake via breast milk exceeds the RfD in 10% of US infants. BFRs including PBDEs, HBCDs and TBBP-A have induced endocrine-, reproductive- and behavior effects in laboratory animals. Furthermore, recent human epidemiological data demonstrated association between exposure to BFRs and similar adverse effects as observed in animal studies. Fish including farmed fish and crude fish oil for human consumption may contain substantial levels of BFRs and infants and toddlers consuming these products on a daily basis may exceed the tolerable daily intake suggesting that fish and fish oil alone represent a risk to human health. This intake comes in addition to exposure from other sources (breast milk, other food, house dust). Because potential harmful concentrations of BFRs and other toxicants occur in fish and fish products, research on a wider range of products is warranted, to assess health hazard related to the contamination of fish and fish products for human consumption. Copyright © 2014. Published by Elsevier Ltd.

  7. Comparison between Two Bromine Containing Free Radical Initiators in PRESAGE®

    Energy Technology Data Exchange (ETDEWEB)

    Park, Hyeonsuk; Ryu, Dongmin; Ye, Sung-Joon [Seoul National University, Seoul (Korea, Republic of)

    2016-10-15

    PRESAGE® is an optically clear 3-D polyurethane dosimeter which contains a halogenated carbon as a free radical initiator and leucomalachite dye. The change of the optical density is known to be linear with respect to the absorbed dose and the sensitivity is related to the carbon–halogen bond dissociation energy of the free radical initiator. Although there are some studies regarding free radical initiators and dye materials, there’s a lack of reports about the effect of other elements like LMG solvent which can be added when there’s a difficulty mixing materials. Also, there are some studies about comparison between free radicals with different kind of halogen atoms but there’s a lack of studies of comparison between initiators with the same halogen atom. In this experiments, two kinds of halocarbon free radical initiator with the same halogen atom (bromine) as well as the effect of the LMG solvent were studied to use the dosimeter as a therapeutic purpose. Effective atomic numbers were also calculated. The initiators with the same halogen atom, CBr{sub 4} and C{sub 2}H{sub 2}Br{sub 4}, reacted totally differently. CBr{sub 4} was more sensitive to the radiation and emitted maximum 4 times more free radicals upon irradiation with no additional effective atomic number but the absorbance after irradiation was highly variable with time. For stable measurement, C{sub 2}H{sub 2}Br{sub 4} would be more appropriate as a free radical initiator.

  8. Extended analysis of fifth spectrum of bromine: Br V

    International Nuclear Information System (INIS)

    Riyaz, A.; Tauheed, A.; Rahimullah, K.

    2014-01-01

    The fifth spectrum of bromine (Br V) has been studied in the 200–2400 Å wavelength region. The spectrum was photographed on a 3-m normal incidence vacuum spectrograph at the St. Francis Xavier University, Antigonish (Canada) and 6.65-m grazing incidence spectrograph at the Zeeman laboratory (Amsterdam). The light sources used were a triggered spark and sliding spark. The ground configuration of Br V is 4s 2 4p. The excited configurations 4s4p 2 +4s 2 (4d+5d+5s+6s+7s+5g+6g)+4s4p(5p+4f)+4p 2 4d in the even parity system and the 4p 3 +4s 2 (5p+6p+7p+4f)+4s4p4d+4s4p5s configurations in the odd parity system have been studied. Relativistic Hartree–Fock (HFR) and least squares fitted (LSF) parametric calculations have been used to interpret the observed spectrum. 99 levels of Br V have now been established, 43 being new. Among 394 classified spectral lines, 181 are newly classified. The level 4s 2 7s 2 S 1/2 is revised. We estimate the accuracy of our measured wavelengths for sharp and unblended lines to be±0.005 Å. The ionization limit is determined as 479,657±200 cm −1 (59.470±0.025 eV). - Highlights: • The spectrum of Br was recorded on a 3-m spectrograph with triggered spark source. • Atomic transitions for Br V were identified to established new energy levels. • CI calculations with relativistic corrections were made for theoretical predictions. • Weighted oscillator strength (gf) and transition probabilities (gA) were calculated. • Ionization potential of Br V was determined experimentally

  9. Sulphur-rich volcanic eruptions and stratospheric aerosols

    Science.gov (United States)

    Rampino, M. R.; Self, S.

    1984-01-01

    Data from direct measurements of stratospheric optical depth, Greenland ice-core acidity, and volcanological studies are compared, and it is shown that relatively small but sulfur-rich volcanic eruptions can have atmospheric effects equal to or even greater than much larger sulfur-poor eruptions. These small eruptions are probably the most frequent cause of increased stratospheric aerosols. The possible sources of the excess sulfur released in these eruptions are discussed.

  10. Long-term evolution of upper stratospheric ozone at selected stations of the Network for the Detection of Stratospheric Change (NDSC)

    NARCIS (Netherlands)

    Steinbrecht, W; Claude, H; Schönenborn, F; McDermid, I S; Leblanc, T; Godin, S; Song, T; Swart, D P J; Meijer, Y J; Bodeker, G E; Connor, B J; Kämpfer, N; Hocke, K; Calisesi, Y; Schneider, N; Noë, J de la; Parrish, A D; Boyd, I S; Brühl, C; Steil, B; Giorgetta, M A; Manzini, E; Thomason, L W; Zawodny, J M; McCormick, M P; Russell, J M; Bhartia, P K; Stolarski, R S; Hollandsworth-Frith, S M

    2006-01-01

    The long-term evolution of upper stratospheric ozone has been recorded by lidars and microwave radiometers within the ground-based Network for the Detection of Stratospheric Change (NDSC), and by the space-borne Solar Backscatter Ultra-Violet instruments (SBUV), Stratospheric Aerosol and Gas

  11. Bromine-77-labeled estrogen receptor-binding radiopharmaceuticals for breast tumor imaging

    International Nuclear Information System (INIS)

    McElvany, K.D.

    1985-01-01

    Two derivatives of 16α-bromoestradiol, both with and without an 11β-methoxy substituent, have been labeled with bromine-77 and evaluated as potential breast tumor imaging agents. Extensive characterization of these radiotracers in animal models has demonstrated their effective concentration in estrogen target tissues. Preliminary clinical studies have demonstrated the potential of radiolabeled estrogens for breast tumor imaging; however, the suboptimal decay properties of bromine-77 limit the utility of these agents in imaging studies. These results with 77 -Br-labeled estrogens suggest that estrogen derivatives labeled with other radionuclides should provide enhanced image resolution with various imaging devices. Although the decay characteristics of bromine-77 are such that it is not ideally suited to imaging with conventional gamma cameras, it may be a useful radionuclide for therapeutic applications

  12. Determination by neutron activation analysis of loss of arsenic, antimony, bromine and mercury during lyophilization

    International Nuclear Information System (INIS)

    Carlson, M.; Litman, R.

    1978-01-01

    Neutron activation analysis has been used to monitor the loss of arsenic, as dimethylarsinic acid, (CH 3 ) 2 AsOOH, or as sodium arsenate (Na 2 HAsO 4 .7H 2 O), antimony (as potassium antimony, tartrate, KSbC 4 O 7 .1/2H 2 O) and bromine (as bromide ion) during lyophilization of acidified and neutral aqueous synthetic and environmental samples. Losses of Sb and As ranged from zero to 60%, while losses of bromine were constant (at 91%) in acidic solutions. The variable losses of As and Sb were due solely to the presence of and partial decomposition of the (CH 3 ) 2 AsOOH. Electrochemical oxidation of Br - to Br 2 is responsible for the high losses of bromine. In addition losses of mercury (as methylmercuric chloride) were 1O0% in both acidic and neutral aqueous synthetic samples during lyophilization. (author)

  13. Use of bromine as biocide in cooling waters (Preprint No. CA-19)

    Energy Technology Data Exchange (ETDEWEB)

    Sriraman, A K [Bhabha Atomic Research Centre, Bombay (India). Water Chemistry Div.

    1989-04-01

    In all fresh water circuits, the slime forming bacteria develop an insulating layer on the condenser surfaces. If these bacteria are not controlled, they induce bacterial promoted corrosion of the materials in contact with cooling water. Chlorination is effective against slime forming bacteria, fungi and algae. The algistatic nature of the chlorine is partly compensated by the use of other non-oxidisable biocides. Amongst the various alternative biocides such as bromine, methyl bis-isocyanate, sodium pentachlorophenate etc, bromine is the most simple biocide, which is being increasingly used in cooling water systems. In this context, the chemistry of bromination and its bactericidal properties is examined along with those of chlorination. (author). 7 refs., 3 tabs., 2 figs.

  14. Effect of greenhouse gas emissions on stratospheric ozone depletion

    NARCIS (Netherlands)

    Velders GJM; LLO

    1997-01-01

    The depletion of the ozone layer is caused mainly by the increase in emissions of chlorine- and bromine-containing compounds like CFCs, halons, carbon tetrachloride, methyl chloroform and methyl bromide. Emissions of greenhouse gases can affect the depletion of the ozone layer through atmospheric

  15. Transport of Ice into the Stratosphere and the Humidification of the Stratosphere over the 21st Century

    Science.gov (United States)

    Dessler, A. E.; Ye, H.; Wang, T.; Schoeberl, M. R.; Oman, L. D.; Douglass, A. R.; Butler, A. H.; Rosenlof, K. H.; Davis, S. M.; Portmann, R. W.

    2016-01-01

    Climate models predict that tropical lower-stratospheric humidity will increase as the climate warms. We examine this trend in two state-of-the-art chemistry-climate models. Under high greenhouse gas emissions scenarios, the stratospheric entry value of water vapor increases by approx. 1 part per million by volume (ppmv) over this century in both models. We show with trajectory runs driven by model meteorological fields that the warming tropical tropopause layer (TTL) explains 50-80% of this increase. The remainder is a consequence of trends in evaporation of ice convectively lofted into the TTL and lower stratosphere. Our results further show that, within the models we examined, ice lofting is primarily important on long time scales - on interannual time scales, TTL temperature variations explain most of the variations in lower stratospheric humidity. Assessing the ability of models to realistically represent ice-lofting processes should be a high priority in the modeling community.

  16. Regional variation and possible sources of brominated contaminants in breast milk from Japan

    International Nuclear Information System (INIS)

    Fujii, Yukiko; Ito, Yoshiko; Harada, Kouji H.; Hitomi, Toshiaki; Koizumi, Akio; Haraguchi, Koichi

    2012-01-01

    This study focuses on the regional trends and possible sources of brominated organic contaminants accumulated in breast milk from mothers in southeastern (Okinawa) and northwestern (Hokkaido) areas of Japan. For persistent brominated flame retardants, polybrominated diphenyl ethers (PBDEs; major components, BDE-47 and BDE-153) were distributed at higher levels in mothers from Okinawa (mean, 2.1 ng/g lipid), while hexabromobenzene (HeBB) and its metabolite 1,2,4,5-tetrabromobenzene were more abundantly detected in mothers from Hokkaido (0.86 and 2.6 ng/g lipid), suggesting that there are regional differences in their exposure in Japan. We also detected naturally produced brominated compounds, one of which was identified as 2′-methoxy-2,3′,4,5′-tetrabromodiphenyl ether (2′-MeO-BDE68) at higher levels in mothers from Okinawa (0.39 ng/g lipid), while the other was identified as 3,3′,4,4′-tetrabromo-5,5′-dichloro-2,2′-dimethyl-1,1′-bipyrrole in mothers from Hokkaido (0.45 ng/g lipid). The regional variation may be caused by source differences, i.e. southern seafood for MeO-PBDEs and northern biota for halogenated bipyrroles in the Japanese coastal water. - Highlights: ► In this study, we detected brominated organic contaminants in Japanese breast milk. ► Naturally produced brominated organic contaminants were also detected. ► Northern and southern Japan showed regional differences in these contaminants. ► Exposure to the contaminants is suggested to arise from different specific sources. - Brominated organic contaminants were detected in Japanese breast milk.

  17. Complete Reductive Dehalogenation of Brominated Biphenyls by Anaerobic Microorganisms in Sediment

    Science.gov (United States)

    Bedard, Donna L.; Van Dort, Heidi M.

    1998-01-01

    We sought to determine whether microorganisms from the polychlorinated biphenyl (PCB)-contaminated sediment in Woods Pond (Lenox, Mass.) could dehalogenate brominated biphenyls. The PCB dechlorination specificities for the microorganisms in this sediment have been well characterized. This allowed us to compare the dehalogenation specificities for brominated biphenyls and chlorinated biphenyls within a single sediment. Anaerobic sediment microcosms were incubated separately at 25°C with 16 different mono- to tetrabrominated biphenyls (350 μM) and disodium malate (10 mM). Samples were extracted and analyzed by gas chromatography with an electron capture detector and a mass spectrometer detector at various times for up to 54 weeks. All of the tested brominated biphenyls were dehalogenated. For most congeners, including 2,6-dibromobiphenyl (26-BB) and 24-25-BB, the dehalogenation began within 1 to 2 weeks. However, for 246-BB and 2-2-BB, debromination was first observed at 7 and 14 weeks, respectively. Most intermediate products did not persist, but when 2-2-BB was produced as a dehalogenation product, it persisted for at least 15 weeks before it was dehalogenated to 2-BB and then to biphenyl. The dehalogenation specificities for brominated and chlorinated biphenyls were similar: meta and para substituents were generally removed first, and ortho substituents were more recalcitrant. However, the brominated biphenyls were better dehalogenation substrates than the chlorinated biphenyls. All of the tested bromobiphenyls, including those with ortho and unflanked meta and para substituents, were ultimately dehalogenated to biphenyl, whereas their chlorinated counterparts either were not dehalogenation substrates or were only partially dehalogenated. Our data suggest that PCB-dechlorinating microorganisms may be able to dehalogenate brominated biphenyls and may exhibit a relaxed specificity for these substrates. PMID:16349530

  18. Bromination of Marine Dissolved Organic Matter following Full Scale Electrochemical Ballast Water Disinfection.

    Science.gov (United States)

    Gonsior, Michael; Mitchelmore, Carys; Heyes, Andrew; Harir, Mourad; Richardson, Susan D; Petty, William Tyler; Wright, David A; Schmitt-Kopplin, Philippe

    2015-08-04

    An extensively diverse array of brominated disinfection byproducts (DBPs) were generated following electrochemical disinfection of natural coastal/estuarine water, which is one of the main treatment methods currently under consideration for ballast water treatment. Ultra-high-resolution mass spectrometry revealed 462 distinct brominated DBPs at a relative abundance in the mass spectra of more than 1%. A brominated DBP with a relative abundance of almost 22% was identified as 2,2,4-tribromo-5-hydroxy-4-cyclopentene-1,3-dione, which is an analogue to several previously described 2,2,4-trihalo-5-hydroxy-4-cyclopentene-1,3-diones in drinking water. Several other brominated molecular formulas matched those of other known brominated DBPs, such as dibromomethane, which could be generated by decarboxylation of dibromoacetic acid during ionization, dibromophenol, dibromopropanoic acid, dibromobutanoic acid, bromohydroxybenzoic acid, bromophenylacetic acid, bromooxopentenoic acid, and dibromopentenedioic acid. Via comparison to previously described chlorine-containing analogues, bromophenylacetic acid, dibromooxopentenoic acid, and dibromopentenedioic acid were also identified. A novel compound at a 4% relative abundance was identified as tribromoethenesulfonate. This compound has not been previously described as a DBP, and its core structure of tribromoethene has been demonstrated to show toxicological implications. Here we show that electrochemical disinfection, suggested as a candidate for successful ballast water treatment, caused considerable production of some previously characterized DBPs in addition to novel brominated DBPs, although several hundred compounds remain structurally uncharacterized. Our results clearly demonstrate that electrochemical and potentially direct chlorination of ballast water in estuarine and marine systems should be approached with caution and the concentrations, fate, and toxicity of DBP need to be further characterized.

  19. Delivery of halogenated very short-lived substances from the west Indian Ocean to the stratosphere during the Asian summer monsoon

    Directory of Open Access Journals (Sweden)

    A. Fiehn

    2017-06-01

    Full Text Available Halogenated very short-lived substances (VSLSs are naturally produced in the ocean and emitted to the atmosphere. When transported to the stratosphere, these compounds can have a significant influence on the ozone layer and climate. During a research cruise on RV Sonne in the subtropical and tropical west Indian Ocean in July and August 2014, we measured the VSLSs, methyl iodide (CH3I and for the first time bromoform (CHBr3 and dibromomethane (CH2Br2, in surface seawater and the marine atmosphere to derive their emission strengths. Using the Lagrangian particle dispersion model FLEXPART with ERA-Interim meteorological fields, we calculated the direct contribution of observed VSLS emissions to the stratospheric halogen burden during the Asian summer monsoon. Furthermore, we compare the in situ calculations with the interannual variability of transport from a larger area of the west Indian Ocean surface to the stratosphere for July 2000–2015. We found that the west Indian Ocean is a strong source for CHBr3 (910 pmol m−2 h−1, very strong source for CH2Br2 (930 pmol m−2 h−1, and an average source for CH3I (460 pmol m−2 h−1. The atmospheric transport from the tropical west Indian Ocean surface to the stratosphere experiences two main pathways. On very short timescales, especially relevant for the shortest-lived compound CH3I (3.5 days lifetime, convection above the Indian Ocean lifts oceanic air masses and VSLSs towards the tropopause. On a longer timescale, the Asian summer monsoon circulation transports oceanic VSLSs towards India and the Bay of Bengal, where they are lifted with the monsoon convection and reach stratospheric levels in the southeastern part of the Asian monsoon anticyclone. This transport pathway is more important for the longer-lived brominated compounds (17 and 150 days lifetime for CHBr3 and CH2Br2. The entrainment of CHBr3 and CH3I from the west Indian Ocean to the stratosphere during the

  20. 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.

  1. Effects of Greenhouse Gas Increase and Stratospheric Ozone Depletion on Stratospheric Mean Age of Air in 1960-2010

    Science.gov (United States)

    Li, Feng; Newman, Paul; Pawson, Steven; Perlwitz, Judith

    2018-01-01

    The relative impacts of greenhouse gas (GHG) increase and stratospheric ozone depletion on stratospheric mean age of air in the 1960-2010 period are quantified using the Goddard Earth Observing System Chemistry-�Climate Model. The experiment compares controlled simulations using a coupled atmosphere-�ocean version of the Goddard Earth Observing System Chemistry-�Climate Model, in which either GHGs or ozone depleting substances, or both factors evolve over time. The model results show that GHGs and ozone-depleting substances have about equal contributions to the simulated mean age decrease, but GHG increases account for about two thirds of the enhanced strength of the lower stratospheric residual circulation. It is also found that both the acceleration of the diabatic circulation and the decrease of the mean age difference between downwelling and upwelling regions are mainly caused by GHG forcing. The results show that ozone depletion causes an increase in the mean age of air in the Antarctic summer lower stratosphere through two processes: (1) a seasonal delay in the Antarctic polar vortex breakup that inhibits young midlatitude air from mixing with the older air inside the vortex, and (2) enhanced Antarctic downwelling that brings older air from middle and upper stratosphere into the lower stratosphere.

  2. Impacts of Stratospheric Black Carbon on Agriculture

    Science.gov (United States)

    Xia, L.; Robock, A.; Elliott, J. W.

    2017-12-01

    A regional nuclear war between India and Pakistan could inject 5 Tg of soot into the stratosphere, which would absorb sunlight, decrease global surface temperature by about 1°C for 5-10 years and have major impacts on precipitation and the amount of solar radiation reaching Earth's surface. Using two global gridded crop models forced by one global climate model simulation, we investigate the impacts on agricultural productivity in various nations. The crop model in the Community Land Model 4.5 (CLM-crop4.5) and the parallel Decision Support System for Agricultural Technology (pDSSAT) in the parallel System for Integrating Impact Models and Sectors are participating in the Global Gridded Crop Model Intercomparison. We force these two crop models with output from the Whole Atmospheric Community Climate Model to characterize the global agricultural impact from climate changes due to a regional nuclear war. Crops in CLM-crop4.5 include maize, rice, soybean, cotton and sugarcane, and crops in pDSSAT include maize, rice, soybean and wheat. Although the two crop models require a different time frequency of weather input, we downscale the climate model output to provide consistent temperature, precipitation and solar radiation inputs. In general, CLM-crop4.5 simulates a larger global average reduction of maize and soybean production relative to pDSSAT. Global rice production shows negligible change with climate anomalies from a regional nuclear war. Cotton and sugarcane benefit from a regional nuclear war from CLM-crop4.5 simulation, and global wheat production would decrease significantly in the pDSSAT simulation. The regional crop yield responses to a regional nuclear conflict are different for each crop, and we present the changes in production on a national basis. These models do not include the crop responses to changes in ozone, ultraviolet radiation, or diffuse radiation, and we would like to encourage more modelers to improve crop models to account for those

  3. Photochemistry of pyrene with water at low temperature: study of atmospherical and astrochemical interest.

    Science.gov (United States)

    Guennoun, Zohra; Aupetit, Christian; Mascetti, Joëlle

    2011-03-17

    Photochemistry of a polyaromatic hydrocarbon, pyrene C(16)H(10), with water has been investigated at cryogenic temperatures. Photoprocessing of this species, performed at λ > 235 nm, in argon matrices, adsorbed onto amorphous water surfaces, and trapped in solid water, led to the formation of ketonic isomers, C(16)H(10)O, and possibly quinones. These species have been identified for the first time by infrared spectroscopy with the support of isotopic substitution experiments and DFT calculations. These oxidized pyrene-like species, of atmospherical and astrochemical interest, most likely arise from a tautomeric rearrangement of their analogous hydroxylated molecules, these latter being formed by reaction of water with pyrene cations.

  4. 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.

  5. Photochemistry of methane and the formation of hydrocyanic acid (HCN) in the earth's early atmosphere

    Science.gov (United States)

    Zahnle, K. J.

    1986-01-01

    A one-dimensional photochemical model is used to analyze the photochemistries of CH4 and HCN in the primitive terrestrial atmosphere. CH4, N2, and HCN photolysis are examined. The background atmosphere and boundary conditions applied in the analysis are described. The formation of HCN as a by-product of N2 and CH4 photolysis is investigated; the effects of photodissociation and rainfall on HCN is discussed. The low and high CH4 mixing ratios and radical densities are studied.

  6. Modulations of stratospheric ozone by volcanic eruptions

    Science.gov (United States)

    Blanchette, Christian; Mcconnell, John C.

    1994-01-01

    We have used a time series of aerosol surface based on the measurements of Hofmann to investigate the modulation of total column ozone caused by the perturbation to gas phase chemistry by the reaction N2O5(gas) + H2O(aero) yields 2HNO3(gas) on the surface of stratospheric aerosols. We have tested a range of values for its reaction probability, gamma = 0.02, 0.13, and 0.26 which we compared to unperturbed homogeneous chemistry. Our analysis spans a period from Jan. 1974 to Oct. 1994. The results suggest that if lower values of gamma are the norm then we would expect larger ozone losses for highly enhanced aerosol content that for larger values of gamma. The ozone layer is more sensitive to the magnitude of the reaction probability under background conditions than during volcanically active periods. For most conditions, the conversion of NO2 to HNO3 is saturated for reaction probability in the range of laboratory measurements, but is only absolutely saturated following major volcanic eruptions when the heterogeneous loss dominates the losses of N2O5. The ozone loss due to this heterogeneous reaction increases with the increasing chlorine load. Total ozone losses calculated are comparable to ozone losses reported from TOMS and Dobson data.

  7. HIGH-TEMPERATURE PHOTOCHEMISTRY IN THE ATMOSPHERE OF HD 189733b

    International Nuclear Information System (INIS)

    Line, M. R.; Yung, Y. L.; Liang, M. C.

    2010-01-01

    Recent infrared spectroscopy of hot exoplanets is beginning to reveal their atmospheric composition. Deep within the planetary atmosphere, the composition is controlled by thermochemical equilibrium. Photochemistry becomes important higher in the atmosphere, at levels above ∼1 bar. These two chemistries compete between ∼1 and 10 bars in hot-Jupiter-like atmospheres, depending on the strength of the eddy mixing and temperature. HD 189733b provides an excellent laboratory in which to study the consequences of chemistry of hot atmospheres. The recent spectra of HD 189733b contain signatures of CH 4 , CO 2 , CO, and H 2 O. Here we identify the primary chemical pathways that govern the abundances of CH 4 , CO 2 , CO, and H 2 O in the cases of thermochemical equilibrium chemistry, photochemistry, and their combination. Our results suggest that the disequilibrium mechanisms can significantly enhance the abundances of these species above their thermochemical equilibrium value, so some caution must be taken when assuming that an atmosphere is in strict thermochemical equilibrium.

  8. General patterns in the photochemistry of pregna-1,4-dien-3,20-diones.

    Science.gov (United States)

    Ricci, Andrea; Fasani, Elisa; Mella, Mariella; Albini, Angelo

    2003-05-30

    The photochemistry of six pregna-1,4-dien-3,20-diones has been compared and found to involve both the cyclohexadienone moiety in ring A and the isolated ketone at C-20. The two reactions take place proportionally to the fraction of light absorbed by each chromophore. The cross-conjugated ketone absorbs predominantly or exclusively at both 254 and 366 nm and undergoes the "lumi" rearrangement to bicyclo[3.1.0]hex-3-en-2-one. The quantum yield of the reaction diminished somewhat with increasing lambda(exc), e.g., for prednisolone Phi(254) (nm) = 0.42, Phi(366) (nm) = 0.3. A much stronger lowering is caused by halogen substitution in position 9 (by a factor of 3 for F, >50 for Cl), apparently due to a shortened triplet lifetime caused by heavy atom effect. At 310 nm, both chromophores absorb to a comparable degree and both may react. The reaction at C(20) ketone involves either quite efficient alpha-cleavage (C(17)-C(20)) for compounds bearing an acetal or hydroxyl function at C(17) or less effective (by a factor of ca. 10) hydrogen abstraction from the 18-methyl group in the other cases (finally resulting in Norrish II fragmentation or Yang cyclization). The results allow generalizing how the substitution pattern surrounding each chromophore affects the photoreactivity at that site and the competition between the two modes, allowing predicting the photochemistry of this family of antiinflammatory drugs.

  9. Modeling of synchrotron-based laboratory simulations of Titan's ionospheric photochemistry

    Science.gov (United States)

    Carrasco, Nathalie; Peng, Zhe; Pernot, Pascal

    2014-11-01

    The APSIS reactor has been designed to simulate in the laboratory with a VUV synchrotron irradiation the photochemistry occurring in planetary upper atmospheres. A N2-CH4 Titan-like gas mixture has been studied, whose photochemistry in Titan's ionospheric irradiation conditions leads to a coupled chemical network involving both radicals and ions. In the present work, an ion-neutral coupled model is developed to interpret the experimental data, taking into account the uncertainties on the kinetic parameters by Monte Carlo sampling. The model predicts species concentrations in agreement with mass spectrometry measurements of the methane consumption and product blocks intensities. Ion chemistry and in particular dissociative recombination are found to be very important through sensitivity analysis. The model is also applied to complementary environmental conditions, corresponding to Titan's ionospheric average conditions and to another existing synchrotron setup. An innovative study of the correlations between species concentrations identifies two main competitive families, leading respectively to saturated and unsaturated species. We find that the unsaturated growth family, driven by C2H2 , is dominant in Titan's upper atmosphere, as observed by the Cassini INMS. But the saturated species are substantially more intense in the measurements of the two synchrotron experimental setups, and likely originate from catalysis by metallic walls of the reactors.

