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  • 1
    Electronic Resource
    Electronic Resource
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 29 (1997), S. 695-704 
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The Cl- and Br- initiated oxidations of CHCl(DOUBLEBOND)CCl2 in 700 torr of air at 296 K have been studied using a Fourier transform infrared spectrometer. Rate constants k(Cl+CHCl(DOUBLEBOND)CCl2)=(7.2±0.8)×10-11 and k(Br+CHCl(DOUBLEBOND)CCl2)=(1.1±0.4)×10-13 cm3 molecule-1 s-1 were determined using a relative rate technique with ethane and ethylene as references, respectively. The major products observed were CHXClC(O)Cl, (X=Cl or Br), CHClO, and CCl2O. Combining results obtained for the Cl-initiated oxidation of CHCl2(SINGLEBOND)CHCl2, we deduced that Cl-addition on trichloroethylene occurs via channel 1a, Cl+CHCl(DOUBLEBOND)CCl2→ CHCl2(SINGLEBOND)CCl2, (100±12)%. Self-reaction of the subsequently generated peroxy radicals CHCl2(SINGLEBOND)CCl2O2 leads to CHCl2CCl2O radicals which were found to decompose via channel 8a, CHCl2C(O)Cl+Cl, (91±11)% of the time, and channel 8b, CHCl2+CCl2O, (9±2)%. The reaction Br+CHCl(DOUBLEBOND)CCl2→CHBrCl(SINGLEBOND)CCl2 (17a) accounted for ≥(96±11)% of the total reaction. Decomposition of the CHBrCl(SINGLEBOND)CCl2O radicals proceeds (≥93±11)% via CHBrClC(O)Cl+Cl. As part of this work, k(Cl+CHCl2C(O)Cl)=(3.6±0.6)×10-14 and k(Cl+CHCl2(SINGLEBOND)CHCl2)=(1.9±0.2)×10-13 cm3 molecule-1 s-1 were measured. Errors reported above include statistical uncertainties (2σ) and estimated systematic uncertainties. © 1997 John Wiley & Sons, Inc. Int J Chem Kinet: 29: 695-704, 1997.
    Additional Material: 8 Ill.
    Type of Medium: Electronic Resource
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  • 2
    Publication Date: 2016-10-04
    Description: We carry out a case study of the transport and chemistry of bromoform and its product gases (PGs) in a sea breeze driven convective episode on 19 November 2011 along the North West coast of Borneo during the "Stratospheric ozone: Halogen Impacts in a Varying Atmosphere" (SHIVA) campaign. We use ground based, ship, aircraft and balloon sonde observations made during the campaign, and a 3-D regional online transport and chemistry model capable of resolving clouds and convection explicitly that includes detailed bromine chemistry. The model simulates the temperature, wind speed, wind direction fairly well for the most part, and adequately captures the convection location, timing, and intensity. The simulated transport of bromoform from the boundary layer up to 12 km compares well to aircraft observations to support our conclusions. The model makes several predictions regarding bromine transport from the boundary layer to the level of convective detrainment (11 to 12 km). First, the majority of bromine undergoes this transport as bromoform. Second, insoluble organic bromine carbonyl species are transported to between 11 and 12 km, but only form a small proportion of the transported bromine. Third, soluble bromine species, which include bromine organic peroxides, hydrobromic acid (HBr), and hypobromous acid (HOBr), are washed out efficiently within the core of the convective column. Fourth, insoluble inorganic bromine species (principally Br2) are not washed out of the convective column, but are also not transported to the altitude of detrainment in large quantities. We expect that Br2 will make a larger relative contribution to the total vertical transport of bromine atoms in scenarios with higher CHBr3 mixing ratios in the boundary layer, which have been observed in other regions. Finally, given the highly detailed description of the chemistry, transport and washout of bromine compounds within our simulations, we make a series of recommendations about the physical and chemical processes that should be represented in 3-D chemical transport models (CTMs) and chemistry climate models (CCMs), which are the primary theoretical means of estimating the contribution made by CHBr3 and other very short-lived substances (VSLS) to the stratospheric bromine budget.
