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    Original Research Papers

    Trichloroethene and tetrachloroethene: tropospheric probes for Cl- and Br-atom reactions during the polar sunrise

    Authors:

    P. A. Ariya ,

    Centre for Atmospheric Chemistry and Department of Chemistry, York University, CA
    About P. A.
    Present address: Max Planck Institute for Chemistry, Air Chemistry Division, P. O. Box 3060, 55020 Mainz, Germany.
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    V. Catoire,

    Centre for Atmospheric Chemistry and Department of Chemistry, York University, CA
    About V.
    Present address: CNRS/Laboratoire de Physique et Chimie de l'Environment, 45071 Orleans Cedex 2, France.
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    R. Sander,

    Centre for Atmospheric Chemistry and Department of Chemistry, York University, CA
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    H. Niki,

    Centre for Atmospheric Chemistry and Department of Chemistry, York University, CA
    About H.
    Deceased.
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    G. W. Harris

    Centre for Atmospheric Chemistry and Department of Chemistry, York University, CA
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    Abstract

    We report the results of laboratory and modeling investigations of the atmospheric fate of chlorinated ethenes and their role as indicators of halogen reactions in the springtime Arctic troposphere. The kinetics and mechanism of the gas-phase reactions of Cl- and Br-atoms with tetrachloroethene were studied using a Fourier transform infrared spectrometer (FTIR) in 93.3 kPa air and T = 296 ± 2 K. Along with our previous study on Cl and Br atom reactions of trichloroethene, using the known rate of the Cl + ethane reaction as reference, the values of 7.2 ± 0.2 × 10-11 and 3.8 ± 0.2 × 10-11 cm3 molecule-1 s-1 were obtained for the Cl-atom reaction rate constants of tri- and tetrachloroethene, respectively. For the Br-atom reactions, using ethene and propane as the reference molecules, we report the absolute values of 1.1 ± 0.1 × 10-13 and 9.0 ± 0.1 × 10-17 cm3 molecule-1 s-1 for the rates of Br attack on tri- and tetrachloroethene. The major products were XCl2C-C(O)Cl (X = H in trichloroethene and X = Cl in tetrachloroethene) and XBrClC-C(O)Cl in Cl-atom and Br-atom initiated reactions, respectively. We also observed phosgene and formyl chloride in the reactions of trichloroethene and phosgene in the tetrachloroethene reactions and report the branching ratios for these channels. Our observations show that the addition of Cl-atoms to the less substituted carbon is the major reaction pathway and that a Cl-atom is subsequently released after either Cl- or Br-atoms add to trichloroethene or tetrachloroethene, leading to the recycling of active halogen. We carried out a box modelling exercise to apply the kinetic and mechanistic information obtained in this work to the interpretation of measurements of C2HCl3, C2Cl4 and other hydrocarbons in the Arctic troposphere. Our results demonstrate that the presence of both Cl- and Br-atoms is required to explain the decreases in the concentrations of these species during ozone depletion events in the Arctic, that the amount of Cl- and Br-atoms required to account for the observed decreases of chlorinated ethenes is also sufficient to completely destroy ozone. However, at the low concentrations of chlorinated species observed, the cycling of Br to Cl through the studied reactions is not a significant effect in the atmosphere.

    How to Cite: Ariya, P.A., Catoire, V., Sander, R., Niki, H. and Harris, G.W., 1997. Trichloroethene and tetrachloroethene: tropospheric probes for Cl- and Br-atom reactions during the polar sunrise. Tellus B: Chemical and Physical Meteorology, 49(5), pp.583–591. DOI: http://doi.org/10.3402/tellusb.v49i5.16011
      Published on 01 Jan 1997
    Peer Reviewed
     CC BY 4.0
     Accepted on 28 Apr 1997            Submitted on 27 Sep 1996

    References

    1. Abbatt , J. P. D . 1994 . Heterogenous reaction of HOBr with HBr and HCl on ice surfaces at 228 K . Geophys. Res. Lett . 21 , 665 – 668 .  

    2. Ariya , P. A . 1996 . Studies of tropospheric halogen chemistry: laboratory and field measurements , PhD Thesis , York University , Canada .  