  10. VUV spectroscopy and photochemistry of five interstellar and putative prebiotic molecules

    Science.gov (United States)

    Schwell, M.; Gaie-Levrel, F.; Bénilan, Y.; Gazeau, M.-C.; Fray, N.; Saul, G.; Champion, N.; Leach, S.; Guillemin, J.-C.

    2012-02-01

    For many years, our group has been investigating the VUV spectroscopy and photochemistry of molecules of astrophysical (Jochims et al. 2006a,b; Leach et al. 2008; Schwell et al. 2012) and prebiotic interest (Schwell et al. 2006). Polyynes and cyano-polyynes that are abundant in the interstellar medium (ISM) and in planetary atmospheres, have been investigated too (e.g. Fray et al. 2010). An aerosol source for reactive and thermo-labile compounds has been developed (Gaie-Levrel et al. 2011) to perform gas-phase measurements. These are necessary to measure intrinsic molecular properties and to compare to quantum chemical calculations. Besides measuring absolute absorption and photoionization cross sections, dissociative channels and their involved excited states are identified for a number of molecules of interstellar interest. Branching ratios of the respective elementary photoreactions are determined in order to understand and model the photochemistry occurring in the ISM. Some very recent results on the dissociative photoionization of methylformate (MF), glycolaldehyde (GA), dimethylether (DIM), aminoacetonitrile (AAC) and cyanoacetylene (CA), are presented here.

  11. Unintentional production of persistent chlorinated and brominated organic pollutants during iron ore sintering processes.

    Science.gov (United States)

    Li, Sumei; Liu, Guorui; Zheng, Minghui; Liu, Wenbin; Li, Jinhui; Wang, Mei; Li, Changliang; Chen, Yuan

    2017-06-05

    Iron ore sintering (SNT) processes are major sources of unintentionally produced chlorinated persistent organic pollutants (POPs), including polychlorinated dibenzo-p-dioxins/dibenzofurans (PCDD/Fs), polychlorinated biphenyls (PCBs), and polychlorinated naphthalenes (PCNs). However, few studies of emissions of brominated POPs, such as polybrominated dibenzo-p-dioxins/dibenzofurans (PBDD/Fs) and polybrominated diphenyl ethers (PBDEs), during SNT have been performed. Stack gas and fly ash samples from six typical SNT plants in China were collected and analyzed to determine the concentrations and profiles of PCDD/Fs, PCBs, PCNs, PBDD/Fs, and PBDEs, as well as any correlations among these compounds. The PCDD/F, PCB, PCN, PBDD/F, and PBDE emission factors were 2.47, 0.61, 552, 0.32, and 107μgt -1 , respectively (109, 4.07, 10.4, 4.41 and 0.02ng toxic equivalents t -1 , respectively). PCBs were the most abundant compounds by mass, while PCNs were the next most abundant, contributing 51% and 42% to the total POP concentration, respectively. However, PCDD/Fs were the dominant contributors to the chlorinated and brominated POP toxic equivalent concentrations, contributing 89% to the total toxic equivalent concentration. The PCDD/F and other chlorinated and brominated POP concentrations were positively correlated, indicating that chlorinated and brominated POP emissions could be synergistically decreased using the best available technologies/best environmental practices already developed for PCDD/Fs. Copyright © 2017 Elsevier B.V. All rights reserved.

  12. Interaction of chelate cyclopentadienyl compounds of zirconium and hafnium with bromine

    International Nuclear Information System (INIS)

    Brajnina, Eh.M.; Minacheva, M.Kh.

    1975-01-01

    Interaction of bromine with Zr and Hf dibenzoylmethane (DBM) compounds of following type: (DBM) 4 M, CpM(DBM) 3 and Cp 2 M(DBM) 2 leads to the formation of (DBM) 2 MBr 2 , (DBM) 3 MBr and CpZr(DBM) 2 Br in the rations which depend on the conditions of the reaction (Cp=C 5 H 5 )

  13. XAS AND XPS CHARACTERIZATION OF MERCURY BINDING ON BROMINATED ACTIVATED CARBON

    Science.gov (United States)

    Brominated powdered activated carbon sorbents have been shown to e quite effective for mercury capture when injected into the flue gas duct at coal-fired power plants and are especially useful when buring Western low-chlorine subbituminous coals. X-ray absorption spectroscopy (X...

  14. Degradation of brominated flame retardant in computer housing plastic by supercritical fluids.

    Science.gov (United States)

    Wang, Yanmin; Zhang, Fu-Shen

    2012-02-29

    The degradation process of brominated flame retardant (BFR) and BFR-containing waste computer housing plastic in various supercritical fluids (water, methanol, isopropanol and acetone) was investigated. The results showed that the debromination and degradation efficiencies, final products were greatly affected by the solvent type. Among the four tested solvents, isopropanol was the most suitable solvent for the recovery of oil from BFR-containing plastic for its (1) excellent debromination effectiveness (debromination efficiency 95.7%), (2) high oil production (60.0%) and (3) mild temperature and pressure requirements. However, in this case, the removed bromine mostly existed in the oil. Introduction of KOH into the sc-isopropanol could capture almost all the inorganic bromine from the oil thus bromine-free oil could be obtained. Furthermore, KOH could enhance the depolymerization of the plastic. The obtained oil mainly consisted of single- and duplicate-ringed aromatic compounds in a carbon range of C9-C17, which had alkyl substituents or aliphatic bridges, such as butyl-benzene, (3-methylbutyl)-benzene, 1,1'-(1,3-propanediyl)bis benzene. Phenol, alkyl phenols and esters were the major oxygen-containing compounds in the oil. This study provides an efficient approach for debromination and simultaneous recovering valuable chemicals from BFR-containing plastic in e-waste. Copyright © 2011 Elsevier B.V. All rights reserved.

  15. Preparation of radioactive labelled compounds. Pt. 2. 82Br labelled organic bromine compounds by isotopic exchange

    International Nuclear Information System (INIS)

    Otto, R.

    1988-05-01

    Studies on isotopic exchange between organic bromine compounds and 82 Br labelled dioxane dibromide in the presence of AlCl 3 are described. The results obtained enable to develop a simple and quick preparation method for the labelling with 82 Br [fr

  16. Bromine content in some seaweeds of Goa (Central West Coast of India)

    Digital Repository Service at National Institute of Oceanography (India)

    Naqvi, S.W.A.; Mittal, P.K.; Kamat, S.Y.; Solimabi; Reddy, C.V.G.

    in chloroform at 400 and 650 nm. The bromine content, on a dry dry weight basis, varied from 0.024 to 0.024% for the green algae, from 0.020 to 0.400% for the algae, and from 0.015 to 0.054% for the brown algae. Only two species @iChondria armata@@ and @i...

  17. Brominated Flame Retardants and their metabolites: Novel insights into endocrine disruptive properties.

    NARCIS (Netherlands)

    Fernández Cantón, R.|info:eu-repo/dai/nl/304831530

    2008-01-01

    Brominated flame retardants (BFRs) are chemicals that are added to materials to inhibit or suppress ignition and are incorporated during the manufacture of e.g. electronic equipment, furniture, construction materials and textiles. BFRs have become an increasingly important group of organohalogen

  18. Relationship among iodine, bromine and chlorine concentrations in cow's milk in Japan

    International Nuclear Information System (INIS)

    Ohno, Shigeru; Itoh, Takashi; Morishima, Hiroshige; Honda, Yoshihide.

    1989-01-01

    In order to know the relationship among some elements in biological materials, iodine, bromine and chlorine concentrations in cow's milk samples in Japan were determined by the thermal neutron activation analysis using a low power research reactor and a Van de Graaff accelerator. The iodine contents in cow's milk samples ranged from 0.041 to 0.316 ppm with an average of 0.096 ppm. The bromine and chlorine in these samples ranged from 2.3 to 11.1 ppm and from 475 to 1650 ppm, respectively. The average concentration of the bromine was calculated to be 5.6 ppm and that of the chlorine was 853 ppm. The relationship among iodine, bromine and chlorine concentrations in cow's milk samples in Japan was studied with a regression analysis. It was suggested that the correlation has a power function as follows; Y = K(Z) -A where, Y is elemental concentration in ppm, Z is atomic number of element, A (=7.4) is exponent and K (=14.7) is a constant. (author)

  19. Ullmann-type coupling of brominated tetrathienoanthracene on copper and silver

    Czech Academy of Sciences Publication Activity Database

    Gutzler, R.; Cardenas, L.; Lipton-Duffin, J.; El Garah, M.; Dinca, L.E.; Szakacs, C.E.; Fu, Ch.; Gallagher, M.; Vondráček, Martin; Rybachuk, M.; Perepichka, D.F.; Rosei, F.

    2014-01-01

    Roč. 6, č. 5 (2014), 2660-2668 ISSN 2040-3364 R&D Projects: GA MŠk(CZ) LM2011029 Institutional support: RVO:68378271 Keywords : Ullmann reaction * brominated tetrathienoanthracene * high resolution photoemission * STM Subject RIV: BM - Solid Matter Physics ; Magnetism Impact factor: 7.394, year: 2014

  20. Preliminary study on the occurrence of brominated organic compounds in Dutch marine organisms

    NARCIS (Netherlands)

    Kotterman, M.J.J.; Veen, van der I.; Hesselingen, van J.M.; Leonards, P.E.G.; Osinga, R.; Boer, de J.

    2003-01-01

    The extracts of three marine organisms; the ascidian Ciona intestinalis, the brown seaweed Sargassum muticum and the sponge Halichondria panicea, all elicited a number of brominated compounds, some of which were tentatively identified. Tribromophenol was observed in all species. This compound, also

  1. Kinetics of aerobic cometabolic biodegradation of chlorinated and brominated aliphatic hydrocarbons: A review.

    Science.gov (United States)

    Jesus, João; Frascari, Dario; Pozdniakova, Tatiana; Danko, Anthony S

    2016-05-15

    This review analyses kinetic studies of aerobic cometabolism (AC) of halogenated aliphatic hydrocarbons (HAHs) from 2001-2015 in order to (i) compare the different kinetic models proposed, (ii) analyse the estimated model parameters with a focus on novel HAHs and the identification of general trends, and (iii) identify further research needs. The results of this analysis show that aerobic cometabolism can degrade a wide range of HAHs, including HAHs that were not previously tested such as chlorinated propanes, highly chlorinated ethanes and brominated methanes and ethanes. The degree of chlorine mineralization was very high for the chlorinated HAHs. Bromine mineralization was not determined for studies with brominated aliphatics. The examined research period led to the identification of novel growth substrates of potentially high interest. Decreasing performance of aerobic cometabolism were found with increasing chlorination, indicating the high potential of aerobic cometabolism in the presence of medium- and low-halogenated HAHs. Further research is needed for the AC of brominated aliphatic hydrocarbons, the potential for biofilm aerobic cometabolism processes, HAH-HAH mutual inhibition and the identification of the enzymes responsible for each aerobic cometabolism process. Lastly, some indications for a possible standardization of future kinetic studies of HAH aerobic cometabolism are provided. Copyright © 2016 Elsevier B.V. All rights reserved.

  2. Biodegradation of brominated aromatics by cultures and laccase of Trametes versicolor

    Czech Academy of Sciences Publication Activity Database

    Uhnáková, Bronislava; Petříčková, Alena; Biedermann, David; Homolka, Ladislav; Vejvoda, Vojtěch; Bednář, P.; Papoušková, B.; Šulc, Miroslav; Martínková, Ludmila

    2009-01-01

    Roč. 76, č. 6 (2009), s. 826-832 ISSN 0045-6535 R&D Projects: GA MŠk 2B06151 Institutional research plan: CEZ:AV0Z50200510 Keywords : Brominated phenols * Tetrabromobisphenol A * Laccase Subject RIV: CE - Biochemistry Impact factor: 3.253, year: 2009

  3. The distribution of lignin in white birch wood as determined by bromination with TEM-EDXA

    International Nuclear Information System (INIS)

    Saka, S.; Goring, D.A.I.

    1988-01-01

    Ultraviolet absorbance and bromine uptake were measured on various morphological regions of birch wood. To facilitate precise comparison, observations were made on identical locations in successive cross sections. From the data, the concentration of lignin and the ratio of the guaiacyl to syringyl residues were determined. The results obtained were then compared with the previous findings from the use of UV microscopy alone

  4. Tracing organophosphorus and brominated flame retardants and plasticizers in an estuarine food web

    NARCIS (Netherlands)

    Brandsma, S.H.; Leonards, P.E.G.; Leslie, H.A.; de Boer, J.

    2015-01-01

    Nine organophosphorus flame retardants (PFRs) were detected in a pelagic and benthic food web of the Western Scheldt estuary, The Netherlands. Concentrations of several PFRs were an order of magnitude higher than those of the brominated flame retardants (BFRs). However, the detection frequency of

  5. Forcing of stratospheric chemistry and dynamics during the Dalton Minimum

    Science.gov (United States)

    Anet, J. G.; Muthers, S.; Rozanov, E.; Raible, C. C.; Peter, T.; Stenke, A.; Shapiro, A. I.; Beer, J.; Steinhilber, F.; Brönnimann, S.; Arfeuille, F.; Brugnara, Y.; Schmutz, W.

    2013-11-01

    The response of atmospheric chemistry and dynamics to volcanic eruptions and to a decrease in solar activity during the Dalton Minimum is investigated with the fully coupled atmosphere-ocean chemistry general circulation model SOCOL-MPIOM (modeling tools for studies of SOlar Climate Ozone Links-Max Planck Institute Ocean Model) covering the time period 1780 to 1840 AD. We carried out several sensitivity ensemble experiments to separate the effects of (i) reduced solar ultra-violet (UV) irradiance, (ii) reduced solar visible and near infrared irradiance, (iii) enhanced galactic cosmic ray intensity as well as less intensive solar energetic proton events and auroral electron precipitation, and (iv) volcanic aerosols. The introduced changes of UV irradiance and volcanic aerosols significantly influence stratospheric dynamics in the early 19th century, whereas changes in the visible part of the spectrum and energetic particles have smaller effects. A reduction of UV irradiance by 15%, which represents the presently discussed highest estimate of UV irradiance change caused by solar activity changes, causes global ozone decrease below the stratopause reaching as much as 8% in the midlatitudes at 5 hPa and a significant stratospheric cooling of up to 2 °C in the mid-stratosphere and to 6 °C in the lower mesosphere. Changes in energetic particle precipitation lead only to minor changes in the yearly averaged temperature fields in the stratosphere. Volcanic aerosols heat the tropical lower stratosphere, allowing more water vapour to enter the tropical stratosphere, which, via HOx reactions, decreases upper stratospheric and mesospheric ozone by roughly 4%. Conversely, heterogeneous chemistry on aerosols reduces stratospheric NOx, leading to a 12% ozone increase in the tropics, whereas a decrease in ozone of up to 5% is found over Antarctica in boreal winter. The linear superposition of the different contributions is not equivalent to the response obtained in a simulation

  6. Towards constraining the stratosphere-troposphere exchange of radiocarbon: strategies of stratospheric 14CO2 measurements using AirCore

    Science.gov (United States)

    Chen, Huilin; Paul, Dipayan; Meijer, Harro; Miller, John; Kivi, Rigel; Krol, Maarten

    2016-04-01

    Radiocarbon (14C) plays an important role in the carbon cycle studies to understand both natural and anthropogenic carbon fluxes, but also in atmospheric chemistry to constrain hydroxyl radical (OH) concentrations in the atmosphere. Apart from the enormous 14C emissions from nuclear bomb testing in the 1950s and 1960s, radiocarbon is primarily produced in the stratosphere due to the cosmogenic production. To this end, better understanding the stratospheric radiocarbon source is very useful to advance the use of radiocarbon for these applications. However, stratospheric 14C observations have been very limited so that there are large uncertainties on the magnitude and the location of the 14C production as well as the transport of radiocarbon from the stratosphere to the troposphere. Recently we have successfully made stratospheric 14C measurements using AirCore samples from Sodankylä, Northern Finland. AirCore is an innovative atmospheric sampling system, which passively collects atmospheric air samples into a long piece of coiled stainless steel tubing during the descent of a balloon flight. Due to the relatively low cost of the consumables, there is a potential to make such AirCore profiling in other parts of the world on a regular basis. In this study, we simulate the 14C in the atmosphere and assess the stratosphere-troposphere exchange of radiocarbon using the TM5 model. The Sodankylä radiocarbon measurements will be used to verify the performance of the model at high latitude. Besides this, we will also evaluate the influence of different cosmogenic 14C production scenarios and the uncertainties in the OH field on the seasonal cycles of radiocarbon and on the stratosphere-troposphere exchange, and based on the results design a strategy to set up a 14C measurement program using AirCore.

  7. Reactive hydro- end chlorocarbons in the troposphere and lower stratosphere : sources, distributions, and chemical impact

    Science.gov (United States)

    Scheeren, H. A.

    2003-09-01

    The work presented in this thesis focuses on measurements of chemical reactive C2 C7 non-methane hydrocarbons (NMHC) and C1 C2 chlorocarbons with atmospheric lifetimes of a few hours up to about a year. The group of reactive chlorocarbons includes the most abundant atmospheric species with large natural sources, which are chloromethane (CH3Cl), dichloromethane (CH2Cl2), and trichloromethane (CHCl3), and tetrachloroethylene (C2Cl4) with mainly anthropogenic sources. The NMHC and chlorocarbons are present at relatively low quantities in our atmosphere (10-12 10-9 mol mol-1 of air). Nevertheless, they play a key role in atmospheric photochemistry. For example, the oxidation of NMHC plays a dominant role in the formation of ozone in the troposphere, while the photolysis of chlorocarbons contributes to enhanced ozone depletion in the stratosphere. In spite of their important role, however, their global source and sinks budgets are still poorly understood. Hence, this study aims at improving our understanding of the sources, distribution, and chemical role of reactive NMHC and chlorocarbons in the troposphere and lower stratosphere. To meet this aim, a comprehensive data set of selected C2 C7 NMHC and chlorocarbons has been analyzed, derived from six aircraft measurement campaigns with two different jet aircrafts (the Dutch TUD/NLR Cessna Citation PH-LAB, and the German DLR Falcon) conducted between 1995 and 2001 (STREAM 1995 and 1997 and 1998, LBA-CLAIRE 1998, INDOEX 1999, MINOS 2001). The NMHC and chlorocarbons have been detected by gas-chromatography (GC-FID/ECD) in pre-concentrated whole air samples collected in stainless steel canister on-board the measurement aircrafts. The measurement locations include tropical (Maldives/Indian Ocean and Surinam), midlatitude (Western Europe and Canada) and polar regions (Lapland/northern Sweden) between the equator to about 70ºN, covering different seasons and pollution levels in the troposphere and lower stratosphere. Of

  8. Tiny Ultraviolet Polarimeter for Earth Stratosphere from Space Investigation

    Science.gov (United States)

    Nevodovskyi, P. V.; Morozhenko, O. V.; Vidmachenko, A. P.; Ivakhiv, O.; Geraimchuk, M.; Zbrutskyi, O.

    2015-09-01

    One of the reasons for climate change (i.e., stratospheric ozone concentrations) is connected with the variations in optical thickness of aerosols in the upper sphere of the atmosphere (at altitudes over 30 km). Therefore, aerosol and gas components of the atmosphere are crucial in the study of the ultraviolet (UV) radiation passing upon the Earth. Moreover, a scrupulous study of aerosol components of the Earth atmosphere at an altitude of 30 km (i.e., stratospheric aerosol), such as the size of particles, the real part of refractive index, optical thickness and its horizontal structure, concentration of ozone or the upper border of the stratospheric ozone layer is an important task in the research of the Earth climate change. At present, the Main Astronomical Observatory of the National Academy of Sciences (NAS) of Ukraine, the National Technical University of Ukraine "KPI"and the Lviv Polytechnic National University are engaged in the development of methodologies for the study of stratospheric aerosol by means of ultraviolet polarimeter using a microsatellite. So fare, there has been created a sample of a tiny ultraviolet polarimeter (UVP) which is considered to be a basic model for carrying out space experiments regarding the impact of the changes in stratospheric aerosols on both global and local climate.

  9. Impact of lower stratospheric ozone on seasonal prediction systems

    Directory of Open Access Journals (Sweden)

    Kelebogile Mathole

    2014-03-01

    Full Text Available We conducted a comparison of trends in lower stratospheric temperatures and summer zonal wind fields based on 27 years of reanalysis data and output from hindcast simulations using a coupled ocean-atmospheric general circulation model (OAGCM. Lower stratospheric ozone in the OAGCM was relaxed to the observed climatology and increasing greenhouse gas concentrations were neglected. In the reanalysis, lower stratospheric ozone fields were better represented than in the OAGCM. The spring lower stratospheric/ upper tropospheric cooling in the polar cap observed in the reanalysis, which is caused by a direct ozone depletion in the past two decades and is in agreement with previous studies, did not appear in the OAGCM. The corresponding summer tropospheric response also differed between data sets. In the reanalysis, a statistically significant poleward trend of the summer jet position was found, whereas no such trend was found in the OAGCM. Furthermore, the jet position in the reanalysis exhibited larger interannual variability than that in the OAGCM. We conclude that these differences are caused by the absence of long-term lower stratospheric ozone changes in the OAGCM. Improper representation or non-inclusion of such ozone variability in a prediction model could adversely affect the accuracy of the predictability of summer rainfall forecasts over South Africa.

  10. Stratospheric ozone: History and concepts and interactions with climate

    Directory of Open Access Journals (Sweden)

    Bekki S.

    2009-02-01

    Full Text Available Although in relatively low concentration of a few molecules per million of e e air molecules, atmospheric ozone (trioxygen O3 is essential to sustaining life on the surface of the Earth. Indeed, by absorbing solar radiation between 240 and 320 nm, it shields living organisms including humans from the very harmful ultraviolet radiation UV-B. About 90% of the ozone resides in the stratosphere, a region that extends from the tropopause, whose altitude ranges from 7 km at the poles to 17 km in the tropics, to the stratopause located at about 50 km altitude. Stratospheric ozone is communally referred as the « ozone layer ». Unlike the atmosphere surrounding it, the stratosphere is vertically stratified and stable because the temperature increases with height within it. This particularity originates from heating produced by the absorption of UV radiation by stratospheric ozone. The present chapter describes the main mechanisms that govern the natural balance of ozone in the stratosphere, and its disruption under the influence of human activities.

  11. Impact of major volcanic eruptions on stratospheric water vapour

    Directory of Open Access Journals (Sweden)

    M. Löffler

    2016-05-01

    Full Text Available Volcanic eruptions can have a significant impact on the Earth's weather and climate system. Besides the subsequent tropospheric changes, the stratosphere is also influenced by large eruptions. Here changes in stratospheric water vapour after the two major volcanic eruptions of El Chichón in Mexico in 1982 and Mount Pinatubo on the Philippines in 1991 are investigated with chemistry–climate model simulations. This study is based on two simulations with specified dynamics of the European Centre for Medium-Range Weather Forecasts Hamburg – Modular Earth Submodel System (ECHAM/MESSy Atmospheric Chemistry (EMAC model, performed within the Earth System Chemistry integrated Modelling (ESCiMo project, of which only one includes the long-wave volcanic forcing through prescribed aerosol optical properties. The results show a significant increase in stratospheric water vapour induced by the eruptions, resulting from increased heating rates and the subsequent changes in stratospheric and tropopause temperatures in the tropics. The tropical vertical advection and the South Asian summer monsoon are identified as sources for the additional water vapour in the stratosphere. Additionally, volcanic influences on tropospheric water vapour and El Niño–Southern Oscillation (ENSO are evident, if the long-wave forcing is strong enough. Our results are corroborated by additional sensitivity simulations of the Mount Pinatubo period with reduced nudging and reduced volcanic aerosol extinction.

  12. Stratospheric Water and OzOne Satellite Homogenized (SWOOSH) data set

    Data.gov (United States)

    National Oceanic and Atmospheric Administration, Department of Commerce — The Stratospheric Water and Ozone Satellite Homogenized (SWOOSH) data set is a merged record of stratospheric ozone and water vapor measurements taken by a number of...

  13. Distribution of copper, silver and gold during thermal treatment with brominated flame retardants

    International Nuclear Information System (INIS)

    Oleszek, Sylwia; Grabda, Mariusz; Shibata, Etsuro; Nakamura, Takashi

    2013-01-01

    Highlights: • Copper, silver and gold during thermal treatment with brominated flame retardants. • Distribution of copper, silver and gold during thermal processing. • Thermodynamic considerations of the bromination reactions. - Abstract: The growing consumption of electric and electronic equipment results in creating an increasing amount of electronic waste. The most economically and environmentally advantageous methods for the treatment and recycling of waste electric and electronic equipment (WEEE) are the thermal techniques such as direct combustion, co-combustion with plastic wastes, pyrolysis and gasification. Nowadays, this kind of waste is mainly thermally treated in incinerators (e.g. rotary kilns) to decompose the plastics present, and to concentrate metals in bottom ash. The concentrated metals (e.g. copper, precious metals) can be supplied as a secondary raw material to metal smelters, while the pyrolysis of plastics allows the recovery of fuel gases, volatilising agents and, eventually, energy. Indeed, WEEE, such as a printed circuit boards (PCBs) usually contains brominated flame retardants (BFRs). From these materials, hydrobromic acid (HBr) is formed as a product of their thermal decomposition. In the present work, the bromination was studied of copper, silver and gold by HBr, originating from BFRs, such as Tetrabromobisphenol A (TBBPA) and Tetrabromobisphenol A-Tetrabromobisophenol A diglycidyl ether (TTDE) polymer; possible volatilization of the bromides formed was monitored using a thermo-gravimetric analyzer (TGA) and a laboratory-scale furnace for treating samples of metals and BFRs under an inert atmosphere and at a wide range of temperatures. The results obtained indicate that up to about 50% of copper and silver can evolve from sample residues in the form of volatile CuBr and AgBr above 600 and 1000 °C, respectively. The reactions occur in the molten resin phase simultaneously with the decomposition of the brominated resin. Gold is

  14. Monitoring of WEEE plastics in regards to brominated flame retardants using handheld XRF

    Energy Technology Data Exchange (ETDEWEB)

    Aldrian, Alexia, E-mail: alexia.aldrian@unileoben.ac.at [Chair of Waste Processing Technology and Waste Management, Montanuniversitaet Leoben, Franz-Josef-Straße 18, 8700 Leoben (Austria); Ledersteger, Alfred, E-mail: a.ledersteger@saubermacher.at [Saubermacher Dienstleistungs AG, Hans-Roth-Straße 1, 8073 Feldkirchen bei Graz (Austria); Pomberger, Roland, E-mail: roland.pomberger@unileoben.ac.at [Chair of Waste Processing Technology and Waste Management, Montanuniversitaet Leoben, Franz-Josef-Straße 18, 8700 Leoben (Austria)

    2015-02-15

    Highlights: • Specification of an empirical factor for conversion from bromine to PBB and PBDE. • The handheld XRF device was validated for this particular application. • A very large number of over 4600 pieces of monitor housings was analysed. • The recyclable fraction mounts up to 85% for TV but only 53% of PC waste plastics. • A high percentage of pieces with bromine contents of over 50,000 ppm was obtained. - Abstract: This contribution is focused on the on-site determination of the bromine content in waste electrical and electronic equipment (WEEE), in particular waste plastics from television sets (TV) and personal computer monitors (PC) using a handheld X-ray fluorescence (XRF) device. The described approach allows the examination of samples in regards to the compliance with legal specifications for polybrominated biphenyls (PBBs) and polybrominated diphenyl ethers (PBDEs) directly after disassembling and facilitates the sorting out of plastics with high contents of brominated flame retardants (BFRs). In all, over 3000 pieces of black (TV) and 1600 pieces of grey (PC) plastic waste were analysed with handheld XRF technique for this study. Especially noticeable was the high percentage of pieces with a bromine content of over 50,000 ppm for TV (7%) and PC (39%) waste plastics. The applied method was validated by comparing the data of handheld XRF with results obtained by GC–MS. The results showed the expected and sufficiently accurate correlation between these two methods. It is shown that handheld XRF technique is an effective tool for fast monitoring of large volumes of WEEE plastics in regards to BFRs for on-site measurements.

