Observational constraints on the kinetics of the ClO‐BrO and ClO‐ClO ozone loss cycles in the Arctic winter stratosphere

Geophysical Research Letters - Tập 34 Số 5 - 2007
A. Butz1,2, Hartmut Bösch1,3, C. Camy‐Peyret2, M. Dorf1, Andreas Engel4, Sébastien Payan2, Klaus Pfeilsticker1
1Institut für Umweltphysik, University of Heidelberg, Heidelberg, Germany
2Laboratoire de Physique Moléculaire pour l'Atmosphère et l'Astrophysique Université Pierre et Marie Curie Paris France
3JPL - Jet Propulsion Laboratory (4800 Oak Grove Drive, Pasadena, CA 91109-8099, USA - United States)
4Institut für Atmosphäre und Umwelt J. W. Goethe University of Frankfurt Frankfurt Germany

Tóm tắt

Observations of the balloon‐borne LPMA/DOAS remote sensing instruments performed in the Arctic stratosphere in February 1999 are used to constrain a photochemical model. Measurements of all relevant nitrogen, chlorine, and bromine species indicate that moderate heterogeneous chlorine activation occurred in a filament of the Arctic vortex. Model‐measurement comparisons for OClO serve as an indicator of how well various scenarios of the involved reaction kinetics, in particular of the ClO‐BrO and the ClO‐ClO cycles, reproduce the observations. Recent suggestions for the photolysis rate of the ClO dimer, the equilibrium constant between ClO dimer and monomer, the rate of the ClO‐ClO association reaction, and the branching ratio of the ClO‐BrO reaction are consistent with the observations. Formation of an unstable isomer of ClONO2 cannot be reconciled with the observations. Modeled odd oxygen loss rates can be larger by 10% to 20% for the updated reaction kinetics compared to standard recommendations.

Từ khóa


Tài liệu tham khảo

10.1021/j100365a033

10.5194/acp-6-1293-2006

Camy‐Peyret C. P.Jeseck T.Hawat G.Durry S.Payan G.Berube L.Rochette andD.Huguenin(1995) The LPMA balloon‐borne FTIR spectrometer: Remote sensing of atmospheric constituents paper presented at12th Symposium on Rocket and Balloon Programmes and Related Research Eur. Space Agency Lillehammer Norway.

10.1029/2004JD005035

10.1029/98JD02597

10.5194/acp-6-2483-2006

10.5194/acp-5-919-2005

10.1029/2001JD000584

European Ozone Research Coordinating Unit(1999) The Northern Hemisphere stratosphere in the winter of 1998/1999 report Cambridge U.K.

10.1364/AO.39.002377

10.1029/2005GL025466

10.1029/98GL01933

10.1021/jp044142h

10.1029/2002GL016008

10.1023/B:JOCH.0000044423.21004.8e

Sander S. et al. (2000) Chemical kinetics and photochemical data for use in stratospheric modeling: Supplement to evaluation 12: Update of key reactions JPL Publ. 00‐03.

Sander S. et al. (2003) Chemical kinetics and photochemical data for use in atmospheric studies JPL Publ. 02‐25.

Sander S. et al. (2006) Chemical kinetics and photochemical data for use in atmospheric studies JPL Publ. 06‐2.

10.1029/2003JD003811

10.1364/AO.35.006041

10.5194/acp-5-693-2005

World Meteorological Organization(2003) Scientific assessment of ozone depletion: 2002 Rep. 47 Global Ozone Res. and Monit. Proj. Geneva.