    3. Ariya , P. A. , Jobson , B. T. , Sander , R. , Niki , H. , Hopper , F. and Harris , G. W . 1997 . Measurements of C2-C7 hydrocarbons during the polar sunrise 1994 experiment: further evidence for halogen chemistry in the troposphere . J. Geophys. Res . , in press .  

    4. Atkinson , R. , Aschmann , S. M . 1987 . Kinetics of the gas phase reaction of Cl atoms with chlorinated ethenes at 298 + 2 K and atmospheric pressure . Int. J. Chem. Kinet . 19 , 1097 – 1105 .  

    5. Atkinson , R. and Carter , W. P. L . 1991 . Reactions of alkoxy radicals under atmospheric conditions: The relative importance of decomposition versus reaction with 02 , J. Atm. Chem . 13 , 195 – 210 .  

    6. Barrie , L. A. , Bottenheim , J. W. , Schnell , R. C. , Crutzen , P. J. and Rasmussen , R. A . 1988 . Ozone destruction and photochemical reactions at polar sunrise in the lower Arctic atmosphere . Nature 334 , 138 – 141 .  

    7. Barrie , L. A. , Staebler , R. , Toom , D. , Georgi , B. , Den Hartog , G. , Landsberger , S. and Wu , D . 1994 . Arctic aerosol size-segregated chemical observations in rela-tion to ozone depletion during Polar Sunrise Experi-ment 1992 . J. Geophys. Res . 99 , 25439 – 25451 .  

    8. Bertrand , L. , Franklin , J. A. , Goldfinger , P. and Huybrechts , G . 1968 . The point of attack of a chlorine atom on trichloroethylene . J. Phys. Chem . 72 , 3926 – 3928 .  

    9. Bottenheim , J. W. , Barrie , L. A. , Atlas , E. , Heidt , L. E. , Niki , H. , Rasmussen , R. A. and Shepson , P. B . 1990 . Depletion of lower tropospheric ozone during Arctic spring: the polar sunrise experiment 1988 . J. Geophys. Res . 95 , 18555 – 18568 .  

    10. Catoire , V. , Ariya , P. A. , Niki , H. and Harris , G. W . 1996. FTIR study of Cl- and Br-atom initiated oxida-tion of trichloroethylene. Int. J. Chem. Kinet. in press.  

    11. Cvetanovic , R. J. , Singleton , D. L. and Paraskevo-poulos , G . 1979 . Evaluations of the mean values and standard errors of rate constants and their temperature coefficients . J. Phys. Chem . 83 , 50 .  

    12. DeMore , W. B. , Sander , S. P. , Golden , D. M. , Hampson , R. F. , Kurylo , M. J. , Howard , C. J. , Ravishankara , A. R. , Kolb , C. E. and Molina , M. J . 1994. Chemical kinetics and photochemical data for use in strato-spheric modeling. JPL Publication 11.  

    13. Huybrechts , G. and Meyers , L . 1966 . Gas-phase chlorine photosensitized oxidation of trichloroethylene . Trans. Faraday Soc . 62 , 2191 – 2199 .  

    14. Huybrechts , G. , Olbregto , L. and Thomas , K . 1967 . Gas-phase chlorine-photosensitized oxidation and oxygen-inhibited photochlorination of tetrachloroethylene and pentachloroethylene . Trans. Faraday Soc . 63 , 1647 – 1655 .  

    15. Jobson , B. T. , Niki , H. , Yokouchi , Y. , Bottenheim , J. , Hopper , F. and Leaitch , R . 1994 . Measurements of C2-C6 hydrocarbons during the polar sunrise 1992 experiment: evidence for Cl atom and Br atom chemistry . J. Geophys. Res . 99 , 25355 – 25368 .  

    16. Kleindienst , T. E. , Shepson , P. B. , Nero , C. M. and Bufalini , J. J . 1989 . The production of chlorine atoms of the reaction of OH with chlorinated hydrocarbons . Int. J. Chem. Kinet . 21 , 863 – 884 .  

    17. Le Bras , G. and Platt , U . 1995 . A possible mechanism for combined chlorine and bromine catalyzed destruc-tion of tropospheric ozone in the Arctic . Geophys. Res. Lett . 22 , 599 – 602 .  