  15. Brominated flame retardants and the formation of dioxins and furans in fires and combustion

    Energy Technology Data Exchange (ETDEWEB)

    Zhang, Mengmei [State key laboratory of clean energy utilisation, Institute for Thermal Power Engineering, Zhejiang University, Hangzhou (China); Buekens, Alfons [State key laboratory of clean energy utilisation, Institute for Thermal Power Engineering, Zhejiang University, Hangzhou (China); Formerly with Chemical Engineering department, Vrije Universiteit Brussel, Brussels (Belgium); Li, Xiaodong, E-mail: lixd@zju.edu.cn [State key laboratory of clean energy utilisation, Institute for Thermal Power Engineering, Zhejiang University, Hangzhou (China)

    2016-03-05

    Highlights: • BFRs (PBDEs, HBCD and TBBP-A) are the main sources of PBDD/Fs in combustion process. • Precursor formation is the most relevant pathway for PBDD/Fs formation. • Adding bromine into combustion system can enhance the formation of PCDD/Fs. • Primitive recycling of e-waste produces the largest amounts of PBDD/Fs. - Abstract: The widespread use and increasing inventory of brominated flame retardants (BFRs) have caused considerable concern, as a result of BFRs emissions to the environment and of the formation of both polybrominated dibenzo-p-dioxins and dibenzofurans (PBDD/Fs) and mixed polybromochloro-dibenzo-p-dioxins and dibenzofurans (PBCDD/Fs or PXDD/Fs). Structural similarities between PBDD/Fs and polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs) suggest the existence of comparable formation pathways of both PBDD/Fs and PCDD/Fs, yet BFRs also act as specific precursors to form additional PBDD/Fs. Moreover, elementary bromine (Br{sub 2}) seems to facilitate chlorination by bromination of organics, followed by Br/Cl-exchange based on displacement through the more reactive halogen. Overall, PBDD/Fs form through three possible pathways: precursor formation, de novo formation, and dispersion of parts containing BFRs as impurities and surviving a fire or other events. The present review summarises the formation mechanisms of both brominated (PBDD/Fs) and mixed dioxins (PXDD/Fs with X = Br or Cl) from BFRs, recaps available emissions data of PBDD/Fs and mixed PXDD/Fs from controlled waste incineration, uncontrolled combustion sources and accidental fires, and identifies and analyses the effects of several local factors of influence, affecting the formation of PBDD/Fs and mixed PXDD/Fs during BFRs combustion.

  16. SWIFT: Semi-empirical and numerically efficient stratospheric ozone chemistry for global climate models

    OpenAIRE

    Kreyling, Daniel; Wohltmann, Ingo; Lehmann, Ralph; Rex, Markus

    2015-01-01

    The SWIFT model is a fast yet accurate chemistry scheme for calculating the chemistry of stratospheric ozone. It is mainly intended for use in Global Climate Models (GCMs), Chemistry Climate Models (CCMs) and Earth System Models (ESMs). For computing time reasons these models often do not employ full stratospheric chem- istry modules, but use prescribed ozone instead. This can lead to insufficient representation between stratosphere and troposphere. The SWIFT stratospheric ozone chem...

  17. International Workshop on Stratospheric Aerosols: Measurements, Properties, and Effects

    Science.gov (United States)

    Pueschel, Rudolf F. (Editor)

    1991-01-01

    Following a mandate by the International Aerosol Climatology Program under the auspices of International Association of Meteorology and Atmospheric Physics International Radiation Commission, 45 scientists from five nations convened to discuss relevant issues associated with the measurement, properties, and effects of stratospheric aerosols. A summary is presented of the discussions on formation and evolution, transport and fate, effects on climate, role in heterogeneous chemistry, and validation of lidar and satellite remote sensing of stratospheric aerosols. Measurements are recommended of the natural (background) and the volcanically enhanced aerosol (sulfuric acid and silica particles), the exhaust of shuttle, civil aviation and supersonic aircraft operations (alumina, soot, and ice particles), and polar stratospheric clouds (ice, condensed nitric and hydrochloric acids).

  18. Effects of stratospheric perturbations on the solar radiation budget

    International Nuclear Information System (INIS)

    Luther, F.M.

    1978-04-01

    The changes in solar absorption and in local heating rates due to perturbations to O 3 and NO 2 concentrations caused by stratospheric injection of NO/sub x/ and CFM pollutants are assessed. The changes in species concentration profiles are derived from theoretical calculations using a transport-kinetics model. Because of significant changes in our understanding of stratospheric chemistry during the past year, the assessment of the effect of stratospheric perturbations on the solar radiation budget differs from previous assessments. Previously, a reduction in O 3 due to an NO/sub x/ injection caused a net decrease in the gaseous solar absorption;now the same perturbation leads to a net increase. The implication of these changes on the surface temperature is also discussed

  19. Toward autonomous measurements of photosynthetic electron transport rates: An evaluation of active fluorescence-based measurements of photochemistry

    NARCIS (Netherlands)

    Silsbe, G.M.; Oxborough, K.; Suggett, D.J.; Forster, R.M.; Ihnken, S.; Komárek, O.; Lawrenz, E.; Prášil, O.; Röttgers, R.; Šicner, M.; Simis, S.G.H.; Van Dijk, M.A.; Kromkamp, J.C.

    2015-01-01

    This study presents a methods evaluation and intercalibration of active fluorescence-based measurements of the quantum yield ( inline image) and absorption coefficient ( inline image) of photosystem II (PSII) photochemistry. Measurements of inline image, inline image, and irradiance (E) can be

  20. The Electrodeless Discharge Lamp: a Prospective Tool for Photochemistry - Part 4. Temperature- and Envelope Material-Dependent Emission Characteristics

    Czech Academy of Sciences Publication Activity Database

    Müller, P.; Klán, P.; Církva, Vladimír

    2003-01-01

    Roč. 158, č. 1 (2003), s. 1-5 ISSN 1010-6030 R&D Projects: GA ČR GA203/02/0879 Institutional research plan: CEZ:AV0Z4072921 Keywords : photochemistry * microwave * electrodeless discharge lamp Subject RIV: CC - Organic Chemistry Impact factor: 1.693, year: 2003

  1. The Elecrodeless Discharge Lamp: A Prospective Tool for Photochemistry Part 5. Fill Material-Dependent Emission Characteristics

    Czech Academy of Sciences Publication Activity Database

    Müller, P.; Klán, P.; Církva, Vladimír

    2005-01-01

    Roč. 171, Vol.1 (2005), s. 51-57 ISSN 1010-6030 R&D Projects: GA ČR GA203/02/0879 Institutional research plan: CEZ:AV0Z4072921 Keywords : photochemistry * microwave * spectra Subject RIV: CC - Organic Chemistry Impact factor: 2.286, year: 2005

  2. Tibetan Plateau glacier and hydrological change under stratospheric aerosol injection

    Science.gov (United States)

    Ji, D.

    2017-12-01

    As an important inland freshwater resource, mountain glaciers are highly related to human life, they provide water for many large rivers and play a very important role in regional water cycles. The response of mountain glaciers to future climate change is a topic of concern especially to the many people who rely on glacier-fed rivers for purposes such as irrigation. Geoengineering by stratospheric aerosol injection is a method of offsetting the global temperature rise from greenhouse gases. How the geoengineering by stratospheric aerosol injection affects the mass balance of mountain glaciers and adjacent river discharge is little understood. In this study, we use regional climate model WRF and catchment-based river model CaMa-Flood to study the impacts of stratospheric aerosol injection to Tibetan Plateau glacier mass balance and adjacent river discharge. To facilitate mountain glacier mass balance study, we improve the description of mountain glacier in the land surface scheme of WRF. The improvements include: (1) a fine mesh nested in WRF horizontal grid to match the highly non-uniform spatial distribution of the mountain glaciers, (2) revising the radiation flux at the glacier surface considering the surrounding terrain. We use the projections of five Earth system models for CMIP5 rcp45 and GeoMIP G4 scenarios to drive the WRF and CaMa-Flood models. The G4 scenario, which uses stratospheric aerosols to reduce the incoming shortwave while applying the rcp4.5 greenhouse gas forcing, starts stratospheric sulfate aerosol injection at a rate of 5 Tg per year over the period 2020-2069. The ensemble projections suggest relatively slower glacier mass loss rates and reduced river discharge at Tibetan Plateau and adjacent regions under geoengineering scenario by stratospheric aerosol injection.

  3. Variability of Irreversible Poleward Transport in the Lower Stratosphere

    Science.gov (United States)

    Olsen, Mark; Douglass, Anne; Newman, Paul; Nash, Eric; Witte, Jacquelyn; Ziemke, Jerry

    2011-01-01

    The ascent and descent of the Brewer-Dobson circulation plays a large role in determining the distributions of many constituents in the extratropical lower stratosphere. However, relatively fast, quasi-horizontal transport out of the tropics and polar regions also significantly contribute to determining these distributions. The tropical tape recorder signal assures that there must be outflow from the tropics into the extratropical lower stratosphere. The phase of the quasi-biennial oscillation (QBO) and state of the polar vortex are known to modulate the transport from the tropical and polar regions, respectively. In this study we examine multiple years of ozone distributions in the extratropical lower stratosphere observed by the Aura Microwave Limb Sounder (MLS) and the Aura High Resolution Dynamic Limb Sounder (HIRDLS). The distributions are compared with analyses of irreversible, meridional isentropic transport. We show that there is considerable year-to-year seasonal variability in the amount of irreversible transport from the tropics, which is related to both the phase of the QBO and the state of the polar vortex. The reversibility of the transport is consistent with the number of observed breaking waves. The variability of the atmospheric index of refraction in the lower stratosphere is shown to be significantly correlated with the wave breaking and amount of irreversible transport. Finally, we will show that the seasonal extratropical stratosphere to troposphere transport of ozone can be substantially modulated by the amount of irreversible meridional transport in the lower stratosphere and we investigate how observable these differences are in data of tropospheric ozone.

  4. Impact and mitigation of stratospheric ozone depletion by chemical rockets

    International Nuclear Information System (INIS)

    Mcdonald, A.J.

    1992-03-01

    The American Institute of Aeronautics and Astronautics (AIAA) conducted a workshop in conjunction with the 1991 AIAA Joint Propulsion Conference in Sacramento, California, to assess the impact of chemical rocket propulsion on the environment. The workshop included recognized experts from the fields of atmospheric physics and chemistry, solid rocket propulsion, liquid rocket propulsion, government, and environmental agencies, and representatives from several responsible environmental organizations. The conclusion from this workshop relative to stratospheric ozone depletion was that neither solid nor liquid rocket launchers have a significant impact on stratospheric ozone depletion, and that there is no real significant difference between the two

  5. Laser Photochemistry.

    Science.gov (United States)

    1981-07-01

    inverted by the first, i.e., at the moment of time t = T, such that i = (2n+)lT, where 0 is the Rabi frequency (Oraevski et al., 1976). . classical... anisotropic molecule present. CW HeNe, Ar+ and Kr+ lasers are used, and the filter method is necessary because of time-scales lo8 - 10ll Hz. Some general...e.g., truncated harmonic oscillator, square well, spherically symmetric Morse or Lennard-Jones, anisotropic (angle-dependent) Morse or Lennard-Jones

  6. EUV-VUV photochemistry in the upper atmospheres of Titan and the early Earth

    Science.gov (United States)

    Imanaka, H.; Smith, M. A.

    2010-12-01

    Titan, the organic-rich moon of Saturn, possesses a thick atmosphere of nitrogen, globally covered with organic haze layers. The recent Cassini’s INMS and CAPS observations clearly demonstrate the importance of complex organic chemistry in the ionosphere. EUV photon radiation is the major driving energy source there. Our previous laboratory study of the EUV-VUV photolysis of N2/CH4 gas mixtures demonstrates a unique role of nitrogen photoionization in the catalytic formation of complex hydrocarbons in Titan’s upper atmosphere (Imanaka and Smith, 2007, 2009). Such EUV photochemistry could also have played important roles in the formation of complex organic molecules in the ionosphere of the early Earth. It has been suggested that the early Earth atmosphere may have contained significant amount of reduced species (CH4, H2, and CO) (Kasting, 1990, Pavlov et al., 2001, Tian et al., 2005). Recent experimental study, using photon radiation at wavelengths longer than 110 nm, demonstrates that photochemical organic haze could have been generated from N2/CO2 atmospheres with trace amounts of CH4 or H2 (Trainer et al., 2006, Dewitt et al., 2009). However, possible EUV photochemical processes in the ionosphere are not well understood. We have investigated the effect of CO2 in the possible EUV photochemical processes in simulated reduced early Earth atmospheres. The EUV-VUV photochemistry using wavelength-tunable synchrotron light between 50 - 150 nm was investigated for gas mixtures of 13CO2/CH4 (= 96.7/3.3) and N2/13CO2/CH4 (= 90/6.7/3.3). The onsets of unsaturated hydrocarbon formation were observed at wavelengths shorter than the ionization potentials of CO2 and N2, respectively. This correlation indicates that CO2 can play a similar catalytic role to N2 in the formation of heavy organic species, which implies that EUV photochemistry might have significant impact on the photochemical generation of organic haze layers in the upper atmosphere of the early Earth.

  7. Comparative study of the formation of brominated disinfection byproducts in UV/persulfate and UV/H2O2 oxidation processes in the presence of bromide.

    Science.gov (United States)

    Wang, Lu; Ji, Yuefei; Lu, Junhe; Kong, Deyang; Yin, Xiaoming; Zhou, Quansuo

    2017-10-01

    The objective of this research was to compare the transformation of Br - and formation of brominated byproducts in UV/persulfate (PS) and UV/H 2 O 2 processes. It was revealed that Br - was efficiently transformed to free bromine which reacted with humic acid (HA) or dihydroxybenzoic acid resulting in the formation of brominated byproducts such as bromoacetic acids (BAAs) in UV/PS system. In contrast, no free bromine and brominated byproducts could be detected in UV/H 2 O 2 system, although the oxidization of Br - was evident. We presumed that the oxidation of Br - by hydroxyl radicals led to the formation of bromine radicals. However, the bromine radical species could be immediately reduced back to Br - by H 2 O 2 before coupling to each other to form free bromine, which explains the undetection of free bromine and BAAs in UV/H 2 O 2 . In addition to free bromine, we found that the phenolic functionalities in HA molecules, which served as the principal reactive sites for free chlorine attack, could be in situ generated when HA was exposed to free radicals. This study demonstrates that UV/H 2 O 2 is more suitable than UV/PS for the treatment of environmental matrices containing Br - . Graphical abstract Graphical abstract.

  8. Prenatal Exposure to Organohalogens, Including Brominated Flame Retardants, Influences Motor, Cognitive, and Behavioral Performance at School Age

    NARCIS (Netherlands)

    Roze, Elise; Meijer, Lisethe; Bakker, Attie; Van Braeckel, Koenraad N. J. A.; Sauer, Pieter J. J.; Bos, Arend F.

    2009-01-01

    BACKGROUND: Organohalogen compounds (OHCs) are known to have neurotoxic effects on the developing brain. OBJECTIVE: We investigated the influence of prenatal exposure to OHCs, including brominated flame retardants, on motor, cognitive, and behavioral outcome in healthy children of school age.

  9. Photochemistry of fluorinated 4-iodophenylnitrenes: matrix isolation and spectroscopic characterization of phenylnitrene-4-yls.

    Science.gov (United States)

    Grote, Dirk; Sander, Wolfram

    2009-10-02

    The photochemistry of a series of fluorinated p-iodophenyl azides 2 has been investigated using matrix isolation IR and EPR spectroscopy. In all cases, the corresponding phenylnitrenes 1 were formed as primary photoproducts. Further irradiation of the nitrenes 1 resulted in the formation of azirines 3, ketenimines 4, and nitreno radicals 5. The yield of 5 depends on the number of ortho fluorine substituents: with two ortho fluorine atoms the highest yield is observed, whereas without fluorine atoms the yield is too low for IR spectroscopic detection. The interconversion between the isomers 1, 3, and 4 proved to be rather complex. If the fluorine atoms are distributed unsymmetrically, two isomers of azirines 3 and ketenimines 4 can be formed. The yields of these isomers depend critically on the irradiation conditions.

  10. New concepts in therapeutic photomedicine: photochemistry, optical targeting and the therapeutic window

    International Nuclear Information System (INIS)

    Parrish, J.A.

    1981-01-01

    Advances in optics technology, synthetic photochemistry, and the science of photobiology make it possible to think beyond phototherapy and photochemotherapy which is dependent on direct photochemical alteration of metabolites or direct phototoxic insult to cells. This report discusses another gender of photomedicine therapy which includes in vivo photoactivation of medicines, photon-dependent drug delivery, and manipulation of host and exposure source to maximize therapeutic index. These therapeutic manipulations are made possible because the skin is highly overperfused and because non-ionizing electromagnetic radiation that enters skin and blood has adequate photon energy to cause electronic excitation. Radiation of 320-800 nm is not very directly phototoxic, is absorbed by a variety of relatively nontoxic photolabile molecules and has an internal dosimetric depth profile. This radiation can therefore be used to activate, deactivate, bind, release or biotransform medications in vivo in skin or other organs. The photochemist, synthetic chemist and photobiologist can collaborate to significantly increase therapeutic possibilities

  11. Combined In Situ Illumination-NMR-UV/Vis Spectroscopy: A New Mechanistic Tool in Photochemistry.

    Science.gov (United States)

    Seegerer, Andreas; Nitschke, Philipp; Gschwind, Ruth M

    2018-06-18

    Synthetic applications in photochemistry are booming. Despite great progress in the development of new reactions, mechanistic investigations are still challenging. Therefore, we present a fully automated in situ combination of NMR spectroscopy, UV/Vis spectroscopy, and illumination to allow simultaneous and time-resolved detection of paramagnetic and diamagnetic species. This optical fiber-based setup enables the first acquisition of combined UV/Vis and NMR spectra in photocatalysis, as demonstrated on a conPET process. Furthermore, the broad applicability of combined UVNMR spectroscopy for light-induced processes is demonstrated on a structural and quantitative analysis of a photoswitch, including rate modulation and stabilization of transient species by temperature variation. Owing to the flexibility regarding the NMR hardware, temperature, and light sources, we expect wide-ranging applications of this setup in various research fields. © 2018 The Authors. Published by Wiley-VCH Verlag GmbH & Co. KGaA.

  12. 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.

  13. Bond selective photochemistry in CH2BrI through electronic excitation at 210 nm

    International Nuclear Information System (INIS)

    Butler, L.J.; Hintsa, E.J.; Lee, Y.T.

    1986-01-01

    To explore the possibility of bond selective photochemistry in an excited electronic state, we have studied the photolysis of CH 2 BrI in a molecular beam at 210 nm. Following the direct local excitation of a repulsive transition on the C--Br bond at 210 nm, the fragments were detected by time-of-flight mass spectrometry. The dominant channel was found to be C--Br fission (60%) releasing an average of 15 kcal/mol into translation with the remainder reacting to form CH 2 +IBr and CH 2 +I+Br. There was no evidence for the primary fission of the C--I bond, making this the first clear example of the selective cleavage of a stronger bond in a molecule over the weakest one

  14. 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

  15. Modification of porous silicon rugate filters through thiol-yne photochemistry

    International Nuclear Information System (INIS)

    Soeriyadi, Alexander H.; Zhu, Ying; Gooding, J. Justin; Reece, Peter

    2014-01-01

    Porous silicon (PSi) has a considerable potential as biosensor platform. In particular, the ability to modify the surface chemistry of porous silicon is of interest. Here we present a generic method to modify the surface of porous silicon through thiol-yne photochemistry initiated by a radical initiator. Firstly, a freshly etched porous silicon substrate is modified through thermal hydrosilylation with 1,8-nonadiyne to passivate the surface and introduce alkyne functionalities. The alkyne functional surface could then be further reacted with thiol species in the presence of a radical initiator and UV light. Functionalization of the PSi rugate filter is followed with optical reflectivity measurements as well as high resolution X-ray photoelectron spectroscopy (XPS)

  16. Automatic generation of active coordinates for quantum dynamics calculations: Application to the dynamics of benzene photochemistry

    International Nuclear Information System (INIS)

    Lasorne, Benjamin; Sicilia, Fabrizio; Bearpark, Michael J.; Robb, Michael A.; Worth, Graham A.; Blancafort, Lluis

    2008-01-01

    A new practical method to generate a subspace of active coordinates for quantum dynamics calculations is presented. These reduced coordinates are obtained as the normal modes of an analytical quadratic representation of the energy difference between excited and ground states within the complete active space self-consistent field method. At the Franck-Condon point, the largest negative eigenvalues of this Hessian correspond to the photoactive modes: those that reduce the energy difference and lead to the conical intersection; eigenvalues close to 0 correspond to bath modes, while modes with large positive eigenvalues are photoinactive vibrations, which increase the energy difference. The efficacy of quantum dynamics run in the subspace of the photoactive modes is illustrated with the photochemistry of benzene, where theoretical simulations are designed to assist optimal control experiments

  17. SAGE measurements of the stratospheric aerosol dispersion and loading from the Soufriere Volcano

    Science.gov (United States)

    Mccormick, M. P.; Kent, G. S.; Yue, G. K.; Cunnold, D. M.

    1981-01-01

    Explosions of the Soufriere volcano on the Caribbean Island of St. Vincent reduced two major stratospheric plumes which the stratospheric aerosol and gas experiment (SAGE) satellite tracked to West Africa and the North Atlantic Ocean. The total mass of the stratospheric ejecta measured is less than 0.5% of the global stratospheric aerosol burden. No significant temperature or climate perturbation is expected. It is found that the movement and dispersion of the plumes agree with those deduced from high altitude meteorological data and dispersion theory. The stratospheric aerosol dispersion and loading from the Soufrier volcano was measured.

  18. Mechanistic reappraisal of early stage photochemistry in the light-driven enzyme protochlorophyllide oxidoreductase.

    Directory of Open Access Journals (Sweden)

    Derren J Heyes

    Full Text Available The light-driven enzyme protochlorophyllide oxidoreductase (POR catalyzes the reduction of protochlorophyllide (Pchlide to chlorophyllide (Chlide. This reaction is a key step in the biosynthesis of chlorophyll. Ultrafast photochemical processes within the Pchlide molecule are required for catalysis and previous studies have suggested that a short-lived excited-state species, known as I675*, is the first catalytic intermediate in the reaction and is essential for capturing excitation energy to drive subsequent hydride and proton transfers. The chemical nature of the I675* excited state species and its role in catalysis are not known. Here, we report time-resolved pump-probe spectroscopy measurements to study the involvement of the I675* intermediate in POR photochemistry. We show that I675* is not unique to the POR-catalyzed photoreduction of Pchlide as it is also formed in the absence of the POR enzyme. The I675* species is only produced in samples that contain both Pchlide substrate and Chlide product and its formation is dependent on the pump excitation wavelength. The rate of formation and the quantum yield is maximized in 50∶50 mixtures of the two pigments (Pchlide and Chlide and is caused by direct energy transfer between Pchlide and neighboring Chlide molecules, which is inhibited in the polar solvent methanol. Consequently, we have re-evaluated the mechanism for early stage photochemistry in the light-driven reduction of Pchlide and propose that I675* represents an excited state species formed in Pchlide-Chlide dimers, possibly an excimer. Contrary to previous reports, we conclude that this excited state species has no direct mechanistic relevance to the POR-catalyzed reduction of Pchlide.

  19. 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.

  20. Atmospheric photochemistry at a fatty acid coated air/water interface

    Science.gov (United States)

    George, Christian; Rossignol, Stéphanie; Passananti, Monica; Tinel, Liselotte; Perrier, Sebastien; Kong, Lingdong; Brigante, Marcello; Bianco, Angelica; Chen, Jianmin; Donaldson, James

    2017-04-01

    Over the past 20 years, interfacial processes have become increasingly of interest in the field of atmospheric chemistry, with many studies showing that environmental surfaces display specific chemistry and photochemistry, enhancing certain reactions and acting as reactive sinks or sources for various atmospherically relevant species. Many molecules display a free energy minimum at the air-water interface, making it a favored venue for compound accumulation and reaction. Indeed, surface active molecules have been shown to undergo specific photochemistry at the air-water interface. This presentation will address some recent surprises. Indeed, while fatty acids are believed to be photochemically inert in the actinic region, complex volatile organic compounds (VOCs) are produced during illumination of an air-water interface coated solely with a monolayer of carboxylic acid. When aqueous solutions containing nonanoic acid (NA) at bulk concentrations that give rise to just over monolayer NA coverage are illuminated with actinic radiation, saturated and unsaturated aldehydes are seen in the gas phase and more highly oxygenated products appear in the aqueous phase. This chemistry is probably initiated by triplet state NA molecules excited by direct absorption of actinic light at the water surface. As fatty acids covered interfaces are ubiquitous in the environment, such photochemical processing will have a significant impact on local ozone and particle formation. In addition, it was shown recently that a heterogeneous reaction between SO2 and oleic acid (OA; an unsaturated fatty acid) takes place and leads efficiently to the formation of organosulfur products. Here, we demonstrate that this reaction proceeds photochemically on various unsaturated fatty acids compounds, and may therefore have a general environmental impact. This is probably due to the chromophoric nature of the SO2 adduct with C=C bonds, and means that the contribution of this direct addition of SO2 could

  1. Effects of Model Chemistry and Data Biases on Stratospheric Ozone Assimilation

    National Research Council Canada - National Science Library

    Coy, L; Allen, D. R; Eckermann, S. D; McCormack, J. P; Stajner, I; Hogan, T. F

    2007-01-01

    .... In this study, O-F statistics from the Global Ozone Assimilation Testing System (GOATS) are used to examine how ozone assimilation products and their associated O-F statistics depend on input data biases and ozone photochemistry parameterizations (OPP...

  2. Air Revitalization System Enables Excursions to the Stratosphere

    Science.gov (United States)

    2015-01-01

    Paragon Space Development Corporation, based in Tucson, Arizona has had a long history of collaboration with NASA, including developing a modular air purification system under the Commercial Crew Development Program, designed to support the commercial space sector. Using that device and other NASA technology, startup company World View is now gearing up to take customers on helium balloon rides to the stratosphere.