    Type: Article , NonPeerReviewed , info:eu-repo/semantics/article
    Format: text
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  • 3
    Publication Date: 2019-07-17
    Repository Name: EPIC Alfred Wegener Institut
    Type: Article , isiRev
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  • 4
    Publication Date: 2019-07-17
    Repository Name: EPIC Alfred Wegener Institut
    Type: Article , isiRev
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  • 5
    Publication Date: 2019-07-17
    Description: This paper presents extensive {bias determination} analyses of ozone observations from the Atmospheric Chemistry Experiment (ACE) satellite instruments: the ACE Fourier Transform Spectrometer (ACE-FTS) and the Measurement of Aerosol Extinction in the Stratosphere and Troposphere Retrieved by Occultation (ACE-MAESTRO) instrument. Here we compare the latest ozone data products from ACE-FTS and ACE-MAESTRO with coincident observations from nearly 20 satellite-borne, airborne, balloon-borne and ground-based instruments, by analysing volume mixing ratio profiles and partial column densities. The ACE-FTS version 2.2 Ozone Update product reports more ozone than most correlative measurements from the upper troposphere to the lower mesosphere. At altitude levels from 16 to 44 km, the average values of the mean relative differences are nearly all within +1 to +8%. At higher altitudes (4560 km), the ACE-FTS ozone amounts are significantly larger than those of the comparison instruments, with mean relative differences of up to +40% (about +20% on average). For the ACE-MAESTRO version 1.2 ozone data product, mean relative differences are within ±10% (average values within ±6%) between 18 and 40 km for both the sunrise and sunset measurements. At higher altitudes (~3555 km), systematic biases of opposite sign are found between the ACE-MAESTRO sunrise and sunset observations. While ozone amounts derived from the ACE-MAESTRO sunrise occultation data are often smaller than the coincident observations (with mean relative differences down to −10%), the sunset occultation profiles for ACE-MAESTRO show results that are qualitatively similar to ACE-FTS, indicating a large positive bias (mean relative differences within +10 to +30%) in the 4555 km altitude range. In contrast, there is no significant systematic difference in bias found for the ACE-FTS sunrise and sunset measurements.
    Repository Name: EPIC Alfred Wegener Institut
    Type: Article , isiRev
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  • 6
    Publication Date: 2019-07-17
    Description: Part of the abstract: The Michelson Interferometer for Passive AtmosphericSounding (MIPAS), on-board the European ENVIronmentalSATellite (ENVISAT) launched on 1 March 2002,is a middle infrared Fourier Transform spectrometer measuringthe atmospheric emission spectrum in limb sounding geometry.The instrument is capable to retrieve the vertical distributionMIPAS data were re-processed by ESA using updated versions ofthe Instrument Processing Facility (IPF v4.61 and v4.62) andprovided a complete set of level-2 operational products (geolocatedvertical profiles of temperature and volume mixingratio of H2O, O3, HNO3, CH4, N2O and NO2). MIPAS operated in its standard observation mode for approximately two years, from July 2002 to March 2004. MIPAS data were re-processed by ESA using updated versions of the Instrument Processing Facility (IPF v4.61 and v4.62) and provided a complete set of level-2 operational products (geolocated vertical profiles of temperature and volume mixing ratio of H2O, O3, HNO3, CH4, N2O and NO2). MIPAS operated in its standard observation mode from July 2002 to March 2004, covering the altitude range from the mesosphere to the upper troposphere with relatively high vertical resolution (about 3 km in the stratosphere). In this paper, we report a detailed description of the validation of MIPAS-ENVISAT operational ozone data, that was based on the comparison between MIPAS v4.61 (and, to a lesser extent, v4.62) O3 VMR profilesand a comprehensive set of correlative data, including observations from ozone sondes, ground-based lidar, FTIR and microwave radiometers, remote-sensing and in situ instruments on-board stratospheric aircraft and balloons, concurrent satellite sensors and ozone fields assimilated by theEuropean Center for Medium-range Weather Forecasting. A clear indication of the validity of MIPAS O3 vertical profiles is obtained for most of the stratosphere, where the mean relative difference with the individual correlative data sets is always lower than ±10%. Furthermore, these differences always fall within the combined systematic error (from1 hPa to 50 hPa) and the standard deviation is fully consistent with the random error of the comparison (from 1 hPa to 3040 hPa).
    Repository Name: EPIC Alfred Wegener Institut
    Type: Article , isiRev
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  • 7
    Publication Date: 2019-07-17
    Repository Name: EPIC Alfred Wegener Institut
    Type: Article , isiRev
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