    18. Mathias , E. , Sanhueza , E. , Hisatsune , I. C. and Heicklen , J . 1974 . The chlorine atom sensitized oxida-tion and the ozonolysis of C2Cl4 . Can. J. Chem . 52 , 3852 – 3860 .  

    19. Muthuramu , K. , Shepson , P. B. , Bottenheim , J. W. , Jobson , B. T. , Niki , H. and Anlauf , K. G . 1994 . Rela-tionships between organic nitrates and surface ozone destruction during Polar Sunrise Experiment 1992 , J. Geophys. Res . 99 , 25369 – 25378 .  

    20. Niki , H. , Maker , P. D. , Savage , C. M. and Breitenbach , L. P . 1980 . FTIR studies of the Cl-atom initiated oxidation of CHCl2 and CHCl3 . Int. J. Chem. Kinet . 12 , 1001 – 1012 .  

    21. Niki , H. , Maker , P. D. , Savage , C. M. and Breitenbach , L. P . 1982 . Fourier Transform Infrared studies of the self reaction of C2H5O2 radicals . J. Phys. Chem . 86 , 3825 – 3829 .  

    22. Oltmans , S. J. , Barrie , L. A. , Atlas , E. A. , Heidt , L. E. , Niki , H. , Rasmussen , R. A. and Shepson , P. B . 1989 . Seasonal surface ozone and filterable bromine rela-tionships in the high Arctic . Atmos. Environ . 23 , 2431 – 2441 .  

    23. Pszenny , A. A. P. , Keene , W. C. , Jacob , D. J. , Fan , S. , Maben , J. R. , Zewto , M. P. , Springer-Young , M. and Galloway , J. N . 1993 . Evidence of inorganic chlorine gases other than hydrogen chloride in marine surface air . J. Geophys. Res. Lett . 20 , 699 – 702 .  

    24. Sander , R. and Crutzen , P. J . 1996 . Model Study indicat-ing halogen activation and ozone destruction in polluted air masses transported to the sea . J. Geophys. Res . 101D , 9121 – 9138 .  

    25. Sander , R. , Vogt , R. , Harris , G. W. and Crutzen , P. J . 1997 . Modeling the chemistry of ozone, halogen compounds and hydrocarbons during arctic spring . Tellus 49B , 522 – 532 .  

    26. Seakins , P. W. , Pilling , M. J. , Niiranen , J. T. , Gutman , D. and Krasnoperov , L. N . 1992 . Kinetics and thermochemistry of R +HBr = RH + Br reactions: determina-tions of the heat of formation of C2H5, i-C3H7, sec-C4H9 and t-C4H9 . J. Phys. Chem . 96 , 9847 – 9855 .  

    27. Sanhueza , E. , Hisatsune , I. C. and Heicklen , J . 1976 . Oxidation of haloethylenes . Chem. Re v . 76 , 801 – 826 .  

    28. Shi , J. , Wallington , T. J. and Kaiser , E. W . 1993 . FTIR study of the Cl-initiated oxidation of C2H5Cl: reactions of the alkoxy radical CH3CHClO . J. Phys. Chem . 97 , 6184 – 6192 .  

    29. Vogt , R. , Crutzen , P. J. and Sander , R . 1996 . A mechan-ism for halogen release from sea-salt aerosol in the remote marine boundary layer . Nature 382 , 327 – 330 .  

    30. Wayne , R. P . 1991 . Chemistry of atmosphere , 2nd edition . Oxford University Press , Oxford, UK .  

    31. World Meterological Organization . 1995 . Global ozone research and monitoring project, report no. 37, Scient-ific assessment of ozone depletion: 1994 .  

    32. Yarwood , G. , Peng , N. and Niki , H . 1992 . FTIR spectro-scopic study of the Cl- and Br-atom initiated oxidation of ethene . Int. J. Chem. Kinet . 24 , 369 – 393 .  

    33. Yokouchi , Y. , Akimoto , H. , Barrie , L. A. , Bottenheim , J. W. , Anlauf , K. G. and Jobson , B. T . 1994 . Serial gschromatographic/mass spectrometric measurements of some volatile organic compounds in the Arctic atmosphere during the 1992 polar sunrise experiment . J. Geophys. Res . 99D , 25379 – 25389 .  

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