  3. An ultrahot gas-giant exoplanet with a stratosphere.

    Science.gov (United States)

    Evans, Thomas M; Sing, David K; Kataria, Tiffany; Goyal, Jayesh; Nikolov, Nikolay; Wakeford, Hannah R; Deming, Drake; Marley, Mark S; Amundsen, David S; Ballester, Gilda E; Barstow, Joanna K; Ben-Jaffel, Lotfi; Bourrier, Vincent; Buchhave, Lars A; Cohen, Ofer; Ehrenreich, David; García Muñoz, Antonio; Henry, Gregory W; Knutson, Heather; Lavvas, Panayotis; Etangs, Alain Lecavelier des; Lewis, Nikole K; López-Morales, Mercedes; Mandell, Avi M; Sanz-Forcada, Jorge; Tremblin, Pascal; Lupu, Roxana

    2017-08-02

    Infrared radiation emitted from a planet contains information about the chemical composition and vertical temperature profile of its atmosphere. If upper layers are cooler than lower layers, molecular gases will produce absorption features in the planetary thermal spectrum. Conversely, if there is a stratosphere-where temperature increases with altitude-these molecular features will be observed in emission. It has been suggested that stratospheres could form in highly irradiated exoplanets, but the extent to which this occurs is unresolved both theoretically and observationally. A previous claim for the presence of a stratosphere remains open to question, owing to the challenges posed by the highly variable host star and the low spectral resolution of the measurements. Here we report a near-infrared thermal spectrum for the ultrahot gas giant WASP-121b, which has an equilibrium temperature of approximately 2,500 kelvin. Water is resolved in emission, providing a detection of an exoplanet stratosphere at 5σ confidence. These observations imply that a substantial fraction of incident stellar radiation is retained at high altitudes in the atmosphere, possibly by absorbing chemical species such as gaseous vanadium oxide and titanium oxide.

  4. Chlorine activation and ozone destruction in the northern lowermost stratosphere

    NARCIS (Netherlands)

    Lelieveld, J; Bregman, A; Scheeren, HA; Strom, J; Carslaw, KS; Fischer, H; Siegmund, PC; Arnold, F

    1999-01-01

    We report aircraft measurements from the Stratosphere-Troposphere Experiments by Aircraft Measurements (STREAM) II campaign, performed during February 1995 from Kiruna, northern Sweden, near 67 degrees N latitude. We have measured trace species, e.g., O-3, nitrogen compounds, HCl, hydrocarbons, CO,

  5. Sulfuric acid deposition from stratospheric geoengineering with sulfate aerosols

    KAUST Repository

    Kravitz, Ben

    2009-07-28

    We used a general circulation model of Earth\\'s climate to conduct geoengineering experiments involving stratospheric injection of sulfur dioxide and analyzed the resulting deposition of sulfate. When sulfur dioxide is injected into the tropical or Arctic stratosphere, the main additional surface deposition of sulfate occurs in midlatitude bands, because of strong cross-tropopause flux in the jet stream regions. We used critical load studies to determine the effects of this increase in sulfate deposition on terrestrial ecosystems by assuming the upper limit of hydration of all sulfate aerosols into sulfuric acid. For annual injection of 5 Tg of SO2 into the tropical stratosphere or 3 Tg of SO2 into the Arctic stratosphere, neither the maximum point value of sulfate deposition of approximately 1.5 mEq m−2 a−1 nor the largest additional deposition that would result from geoengineering of approximately 0.05 mEq m−2 a−1 is enough to negatively impact most ecosystems.

  6. Sulfuric acid deposition from stratospheric geoengineering with sulfate aerosols

    KAUST Repository

    Kravitz, Ben; Robock, Alan; Oman, Luke; Stenchikov, Georgiy L.; Marquardt, Allison B.

    2009-01-01

    We used a general circulation model of Earth's climate to conduct geoengineering experiments involving stratospheric injection of sulfur dioxide and analyzed the resulting deposition of sulfate. When sulfur dioxide is injected into the tropical or Arctic stratosphere, the main additional surface deposition of sulfate occurs in midlatitude bands, because of strong cross-tropopause flux in the jet stream regions. We used critical load studies to determine the effects of this increase in sulfate deposition on terrestrial ecosystems by assuming the upper limit of hydration of all sulfate aerosols into sulfuric acid. For annual injection of 5 Tg of SO2 into the tropical stratosphere or 3 Tg of SO2 into the Arctic stratosphere, neither the maximum point value of sulfate deposition of approximately 1.5 mEq m−2 a−1 nor the largest additional deposition that would result from geoengineering of approximately 0.05 mEq m−2 a−1 is enough to negatively impact most ecosystems.

  7. Stratospheric Ozone Reactive Chemicals Generated by Space Launches Worldwide.

    Science.gov (United States)

    1994-11-01

    I ODCs). Their carbon - chlorine bond is severed in the stratosphere by solar photolysis or reaction. Once the carbon-chlorine bond is broken, the...include the Russian Proton and Energia , and the Chinese Long March series. Roughly half (seven per year) of the Ariane 4 launches use two solid strap-ons

  8. Reduction of photosynthetically active radiation under extreme stratospheric aerosol loads

    International Nuclear Information System (INIS)

    Gerstl, S.A.W.; Zardecki, A.

    1981-08-01

    The recently published hypothesis that the Cretaceous-Tertiary extinctions might be caused by an obstruction of sunlight is tested by model calculations. First we compute the total mass of stratospheric aerosols under normal atmospheric conditions for four different (measured) aerosol size distributions and vertical profiles. For comparison, the stratospheric dust masses after four volcanic eruptions are also evaluated. Detailed solar radiative transfer calculations are then performed for artificially increased aerosol amounts until the postulated darkness scenario is obtained. Thus we find that a total stratospheric aerosol mass between 1 and 4 times 10 1 g is sufficient to reduce photosynthesis to 10 -3 of normal. We also infer from this result tha the impact of a 0.4- to 3-km-diameter asteroid or a close encounter with a Halley-size comet may deposit that amount of particulates into the stratosphere. The darkness scenario of Alvarez et al. is thus shown to be a possible extinction mechanism, even with smaller size asteroids of comets than previously estimated

  9. Tritium Records to Trace Stratospheric Moisture Inputs in Antarctica

    Science.gov (United States)

    Fourré, E.; Landais, A.; Cauquoin, A.; Jean-Baptiste, P.; Lipenkov, V.; Petit, J.-R.

    2018-03-01

    Better assessing the dynamic of stratosphere-troposphere exchange is a key point to improve our understanding of the climate dynamic in the East Antarctica Plateau, a region where stratospheric inputs are expected to be important. Although tritium (3H or T), a nuclide naturally produced mainly in the stratosphere and rapidly entering the water cycle as HTO, seems a first-rate tracer to study these processes, tritium data are very sparse in this region. We present the first high-resolution measurements of tritium concentration over the last 50 years in three snow pits drilled at the Vostok station. Natural variability of the tritium records reveals two prominent frequencies, one at about 10 years (to be related to the solar Schwabe cycles) and the other one at a shorter periodicity: despite dating uncertainty at this short scale, a good correlation is observed between 3H and Na+ and an anticorrelation between 3H and δ18O measured on an individual pit. The outputs from the LMDZ Atmospheric General Circulation Model including stable water isotopes and tritium show the same 3H-δ18O anticorrelation and allow further investigation on the associated mechanism. At the interannual scale, the modeled 3H variability matches well with the Southern Annular Mode index. At the seasonal scale, we show that modeled stratospheric tritium inputs in the troposphere are favored in winter cold and dry conditions.

  10. UV spectroscopy applied to stratospheric chemistry, methods and results

    Energy Technology Data Exchange (ETDEWEB)

    Karlsen, K.

    1996-03-01

    The publication from the Norwegian Institute for Air Research (NILU) deals with an investigation done on stratospheric chemistry by UV spectroscopy. The scientific goals are briefly discussed, and it gives the results from the measuring and analysing techniques used in the investigation. 6 refs., 11 figs.

  11. Quantifying pollution transport from the Asian monsoon anticyclone into the lower stratosphere

    Directory of Open Access Journals (Sweden)

    F. Ploeger

    2017-06-01

    Full Text Available Pollution transport from the surface to the stratosphere within the Asian monsoon circulation may cause harmful effects on stratospheric chemistry and climate. Here, we investigate air mass transport from the monsoon anticyclone into the stratosphere using a Lagrangian chemistry transport model. We show how two main transport pathways from the anticyclone emerge: (i into the tropical stratosphere (tropical pipe, and (ii into the Northern Hemisphere (NH extratropical lower stratosphere. Maximum anticyclone air mass fractions reach around 5 % in the tropical pipe and 15 % in the extratropical lowermost stratosphere over the course of a year. The anticyclone air mass fraction correlates well with satellite hydrogen cyanide (HCN and carbon monoxide (CO observations, confirming that pollution is transported deep into the tropical stratosphere from the Asian monsoon anticyclone. Cross-tropopause transport occurs in a vertical chimney, but with the pollutants transported quasi-horizontally along isentropes above the tropopause into the tropics and NH.

  12. Titan's Stratospheric Condensibles at High Northern Latitudes During Northern Winter

    Science.gov (United States)

    Anderson, Carrie; Samuelson, R.; Achterberg, R.

    2012-01-01

    The Infrared Interferometer Spectrometer (IRIS) instrument on board Voyager 1 caught the first glimpse of an unidentified particulate feature in Titan's stratosphere that spectrally peaks at 221 per centimeter. Until recently, this feature that we have termed 'the haystack,' has been seen persistently at high northern latitudes with the Composite Infrared Spectrometer (CIRS) instrument onboard Cassini, The strength of the haystack emission feature diminishes rapidly with season, becoming drastically reduced at high northern latitudes, as Titan transitions from northern winter into spring, In contrast to IRIS whose shortest wavenumber was 200 per centimeter, CIRS extends down to 10 per centimeter, thus revealing an entirely unexplored spectral region in which nitrile ices have numerous broad lattice vibration features, Unlike the haystack, which is only found at high northern latitudes during northern winter/early northern spring, this geometrically thin nitrile cloud pervades Titan's lower stratosphere, spectrally peaking at 160 per centimeter, and is almost global in extent spanning latitudes 85 N to 600 S, The inference of nitrile ices are consistent with the highly restricted altitude ranges over which these features are observed, and appear to be dominated by a mixture of HCN and HC3N, The narrow range in altitude over which the nitrile ices extend is unlike the haystack, whose vertical distribution is significantly broader, spanning roughly 70 kilometers in altitude in Titan's lower stratosphere, The nitrile clouds that CIRS observes are located in a dynamically stable region of Titan's atmosphere, whereas CH4 clouds, which ordinarily form in the troposphere, form in a more dynamically unstable region, where convective cloud systems tend to occur. In the unusual situation where Titan's tropopause cools significantly from the HASI 70.5K temperature minimum, CH4 should condense in Titan's lower stratosphere, just like the aforementioned nitrile clouds, although

  13. Impacts of Stratospheric Sulfate Geoengineering on PM2.5

    Science.gov (United States)

    Robock, A.; Xia, L.; Tilmes, S.; Mills, M. J.; Richter, J.; Kravitz, B.; MacMartin, D.

    2017-12-01

    Particulate matter (PM) includes sulfate, nitrate, organic carbon, elemental carbon, soil dust, and sea salt. The first four components are mostly present near the ground as fine particulate matter with a diameter less than 2.5 µm (PM2.5), and these are of the most concern for human health. PM is efficiently scavenged by precipitation, which is its main atmospheric sink. Here we examine the impact of stratospheric climate engineering on this important pollutant and health risk, taking advantage of two sets of climate model simulations conducted at the National Center for Atmospheric Research. We use the full tropospheric and stratospheric chemistry version of the Community Earth System Model - Community Atmospheric Model 4 (CESM CAM4-chem) with a horizontal resolution of 0.9° x 1.25° lat-lon to simulate a stratospheric sulfate injection climate intervention of 8 Tg SO2 yr-1 combined with an RCP6.0 global warming forcing, the G4 Specified Stratospheric Aerosol (G4SSA) scenario. We also analyze the output from a 20-member ensemble of Community Earth System Model, version 1 with the Whole Atmosphere Community Climate Model as its atmospheric component (CESM1(WACCM)) simulations, also at 0.9° x 1.25° lat-lon resolution, with sulfur dioxide injection at 15°N, 15°S, 30°N, and 30°S varying in time to balance RCP8.5 forcing. While the CESM CAM4-chem model has full tropospheric and stratospheric chemistry, CESM1(WACCM) has an internally generated quasi-biennial oscillation and a comprehensive tropospheric and stratospheric sulfate aerosol treatment, but only stratospheric chemistry. For G4SSA, there are a global temperature reduction of 0.8 K and global averaged precipitation decrease of 3% relative to RCP6.0. The global averaged surface PM2.5 reduces about 1% compared with RCP6.0, mainly over Eurasian and East Asian regions in Northern Hemisphere winter. The PM2.5 concentration change is a combination of effects from tropospheric chemistry and precipitation

  14. Determination of organic-bound chlorine and bromine in human body fluids by neutron activation analysis

    International Nuclear Information System (INIS)

    McKinney, J.D.; Abusamra, A.; Reed, J.H.

    1983-01-01

    The levels of organic-bound chlorine and bromine in human milk and serum are determined by neutron activation analysis. Desalted milk and serum fractions are irradiated with neutrons in a nuclear reactor and the resulting γ-rays of 38 Cl and 80 Br are measured. The desalting procedure, achieved by using Bio-Gel molecular sieves, virtually removes all ionic chloride and bromides from milk and serum. Radioactive tracer studies with polychlorinated biphenyl- 14 C indicate a recovery of 90% through the Bio-Gel column. The total organic chlorine in 2.2-(4-chlorophenyl)-1,1-dichloroethane spiked milk and heptachlor spiked milk, determined after being desalted and irradiated according to this procedure, substantiates a good recovery of the added spike. The lower limits of detection of organic-bound chlorine and bromine in milk or serum are 50 and 5 parts per billion (ppb), respectively

  15. The Determination of Bromine in Wheat, Flour and Bread by Neutron Activation Analysis. RCN Report

    International Nuclear Information System (INIS)

    Das, H.A.; Hoede, D.; Zonderhuis, J.

    1969-07-01

    Gaseous germicides are commonly used to improve the tenability of wheat. The bulk material is exposed to a gas which is highly poisonous to fungi. Methylene and ethylene dibromide are often used for this purpose. Traces of these compounds in wheat, flour and bread are dangerous. Consequently, the persistence of these gases should be determined experimentally. This implies that sensitive methods to detect traces of methylene and ethylene dibromide must be available. Neutron activation analysis can be used to determine the total amount of bromine present in the sample. This datum is a useful addition to the gaschromato-graphic determinations of the compounds involved. A routine method for the determination of bromine in corn, flour and bread has been developed and is described in the text

  16. A Quaternized Polysulfone Membrane for Zinc-Bromine Redox Flow Battery

    Directory of Open Access Journals (Sweden)

    Mingqiang Li

    2014-01-01

    Full Text Available A quaternized polysulfone (QNPSU composite membrane is fabricated for zinc-bromine redox flow battery. The structure of the membrane is examined by FT-IR spectra and SEM. The conductivity of the membrane is tested by electrochemical analyzer. After a zinc-bromine battery with this composite membrane is operated at different voltage while charging and at different current while discharging to examine the performance of the membrane, it is found that the discharge voltage was 0.9672 V and the power density was 6 mW/cm2 at a current of 0.1 A, which indicated that the novel composite membrane is a promising material for the flow battery.

  17. Simulation of dual carbon-bromine stable isotope fractionation during 1,2-dibromoethane degradation.

    Science.gov (United States)

    Jin, Biao; Nijenhuis, Ivonne; Rolle, Massimo

    2018-06-01

    We performed a model-based investigation to simultaneously predict the evolution of concentration, as well as stable carbon and bromine isotope fractionation during 1,2-dibromoethane (EDB, ethylene dibromide) transformation in a closed system. The modelling approach considers bond-cleavage mechanisms during different reactions and allows evaluating dual carbon-bromine isotopic signals for chemical and biotic reactions, including aerobic and anaerobic biological transformation, dibromoelimination by Zn(0) and alkaline hydrolysis. The proposed model allowed us to accurately simulate the evolution of concentrations and isotope data observed in a previous laboratory study and to successfully identify different reaction pathways. Furthermore, we illustrated the model capabilities in degradation scenarios involving complex reaction systems. Specifically, we examined (i) the case of sequential multistep transformation of EDB and the isotopic evolution of the parent compound, the intermediate and the reaction product and (ii) the case of parallel competing abiotic pathways of EDB transformation in alkaline solution.

  18. Early work on the stratospheric ozone depletion-CFC issue

    Science.gov (United States)

    Molina, M.

    2012-12-01

    I became involved with the atmospheric chemistry of chlorofluorocarbons (CFCs) shortly after joining Sherry Rowland's research group at the University of California, Irvine, in 1973. CFCs had been detected in the troposphere by James Lovelock in 1971, and the question we set out to answer was the fate of these compounds of industrial origin in the environment, as well as possibly identifying any consequences of their accumulation in the atmosphere. After examining many potential sinks for these compounds we realized that because of their unusual stability the most likely destruction process was photolysis in the stratosphere. I carried out measurements of the absorption spectra of these compounds in the near ultraviolet; previous work involved only spectra in the far ultraviolet, not relevant for atmospheric chemistry. The results indicated that photolysis would take place in the upper stratosphere. I subsequently carried out calculations using one-dimensional atmospheric models to estimate their atmospheric residence times, which turned out to be many decades. We realized that the chlorine atoms generated by photolysis of the CFCs would participate in a catalytic chain reaction that would efficiently destroy ozone. Furthermore, we estimated that the amount of CFCs produced industrially was comparable to the amount of nitric oxide produced naturally in the stratosphere by the decomposition of nitrous oxide; work by Paul Crutzen and Harold Johnston had indicated that the abundance of ozone in the stratosphere was controlled by nitric oxide. We then formulated the hypothesis that the continued release of CFCs to the environment posed a threat to the stability of the ozone layer, and published our results in the journal Nature in 1974. The publication was noticed almost exclusively by the community of experts in stratospheric chemistry, and hence Sherry Rowland and I decided at that time that it was our responsibility to communicate this finding to society at large

  19. Solar wind control of stratospheric temperatures in Jupiter's auroral regions?

    Science.gov (United States)

    Sinclair, James Andrew; Orton, Glenn; Kasaba, Yasumasa; Sato, Takao M.; Tao, Chihiro; Waite, J. Hunter; Cravens, Thomas; Houston, Stephen; Fletcher, Leigh; Irwin, Patrick; Greathouse, Thomas K.

    2017-10-01

    Auroral emissions are the process through which the interaction of a planet’s atmosphere and its external magnetosphere can be studied. Jupiter exhibits auroral emission at a multitude of wavelengths including the X-ray, ultraviolet and near-infrared. Enhanced emission of CH4 and other stratospheric hydrocarbons is also observed coincident with Jupiter’s shorter-wavelength auroral emission (e.g. Caldwell et al., 1980, Icarus 44, 667-675, Kostiuk et al., 1993, JGR 98, 18823). This indicates that auroral processes modify the thermal structure and composition of the auroral stratosphere. The exact mechanism responsible for this auroral-related heating of the stratosphere has however remained elusive (Sinclair et al., 2017a, Icarus 292, 182-207, Sinclair et al., 2017b, GRL, 44, 5345-5354). We will present an analysis of 7.8-μm images of Jupiter measured by COMICS (Cooled Mid-Infrared Camera and Spectrograph, Kataza et al., 2000, Proc. SPIE(4008), 1144-1152) on the Subaru telescope. These images were acquired on January 11th, 12th, 13th, 14th, February 4, 5th and May 17th, 18th, 19th and 20th in 2017, allowing the daily variability of Jupiter’s auroral-related stratospheric heating to be tracked. Preliminary results suggest lower stratospheric temperatures are directly forced by the solar wind dynamical pressure. The southern auroral hotspot exhibited a significant increase in brightness temperature over a 24-hour period. Over the same time period, a solar wind propagation model (Tao et al. 2005, JGR 110, A11208) predicts a strong increase in the solar wind dynamical pressure at Jupiter.

  20. A change of seasons in Saturn's stratosphere from Cassini/CIRS: evolution of the equatorial oscillation and reversal of hemispheric transport.

    Science.gov (United States)

    Guerlet, Sandrine; Fouchet, Thierry; Hesman, Brigette; Bjoraker, Gordon; Spiga, Aymeric; Cassini/CIRS Team

    2016-10-01

    Due to its axial tilt of 26.7°, Saturn's atmosphere undergoes significant seasonal variations in insolation that impact its thermal structure, chemistry and dynamics. The exceptional longevity of the Cassini mission enables us to uniquely investigate these changes over almost half a Saturn year. In this study, thermal infrared spectra acquired in 2015 by CIRS in limb viewing geometry are analyzed to map the temperature and the meridional distribution of five hydrocarbons from the lower to the upper stratosphere (10 mbar - 10 microbar). These new maps represent a snapshot of Saturn's atmosphere at the end of the northern spring and are compared to previous results obtained during northern winter (2005/2006) and early spring (2010/2011) (Guerlet et al., Icarus, 2009; Sylvestre et al., Icarus, 2015). Spectacular seasonal changes in temperature are observed, not only at high latitudes where the most extreme insolation variations take place, but also at 20N-20S where the mechanical forcing of the equatorial oscillation induces temperature anomalies of up to +/-20K. These results are compared with predictions from a radiative climate model (Guerlet et al., Icarus, 2014). Apart from the equatorial region, the seasonal warming and cooling trends observed by CIRS are, to first order, consistent with the predictions. One notable exception is that the region under the ring's shadow is found warmer than expected from the radiative model, both in 2005 and 2015. The spatial distribution of hydrocarbons, by-products of the methane photochemistry, also undergoes significant seasonal change in the upper stratosphere. In 2005, a local maximum of hydrocarbons was observed at 20-30N, at odds with the low photochemical production in this region (under the ring's shadow at that time). Together with the high temperature anomaly, we had interpreted this result as the signature of a downwelling branch of the meridional circulation. In 2015, not only has this local maximum vanished, but a

  1. Gondola development for CNES stratospheric balloons

    Science.gov (United States)

    Vargas, A.; Audoubert, J.; Cau, M.; Evrard, J.; Verdier, N.

    (over the line of sight) than with dedicated RF system, which requires balloon visibility from the ground station. For long duration flights (3 months) of Infra Red Montgolfieres, a house keeping gondola has been developed, using the Inmarsat C standard to have communication all around the world (up to N or S 80 ° latitude) with an automatic switching between the 4 geostationnary Inmarsat satellites. After validation flights performed from Bauru / Brazil. (2000 & 2001) and Kiruna/Sweden (2002), the first operational flights took place from Bauru in February 2003 during ENVISAT validation campaign. The next flights will be realized in the framework of the Hibiscus campaign planned in February 2004 in Bauru.. The Balloon Division was involved in the Franco / Japanese HSFD II project which consists to drop a mock-up of the Japanese HOPE-X space shuttle from a stratospheric balloon to validate its flight from the altitude of 30 km. We developed a specific gondola as a service module for the HOPE-X shuttle, providing power and GPS radio-frequency signal during the balloon flight phase, telemetry end remote control radio frequency links and separation system with pyrotechnic cutters for the drop of the shuttle. A successful flight was performed at Kiruna in July 2003. Concerning gondola with pointing system, the study of a big g-ray telescope (8 m of focal length), started by the end of 2002. For this 1 ton gondola, the telescope stabilization system will be based on control moment gyro (CMG). The CMG system has been designed and will be manufactured and validated during 2004. The first flight of this g-ray gondola is planned for 2006. The progress, status and future plans concerning these gondola developments will be presented.

  2. Study of the liquid vapor equilibrium in the bromine-hydrobromic acid-water system

    Science.gov (United States)

    Benizri, R.; Lessart, P.; Courvoisier, P.

    1984-01-01

    A glass ebullioscope was built and at atmospheric pressure, liquid-vapor equilibria relative to the Br2-HBr-H2O system, in the concentration range of interest for evaluation of the Mark 13 cycle was studied. Measurements were performed for the brome-azeotrope (HBr-H2O) pseudo-binary system and for the ternary system at temperatures lower than 125 C and in the bromine concentration range up to 13% wt.

  3. Hydrostatic pressure study of MBE CdMnTe doped bromine

    Energy Technology Data Exchange (ETDEWEB)

    Szczytko, J.; Wasek, D.; Przybytek, J.; Baj, M. [Institute of Experimental Physics, Warsaw University, Warsaw (Poland); Waag, A. [Physikalisches Institut, Universitaet Wuerzburg, Wuerzburg (Germany)

    1995-12-31

    We present Hall effect and resistivity measurements as a function of pressure performed on MBE-grown Cd{sub 1-x}Mn{sub x}Te (with x=0.14) layer doped with bromine. The experimental data were analysed using positive and negative U model of Br centers. We found that both models could reproduce the experimental points, but in the case of positive U modes - only under assumption that the sample was completely uncompensated. (author). 6 refs, 3 figs.

  4. Hydrostatic pressure study of MBE CdMnTe doped bromine

    International Nuclear Information System (INIS)

    Szczytko, J.; Wasek, D.; Przybytek, J.; Baj, M.; Waag, A.

    1995-01-01

    We present Hall effect and resistivity measurements as a function of pressure performed on MBE-grown Cd 1-x Mn x Te (with x=0.14) layer doped with bromine. The experimental data were analysed using positive and negative U model of Br centers. We found that both models could reproduce the experimental points, but in the case of positive U modes - only under assumption that the sample was completely uncompensated. (author)

  5. Assessing oestrogenic effects of brominated flame retardants Hexabromocyclododecane and Tetrabromobisphenol A on MCF-7 cells

    Czech Academy of Sciences Publication Activity Database

    Dorosh, Andriy; Děd, Lukáš; Elzeinová, Fatima; Pěknicová, Jana

    2010-01-01

    Roč. 56, - (2010), s. 35-39 ISSN 0015-5500 R&D Projects: GA MŠk(CZ) 1M06011; GA MŠk(CZ) 2B06151 Institutional research plan: CEZ:AV0Z50520701 Keywords : endocrine disruptors * BRF - brominated flame retardant * MCF-7 cells * TFF1 - trefoil factor Subject RIV: DN - Health Impact of the Environment Quality Impact factor: 0.729, year: 2010

  6. Brominated and organophosphate flame retardants in selected consumer products on the Japanese market in 2008

    International Nuclear Information System (INIS)

    Kajiwara, Natsuko; Noma, Yukio; Takigami, Hidetaka

    2011-01-01

    Highlights: → We examined the flame retardants in electronics, curtains, wallpaper and insulator. → Use of alternative brominated and organophosphate flame retardants was suggested. → All the products investigated also contained PBDEs, TBBPA and polybromophenols. → Incorporation of recycled materials containing hazardous substance was suggested. - Abstract: The concentrations of traditional brominated flame retardants (BFRs) and organophosphate flame retardants (OPFRs) in new consumer products, including electronic equipment, curtains, wallpaper, and building materials, on the Japanese market in 2008 were investigated. Although some components of the electronic equipment contained bromine at concentrations on the order of percent by weight, as indicated by X-ray fluorescence analysis, the bromine content could not be fully accounted for by the BFRs analyzed in this study, which included polybrominated diphenylethers, decabromodiphenyl ethane, tetrabromobisphenol A, polybromophenols, and hexabromocyclododecanes. These results suggest the use of alternative BFRs such as newly developed formulations derived from tribromophenol, tetrabromobisphenol A, or both. Among the 11 OPFRs analyzed, triphenylphosphate was present at the highest concentrations in all the products investigated, which suggests the use of condensed-type OPFRs as alternative flame retardants, because they contain triphenylphosphate as an impurity. Tripropylphosphate was not detected in any samples; and trimethylphosphate, tributyl tris(2-butoxyethyl)phosphate, and tris(1,3-dichloro-2-propyl)phosphate were detected in only some components and at low concentrations. Note that all the consumer products evaluated in this study also contained traditional BFRs in amounts that were inadequate to impart flame retardancy, which implies the incorporation of recycled plastic materials containing BFRs that are of global concern.

