Atmospheric Chemistry and Physics Discussions
www.atmos-chem-phys-discuss.net
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9
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2009
10.5194/acpd-9-20103-2009
http://www.atmos-chem-phys-discuss.net/9/20103/2009/
http://www.atmos-chem-phys-discuss.net/9/20103/2009/acpd-9-20103-2009.html
http://www.atmos-chem-phys-discuss.net/9/20103/2009/acpd-9-20103-2009.pdf
20103
20143
2009-09-25
First remote sensing measurements of ClOOCl along with ClO and ClONO<sub>2</sub> in activated and deactivated Arctic vortex conditions using new ClOOCl IR absorption cross sections
G. Wetzel
gerald.wetzel@kit.edu
H. Oelhaf
O. Kirner
R. Ruhnke
F. Friedl-Vallon
A. Kleinert
G. Maucher
H. Fischer
M. Birk
G. Wagner
A. Engel
Institut für Meteorologie und Klimaforschung (IMK), Karlsruhe Institute of Technology (KIT), Karlsruhe, Germany
Deutsches Zentrum für Luft und Raumfahrt, Institut für Methodik der Fernerkundung, Wessling, Germany
Institut für Atmosphäre und Umwelt, J. W. Goethe Universität Frankfurt, Frankfurt, Germany
Active chlorine species play a dominant role in the catalytic
destruction of stratospheric ozone in the polar vortices during the
late winter and early spring seasons. Recently, the correct
understanding of the ClO dimer cycle was challenged by the release of
new laboratory absorption cross sections (Pope et al., 2007) yielding
significant model underestimates of observed ClO and ozone loss (von
Hobe et al., 2007). Under this aspect, Arctic stratospheric limb
emission measurements carried out by the balloon version of the
Michelson Interferometer for Passive Atmospheric Sounding (MIPAS-B)
from Kiruna (Sweden) on 11 January 2001 and 20/21 March 2003 have been
reanalyzed with regard to the chlorine reservoir species
ClONO<sub>2</sub> and the active species, ClO and ClOOCl
(Cl<sub>2</sub>O<sub>2</sub>). New laboratory measurements of IR absorption
cross sections of ClOOCl for various temperatures and pressures
allowed for the first time the retrieval of ClOOCl mixing
ratios from remote sensing measurements. High values of active
chlorine (ClO<sub>x</sub>) of roughly 2.3 ppbv at 20 km
were observed by MIPAS-B in the cold mid-winter Arctic vortex on
11 January 2001. While nighttime ClOOCl shows enhanced values
of nearly 1.1 ppbv at 20 km, ClONO<sub>2</sub> mixing
ratios are less than 0.1 ppbv at this altitude. In contrast,
high ClONO<sub>2</sub> mixing ratios of nearly 2.4 ppbv at
20 km have been observed in the late winter Arctic vortex on
20 March 2003. No significant ClO<sub>x</sub> amounts are detectable on
this date since most of the active chlorine has already recovered to
its main reservoir species ClONO<sub>2</sub>. The observed values of
ClO<sub>x</sub> and ClONO<sub>2</sub> are in line with the established
chlorine chemistry. The thermal equilibrium constants between the
dimer formation and its dissociation, as derived from the balloon
measurements, are on the lower side of reported data and in good
agreement with values recommended by von Hobe
et al. (2007). Calculations with the ECHAM/MESSy Atmospheric Chemistry
model (EMAC) using established kinetics show similar chlorine
activation and deactivation, compared to the measurements in January
2001 and March 2003, respectively.
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