  7. Induced production of brominated aromatic compounds in the alga Ceramium tenuicorne.

    Science.gov (United States)

    Dahlgren, Elin; Enhus, Carolina; Lindqvist, Dennis; Eklund, Britta; Asplund, Lillemor

    2015-11-01

    In the Baltic Sea, high concentrations of toxic brominated aromatic compounds have been detected in all compartments of the marine food web. A growing body of evidence points towards filamentous algae as a natural producer of these chemicals. However, little is known about the effects of environmental factors and life history on algal production of brominated compounds. In this study, several congeners of methoxylated polybrominated diphenyl ethers (MeO-PBDEs), hydroxylated polybrominated diphenyl ethers (OH-PBDEs) and brominated phenols (BPs) were identified in a naturally growing filamentous red algal species (Ceramium tenuicorne) in the Baltic Sea. The identified substances displayed large seasonal variations in the alga with a concentration peak in July. Production of MeO-/OH-PBDEs and BPs by C. tenuicorne was also established in isolated clonal material grown in a controlled laboratory setting. Based on three replicates, herbivory, as well as elevated levels of light and salinity in the culture medium, significantly increased the production of 2,4,6-tribromophenol (2,4,6-TBP). Investigation of differences in production between the isomorphic female, male and diploid clonal life stages of the alga grown in the laboratory revealed a significantly higher production of 2,4,6-TBP in the brackish water female gametophytes, compared to the corresponding marine gametophytes. Even higher concentrations of 2,4,6-TBP were produced by marine male gametophytes and sporophytes.

  8. High Performance Hydrogen/Bromine Redox Flow Battery for Grid-Scale Energy Storage

    Energy Technology Data Exchange (ETDEWEB)

    Cho, KT; Ridgway, P; Weber, AZ; Haussener, S; Battaglia, V; Srinivasan, V

    2012-01-01

    The electrochemical behavior of a promising hydrogen/bromine redox flow battery is investigated for grid-scale energy-storage application with some of the best redox-flow-battery performance results to date, including a peak power of 1.4 W/cm(2) and a 91% voltaic efficiency at 0.4 W/cm(2) constant-power operation. The kinetics of bromine on various materials is discussed, with both rotating-disk-electrode and cell studies demonstrating that a carbon porous electrode for the bromine reaction can conduct platinum-comparable performance as long as sufficient surface area is realized. The effect of flow-cell designs and operating temperature is examined, and ohmic and mass-transfer losses are decreased by utilizing a flow-through electrode design and increasing cell temperature. Charge/discharge and discharge-rate tests also reveal that this system has highly reversible behavior and good rate capability. (C) 2012 The Electrochemical Society. [DOI: 10.1149/2.018211jes] All rights reserved.

  9. Measurement and human exposure assessment of brominated flame retardants in household products from South China.

    Science.gov (United States)

    Chen, She-Jun; Ma, Yun-Juan; Wang, Jing; Tian, Mi; Luo, Xiao-Jun; Chen, Da; Mai, Bi-Xian

    2010-04-15

    Brominated flame retardants (BFRs), polybrominated diphenyl ethers (PBDEs), and decabromodiphenyl ethane (DBDPE) were examined in household products in the Pearl River Delta, South China, including electronic appliances, furniture and upholstery, car interiors, and raw materials for electronics. The concentrations of PBDEs derived from penta-BDE mixture were much lower (electronic products and their reuse might be also a potential important source of discontinued PBDEs to the environment. DBDPE was found in 20.0% of all the samples, ranging from 311 to 268,230 ng/g. PBDE congener profiles in both the household products and raw materials suggest that some less brominated BDEs in the environment may be derived from the decomposition of higher brominated PBDEs in PBDE-containing products in process of the manufacturing, use and/or recycling. Human exposure to PBDEs from household products via inhalation ranged from 175 to 612 pg/kg bw day, accounting for a small proportion of the total daily exposure via indoor inhalation. Despite the low deleterious risk associated with household products with regard to PBDEs, they are of special concern because of the relatively higher exposures observed for young children and further work is required. 2009 Elsevier B.V. All rights reserved.

  10. Bromine incorporation into five DBP classes upon chlorination of water with extremely low SUVA values.

    Science.gov (United States)

    Hong, Huachang; Yan, Xiaoqing; Song, Xuhui; Qin, Yanyan; Sun, Hongjie; Lin, Hongjun; Chen, Jianrong; Liang, Yan

    2017-07-15

    The main objective of this study was to assess the effects of disinfection conditions on bromine incorporation into disinfection by-products (DBPs) during chlorination of water with low specific UV absorbance (SUVA). Five classes of DBPs were included: trihalomethanes (THMs), dihaloacetic acids (di-HAAs), trihaloacetic acids (tri-HAAs), dihaloacetonitriles (DHANs) and trihalonitromethanes (THNMs). Results showed that the bromine utilization in DBPs formation was positive related with reaction time, pH and temperature. On the other hand, the bromine substitution factors (BSFs) of DBPs were generally increased with pH (except tri-HAAs) and bromide concentration, but decreased with the reaction time, temperature and chlorine dose. Moreover, the BSFs values varied with DBP classes with the ranking being as following: THNMs≫DHANs≫tri-HAAs>THM≈di-HAAs. These results were mostly similar with the references, yet the pH effect on BSFs as well as the rank of BSFs for different DBP classes may differ with the specific UV absorbance of organic matter. Copyright © 2017 Elsevier B.V. All rights reserved.

  11. Measurement and human exposure assessment of brominated flame retardants in household products from South China

    Energy Technology Data Exchange (ETDEWEB)

    Chen Shejun [State Key Laboratory of Organic Geochemistry, Guangzhou Institute of Geochemistry, Chinese Academy of Sciences, Guangzhou 510640 (China); Ma Yunjuan [State Key Laboratory of Organic Geochemistry, Guangzhou Institute of Geochemistry, Chinese Academy of Sciences, Guangzhou 510640 (China); Zhuhai Environmental Moniorting Center, Zhuhai 519000 (China); Wang Jing; Tian Mi [State Key Laboratory of Organic Geochemistry, Guangzhou Institute of Geochemistry, Chinese Academy of Sciences, Guangzhou 510640 (China); Graduate University of Chinese Academy of Sciences, Beijing 100049 (China); Luo Xiaojun [State Key Laboratory of Organic Geochemistry, Guangzhou Institute of Geochemistry, Chinese Academy of Sciences, Guangzhou 510640 (China); Chen Da [Department of Environmental and Aquatic Animal Health, Virginia Institute of Marine Science, College of William and Mary, Gloucester Point, VA 23062 (United States); Mai Bixian, E-mail: nancymai@gig.ac.cn [State Key Laboratory of Organic Geochemistry, Guangzhou Institute of Geochemistry, Chinese Academy of Sciences, Guangzhou 510640 (China)

    2010-04-15

    Brominated flame retardants (BFRs), polybrominated diphenyl ethers (PBDEs), and decabromodiphenyl ethane (DBDPE) were examined in household products in the Pearl River Delta, South China, including electronic appliances, furniture and upholstery, car interiors, and raw materials for electronics. The concentrations of PBDEs derived from penta-BDE mixture were much lower (<111 ng/g) than those for octa- and deca-BDE commercially derived PBDEs, with maximum values of 15,107 and 1,603,343 ng/g, respectively, in all the household products. Our findings suggest the recycling of old electronic products and their reuse might be also a potential important source of discontinued PBDEs to the environment. DBDPE was found in 20.0% of all the samples, ranging from 311 to 268,230 ng/g. PBDE congener profiles in both the household products and raw materials suggest that some less brominated BDEs in the environment may be derived from the decomposition of higher brominated PBDEs in PBDE-containing products in process of the manufacturing, use and/or recycling. Human exposure to PBDEs from household products via inhalation ranged from 175 to 612 pg/kg bw day, accounting for a small proportion of the total daily exposure via indoor inhalation. Despite the low deleterious risk associated with household products with regard to PBDEs, they are of special concern because of the relatively higher exposures observed for young children and further work is required.

  12. Measurement and human exposure assessment of brominated flame retardants in household products from South China

    International Nuclear Information System (INIS)

    Chen Shejun; Ma Yunjuan; Wang Jing; Tian Mi; Luo Xiaojun; Chen Da; Mai Bixian

    2010-01-01

    Brominated flame retardants (BFRs), polybrominated diphenyl ethers (PBDEs), and decabromodiphenyl ethane (DBDPE) were examined in household products in the Pearl River Delta, South China, including electronic appliances, furniture and upholstery, car interiors, and raw materials for electronics. The concentrations of PBDEs derived from penta-BDE mixture were much lower (<111 ng/g) than those for octa- and deca-BDE commercially derived PBDEs, with maximum values of 15,107 and 1,603,343 ng/g, respectively, in all the household products. Our findings suggest the recycling of old electronic products and their reuse might be also a potential important source of discontinued PBDEs to the environment. DBDPE was found in 20.0% of all the samples, ranging from 311 to 268,230 ng/g. PBDE congener profiles in both the household products and raw materials suggest that some less brominated BDEs in the environment may be derived from the decomposition of higher brominated PBDEs in PBDE-containing products in process of the manufacturing, use and/or recycling. Human exposure to PBDEs from household products via inhalation ranged from 175 to 612 pg/kg bw day, accounting for a small proportion of the total daily exposure via indoor inhalation. Despite the low deleterious risk associated with household products with regard to PBDEs, they are of special concern because of the relatively higher exposures observed for young children and further work is required.

  13. Mechanochemical conversion of brominated POPs into useful oxybromides: a greener approach

    Science.gov (United States)

    Cagnetta, Giovanni; Liu, Han; Zhang, Kunlun; Huang, Jun; Wang, Bin; Deng, Shubo; Wang, Yujue; Yu, Gang

    2016-06-01

    Brominated organic pollutants are considered of great concern for their adverse effect on human health and the environment, so an increasing number of such compounds are being classified as persistent organic pollutants (POPs). Mechanochemical destruction is a promising technology for POPs safe disposal because it can achieve their complete carbonization by solvent-free high energy ball milling at room temperature. However, a large amount of co-milling reagent usually is necessary, so a considerable volume of residue is produced. In the present study a different approach to POPs mechanochemical destruction is proposed. Employing stoichiometric quantities of Bi2O3 or La2O3 as co-milling reagent, brominated POPs are selectively and completely converted into their corresponding oxybromides (i.e. BiOBr and LaOBr), which possess very peculiar properties and can be used for some actual and many more potential applications. In this way, bromine is beneficially reused in the final product, while POPs carbon skeleton is safely destroyed to amorphous carbon. Moreover, mechanochemical destruction is employed in a greener and more sustainable manner.

  14. Integration of Bromine and Cyanogen Bromide Generators for the Continuous-Flow Synthesis of Cyclic Guanidines.

    Science.gov (United States)

    Glotz, Gabriel; Lebl, René; Dallinger, Doris; Kappe, C Oliver

    2017-10-23

    A continuous-flow process for the in situ on-demand generation of cyanogen bromide (BrCN) from bromine and potassium cyanide that makes use of membrane-separation technology is described. In order to circumvent the handling, storage, and transportation of elemental bromine, a continuous bromine generator using bromate-bromide synproportionation can optionally be attached upstream. Monitoring and quantification of BrCN generation was enabled through the implementation of in-line FTIR technology. With the Br 2 and BrCN generators connected in series, 0.2 mmol BrCN per minute was produced, which corresponds to a 0.8 m solution of BrCN in dichloromethane. The modular Br 2 /BrCN generator was employed for the synthesis of a diverse set of biologically relevant five- and six-membered cyclic amidines and guanidines. The set-up can either be operated in a fully integrated continuous format or, where reactive crystallization is beneficial, in semi-batch mode. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  15. Stratospheric changes caused by geoengineering applications: potential repercussions and uncertainties

    Science.gov (United States)

    Kenzelmann, P.; Weisenstein, D.; Peter, T.; Luo, B. P.; Rozanov, E.; Fueglistaler, S.; Thomason, L. W.

    2009-04-01

    Anthropogenic greenhouse gas emissions tend to warm the global climate, calling for significant rapid emission reductions. As potential support measures various ideas for geoengineering are currently being discussed. The assessment of the possible manifold and as yet substantially unexplored repercussions of implementing geoengineering ideas to ameliorate climate change poses enormous challenges not least in the realm of aerosol-cloud-climate interactions. Sulphur aerosols cool the Earth's surface by reflecting short wave radiation. By increasing the amount of sulphur aerosols in the stratosphere, for example by sulphur dioxide injections, part of the anthropogenic climate warming might be compensated due to enhanced albedo. However, we are only at the beginning of understanding possible side effects. One such effect that such aerosol might have is the warming of the tropical tropopause and consequently the increase of the amount of stratospheric water vapour. Using the 2D AER Aerosol Model we calculated the aerosol distributions for yearly injections of 1, 2, 5 and 10 Mt sulphur into the lower tropical stratosphere. The results serve as input for the 3D chemistry-climate model SOCOL, which allows calculating the aerosol effect on stratospheric temperatures and chemistry. In the injection region the continuously formed sulphuric acid condensates rapidly on sulphate aerosol, which eventually grow to such extent that they sediment down to the tropical tropopause region. The growth of the aerosol particles depends on non-linear processes: the more sulphur is emitted the faster the particles grow. As a consequence for the scenario with continuous sulphur injection of totally 10 Mt per year, only 6 Mt sulphur are in the stratosphere if equilibrium is reached. According to our model calculations this amount of sulphate aerosols leads to a net surface forcing of -3.4 W/m2, which is less then expected radiative forcing by doubling of carbon dioxide concentration. Hence

  16. Brominated flame retardants and organochlorine pollutants in eggs of little owls (Athene noctua) from Belgium

    International Nuclear Information System (INIS)

    Jaspers, Veerle; Covaci, Adrian; Maervoet, Johan; Dauwe, Tom; Voorspoels, Stefan; Schepens, Paul; Eens, Marcel

    2005-01-01

    Residues of brominated diphenylethers (PBDEs), organochlorinated pesticides (OCPs) and polychlorinated biphenyls (PCBs) were measured in 40 eggs of little owls (Athene noctua), a terrestrial top predator from Belgium. The major organohalogens detected were PCBs (median 2,600 ng/g lipid, range 790-23000 ng/g lipid). PCB 153,138/163, 170, 180 and 187 were the predominant congeners and constituted 71% of total sum PCBs. PBDEs were measurable in all samples, but their concentrations were much lower than for PCBs, with a range from 29-572 ng/g lipid (median 108 ng/g lipid). The most prevalent PBDE congeners in little owl egg samples were BDE 47, 99 and 153. This profile differs from the profile in marine bird species, for which BDE 47 was the dominant congener, indicating that terrestrial birds may be more exposed to higher brominated BDE congeners than marine birds. The fully brominated BDE 209 could be detected in one egg sample (17 ng/g lipid), suggesting that higher brominated BDEs may accumulate in terrestrial food chains. Brominated biphenyl (BB) 153 was determined in all egg samples, with levels ranging from 0.6 to 5.6 ng/g lipid (median 1.3 ng/g lipid). Additionally, hexabromocyclododecane (HBCD) could be identified and quantified in only two eggs at levels of 20 and 50 ng/g lipid. OCPs were present at low concentrations, suggesting a rather low contamination of the sampled environment with OCPs (median concentrations of sum DDTs: 826 ng/g lipid, sum chlordanes: 1,016 ng/g lipid, sum HCHs: 273 ng/g lipid). Hexachlorobenzene (HCB) and octachlorostyrene (OCS) were also found at low median levels of 134 and 3.4 ng/g lipid, respectively. Concentrations of most analytes were significantly higher in eggs collected from deserted nests in comparison to addled (unhatched) eggs, while eggshell thickness did not differ between deserted and addled eggs. No significant correlations were found between eggshell thickness and the analysed organohalogens. - PBDEs are measurable

  17. Bromine monoxide / sulphur dioxide ratios in relation to volcanological observations at Mt. Etna 2006–2009

    Directory of Open Access Journals (Sweden)

    G. Giuffrida

    2012-12-01

    Full Text Available Over a 3-yr period, from 2006 to 2009, frequent scattered sunlight DOAS measurements were conducted at Mt. Etna at a distance of around 6 km downwind from the summit craters. During the same period and in addition to these measurements, volcanic observations were made by regularly visiting various parts of Mt. Etna. Here, results from these measurements and observations are presented and their relation is discussed. The focus of the investigation is the bromine monoxide/sulphur dioxide (BrO / SO2 ratio, and its variability in relation to volcanic processes. That the halogen/sulphur ratio can serve as a precursor or indicator for the onset of eruptive activity was already proposed by earlier works (e.g. Noguchi and Kamiya 1963; Menyailov, 1975; Pennisi and Cloarec, 1998; Aiuppa et al., 2002. However, there is still a limited understanding today because of the complexity with which halogens are released, depending on magma composition and degassing conditions. Our understanding of these processes is far from complete, for example of the rate and mechanism of bubble nucleation, growth and ascent in silicate melts (Carroll and Holloway, 1994, the halogen vapour-melt partitioning and the volatile diffusivity in the melt (Aiuppa et al., 2009. With this study we aim to add one more piece to the puzzle of what halogen/sulphur ratios might tell about volcanic activities. Our data set shows an increase of the BrO / SO2 ratio several weeks prior to an eruption, followed by a decline before and during the initial phase of eruptive activities. Towards the end of activity or shortly thereafter, the ratio increases to baseline values again and remains more or less constant during quiet phases. To explain the observed evolution of the BrO / SO2 ratio, a first empirical model is proposed. This model suggests that bromine, unlike chlorine and fluorine, is less soluble in the magmatic melt than sulphur. By using the DOAS method to determine SO2, we actually

  18. The ASSET intercomparison of stratosphere and lower mesosphere humidity analyses

    Directory of Open Access Journals (Sweden)

    H. E. Thornton

    2009-02-01

    Full Text Available This paper presents results from the first detailed intercomparison of stratosphere-lower mesosphere water vapour analyses; it builds on earlier results from the EU funded framework V "Assimilation of ENVISAT Data" (ASSET project. Stratospheric water vapour plays an important role in many key atmospheric processes and therefore an improved understanding of its daily variability is desirable. With the availability of high resolution, good quality Michelson Interferometer for Passive Atmospheric Sounding (MIPAS water vapour profiles, the ability of four different atmospheric models to assimilate these data is tested. MIPAS data have been assimilated over September 2003 into the models of the European Centre for Medium Range Weather Forecasts (ECMWF, the Belgian Institute for Space and Aeronomy (BIRA-IASB, the French Service d'Aéronomie (SA-IPSL and the UK Met Office. The resultant middle atmosphere humidity analyses are compared against independent satellite data from the Halogen Occultation Experiment (HALOE, the Polar Ozone and Aerosol Measurement (POAM III and the Stratospheric Aerosol and Gas Experiment (SAGE II. The MIPAS water vapour profiles are generally well assimilated in the ECMWF, BIRA-IASB and SA systems, producing stratosphere-mesosphere water vapour fields where the main features compare favourably with the independent observations. However, the models are less capable of assimilating the MIPAS data where water vapour values are locally extreme or in regions of strong humidity gradients, such as the southern hemisphere lower stratosphere polar vortex. Differences in the analyses can be attributed to the choice of humidity control variable, how the background error covariance matrix is generated, the model resolution and its complexity, the degree of quality control of the observations and the use of observations near the model boundaries. Due to the poor performance of the Met Office analyses the results are not included in

  19. The ASSET intercomparison of stratosphere and lower mesosphere humidity analyses

    Science.gov (United States)

    Thornton, H. E.; Jackson, D. R.; Bekki, S.; Bormann, N.; Errera, Q.; Geer, A. J.; Lahoz, W. A.; Rharmili, S.

    2009-02-01

    This paper presents results from the first detailed intercomparison of stratosphere-lower mesosphere water vapour analyses; it builds on earlier results from the EU funded framework V "Assimilation of ENVISAT Data" (ASSET) project. Stratospheric water vapour plays an important role in many key atmospheric processes and therefore an improved understanding of its daily variability is desirable. With the availability of high resolution, good quality Michelson Interferometer for Passive Atmospheric Sounding (MIPAS) water vapour profiles, the ability of four different atmospheric models to assimilate these data is tested. MIPAS data have been assimilated over September 2003 into the models of the European Centre for Medium Range Weather Forecasts (ECMWF), the Belgian Institute for Space and Aeronomy (BIRA-IASB), the French Service d'Aéronomie (SA-IPSL) and the UK Met Office. The resultant middle atmosphere humidity analyses are compared against independent satellite data from the Halogen Occultation Experiment (HALOE), the Polar Ozone and Aerosol Measurement (POAM III) and the Stratospheric Aerosol and Gas Experiment (SAGE II). The MIPAS water vapour profiles are generally well assimilated in the ECMWF, BIRA-IASB and SA systems, producing stratosphere-mesosphere water vapour fields where the main features compare favourably with the independent observations. However, the models are less capable of assimilating the MIPAS data where water vapour values are locally extreme or in regions of strong humidity gradients, such as the southern hemisphere lower stratosphere polar vortex. Differences in the analyses can be attributed to the choice of humidity control variable, how the background error covariance matrix is generated, the model resolution and its complexity, the degree of quality control of the observations and the use of observations near the model boundaries. Due to the poor performance of the Met Office analyses the results are not included in the intercomparison

  20. Impacts of stratospheric sulfate geoengineering on tropospheric ozone

    Science.gov (United States)

    Xia, Lili; Nowack, Peer J.; Tilmes, Simone; Robock, Alan

    2017-10-01

    A range of solar radiation management (SRM) techniques has been proposed to counter anthropogenic climate change. Here, we examine the potential effects of stratospheric sulfate aerosols and solar insolation reduction on tropospheric ozone and ozone at Earth's surface. Ozone is a key air pollutant, which can produce respiratory diseases and crop damage. Using a version of the Community Earth System Model from the National Center for Atmospheric Research that includes comprehensive tropospheric and stratospheric chemistry, we model both stratospheric sulfur injection and solar irradiance reduction schemes, with the aim of achieving equal levels of surface cooling relative to the Representative Concentration Pathway 6.0 scenario. This allows us to compare the impacts of sulfate aerosols and solar dimming on atmospheric ozone concentrations. Despite nearly identical global mean surface temperatures for the two SRM approaches, solar insolation reduction increases global average surface ozone concentrations, while sulfate injection decreases it. A fundamental difference between the two geoengineering schemes is the importance of heterogeneous reactions in the photochemical ozone balance with larger stratospheric sulfate abundance, resulting in increased ozone depletion in mid- and high latitudes. This reduces the net transport of stratospheric ozone into the troposphere and thus is a key driver of the overall decrease in surface ozone. At the same time, the change in stratospheric ozone alters the tropospheric photochemical environment due to enhanced ultraviolet radiation. A shared factor among both SRM scenarios is decreased chemical ozone loss due to reduced tropospheric humidity. Under insolation reduction, this is the dominant factor giving rise to the global surface ozone increase. Regionally, both surface ozone increases and decreases are found for both scenarios; that is, SRM would affect regions of the world differently in terms of air pollution. In conclusion

  1. Impacts of stratospheric sulfate geoengineering on tropospheric ozone

    Directory of Open Access Journals (Sweden)

    L. Xia

    2017-10-01

    Full Text Available A range of solar radiation management (SRM techniques has been proposed to counter anthropogenic climate change. Here, we examine the potential effects of stratospheric sulfate aerosols and solar insolation reduction on tropospheric ozone and ozone at Earth's surface. Ozone is a key air pollutant, which can produce respiratory diseases and crop damage. Using a version of the Community Earth System Model from the National Center for Atmospheric Research that includes comprehensive tropospheric and stratospheric chemistry, we model both stratospheric sulfur injection and solar irradiance reduction schemes, with the aim of achieving equal levels of surface cooling relative to the Representative Concentration Pathway 6.0 scenario. This allows us to compare the impacts of sulfate aerosols and solar dimming on atmospheric ozone concentrations. Despite nearly identical global mean surface temperatures for the two SRM approaches, solar insolation reduction increases global average surface ozone concentrations, while sulfate injection decreases it. A fundamental difference between the two geoengineering schemes is the importance of heterogeneous reactions in the photochemical ozone balance with larger stratospheric sulfate abundance, resulting in increased ozone depletion in mid- and high latitudes. This reduces the net transport of stratospheric ozone into the troposphere and thus is a key driver of the overall decrease in surface ozone. At the same time, the change in stratospheric ozone alters the tropospheric photochemical environment due to enhanced ultraviolet radiation. A shared factor among both SRM scenarios is decreased chemical ozone loss due to reduced tropospheric humidity. Under insolation reduction, this is the dominant factor giving rise to the global surface ozone increase. Regionally, both surface ozone increases and decreases are found for both scenarios; that is, SRM would affect regions of the world differently in terms of air

  2. Key aspects of stratospheric tracer modeling using assimilated winds

    Directory of Open Access Journals (Sweden)

    B. Bregman

    2006-01-01

    Full Text Available This study describes key aspects of global chemistry-transport models and their impact on stratospheric tracer transport. We concentrate on global models that use assimilated winds from numerical weather predictions, but the results also apply to tracer transport in general circulation models. We examined grid resolution, numerical diffusion, air parcel dispersion, the wind or mass flux update frequency, and time interpolation. The evaluation is performed with assimilated meteorology from the "operational analyses or operational data" (OD from the European Centre for Medium-Range Weather Forecasts (ECMWF. We also show the effect of the mass flux update frequency using the ECMWF 40-year re-analyses (ERA40. We applied the three-dimensional chemistry-transport Tracer Model version 5 (TM5 and a trajectory model and performed several diagnoses focusing on different transport regimes. Covering different time and spatial scales, we examined (1 polar vortex dynamics during the Arctic winter, (2 the large-scale stratospheric meridional circulation, and (3 air parcel dispersion in the tropical lower stratosphere. Tracer distributions inside the Arctic polar vortex show considerably worse agreement with observations when the model grid resolution in the polar region is reduced to avoid numerical instability. The results are sensitive to the diffusivity of the advection. Nevertheless, the use of a computational cheaper but diffusive advection scheme is feasible for tracer transport when the horizontal grid resolution is equal or smaller than 1 degree. The use of time interpolated winds improves the tracer distributions, particularly in the middle and upper stratosphere. Considerable improvement is found both in the large-scale tracer distribution and in the polar regions when the update frequency of the assimilated winds is increased from 6 to 3 h. It considerably reduces the vertical dispersion of air parcels in the tropical lower stratosphere. Strong

  3. Hydroxylated polybrominated diphenyl ethers exhibit different activities on thyroid hormone receptors depending on their degree of bromination.

    Science.gov (United States)

    Ren, Xiao-Min; Guo, Liang-Hong; Gao, Yu; Zhang, Bin-Tian; Wan, Bin

    2013-05-01

    Polybrominated diphenyl ethers (PBDEs) have been shown to disrupt thyroid hormone (TH) functions in experimental animals, and one of the proposed disruption mechanisms is direct binding of hydroxylated PBDE (OH-PBDE) to TH receptors (TRs). However, previous data on TH receptor binding and TH activity of OH-PBDEs were very limited and sometimes inconsistent. In the present paper, we examined the binding potency of ten OH-PBDEs with different degrees of bromination to TR using a fluorescence competitive binding assay. The results showed that the ten OH-PBDEs bound to TR with potency that correlated to their bromination level. We further examined their effect on TR using a coactivator binding assay and GH3 cell proliferation assay. Different TR activities of OH-PBDEs were observed depending on their degree of bromination. Four low-brominated OH-PBDEs (2'-OH-BDE-28, 3'-OH-BDE-28, 5-OH-BDE-47, 6-OH-BDE-47) were found to be TR agonists, which recruited the coactivator peptide and enhanced GH3 cell proliferation. However, three high-brominated OH-PBDEs (3-OH-BDE-100, 3'-OH-BDE-154, 4-OH-BDE-188) were tested to be antagonists. Molecular docking was employed to simulate the interactions of OH-PBDEs with TR and identify the structural determinants for TR binding and activity. According to the docking results, low-brominated OH-PBDEs, which are weak binders but TR agonists, bind with TR at the inner side of its binding pocket, whereas high-brominated compounds, which are potent binders but TR antagonists, reside at the outer region. These results indicate that OH-PBDEs have different activities on TR (agonistic or antagonistic), possibly due to their different binding geometries with the receptor. Copyright © 2013 Elsevier Inc. All rights reserved.

  4. Photochemistry and Gas-Phase FTIR Spectroscopy of Formic Acid Interaction with Anatase Ti18O2 Nanoparticles

    Czech Academy of Sciences Publication Activity Database

    Civiš, Svatopluk; Ferus, Martin; Zukalová, Markéta; Kubát, Pavel; Kavan, Ladislav

    2012-01-01

    Roč. 116, č. 20 (2012), s. 11200-11205 ISSN 1932-7447 R&D Projects: GA AV ČR IAAX00100903; GA AV ČR IAA400400804; GA AV ČR KAN200100801; GA ČR GAP208/10/1678; GA MŠk OC09044 Institutional support: RVO:61388955 Keywords : photochemistry * FTIR spectroscopy * nanoparticles Subject RIV: CF - Physical ; Theoretical Chemistry Impact factor: 4.814, year: 2012

  5. The reaction O((3)P) + HOBr: Temperature dependence of the rate constant and importance of the reaction as an HOBr stratospheric loss process

    Science.gov (United States)

    Nesbitt, F. L.; Monks, P. S.; Payne, W. A.; Stief, L. J.; Toumi, R.

    1995-01-01

    The absolute rate constant for the reaction O((3)P) + HOBr has been measured between T = 233K and 423K using the discharge-flow kinetic technique coupled to mass spectrometric detection. The value of the rate coefficient at room temperature is (2.5 +/- 0.6) x 10(exp -11)cu cm/molecule/s and the derived Arrhenius expression is (1.4 +/- 0.5) x 10(exp -10) exp((-430 +/- 260)/T)cu cm/molecule/s. From these rate data the atmospheric lifetime of HOBr with respect to reaction with O((3)P) is about 0.6h at z = 25 km which is comparable to the photolysis lifetime based on recent measurements of the UV cross section for HOBr. Implications for HOBr loss in the stratosphere have been tested using a 1D photochemical box model. With the inclusion of the rate parameters and products for the O + HOBr reaction, calculated concentration profiles of BrO increase by up to 33% around z = 35 km. This result indicates that the inclusion of the O + HOBr reaction in global atmospheric chemistry models may have an impact on bromine partitioning in the middle atmosphere.

  6. Triplet state photochemistry and the three-state crossing of acetophenone within time-dependent density-functional theory

    Energy Technology Data Exchange (ETDEWEB)

    Huix-Rotllant, Miquel, E-mail: miquel.huix@gmail.com; Ferré, Nicolas, E-mail: nicolas.ferre@univ-amu.fr [Institut de Chimie Radicalaire (UMR-7273), Aix-Marseille Université, CNRS, 13397 Marseille Cedex 20 (France)

    2014-04-07

    Even though time-dependent density-functional theory (TDDFT) works generally well for describing excited states energies and properties in the Franck-Condon region, it can dramatically fail in predicting photochemistry, notably when electronic state crossings occur. Here, we assess the ability of TDDFT to describe the photochemistry of an important class of triplet sensitizers, namely, aromatic ketones. We take acetophenone as a test molecule, for which accurate ab initio results exist in the literature. Triplet acetophenone is generated thanks to an exotic three-state crossing involving one singlet and two triplets states (i.e., a simultaneous intersystem crossing and triplet conical intersection), thus being a stringent test for approximate TDDFT. We show that most exchange-correlation functionals can only give a semi-qualitative picture of the overall photochemistry, in which the three-state crossing is rather represented as a triplet conical intersection separated from the intersystem crossing. The best result overall is given by the double hybrid functional mPW2PLYP, which is even able to reproduce quantitatively the three-state crossing region. We rationalize this results by noting that double hybrid functionals include a larger portion of double excitation character to the excited states.

  7. Biweekly list of papers on radiation chemistry and photochemistry. Annual cumulation with keyword and author indexes. Volume 16. 1983

    International Nuclear Information System (INIS)

    Carmichael, I.C.; Helman, W.P.; Hug, G.L.; Ross, A.B.

    1983-01-01

    The Biweekly List of Papers on Radiation Chemistry and Photochemistry is a current-awareness service published by the Radiation Chemistry Data Center (RCDC), with special emphasis on the kinetics and other properties of transient ions, radicals, and excited species. Papers are included on the radiation chemistry and photochemistry of organic and inorganic systems, biological molecules and polymers, with references to ESR and luminescence studies. Complete coverage is attempted only for those studies which are initiated by light or ionizing radiation, and which provide quantitative physical chemical data such as quantum yields, specific rates, G values, etc. No attempt is made to cover topics such as mechanistic and preparative photochemistry, photosynthesis, photography, and irradiation of metals. The references listed herein are obtained from scanning about 60 current journals as well as Chemical Abstracts, INIS Atomindex and several other publications listing current references. The reference lists, which are issued biweekly, are cumulated annually with the addition of keyword and author indexes. Indexed cumulations were published semiannually for Vol. 4-6 (1971-73) and are published annually for Vol. 7+ (1974+); back copies are available from the National Technical Information Service (NTIS)

  8. Using the Flipchem Photochemistry Model When Fitting Incoherent Scatter Radar Data

    Science.gov (United States)

    Reimer, A. S.; Varney, R. H.

    2017-12-01

    The North face Resolute Bay Incoherent Scatter Radar (RISR-N) routinely images the dynamics of the polar ionosphere, providing measurements of the plasma density, electron temperature, ion temperature, and line of sight velocity with seconds to minutes time resolution. RISR-N does not directly measure ionospheric parameters, but backscattered signals, recording them as voltage samples. Using signal processing techniques, radar autocorrelation functions (ACF) are estimated from the voltage samples. A model of the signal ACF is then fitted to the ACF using non-linear least-squares techniques to obtain the best-fit ionospheric parameters. The signal model, and therefore the fitted parameters, depend on the ionospheric ion composition that is used [e.g. Zettergren et. al. (2010), Zou et. al. (2017)].The software used to process RISR-N ACF data includes the "flipchem" model, which is an ion photochemistry model developed by Richards [2011] that was adapted from the Field LineInterhemispheric Plasma (FLIP) model. Flipchem requires neutral densities, neutral temperatures, electron density, ion temperature, electron temperature, solar zenith angle, and F10.7 as inputs to compute ion densities, which are input to the signal model. A description of how the flipchem model is used in RISR-N fitting software will be presented. Additionally, a statistical comparison of the fitted electron density, ion temperature, electron temperature, and velocity obtained using a flipchem ionosphere, a pure O+ ionosphere, and a Chapman O+ ionosphere will be presented. The comparison covers nearly two years of RISR-N data (April 2015 - December 2016). Richards, P. G. (2011), Reexamination of ionospheric photochemistry, J. Geophys. Res., 116, A08307, doi:10.1029/2011JA016613.Zettergren, M., Semeter, J., Burnett, B., Oliver, W., Heinselman, C., Blelly, P.-L., and Diaz, M.: Dynamic variability in F-region ionospheric composition at auroral arc boundaries, Ann. Geophys., 28, 651-664, https

  9. Rigorous determination of stratospheric water vapor trends from MIPAS observations.

    Science.gov (United States)

    Ceccherini, Simone; Carli, Bruno; Raspollini, Piera; Ridolfi, Marco

    2011-05-09

    The trend of stratospheric water vapor as a function of latitude is estimated by the MIPAS measurements by means of a new method that uses the measurement space solution. The method uses all the information provided by the observations avoiding the artifacts introduced by the a priori information and by the interpolation to different vertical grids. The analysis provides very precise values of the trends that, however, are limited by a relatively large systematic error induced by the radiometric calibration error of the instrument. The results show in the five years from 2005 to 2009 a dependence on latitude of the stratospheric (from 37 to 53 km) water vapor trend with a positive value of (0.41 ± 0.16)%yr-1 in the northern hemisphere and less than 0.16%yr-1 in the southern hemisphere.

  10. Hygienic estimation of population doses due to stratospheric fallout

    International Nuclear Information System (INIS)

    Marej, A.N.; Knizhnikov, V.A.

    1980-01-01

    The hygienic estimation of external and internal irradiation of the USSR population due to stratospheric global fallouts of fission products after nuclear explosions and weapon tests, is carried out. Numerical values which characterize the dose-effect dependence in the case of radiation of marrow, bone tissue and whole body are presented. Values of mean individual and population doses of irradiation due to global fallouts within 1963-1975, types of injury and the number of mortal cases due to malignant neoplasms are presented. A conclusion is made that the contribution of radiation due to stratospheric fallouts in the mortality due to malignant neoplasms is insignificant. Annual radiation doses, conditioned by global fallouts within the period of 1963-1975 constitute but several percent from the dose of radiation of the natural radiation background. Results of estimation of genetic consequences of irradiation due to atmospheric fallouts are presented

  11. Eight years of stratospheric ozone observations at Marambio, Antarctica

    Energy Technology Data Exchange (ETDEWEB)

    Damski, J; Taalas, P [Finnish Meteorological Inst., Helsinki (Finland). Section of Ozone and UV Research

    1996-12-31

    In this work behaviour of the stratospheric ozone using the total ozone and ozone sounding measurements from Marambio (64 deg 14`S, 56 deg 37`W) at Antarctic Peninsula has been studied. The effects of depleted stratospheric ozone to the UV-B-radiation are investigated employing a radiative transfer model, and the Marambio total ozone measurements. The levels of UV-B radiation have been studied from the point of the erythemal UV-B-doses on the horizontal human epidermis. The low values of total ozone at Marambio are also reflected to the received UV-doses which have increased roughly 20-80% (compared to long term average) during austral spring and summer. In respective to the total amount of ozone, the model calculations show that during October the UV-B-doses can be at the same level they should be during normal summer

  12. Wind tunnel tests of stratospheric airship counter rotating propellers

    Directory of Open Access Journals (Sweden)

    Yaxi Chen

    2015-01-01

    Full Text Available Aerodynamic performance of the high-altitude propeller, especially the counter rotation effects, is experimentally studied. Influences of different configurations on a stratospheric airship, included 2-blade counter-rotating propeller (CRP, dual 2-blade single rotation propellers (SRPs and 4-blade SRP, are also indicated. This research indicates that the effect of counter rotation can greatly improve the efficiency. It shows that the CRP configuration results in a higher efficiency than the dual 2-blade SRPs configuration or 4-blade SRP configuration under the same advance ratio, and the CRP configuration also gains the highest efficiency whether under the situation of providing the same trust or absorbing the same power. It concludes that, for a stratospheric airship, the CRP configuration is better than the multiple SRPs configuration or a multi-blade SRP one.

  13. Solar UV radiation variations and their stratospheric and climatic effects

    Science.gov (United States)

    Donnelly, R. F.; Heath, D. F.

    1985-01-01

    Nimbus-7 SBUV measurements of the short-term solar UV variations caused by solar rotation and active-region evolution have determined the amplitude and wavelength dependence for the active-region component of solar UV variations. Intermediate-term variations lasting several months are associated with rounds of major new active regions. The UV flux stays near the peak value during the current solar cycle variation for more than two years and peaks about two years later than the sunspot number. Nimbus-7 measurements have observed the concurrent stratospheric ozone variations caused by solar UV variations. There is now no doubt that solar UV variations are an important cause of short- and long-term stratospheric variations, but the strength of the coupling to the troposphere and to climate has not yet been proven.

  14. Chemical characterization of local and stratospheric plutonium in Ohio soils

    International Nuclear Information System (INIS)

    Muller, R.N.

    1978-01-01

    The chemical nature of plutonium derived from stratospheric fallout and industrial sources was studied in three agricultural soils. The majority of the soil plutonium was associated with a reductant-soluble, hydrous oxide phase that, under most conditions of terrestrial ecosystems, remains essentially immobile. The proportion of plutonium associated with organic matter (0.1N NaOH-extractable) varied among soils, and increased with decreasing particle size in the same soil. In a soil containing 238 Pu from a local fabrication facility and 239 , 240 Pu from stratospheric fallout, isotopic ratios between the NaOH-extractable and residual phases were essentially constant, indicating that, in these soils, plutonium from both sources behaves similarly. The distribution of soil plutonium with particle size appears to be most directly related to the mass of the soil particle

  15. Eight years of stratospheric ozone observations at Marambio, Antarctica

    Energy Technology Data Exchange (ETDEWEB)

    Damski, J.; Taalas, P. [Finnish Meteorological Inst., Helsinki (Finland). Section of Ozone and UV Research

    1995-12-31

    In this work behaviour of the stratospheric ozone using the total ozone and ozone sounding measurements from Marambio (64 deg 14`S, 56 deg 37`W) at Antarctic Peninsula has been studied. The effects of depleted stratospheric ozone to the UV-B-radiation are investigated employing a radiative transfer model, and the Marambio total ozone measurements. The levels of UV-B radiation have been studied from the point of the erythemal UV-B-doses on the horizontal human epidermis. The low values of total ozone at Marambio are also reflected to the received UV-doses which have increased roughly 20-80% (compared to long term average) during austral spring and summer. In respective to the total amount of ozone, the model calculations show that during October the UV-B-doses can be at the same level they should be during normal summer

  16. Infrared emission high spectral resolution atlas of the stratospheric limb

    Science.gov (United States)

    Maguire, William C.; Kunde, Virgil G.; Herath, Lawrence W.

    1989-01-01

    An atlas of high resolution infrared emission spectra identifies a number of gaseous atmospheric features significant to stratospheric chemistry in the 770-900/cm and 1100-1360/cm regions at six zenith angles from 86.7 to 95.1 deg. A balloon-borne Michelson interferometer was flown to obtain about 0.03/cm resolution spectra. Two 10/cm extracts are presented here.

  17. A warming tropical central Pacific dries the lower stratosphere

    Science.gov (United States)

    Ding, Qinghua; Fu, Qiang

    2018-04-01

    The amount of water vapor in the tropical lower stratosphere (TLS), which has an important influence on the radiative energy budget of the climate system, is modulated by the temperature variability of the tropical tropopause layer (TTL). The TTL temperature variability is caused by a complex combination of the stratospheric quasi-biennial oscillation (QBO), tropospheric convective processes in the tropics, and the Brewer-Dobson circulation (BDC) driven by mid-latitude and subtropical atmospheric waves. In 2000, the TLS water vapor amount exhibited a stepwise transition to a dry phase, apparently caused by a change in the BDC. In this study, we present observational and modeling evidence that the epochal change of water vapor between the periods of 1992-2000 and 2001-2005 was also partly caused by a concurrent sea surface temperature (SST) warming in the tropical central Pacific. This SST warming cools the TTL above by enhancing the equatorial wave-induced upward motion near the tropopause, which consequently reduces the amount of water vapor entering the stratosphere. The QBO affects the TLS water vapor primarily on inter-annual timescales, whereas a classical El Niño southern oscillation (ENSO) event has small effect on tropical mean TLS water vapor because its responses are longitudinally out of phase. This study suggests that the tropical central Pacific SST is another driver of TLS water vapor variability on inter-decadal timescales and the tropical SST changes could contribute to about 30% of the step-wise drop of the lower stratospheric water vapor from 1992-2000 to 2001-2005.

  18. Alert with destruction of stratospheric ozone: 95 Nobel Prize Winners

    International Nuclear Information System (INIS)

    Santamaria, J.; Zurita, E.

    1995-01-01

    After briefly summarizing the discoveries of the 95 Nobel Prize Winners in Chemistry related to the threats to the ozone layer by chemical pollutants, we make a soft presentation of the overall problem of stratospheric ozone, starting with the destructive catalytic cycles of the pollutant-based free radicals, following with the diffusion mathematical models in Atmospheric Chemistry, and ending with the increasing annual drama of the ozone hole in the Antarctica. (Author)

  19. A vortex dynamics perspective on stratospheric sudden warmings

    OpenAIRE

    Matthewman, N. J.

    2009-01-01

    A vortex dynamics approach is used to study the underlying mechanisms leading to polar vortex breakdown during stratospheric sudden warmings (SSWs). Observational data are used in chapter 2 to construct climatologies of the Arctic polar vortex structure during vortex-splitting and vortex-displacement SSWs occurring between 1958 and 2002. During vortex-splitting SSWs, polar vortex breakdown is shown to be typically independent of height (barotropic), whereas breakdown during vor...

  20. Future emission scenarios for chemicals that may deplete stratospheric ozone

    International Nuclear Information System (INIS)

    Hammitt, J.K; Camm, Frank; Mooz, W.E.; Wolf, K.A.; Bamezai, Anil; Connel, P.S.; Wuebbles, D.J.

    1990-01-01

    Scenarios are developed for long-term future emissions of seven of the most important manmade chemicals that may deplete ozone and the corresponding effect on stratospheric ozone concentrations is calculated using a one-dimensional atmospheric model. The scenarios are based on detailed analysis of the markets for products that use these chemicals and span a central 90% probability interval for the chemicals joint effect on calculated ozone abundance, assuming no additional regulations. (author). 22 refs., 2 figs., 5 tabs

  1. Long duration balloon flights in the middle stratosphere

    Science.gov (United States)

    Malaterre, P.

    1993-02-01

    Research and development performed by the French Space Agency (CNES) over the past 10 years has given the scientific community the Infrared Montgolfiere, a balloon capable of lifting 50-kg payloads into the stratosphere for periods of several weeks. The Infrared Montgolfiere is a hot air balloon that captures infrared radiation using the earth as a heat source. Thirty flights have been launched so far, some lasting more than sixty days and circling the globe twice.

  2. Location and data collection for long stratospheric balloon flights

    Science.gov (United States)

    Malaterre, P.

    Stratospheric balloons capable of taking a 30 kg scientific payload to an altitude of 22 to 30 km for 1 month or more were developed. In-flight experiments were used to qualify the designs of a pumpkin shaped superpressure balloon and an infrared hot air balloon. Tracking of the flights (location and transmission of the parameters measured on board) was achieved using a telemetry gondola including an ARGOS beacon adapted for operation in the low temperatures encountered.

  3. Influence of an Internally-Generated QBO on Modeled Stratospheric Dynamics and Ozone

    Science.gov (United States)

    Hurwitz, M. M.; Newman, P. A.; Song, I. S.

    2011-01-01

    A GEOS V2 CCM simulation with an internally generated quasi-biennial oscillation (QBO) signal is compared to an otherwise identical simulation without a QBO. In a present-day climate, inclusion of the modeled QBO makes a significant difference to stratospheric dynamics and ozone throughout the year. The QBO enhances variability in the tropics, as expected, but also in the polar stratosphere in some seasons. The modeled QBO also affects the mean stratospheric climate. Because tropical zonal winds in the baseline simulation are generally easterly, there is a relative increase in zonal wind magnitudes in tropical lower and middle stratosphere in the QBO simulation. Extra-tropical differences between the QBO and 'no QBO' simulations thus reflect a bias toward the westerly phase of the QBO: a relative strengthening and poleward shifting the polar stratospheric jets, and a reduction in Arctic lower stratospheric ozone.

  4. Climate change projections and stratosphere-troposphere interaction

    Energy Technology Data Exchange (ETDEWEB)

    Scaife, Adam A.; Fereday, David R.; Butchart, Neal; Hardiman, Steven C. [Met Office Hadley Centre, Exeter (United Kingdom); Spangehl, Thomas; Cubasch, Ulrich; Langematz, Ulrike [Freie Universitaet Berlin, Berlin (Germany); Akiyoshi, Hideharu [National Institute for Environmental Studies, Tsukuba (Japan); Bekki, Slimane [LATMOS-IPSL, UVSQ, UPMC, CNRS/INSU, Paris (France); Braesicke, Peter [University of Cambridge, Cambridge (United Kingdom); Chipperfield, Martyn P. [University of Leeds, School of Earth and Environment, Leeds (United Kingdom); Gettelman, Andrew [National Center for Atmospheric Research, Boulder, CO (United States); Michou, Martine [GAME/CNRM (Meteo France, CNRS), Toulouse (France); Rozanov, Eugene [PMOD/WRC and ETHZ, Davos (Switzerland); Shepherd, Theodore G. [University of Toronto, Toronto, ON (Canada)

    2012-05-15

    Climate change is expected to increase winter rainfall and flooding in many extratropical regions as evaporation and precipitation rates increase, storms become more intense and storm tracks move polewards. Here, we show how changes in stratospheric circulation could play a significant role in future climate change in the extratropics through an additional shift in the tropospheric circulation. This shift in the circulation alters climate change in regional winter rainfall by an amount large enough to significantly alter regional climate change projections. The changes are consistent with changes in stratospheric winds inducing a change in the baroclinic eddy growth rate across the depth of the troposphere. A change in mean wind structure and an equatorward shift of the tropospheric storm tracks relative to models with poor stratospheric resolution allows coupling with surface climate. Using the Atlantic storm track as an example, we show how this can double the predicted increase in extreme winter rainfall over Western and Central Europe compared to other current climate projections. (orig.)

  5. Global assimilation of X Project Loon stratospheric balloon observations

    Science.gov (United States)

    Coy, L.; Schoeberl, M. R.; Pawson, S.; Candido, S.; Carver, R. W.

    2017-12-01

    Project Loon has an overall goal of providing worldwide internet coverage using a network of long-duration super-pressure balloons. Beginning in 2013, Loon has launched over 1600 balloons from multiple tropical and middle latitude locations. These GPS tracked balloon trajectories provide lower stratospheric wind information over the oceans and remote land areas where traditional radiosonde soundings are sparse, thus providing unique coverage of lower stratospheric winds. To fully investigate these Loon winds we: 1) compare the Loon winds to winds produced by a global data assimilation system (DAS: NASA GEOS) and 2) assimilate the Loon winds into the same comprehensive DAS. Results show that in middle latitudes the Loon winds and DAS winds agree well and assimilating the Loon winds have only a small impact on short-term forecasting of the Loon winds, however, in the tropics the loon winds and DAS winds often disagree substantially (8 m/s or more in magnitude) and in these cases assimilating the loon winds significantly improves the forecast of the loon winds. By highlighting cases where the Loon and DAS winds differ, these results can lead to improved understanding of stratospheric winds, especially in the tropics.

  6. The global warming potential of methane reassessed with combined stratosphere and troposphere chemistry

    Science.gov (United States)

    Holmes, C. D.; Archibald, A. T.; Eastham, S. D.; Søvde, O. A.

    2017-12-01

    Methane is a direct and indirect greenhouse gas. The direct greenhouse effect comes from the radiation absorbed and emitted by methane itself. The indirect greenhouse effect comes from radiatively active gases that are produced during methane oxidation: principally O3, H2O, and CO2. Methane also suppresses tropospheric OH, which indirectly affects numerous greenhouses gases and aerosols. Traditionally, the methane global warming potential (GWP) has included the indirect effects on tropospheric O3 and OH and stratospheric H2O, with these effects estimated independently from unrelated tropospheric and stratospheric chemistry models and observations. Using this approach the CH4 is about 28 over 100 yr (without carbon cycle feedbacks, IPCC, 2013). Here we present a comprehensive analysis of the CH4 GWP in several 3-D global atmospheric models capable of simulating both tropospheric and stratospheric chemistry (GEOS-Chem, Oslo CTM3, UKCA). This enables us to include, for the first time, the indirect effects of CH4 on stratospheric O3 and stratosphere-troposphere coupling. We diagnose the GWP from paired simulations with and without a 5% perturbation to tropospheric CH4 concentrations. Including stratospheric chemistry nearly doubles the O3 contribution to CH4 GWP because of O3 production in the lower stratosphere and because CH4 inhibits Cl-catalyzed O3 loss in the upper stratosphere. In addition, stratosphere-troposphere coupling strengthens the chemical feedback on its own lifetime. In the stratosphere, this feedback operates by a CH4 perturbation thickening the stratospheric O3 layer, which impedes UV-driven OH production in the troposphere and prolongs the CH4 lifetime. We also quantify the impact of CH4-derived H2O on the stratospheric HOx cycles but these effects are small. Combining all of the above, these models suggest that the 100-yr GWP of CH4 is over 33.5, a 20% increase over the latest IPCC assessment.

  7. Effects of stratospheric aerosol surface processes on the LLNL two-dimensional zonally averaged model

    International Nuclear Information System (INIS)

    Connell, P.S.; Kinnison, D.E.; Wuebbles, D.J.; Burley, J.D.; Johnston, H.S.

    1992-01-01

    We have investigated the effects of incorporating representations of heterogeneous chemical processes associated with stratospheric sulfuric acid aerosol into the LLNL two-dimensional, zonally averaged, model of the troposphere and stratosphere. Using distributions of aerosol surface area and volume density derived from SAGE 11 satellite observations, we were primarily interested in changes in partitioning within the Cl- and N- families in the lower stratosphere, compared to a model including only gas phase photochemical reactions

  8. Stratospheric aerosol effects from Soufriere Volcano as measured by the SAGE satellite system

    Science.gov (United States)

    Mccormick, M. P.; Kent, G. S.; Yue, G. K.; Cunnold, D. M.

    1982-01-01

    During its April 1979 eruption series, Soufriere Volcano produced two major stratospheric plumes that the SAGE (Stratospheric Aerosol and Gas Experiment) satellite system tracked to West Africa and the North Atlantic Ocean. The total mass of these plumes, whose movement and dispersion are in agreement with those deduced from meteorological data and dispersion theory, was less than 0.5 percent of the global stratospheric aerosol burden; no significant temperature or climate perturbation is therefore expected.

  9. Lidar observations and transfer of stratospheric aerosol over Tomsk in summer period

    Science.gov (United States)

    Novikov, P. V.; Cheremisin, A. A.; Marichev, V. N.; Barashkov, T. O.

    2015-11-01

    The analysis of the stratospheric aerosol origin was carried out by the method of Lagrangian particle trajectories. Stratospheric aerosol was registered by lidar sounding of atmosphere above Tomsk in 2008-2013 in summer time. The analysis of the results had shown that the aerosol content at altitudes of 13-125 km with maximum at 16-18 km can be associated with aerosol transfer from tropical stratospheric reservoir.

  10. 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.

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

    Energy Technology Data Exchange (ETDEWEB)

    De Barros, A. L. F. [Departamento de Física, Centro Federal de Educação Tecnológica Celso Suckow da Fonseca, Av. Maracanã 229, 20271-110 Rio de Janeiro, RJ (Brazil); Mattioda, A. L.; Ricca, A.; Cruz-Diaz, G.A.; Allamandola, L. J. [NASA Ames Research Center, Mail Stop 245-6, Moffett Field, CA 94035-1000 (United States)

    2017-10-20

    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 C{sub 24}H{sub 12}:H{sub 2}O at concentrations of (1:50), (1:150), (1:200), (1:300), and (1:400). Previous UV irradiation studies of anthracene:H{sub 2}O, pyrene:H{sub 2}O, and benzo[ghi]perylene:H{sub 2}O ices at 15 K have shown that aromatic alcohols and ketones, as well as CO{sub 2} and H{sub 2}CO, are formed at very low temperatures. Likewise, here, in addition to the coronene cation, hydroxy-, keto-, and protonated coronene (coronene H{sup +}) 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:H{sub 2}O photoproducts have mid-infrared spectroscopic signatures in the 5–8 μ m 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.

  12. The atmosphere simulation chamber SAPHIR: a tool for the investigation of photochemistry.

    Science.gov (United States)

    Brauers, T.; Bohn, B.; Johnen, F.-J.; Rohrer, R.; Rodriguez Bares, S.; Tillmann, R.; Wahner, A.

    2003-04-01

    On the campus of the Forschungszentrum Jülich we constructed SAPHIR (Simulation of Atmospheric PHotochemistry In a large Reaction Chamber) which was accomplished in fall 2001. The chamber consists of a 280-m^3 double-wall Teflon bag of cylindrical shape that is held by a steel frame. Typically 75% of the outside actinic flux (290~nm~--~420~nm) is available inside the chamber. A louvre system allows switching between full sun light and dark within 40 s giving the opportunity to study relaxation processes of the photo chemical system. The SAPHIR chamber is equipped with a comprehensive set of sensitive instruments including the measurements of OH, HO_2, CO, hydrocarbons, aldehydes, nitrogen-oxides and solar radiation. Moreover, the modular concept of SAPHIR allows fast and flexible integration of new instruments and techniques. In this paper we will show the unique and new features of the SAPHIR chamber, namely the clean air supply and high purity water vapor supply providing a wide range of trace gas concentrations being accessible through the experiments. We will also present examples from the first year of SAPHIR experiment showing the scope of application from high quality instrument inter-comparison and kinetic studies to the simulation of complex mixtures of trace gases at ambient concentrations.

  13. 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.

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

    International Nuclear Information System (INIS)

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

    2017-01-01

    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 C 24 H 12 :H 2 O at concentrations of (1:50), (1:150), (1:200), (1:300), and (1:400). Previous UV irradiation studies of anthracene:H 2 O, pyrene:H 2 O, and benzo[ghi]perylene:H 2 O ices at 15 K have shown that aromatic alcohols and ketones, as well as CO 2 and H 2 CO, 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:H 2 O photoproducts have mid-infrared spectroscopic signatures in the 5–8 μ m 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.

  15. Energy transfer and photochemistry on a metal surface: Mo(CO)6 on Rh(100)

    International Nuclear Information System (INIS)

    Germer, T.A.; Ho, W.

    1989-01-01

    The occurrence of photoinduced reactions on solid surfaces depends on the relative rates between the excited-state decomposition and the energy transfer to the surface. In this study, the photodecomposition of Mo(CO) 6 on Rh(100) at 90 K by 325-nm UV irradiation has been studied as a function of coverage and surface preparation using thermal desorption spectroscopy, electron energy-loss spectroscopy, and photoinduced desorption spectroscopy. It is found that Mo(CO) 6 adsorbs dissociatively on Rh(100) into carbonyl fragments and CO in the first monolayer and molecularly in multilayers. Photoinduced desorption of CO is observed for the multilayers adsorbed onto the dissociated first layer via a nonthermal electronic excitation of adsorbed metal carbonyls. The presence of the metal surface prevents complete decarbonylation as in the gas phase; deexcitation of electronically excited carbonyls is not sufficiently fast to quench all the observed photochemistry. It is also found that Mo(CO) 6 adsorbs molecularly on a presaturated CO ordered overlayer on Rh(100) and undergoes photodissociation to a greater degree than on the dissociated and disordered surface of carbonyl fragments. The ordered CO layer effectively screens the interaction between the molecular carbonyls and the Rh(100) layer surface

  16. Photophysics and Photochemistry of Canonical Nucleobases’ Thioanalogs: From Quantum Mechanical Studies to Time Resolved Experiments

    Directory of Open Access Journals (Sweden)

    Serra Arslancan

    2017-06-01

    Full Text Available Interest in understanding the photophysics and photochemistry of thiated nucleobases has been awakened because of their possible involvement in primordial RNA or their potential use as photosensitizers in medicinal chemistry. The interpretation of the photodynamics of these systems, conditioned by their intricate potential energy surfaces, requires the powerful interplay between experimental measurements and state of the art molecular simulations. In this review, we provide an overview on the photophysics of natural nucleobases’ thioanalogs, which covers the last 30 years and both experimental and computational contributions. For all the canonical nucleobase’s thioanalogs, we have compiled the main steady state absorption and emission features and their interpretation in terms of theoretical calculations. Then, we revise the main topographical features, including stationary points and interstate crossings, of their potential energy surfaces based on quantum mechanical calculations and we conclude, by combining the outcome of different spectroscopic techniques and molecular dynamics simulations, with the mechanism by which these nucleobase analogs populate their triplet excited states, which are at the origin of their photosensitizing properties.

  17. What do PANs Tell us about VOC-NOx Photochemistry in the Urban/Rural Interface?

    Science.gov (United States)

    Roberts, J. M.; Flocke, F. M.; Zheng, W.; Bertman, S.; Marchewka, M.; Williams, E.; Lerner, B.; Kuster, W.; Goldan, P.; Gilman, J.; Sommariva, R.; Trainer, M.; Fehsenfeld, F.

    2006-12-01

    Peroxycarboxylic Nitric Anhydrides (PANs) are co-products of the VOC-NOx photochemistry that is responsible for O3 and secondary organic aerosol (SOA) formation in the troposphere. The relative abundance of the various PAN type compounds can provide important diagnostic information as to the contribution of different VOC sources to these processes. Anthropogenic, biogenic and petrochemical VOC sources have shown distinct profiles of PAN, PPN, MPAN, PiBN, and APAN, which can be analyzed using simple numerical models and compared to the results of detailed chemical mechanisms. One result of these studies is that the PAN compounds can be used to better define the contribution of isoprene to O3 production in the urban/rural interface. Another result is that high relative concentrations of APAN are characteristic of high petrochemical source impact. In addition, changes in the relative abundance of PPN and PAN can indicate the aging of a continental photochemical plume. This paper will present selected results from five field experiments and modeling studies from the Nashville 1999 Southern Oxidant Study up through the TexAQS 2006 study, in and around Houston, TX.

  18. A novel synthesis of polymeric CO via useful hard X-ray photochemistry

    Directory of Open Access Journals (Sweden)

    Michael Pravica

    2016-12-01

    Full Text Available We report on the synchrotron hard X-ray-induced decomposition of strontium oxalate (SrC2O4 pressurized to 7 GPa inside a diamond anvil cell (DAC. After some 4 h of irradiation in a white X-ray synchrotron beam, a dark reddish/brown region formed in the area of irradiation which was surrounded by a yellowish brown remainder in the rest of the sample. Upon depressurization of the sample to ambient conditions, the reacted/decomposed sample was recoverable as a dark brown/red and yellow waxy solid. Synchrotron infrared spectroscopy confirmed the strong presence of CO2 even under ambient conditions with the sample exposed to air and other strongly absorbing regions, suggesting that the sample may likely be polymerized CO (in part with dispersed CO2 and SrO trapped within the polymer. These results will have significant implications in the ability to readily produce and trap CO2 in situ via irradiation of a simple powder for useful hard X-ray photochemistry and in the ability to easily manufacture polymeric CO (via loading of powders in a DAC or high volume press without the need for the dangerous and complex loading of toxic CO. A novel means of X-ray-induced polymerization under extreme conditions has also been demonstrated.

  19. Aerosols from fires: an examination of the effects on ozone photochemistry in the Western United States.

    Science.gov (United States)

    Jiang, Xiaoyan; Wiedinmyer, Christine; Carlton, Annmarie G

    2012-11-06

    This study presents a first attempt to investigate the roles of fire aerosols in ozone (O(3)) photochemistry using an online coupled meteorology-chemistry model, the Weather Research and Foresting model with Chemistry (WRF-Chem). Four 1-month WRF-Chem simulations for August 2007, with and without fire emissions, were carried out to assess the sensitivity of O(3) predictions to the emissions and subsequent radiative feedbacks associated with large-scale fires in the Western United States (U.S.). Results show that decreases in planetary boundary layer height (PBLH) resulting from the radiative effects of fire aerosols and increases in emissions of nitrogen oxides (NO(x)) and volatile organic compounds (VOCs) from the fires tend to increase modeled O(3) concentrations near the source. Reductions in downward shortwave radiation reaching the surface and surface temperature due to fire aerosols cause decreases in biogenic isoprene emissions and J(NO(2)) photolysis rates, resulting in reductions in O(3) concentrations by as much as 15%. Thus, the results presented in this study imply that considering the radiative effects of fire aerosols may reduce O(3) overestimation by traditional photochemical models that do not consider fire-induced changes in meteorology; implementation of coupled meteorology-chemistry models are required to simulate the atmospheric chemistry impacted by large-scale fires.

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

    International Nuclear Information System (INIS)

    Nuevo, Michel; Materese, Christopher K.; Sandford, Scott A.

    2014-01-01

    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 4 H 4 N 2 ) in H 2 O-rich ice mixtures that contain NH 3 , CH 3 OH, or CH 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 2 O, CH 3 OH, and NH 3 , with or without CH 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.

  1. A consistent definition of the Arctic polar vortex breakup in both the lower and upper stratosphere

    Science.gov (United States)

    Choi, W.; Seo, J.

    2014-12-01

    Breakup of the polar vortex is a dominant feature of the seasonal transition from winter to summer in the stratosphere, which significantly affects stratospheric O3 concentration and tropospheric weather. Previously several criteria for the vortex breakup have been suggested based on the potential vorticity (PV) and wind speed, however, those mainly have focused on the lower stratospheric vortex of which spatiotemporal evolution and decay are more continuous than those of the upper stratospheric vortex. To find a consistent criterion for the vortex breakup in both the lower and upper stratosphere, the present study defined a polar vortex breakup day as when PV gradient at the polar vortex edge becomes lower than that at the subtropical edge on the area equivalent latitude based on PV. With applying the new definition to the UK Met Office reanalysis data, the breakup days of the Arctic polar vortices on 18 isentropic levels from 450 K to 1300 K were calculated for the period of 1993-2005. In comparison with CH4, N2O and O3 measured by the ILAS and POAM II/III satellite instruments, the breakup days are well consistent with changes in the distribution of such tracers as well as their zonal standard deviations associated with the vortex structure breaking and irreversible mixing. The vortex breakup in the upper stratosphere occurs more or less a month prior to that in the middle and lower stratosphere while the stratospheric final warming events occurs simultaneously in the upper and lower stratosphere.

  2. Age and gravitational separation of the stratospheric air over Indonesia

    Directory of Open Access Journals (Sweden)

    S. Sugawara

    2018-02-01

    Full Text Available The gravitational separation of major atmospheric components, in addition to the age of air, would provide additional useful information about stratospheric circulation. However, observations of the age of air and gravitational separation are still geographically sparse, especially in the tropics. In order to address this issue, air samples were collected over Biak, Indonesia in February 2015 using four large plastic balloons, each loaded with two compact cryogenic samplers. With a vertical resolution of better than 2 km, air samples from seven different altitudes were analyzed for CO2 and SF6 mole fractions, δ15N of N2, δ18O of O2, and δ(Ar∕N2 to examine the vertically dependent age and gravitational separation of air in the tropical tropopause layer (TTL and the equatorial stratosphere. By comparing their measured mole fractions with aircraft observations in the upper tropical troposphere, we have found that CO2 and SF6 ages increase gradually with increasing altitude from the TTL to 22 km, and then rapidly from there up to 29 km. The CO2 and SF6 ages agree well with each other in the TTL and in the lower stratosphere, but show a significant difference above 24 km. The average values of δ15N of N2, δ18O of O2, and δ(Ar∕N2 all show a small but distinct upward decrease due to the gravitational separation effect. Simulations with a two-dimensional atmospheric transport model indicate that the gravitational separation effect decreases as tropical upwelling is enhanced. From the model calculations with enhanced eddy mixing, it is also found that the upward increase in air age is magnified by horizontal mixing. These model simulations also show that the gravitational separation effect remains relatively constant in the lower stratosphere. The results of this study strongly suggest that the gravitational separation, combined with the age of air, can be used to diagnose air transport processes in the stratosphere.

  3. Stratospheric ozone measurements at Arosa (Switzerland): history and scientific relevance

    Science.gov (United States)

    Staehelin, Johannes; Viatte, Pierre; Stübi, Rene; Tummon, Fiona; Peter, Thomas

    2018-05-01

    Climatic Observatory (LKO) in Arosa (Switzerland), marking the beginning of the world's longest series of total (or column) ozone measurements. They were driven by the recognition that atmospheric ozone is important for human health, as well as by scientific curiosity about what was, at the time, an ill characterised atmospheric trace gas. From around the mid-1950s to the beginning of the 1970s studies of high atmosphere circulation patterns that could improve weather forecasting was justification for studying stratospheric ozone. In the mid-1970s, a paradigm shift occurred when it became clear that the damaging effects of anthropogenic ozone-depleting substances (ODSs), such as long-lived chlorofluorocarbons, needed to be documented. This justified continuing the ground-based measurements of stratospheric ozone. Levels of ODSs peaked around the mid-1990s as a result of a global environmental policy to protect the ozone layer, implemented through the 1987 Montreal Protocol and its subsequent amendments and adjustments. Consequently, chemical destruction of stratospheric ozone started to slow around the mid-1990s. To some extent, this raises the question as to whether continued ozone observation is indeed necessary. In the last decade there has been a tendency to reduce the costs associated with making ozone measurements globally including at Arosa. However, the large natural variability in ozone on diurnal, seasonal, and interannual scales complicates the capacity for demonstrating the success of the Montreal Protocol. Chemistry-climate models also predict a super-recovery of the ozone layer at mid-latitudes in the second half of this century, i.e. an increase of ozone concentrations beyond pre-1970 levels, as a consequence of ongoing climate change. These factors, and identifying potentially unexpected stratospheric responses to climate change, support the continued need to document stratospheric ozone changes. This is particularly valuable at the Arosa site, due

  4. Assessment of PCDD/F and PBDD/F Emissions from Coal-fired Power Plants during Injection of Brominated Activated Carbon for Mercury Control

    Science.gov (United States)

    The effect of the injection of brominated powdered activated carbon (Br-PAC) on the emission of brominated and chlorinated dioxins and furans in coal combustion flue gas has been evaluated. The tests were performed at two U.S. Department of Energy (DOE) demonstration sites where ...

  5. Trophic transfer of naturally produced brominated aromatic compounds in a Baltic Sea food chain.

    Science.gov (United States)

    Dahlgren, Elin; Lindqvist, Dennis; Dahlgren, Henrik; Asplund, Lillemor; Lehtilä, Kari

    2016-02-01

    Brominated aromatic compounds (BACs) are widely distributed in the marine environment. Some of these compounds are highly toxic, such as certain hydroxylated polybrominated diphenyl ethers (OH-PBDEs). In addition to anthropogenic emissions through use of BACs as e.g. flame retardants, BACs are natural products formed by marine organisms such as algae, sponges, and cyanobacteria. Little is known of the transfer of BACs from natural producers and further up in the trophic food chain. In this study it was observed that total sum of methoxylated polybrominated diphenyl ethers (MeO-PBDEs) and OH-PBDEs increased in concentration from the filamentous red alga Ceramium tenuicorne, via Gammarus sp. and three-spined stickleback (Gasterosteus aculeatus) to perch (Perca fluviatilis). The MeO-PBDEs, which were expected to bioaccumulate, increased in concentration accordingly up to perch, where the levels suddenly dropped dramatically. The opposite pattern was observed for OH-PBDEs, where the concentration exhibited a general trend of decline up the food web, but increased in perch, indicating metabolic demethylation of MeO-PBDEs. Debromination was also indicated to occur when progressing through the food chain resulting in high levels of tetra-brominated MeO-PBDE and OH-PBDE congeners in fish, while some penta- and hexa-brominated congeners were observed to be the dominant products in the alga. As it has been shown that OH-PBDEs are potent disruptors of oxidative phosphorylation and that mixtures of different congener may act synergistically in terms of this toxic mode of action, the high levels of OH-PBDEs detected in perch in this study warrants further investigation into potential effects of these compounds on Baltic wildlife, and monitoring of their levels. Copyright © 2015 Elsevier Ltd. All rights reserved.

  6. Dynamics of brominated flame retardants removal in contaminated wastewater sewage sludge under anaerobic conditions.

    Science.gov (United States)

    Stiborova, Hana; Vrkoslavova, Jana; Pulkrabova, Jana; Poustka, Jan; Hajslova, Jana; Demnerova, Katerina

    2015-11-15

    Disposal of solid waste to landfills from waste water sewage treatment plants (WWTPs) serves as a potential source of contamination by polybrominated diphenyl ethers (PBDEs) and hexabromocyclododecane (HBCD). Native microbial communities have been found to degrade a variety of xenobiotics, such as PBDEs and HBCDs. This study investigates the potential of autochthonous microflora to remove 11 PBDE congeners and HBCDs in waste water sludge under anaerobic conditions. Laboratory microcosms were constructed with sewage sludge from the WWTPs of Hradec Kralove and Brno. BDE 209 was detected as the prevailing congener in concentrations 685 and 1403 ng/g dw and the total amounts of 10 lower PBDEs (BDE 28, 47, 49, 66, 85, 99, 100, 153, 154, 183) were 605 and 205 ng/g dw in sludge from Hradec Kralove and Brno, respectively. The levels of HBCD were detected in both sludge lower than 24 ng/g dw. The experiment was carried out for 15 months. After three months of incubation, HBCD was completely degraded to below detection limits. In sewage from both WWTPs, the higher brominated DEs were removed faster than the lower brominated congeners. One exception was tri-BDE, which was degraded completely within 15 months of cultivation. A significant increase in congener tetra-BDE 49 concentrations was observed over the course of the experiment in all tested sewage. The relative distribution of individual congeners among all PBDEs changed after 15 months of the incubation in favour of lower brominated congeners. This indicates that debromination is the major mechanism of anaerobic biodegradation. Despite of the increase of BDE 49, the overall removal of all 11 PBDEs achieved the levels of 47.4 and 68.7% in samples from WWTPs Hradec Kralove and Brno, respectively. Copyright © 2015 Elsevier B.V. All rights reserved.

  7. Bromine cycle in subduction zones through in situ Br monitoring in diamond anvil cells

    Science.gov (United States)

    Bureau, Hélène; Foy, Eddy; Raepsaet, Caroline; Somogyi, Andrea; Munsch, Pascal; Simon, Guilhem; Kubsky, Stefan

    2010-07-01

    The geochemical partitioning of bromine between hydrous haplogranitic melts, initially enriched with respect to Br and aqueous fluids, has been continuously monitored in situ during decompression. Experiments were carried out in diamond anvil cells from 890 °C to room temperature and from 1.7 GPa to room pressure, typically from high P, T conditions corresponding to total miscibility (presence of a supercritical fluid). Br contents were measured in aqueous fluids, hydrous melts and supercritical fluids. Partition coefficients of bromine were characterized at pressure and temperature between fluids, hydrous melts and/or glasses, as appropriate: DBrfluid/melt = (Br) fluid/(Br) melt, ranges from 2.18 to 9.2 ± 0.5 for conditions within the ranges 0.66-1.7 GPa, 590-890 °C; and DBrfluid/glass = (Br) fluid/(Br) glass ranges from 60 to 375 at room conditions. The results suggest that because high pressure melts and fluids are capable of accepting high concentrations of bromine, this element may be efficiently removed from the slab to the mantle source of arc magmas. We show that Br may be highly concentrated in subduction zone magmas and strongly enriched in subduction-related volcanic gases, because its mobility is strongly correlated with that of water during magma degassing. Furthermore, our experimental results suggest that a non negligible part of Br present in the subducted slab may remain in the down-going slab, being transported toward the transition zone. This indicates that the Br cycle in subduction zones is in fact divided in two related but independent parts: (1) a shallower one where recycled Br may leave the slab with a water and silica-bearing "fluid" leading to enriched arc magmas that return Br to the atmosphere. (2) A deeper cycle where Br may be recycled back to the mantle maybe to the transition zone, where it may be present in high pressure water-rich metasomatic fluids.

  8. Determination of the total amount of organically bound chlorine, bromine and iodine in environmental samples by instrumental neutron activation analysis

    Energy Technology Data Exchange (ETDEWEB)

    Gether, J; Lunde, G [Central Institute for Industrial Research, Oslo (Norway); Steinnes, E [Institutt for Atomenergi, Kjeller (Norway)

    1979-07-01

    The determination of chlorine, bromine and iodine present as non-polar, hydrophobic hydrocarbons in environmental samples is reported. The organohalogen compounds are seprated from water into an organic phase by on-site liquid-liquid extraction, and form biological material by procedures based on lipid phase extraction and codistillation. After removal of inorganic halides by washing with water and concentration of the sample by evaporation of the solvent, the resulting extracts are analyzed for their chlorine, bromine and iodine contents by instrumental neutron activation analysus. Strict attention is paid to the possibility of contamination in every step of the procedure. Background values in routine analysis are approximately 100-200 ng of chlorine, <5 ng of bromine and <3 ng of iodine.

  9. Reaction modelling of Iron Oxide Bromination in the UT-3 thermochemical cycle for Hydrogen production from water

    International Nuclear Information System (INIS)

    Amir-Rusli

    1996-01-01

    Analysis modelling of the iron oxide bromination had been carried out using experiment data from the iron oxide bromination in the UT-3 thermochemical cycle. Iron oxide in the form of pellets were made of the calcination of the mixture of iron oxide, silica, graphite and cellulose at 1473 K. Thermobalance reactor was used to study the kinetic reactions of the iron oxide bromination at a temperature of 473 K for 2 - 6 hours. The data collected from the experiments were used as input for the common models. However, none of these models could not explain the result of the experiments. A new model, a combination of two kinetic reactions : exposed particle and coated particle was created and worked successfully

  10. Magnetically enhanced triode etching of large area silicon membranes in a molecular bromine plasma

    International Nuclear Information System (INIS)

    Wolfe, J.C.; Sen, S.; Pendharkar, S.V.; Mauger, P.; Shimkunas, A.R.

    1992-01-01

    The optimization of a process for etching 125 mm silicon membranes formed on 150 mm wafers and bonded to Pyrex rings is discussed. A magnetically enhanced triode etching system was designed to provide an intense, remote plasma surrounding the membrane while, at the same time, suppressing the discharge over the membrane itself. For the optimized molecular bromine process, the silicon etch rate is 40 nm/min and the selectivity relative to SiO 2 is 160:1. 14 refs., 6 figs

  11. Bromine-quenched high temperature G-M tube with passivated cathode

    International Nuclear Information System (INIS)

    Mitrofanov, N.

    1975-01-01

    A bromine doped self-quenching Geiger-Mueller tube having an operational life expectancy in excess of 1,200 hours at a temperature of 315 0 C is described. The tube comprises a passivated metal coated cathode which is conditioned or aged for operation at room temperature, thus obviating the necessity of thermally cycling the tube at progressively elevated temperatures. Useful metal coatings for the cathode include chromium, platinum, and nickel-copper alloys deposited in a layer less than about 1 mil thick. A method for passivating the metal coated cathode and subsequently conditioning the tube and its contents is disclosed. (auth)

  12. Synthesis of the omega-brominated alpha-trifluoroacetylcycloalkanones and their isoxazole derivatives

    Directory of Open Access Journals (Sweden)

    Flores Alex F. C.

    2006-01-01

    Full Text Available The reactions of a serie of the 2-trifluoroacetyl-1-methoxy-1-cycloalkenes (1a-1e and 2-trifluoroacetylcycloalkanones (2a-2e with molecular bromine to obtain omega-bromo-alpha-trifluoroacetylcycloalkanones (3a-3e, 4a is reported. Was determined that 2-trifluoroacetyl group have established the C-omega as reactive site. The 2-trifluoroacetylcycloalkanones and omega-bromo-alpha-trifluoroacetylcycloalkanones were reacted with hydroxylamine hydrochloride leading to respective 5-trifluoromethyl-5-hydroxy-4,5-dihydro-3,4-polimethyleneisoxazole derivatives (5c-5e and 6c-6e.

  13. PIXE analysis of remaining bromine in fumigated old manuscripts and books

    International Nuclear Information System (INIS)

    Kohno, M.; Yoshida, K.; Moritani, K.; Naito, M.; Enami, K.; Kasajima, H.; Takada, J.; Matsushita, R.

    1999-01-01

    Buddhist scriptures in Reeky University Library have been fumigated regularly for protecting them from vermin. Methyl bromide (CH 3 Br) had been used there till 1985. In order to examine whether the chemical remains on the fumigated objects or not, paper fragments of old manuscripts and books, modern paper placed together with them, and non-fumigated ones were analyzed by PIXE. The bromine concentration of fumigated paper was more than from several tens to several hundreds times higher than non-fumigated ones. (author)

  14. Reactive bromine in the low troposphere of Antarctica. Estimations at two research sites

    OpenAIRE

    Prados-Roman, Cristina; Gómez-Martín, Laura; Puentedura, Olga; Navarro-Comas, Mónica; Iglesias, Javier; Mingo, José Ramón; Pérez, Manuel; Ochoa, Héctor; Barlasina, María Elena; Carbajal, Gerardo; Yela, Margarita

    2018-01-01

    For decades, reactive halogen species (RHS) have been subject of detailed scientific research due to their influence on the oxidizing capacity of the atmosphere and on the climate. From the RHS, those containing bromine are of particular interest in the polar troposphere as a result of their link to ozone depletion events (ODEs) and to the perturbation of the cycle of e.g. the toxic mercury. Given its remoteness and related limited accessibility compared to the Arctic region, the RHS in the A...

  15. Production of krypton isotopes by (p,xn) reactions on bromine

    International Nuclear Information System (INIS)

    Chiengmai, S.N.; Hans, L.; Petter, M.

    1976-06-01

    Radioactive isotopes of the halogens are of great importance when preparing radiopharmaceuticals. 77 Br has mainly been produced by a direct reaction 75 As(α,2n) 77 Br. Recently an indirect way, producing 77 Kr which then decays to 77 Br, has been suggested. Since this provides a convenient method of separation this work develops this idea further making use of high energy protons on bromine Br(p,xn) 77 Kr→ 77 Br. The production cross-section for this reaction has been studied in the proton-energy interval of 20-80 MeV and the optimal production procedures considered. (Auth.)

  16. Introduction of iodine 131 and bromine 82 in antibiotics of tetracycline group

    International Nuclear Information System (INIS)

    Mironov, V.P.; Kudryashov, V.P.; Grushevich, L.E.; Kuz'mina, T.S.

    1983-01-01

    Chloline- and oxytetracycline reactions with iodide-131-and bromide-82-ions in methanol and acetone are studied. It is established that labelled compounds reveal tetracycline (TC) properties in pharmacokinetic experiments on laboratory animals for 20-25 hours after synthesis; the yield of purposeful preparations for radioactive isotopes is 90-95%. Kinetic dependences of iodine-131 and bromine-82-TC yield on acidity and temperature of medium are presented. TC radiation resistance in solutions and in solid state at different temperatures in the range of absorbed doses of 1-10 Mrad is investigated. The possibility of TC radiation sterilization is shown

  17. Theoretical performance of hydrogen-bromine rechargeable SPE fuel cell. [Solid Polymer Electrolyte

    Science.gov (United States)

    Savinell, R. F.; Fritts, S. D.

    1988-01-01

    A mathematical model was formulated to describe the performance of a hydrogen-bromine fuel cell. Porous electrode theory was applied to the carbon felt flow-by electrode and was coupled to theory describing the solid polymer electrolyte (SPE) system. Parametric studies using the numerical solution to this model were performed to determine the effect of kinetic, mass transfer, and design parameters on the performance of the fuel cell. The results indicate that the cell performance is most sensitive to the transport properties of the SPE membrane. The model was also shown to be a useful tool for scale-up studies.

  18. Characterization of Some Real Mixed Plastics from WEEE: A Focus on Chlorine and Bromine Determination by Different Analytical Methods

    Directory of Open Access Journals (Sweden)

    Beatrice Beccagutti

    2016-10-01

    Full Text Available Bromine and chlorine are almost ubiquitous in waste of electrical and electronic equipment (WEEE and the knowledge of their content in the plastic fraction is an essential step for proper end of life management. The aim of this study is to compare the following analytical methods: energy dispersive X-ray fluorescence spectroscopy (ED-XRF, ion chromatography (IC, ion-selective electrodes (ISEs, and elemental analysis for the quantitative determination of chlorine and bromine in four real samples taken from different WEEE treatment plants, identifying the best analytical technique for waste management workers. Home-made plastic standard materials with known concentrations of chlorine or bromine have been used for calibration of ED-XRF and to test the techniques before the sample analysis. Results showed that IC and ISEs, based upon dissolution of the products of the sample combustion, have not always achieved a quantitative absorption of the analytes in the basic solutions and that bromine could be underestimated since several oxidation states occur after combustion. Elemental analysis designed for chlorine determination is subjected to strong interference from bromine and required frequent regeneration and recalibration of the measurement cell. The most reliable method seemed to be the non-destructive ED-XRF. Calibration with home-made standards, having a similar plastic matrix of the samples, enabled us to carry out quantitative determinations, which have been revealed to be satisfactorily accurate and precise. In all the analyzed samples a total concentration of chlorine and/or bromine between 0.6 and 4 w/w% was detected, compromising the feasibility of a mechanical recycling and suggesting the exploration of an alternative route for managing these plastic wastes.

  19. On the impact of aircraft emitted NO{sub x} on upper troposphere photochemistry

    Energy Technology Data Exchange (ETDEWEB)

    Wahner, A; Rohrer, F; Ehhalt, D H [Forschungszentrum Juelich GmbH (Germany). Inst. fuer Atmosphaerische Chemie

    1998-12-31

    The enhanced nitrogen oxide concentrations influence the photochemical production of ozone as well as the steady state concentrations of hydroxyl radicals, OH, in the upper troposphere. That increase is small compared to the impact of NO{sub x} from fossil fuel combustion on boundary layer ozone. A simple quasi 2-D model was used for the latitude band 40 deg - 50 deg N to analyze the reasons for that. The model includes a simplified CH{sub 4} - CO chemistry and the salient sources of upper tropospheric NO{sub x}, namely lightning, stratospheric input, aircraft emissions and fast upward transport of surface emissions. It is shown that the maximum of net O{sub 3} production and OH concentrations occur at much lower NO{sub x} mixing ratios than in the lower troposphere. (author)

  20. On the impact of aircraft emitted NO{sub x} on upper troposphere photochemistry

    Energy Technology Data Exchange (ETDEWEB)

    Wahner, A.; Rohrer, F.; Ehhalt, D.H. [Forschungszentrum Juelich GmbH (Germany). Inst. fuer Atmosphaerische Chemie

    1997-12-31

    The enhanced nitrogen oxide concentrations influence the photochemical production of ozone as well as the steady state concentrations of hydroxyl radicals, OH, in the upper troposphere. That increase is small compared to the impact of NO{sub x} from fossil fuel combustion on boundary layer ozone. A simple quasi 2-D model was used for the latitude band 40 deg - 50 deg N to analyze the reasons for that. The model includes a simplified CH{sub 4} - CO chemistry and the salient sources of upper tropospheric NO{sub x}, namely lightning, stratospheric input, aircraft emissions and fast upward transport of surface emissions. It is shown that the maximum of net O{sub 3} production and OH concentrations occur at much lower NO{sub x} mixing ratios than in the lower troposphere. (author)

  1. Levels of persistent fluorinated, chlorinated and brominated compounds in human blood collected in Sweden in 1997-2000

    Energy Technology Data Exchange (ETDEWEB)

    Lindstroem, G.; Kaerrman, A.; Bavel, B. van [MTM Research Centre, Oerebro Univ. (Sweden); Hardell, L. [Dept. of Oncology, Univ. Hospital, Oerebro (Sweden); Hedlund, B. [Environmental Monitoring Section, Swedish EPA, Stockholm (Sweden)

    2004-09-15

    Levels of persistent fluorinated, chlorinated and brominated compounds in blood collected from the Swedish population have been determined in connection with several exposure and monitoring studies at the MTM Research Centre. A data base with 631 individual congener specific measurements on halogenated POPs such as dioxins, PCBs, HCB, DDE, chlordanes, PBDEs and PFAs including information on residency, age, BMI, diet, occupation, number of children, smoking habits, immunological status etc. has been compiled from samples collected between 1994 and 2004. A brief overview focusing on levels of some persistent chlorinated, brominated and fluorinated, compounds in blood collected in a background population group (n=83) in 1997-2000 is given here.

  2. Treatment of sewage from iodo-bromine industrial plants from the second group cations using carboxyl cationnites

    International Nuclear Information System (INIS)

    Kononova, G.N.; Dolbysheva, A.G.; Ksenzenko, V.I.; Ryazantseva, Zh.I.

    1977-01-01

    Effectiveness has been shown of purifying sewage from iodo-bromine plants from the second Group cations on a carboxyl cationite KB-4P. For strongly mineralized waters as industrial waters from iodo-bromine plants, the selectivity decreases in the series: Ca 2+ > Sr 2+ > Mg 2+ . It has been shown that the determining stage is an outside diffusion. SH nitric acid has been used for regeneration of cationite. The second Group cations are washed off with nitric acid simultaneously and at a high rate. Strontium can be separated from the eluate obtained by the halurgical method

  3. Synchrotron X-ray fluorescence studies of a bromine-labelled cyclic RGD peptide interacting with individual tumor cells

    International Nuclear Information System (INIS)

    Sheridan, Erin J.; Austin, Christopher J. D.; Aitken, Jade B.; Vogt, Stefan; Jolliffe, Katrina A.; Harris, Hugh H.; Rendina, Louis M.

    2013-01-01

    The first example of synchrotron X-ray fluorescence imaging of cultured mammalian cells in cyclic peptide research is reported. The study reports the first quantitative analysis of the incorporation of a bromine-labelled cyclic RGD peptide and its effects on the biodistribution of endogenous elements (for example, K and Cl) within individual tumor cells. The first example of synchrotron X-ray fluorescence imaging of cultured mammalian cells in cyclic peptide research is reported. The study reports the first quantitative analysis of the incorporation of a bromine-labelled cyclic RGD peptide and its effects on the biodistribution of endogenous elements (for example, K and Cl) within individual tumor cells

  4. 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

  5. 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.

  6. Structure and UV-induced photochemistry of 2-furaldehyde dimethylhydrazone isolated in rare gas matrices

    Science.gov (United States)

    Araujo-Andrade, C.; Giuliano, B. M.; Gómez-Zavaglia, A.; Fausto, R.

    2012-11-01

    In this work, a combined matrix isolation FTIR and theoretical DFT(B3LYP)/6-311++G(d,p) study of 2-furaldehyde dimethylhydrazone (2FDH) was performed. According to calculations, two E and two Z conformers exist, the E forms having considerably lower energy than the Z forms. The absence of relevant sterical hindrance between the two substituents around the Cdbnd N bond (dimethylamino and 2-furyl) in the E structures and an extended π-p electron delocalization in the hydrazone moiety determines the higher stability of these species relatively to the Z structures. In the lowest energy form (E-AG) the O-C-Cdbnd N and Cdbnd N-N-Lp (Lp = lone electron pair of amine nitrogen atom) dihedral angles are predicted by the calculations to be -177.2° and 93.7°, respectively. The weak (Ndbnd C)-H⋯O hydrogen bond type interaction (H⋯O distance: 252.2 pm) in form E-AG, together with the absence in this form of the destabilizing interaction between the lone electron pairs of the oxygen and nitrogen atoms existing in E-SG, explains its lower energy in comparison with this latter form. Both E-AG and E-SG conformers could be trapped from room temperature gas phase in low temperature argon and xenon matrices. The high E-SG → E-AG energy barrier (>25 kJ mol-1) explains that, upon increasing the temperature of the matrices no conformational isomerization could be observed. After irradiation of 2FDH with UV-light at λ > 328 and λ > 234 nm, two different photochemistries were observed. Irradiation at lower energy (λ > 328 nm) induced the E-AG → E-SG isomerization. Further irradiation at higher energy (λ > 234 nm) led to a quick consumption of 2FDH and production of furan and dimethylisocyanide.

  7. Ultrafast infrared and UV-vis studies of the photochemistry of methoxycarbonylphenyl azides in solution.

    Science.gov (United States)

    Xue, Jiadan; Luk, Hoi Ling; Eswaran, S V; Hadad, Christopher M; Platz, Matthew S

    2012-06-07

    The photochemistry of 4-methoxycarbonylphenyl azide (2a), 2-methoxycarbonylphenyl azide (3a), and 2-methoxy-6-methoxycarbonylphenyl azide (4a) were studied by ultrafast time-resolved infrared (IR) and UV-vis spectroscopies in solution. Singlet nitrenes and ketenimines were observed and characterized for all three azides. Isoxazole species 3g and 4g are generated after photolysis of 3a and 4a, respectively, in acetonitrile. Triplet nitrene 4e formation correlated with the decay of singlet nitrene 4b. The presence of water does not change the chemistry or kinetics of singlet nitrenes 2b and 3b, but leads to protonation of 4b to produce nitrenium ion 4f. Singlet nitrenes 2b and 3b have lifetimes of 2 ns and 400 ps, respectively, in solution at ambient temperature. The singlet nitrene 4b in acetonitrile has a lifetime of about 800 ps, and reacts with water with a rate constant of 1.9 × 10(8) L·mol(-1)·s(-1) at room temperature. These results indicate that a methoxycarbonyl group at either the para or ortho positions has little influence on the ISC rate, but that the presence of a 2-methoxy group dramatically accelerates the ISC rate relative to the unsubstituted phenylnitrene. An ortho-methoxy group highly stabilizes the corresponding nitrenium ion and favors its formation in aqueous solvents. This substituent has little influence on the ring-expansion rate. These results are consistent with theoretical calculations for the various intermediates and their transition states. Cyclization from the nitrene to the azirine intermediate is favored to proceed toward the electron-deficient ester group; however, the higher energy barrier is the ring-opening process, that is, azirine to ketenimine formation, rendering the formation of the ester-ketenimine (4d') to be less favorable than the isomeric MeO-ketenimine (4d).

  8. Interfacial photochemistry of biogenic surfactants: a major source of abiotic volatile organic compounds.

    Science.gov (United States)

    Brüggemann, Martin; Hayeck, Nathalie; Bonnineau, Chloé; Pesce, Stéphane; Alpert, Peter A; Perrier, Sébastien; Zuth, Christoph; Hoffmann, Thorsten; Chen, Jianmin; George, Christian

    2017-08-24

    Films of biogenic compounds exposed to the atmosphere are ubiquitously found on the surfaces of cloud droplets, aerosol particles, buildings, plants, soils and the ocean. These air/water interfaces host countless amphiphilic compounds concentrated there with respect to in bulk water, leading to a unique chemical environment. Here, photochemical processes at the air/water interface of biofilm-containing solutions were studied, demonstrating abiotic VOC production from authentic biogenic surfactants under ambient conditions. Using a combination of online-APCI-HRMS and PTR-ToF-MS, unsaturated and functionalized VOCs were identified and quantified, giving emission fluxes comparable to previous field and laboratory observations. Interestingly, VOC fluxes increased with the decay of microbial cells in the samples, indicating that cell lysis due to cell death was the main source for surfactants and VOC production. In particular, irradiation of samples containing solely biofilm cells without matrix components exhibited the strongest VOC production upon irradiation. In agreement with previous studies, LC-MS measurements of the liquid phase suggested the presence of fatty acids and known photosensitizers, possibly inducing the observed VOC production via peroxy radical chemistry. Up to now, such VOC emissions were directly accounted to high biological activity in surface waters. However, the results obtained suggest that abiotic photochemistry can lead to similar emissions into the atmosphere, especially in less biologically-active regions. Furthermore, chamber experiments suggest that oxidation (O 3 /OH radicals) of the photochemically-produced VOCs leads to aerosol formation and growth, possibly affecting atmospheric chemistry and climate-related processes, such as cloud formation or the Earth's radiation budget.

  9. 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

  10. Development of Zinc/Bromine Batteries for Load-Leveling Applications: Phase 2 Final Report

    Energy Technology Data Exchange (ETDEWEB)

    CLARK,NANCY H.; EIDLER,PHILLIP

    1999-10-01

    This report documents Phase 2 of a project to design, develop, and test a zinc/bromine battery technology for use in utility energy storage applications. The project was co-funded by the U.S. Department of Energy Office of Power Technologies through Sandia National Laboratories. The viability of the zinc/bromine technology was demonstrated in Phase 1. In Phase 2, the technology developed during Phase 1 was scaled up to a size appropriate for the application. Batteries were increased in size from 8-cell, 1170-cm{sup 2} cell stacks (Phase 1) to 8- and then 60-cell, 2500-cm{sup 2} cell stacks in this phase. The 2500-cm{sup 2} series battery stacks were developed as the building block for large utility battery systems. Core technology research on electrolyte and separator materials and on manufacturing techniques, which began in Phase 1, continued to be investigated during Phase 2. Finally, the end product of this project was a 100-kWh prototype battery system to be installed and tested at an electric utility.

  11. Electrospun Nafion®/Polyphenylsulfone Composite Membranes for Regenerative Hydrogen Bromine Fuel Cells

    Science.gov (United States)

    Park, Jun Woo; Wycisk, Ryszard; Pintauro, Peter N.; Yarlagadda, Venkata; Van Nguyen, Trung

    2016-01-01

    The regenerative H2/Br2-HBr fuel cell, utilizing an oxidant solution of Br2 in aqueous HBr, shows a number of benefits for grid-scale electricity storage. The membrane-electrode assembly, a key component of a fuel cell, contains a proton-conducting membrane, typically based on the perfluorosulfonic acid (PFSA) ionomer. Unfortunately, the high cost of PFSA membranes and their relatively high bromine crossover are serious drawbacks. Nanofiber composite membranes can overcome these limitations. In this work, composite membranes were prepared from electrospun dual-fiber mats containing Nafion® PFSA ionomer for facile proton transport and an uncharged polymer, polyphenylsulfone (PPSU), for mechanical reinforcement, and swelling control. After electrospinning, Nafion/PPSU mats were converted into composite membranes by softening the PPSU fibers, through exposure to chloroform vapor, thus filling the voids between ionomer nanofibers. It was demonstrated that the relative membrane selectivity, referenced to Nafion® 115, increased with increasing PPSU content, e.g., a selectivity of 11 at 25 vol% of Nafion fibers. H2-Br2 fuel cell power output with a 65 μm thick membrane containing 55 vol% Nafion fibers was somewhat better than that of a 150 μm Nafion® 115 reference, but its cost advantage due to a four-fold decrease in PFSA content and a lower bromine species crossover make it an attractive candidate for use in H2/Br2-HBr systems. PMID:28773268

  12. Selected chlorobornanes, polychlorinated naphthalenes and brominated flame retardants in Bjornoya (Bear Island) freshwater biota

    International Nuclear Information System (INIS)

    Evenset, Anita; Christensen, Guttorm N.; Kallenborn, Roland

    2005-01-01

    Levels of selected sparsely investigated persistent organic pollutants (POPs) have been measured in organisms from two Arctic lakes on Bjornoya (Bear Island). Elevated levels of chlorobornanes (CHBs) (up to 46.7 ng/g wet weight=ww), polybrominated diphenyl ethers (PBDEs) (up to 27.2 ng/g ww), polybrominated biphenyls (PBBs) (up to 1.1 ng/g ww) and polychlorinated naphthalenes (PCNs, only 4 congeners) (up to 62.7 pg/g ww), were measured in biota from Lake Ellasjoen. In Lake Oyangen, located only 5 km north of Ellasjoen, levels of these contaminants were significantly lower. δ 15 N-values were 7-10%o higher in organisms from Ellasjoen as compared to Oyangen. This is attributed to biological inputs related to seabird activities. The present study illustrates that contaminants such as CHBs, brominated flame retardants and PCNs accumulate in the Ellasjoen food web in a manner similar to PCBs and conventional organochlorine pesticides. Transport mechanisms that control PCB and DDT distributions, i.e. atmospheric long-range transport and biotransport by seabirds, are also relevant for the contaminants investigated in the present study. - Elevate levels of chlorobornanes, polychlorinated naphthalenes and brominated flame retardants have been measured in biota from a Norwegian Arctic lake

  13. Levelized cost of energy and sensitivity analysis for the hydrogen-bromine flow battery

    Science.gov (United States)

    Singh, Nirala; McFarland, Eric W.

    2015-08-01

    The technoeconomics of the hydrogen-bromine flow battery are investigated. Using existing performance data the operating conditions were optimized to minimize the levelized cost of electricity using individual component costs for the flow battery stack and other system units. Several different configurations were evaluated including use of a bromine complexing agent to reduce membrane requirements. Sensitivity analysis of cost is used to identify the system elements most strongly influencing the economics. The stack lifetime and round-trip efficiency of the cell are identified as major factors on the levelized cost of electricity, along with capital components related to hydrogen storage, the bipolar plate, and the membrane. Assuming that an electrocatalyst and membrane with a lifetime of 2000 cycles can be identified, the lowest cost market entry system capital is 220 kWh-1 for a 4 h discharge system and for a charging energy cost of 0.04 kWh-1 the levelized cost of the electricity delivered is 0.40 kWh-1. With systems manufactured at large scales these costs are expected to be lower.

  14. Brominated diphenyl ethers in the sediments, porewater, and biota of the Chesapeake Bay, USA

    Energy Technology Data Exchange (ETDEWEB)

    Baker, K.; Klosterhaus, S.; Liebert, D.; Stapleton, H. [Maryland Univ., Solomons, MD (United States)

    2004-09-15

    Levels of brominated diphenyl ethers (BDEs) are rapidly increasing in the environment, and in a short time these chemicals have evolved from 'emerging contaminants' to globally-distributed organic pollutants. Recent research demonstrates BDEs are sufficiently stable to be transported long distances in the environment and to accumulate in higher trophic levels. Photolysis and metabolism appear to be dominant loss processes for the parent compounds, generating a variety of lower brominated diphenyl ethers, hydroxylated metabolites, and other products. BDEs are hydrophobic, and therefore their transport in aquatic systems is likely controlled by sorption to sediments and perhaps exchange across the air-water interface. To date, few studies have examined the geochemistry of BDEs in natural waters. In this paper, we review our recent measurements of BDEs in the Chesapeake Bay, a shallow, productive estuary in eastern North America. We focus on the distribution of BDE congeners sediment, porewater, and in faunal benthos along a contamination gradient downstream from a wastewater treatment plant and on the spatial distribution of BDEs in bottom-feeding and pelagic fish species.

  15. Nitrogenous disinfection byproducts in English drinking water supply systems: Occurrence, bromine substitution and correlation analysis.

    Science.gov (United States)

    Bond, Tom; Templeton, Michael R; Mokhtar Kamal, Nurul Hana; Graham, Nigel; Kanda, Rakesh

    2015-11-15

    Despite the recent focus on nitrogenous disinfection byproducts in drinking water, there is limited occurrence data available for many species. This paper analyses the occurrence of seven haloacetonitriles, three haloacetamides, eight halonitromethanes and cyanogen chloride in 20 English drinking water supply systems. It is the first survey of its type to compare bromine substitution factors (BSFs) between the haloacetamides and haloacetonitriles. Concentrations of the dihalogenated haloacetonitriles and haloacetamides were well correlated. Although median concentrations of these two groups were lower in chloraminated than chlorinated surface waters, median BSFs for both in chloraminated samples were approximately double those in chlorinated samples, which is significant because of the higher reported toxicity of the brominated species. Furthermore, median BSFs were moderately higher for the dihalogenated haloacetamides than for the haloacetonitriles. This indicates that, while the dihalogenated haloacetamides were primarily generated from hydrolysis of the corresponding haloacetonitriles, secondary formation pathways also contributed. Median halonitromethane concentrations were remarkably unchanging for the different types of disinfectants and source waters: 0.1 μg · mgTOC(-1) in all cases. Cyanogen chloride only occurred in a limited number of samples, yet when present its concentrations were higher than the other N-DBPs. Concentrations of cyanogen chloride and the sum of the halonitromethanes were not correlated with any other DBPs. Copyright © 2015 Elsevier Ltd. All rights reserved.

  16. Inorganic bromine in organic molecular crystals: Database survey and four case studies

    Science.gov (United States)

    Nemec, Vinko; Lisac, Katarina; Stilinović, Vladimir; Cinčić, Dominik

    2017-01-01

    We present a Cambridge Structural Database and experimental study of multicomponent molecular crystals containing bromine. The CSD study covers supramolecular behaviour of bromide and tribromide anions as well as halogen bonded dibromine molecules in crystal structures of organic salts and cocrystals, and a study of the geometries and complexities in polybromide anion systems. In addition, we present four case studies of organic structures with bromide, tribromide and polybromide anions as well as the neutral dibromine molecule. These include the first observed crystal with diprotonated phenazine, a double salt of phenazinium bromide and tribromide, a cocrystal of 4-methoxypyridine with the neutral dibromine molecule as a halogen bond donor, as well as bis(4-methoxypyridine)bromonium polybromide. Structural features of the four case studies are in the most part consistent with the statistically prevalent behaviour indicated by the CSD study for given bromine species, although they do exhibit some unorthodox structural features and in that indicate possible supramolecular causes for aberrations from the statistically most abundant (and presumably most favourable) geometries.

  17. Iodine-123 and bromine-75 production and development program at Juelich

    International Nuclear Information System (INIS)

    Stoecklin, G.

    1985-01-01

    The iodine-123 and bromine-75 production and development program at the Nuclear Research Center in Juelich as of 1982 is described, and examples of recent 123 I- and 75 Br-analogue tracers that have been developed to the level of clinical trial are given. Iodine-123 is produced via the 127 I(d,6n) 123 Xe → 123 I process and by the 124 Te(p,2n) 123 I and 122 Te(d,n) 123 I reactions. These production methods are critically reviewed. Bromine-75-labeled benzodiazenes have been prepared for in vivo mapping of benzodiazepine receptor sites. The 7-( 75 Br)-5-(2-fluorophenyl)-1-methyl-1,3-dihydro-2H-1,4-benzodiazepine-2-one (BFB) was prepared with a specific activity of > 10 4 Ci/mmole. Finally, preparation and applications of the halogenated amino acid L-3-( 123 I)-iodo-α-methyltyrosine (IMT) and the analogous 75 Br compound (BMT) are reported. Both IMT and BMT have been successfully applied for pancreas imaging and tomography, and IMT has been used for imaging both melanotic and amelanotic malignant melanoma of the eye

  18. Specific role of taurine in the 8-brominated-2'-deoxyguanosine formation.

    Science.gov (United States)

    Asahi, Takashi; Nakamura, Yoshimasa; Kato, Yoji; Osawa, Toshihiko

    2015-11-15

    At the sites of inflammation, hypohalous acids, such as hypochlorous acid and hypobromous acid (HOBr), are produced by myeloperoxidase. These hypohalous acids rapidly react with the primary amino groups to produce haloamines, which are relatively stable and can diffuse long distances and cross the plasma membrane. In this study, we examined the effects of taurine, the most abundant free amino acid in the leukocyte cytosol, on the hypohalous acid-dependent formation of 8-chloro-2'-deoxyguanosine (8-CldG) and 8-bromo-2'-deoxyguanosine (8-BrdG). The reaction of taurine with HOBr yielded taurine bromamine, which is the most stable among other bromamines of amino acids. Taurine also enhanced the bromination of only dG among the four 2'-deoxynucleosides, whereas it inhibited the 8-CldG formation. The specificity of taurine for the enhanced formation of halogenated dG is completely different from that of nicotine, an enhancer of chlorination. The amount of dibrominated taurine (taurine dibromamine) closely correlated with the formation of 8-BrdG, suggesting that taurine dibromamine might be a plausible mediator for the dG bromination in vivo. Copyright © 2015 Elsevier Inc. All rights reserved.

  19. Synthesis of α-Bromine- Terminated Polystyrene Macroinitiator and Its Initiation of MMA Polymerization by ATRP

    Institute of Scientific and Technical Information of China (English)

    2000-01-01

    In the present paper the synthesis of block copolymers via the transformation from living anionic polymerization (LAP) to atom transfer radical polymerization (ATRP) was described. Α-Bromine-terminated polystyrenes(PStBr) in the LAP step was prepared by using n-BuLi as initiator, tetrahydrofuran (THF) as the activator, α-methylstyrene (α-MeSt) as the capping group and liquid bromine (Br2) as the bromating agent. The effects of reaction conditions such as the amounts of α-MeSt, THF, and Br2 as well as molecular weight of polystyrene on the bromating efficiency (BE) and coupling extent (CE) were examined. The present results show that the yield of PStBr obtained was more than 93.8% and the coupling reaction was substantially absent. PStBr was further used as the macroinitiator in the polymerization of methyl-methacrylate(MMA) in the presence of copper(Ⅰ) halogen and 2,2-bipyridine(bpy) complexes. It was found that the molecular weight of the resulted PSt-b-PMMA increased linearly with the increase of the conversion of MMA and the polydispersity was 1.2-1.6. The structures of PStBr and P(St-b-MMA) were characterized by 1H NMR spectra.

  20. Electrospun Nafion®/Polyphenylsulfone Composite Membranes for Regenerative Hydrogen Bromine Fuel Cells.

    Science.gov (United States)

    Park, Jun Woo; Wycisk, Ryszard; Pintauro, Peter N; Yarlagadda, Venkata; Van Nguyen, Trung

    2016-02-29

    The regenerative H₂/Br₂-HBr fuel cell, utilizing an oxidant solution of Br₂ in aqueous HBr, shows a number of benefits for grid-scale electricity storage. The membrane-electrode assembly, a key component of a fuel cell, contains a proton-conducting membrane, typically based on the perfluorosulfonic acid (PFSA) ionomer. Unfortunately, the high cost of PFSA membranes and their relatively high bromine crossover are serious drawbacks. Nanofiber composite membranes can overcome these limitations. In this work, composite membranes were prepared from electrospun dual-fiber mats containing Nafion ® PFSA ionomer for facile proton transport and an uncharged polymer, polyphenylsulfone (PPSU), for mechanical reinforcement, and swelling control. After electrospinning, Nafion/PPSU mats were converted into composite membranes by softening the PPSU fibers, through exposure to chloroform vapor, thus filling the voids between ionomer nanofibers. It was demonstrated that the relative membrane selectivity, referenced to Nafion ® 115, increased with increasing PPSU content, e.g., a selectivity of 11 at 25 vol% of Nafion fibers. H₂-Br₂ fuel cell power output with a 65 μm thick membrane containing 55 vol% Nafion fibers was somewhat better than that of a 150 μm Nafion ® 115 reference, but its cost advantage due to a four-fold decrease in PFSA content and a lower bromine species crossover make it an attractive candidate for use in H₂/Br₂-HBr systems.