ACPD Atmospheric Chemistry and Physics Discussions ACPD 1680-7375 Copernicus GmbH Göttingen, Germany 10.5194/acpd-11-18901-2011 ClOOCl photolysis at high solar zenith angles: analysis of the RECONCILE self-match flight Sumińska-Ebersoldt O. 1 Lehmann R. 2 Wegner T. 1 Grooß{} J.-U. 1 Hösen E. 3 Weigel R. 4 5 Volk C. M. 3 Borrmann S. 4 5 Rex M. 2 Stroh F. 1 von Hobe M. 1 Institute of Energy and Climate Research: Stratosphere (IEK-7), Forschungszentrum Jülich GmbH, Jülich, Germany Alfred Wegener Institute for Polar and Marine Research, Potsdam, Germany Department of Physics, University of Wuppertal, Germany Institute for Physics of the Atmosphere, Johannes Gutenberg Universität Mainz, Germany Particle Chemistry Department, Max Planck-Institute für Chemie, Mainz, Germany 01 07 2011 11 7 18901 18926 This is an open-access article ditributed under the terms of the Creative Commons Attribution License, which permits unrestricted use, distribution, and reproduction in any medium, provided the original author and source are credited. This article is available from http://www.atmos-chem-phys-discuss.net/11/18901/2011/acpd-11-18901-2011.html The full text article is available as a PDF file from http://www.atmos-chem-phys-discuss.net/11/18901/2011/acpd-11-18901-2011.pdf

The photolysis frequency of dichlorine peroxide (ClOOCl) <i>J</i><sub>ClOOCl</sub> is a critical parameter in catalytic cycles destroying ozone in the polar stratosphere. In the atmospherically relevant wavelength region, published laboratory measurements of ClOOCl absorption cross sections and spectra are not in good agreement, resulting in significant discrepancies in <i>J</i><sub>ClOOCl</sub>. Previous investigations of the consistency with atmospheric observations of ClO and ClOOCl have focused on the photochemical equilibrium between ClOOCl formation and photolysis, and thus could only constrain the ratio of <i>J</i><sub>ClOOCl</sub> over the rate constant of the ClO recombination reaction <i>k</i><sub>rec</sub>. Here, we constrain the atmospherically effective <i>J</i><sub>ClOOCl</sub> independent of <i>k</i><sub>rec</sub> using ClO data sampled in the same air masses before and directly after sunrise. Over sunrise, when the ClO/ClOOCl system comes out of thermal equilibrium and the influence of the ClO recombination reaction is negligible, the rise in ClO concentration is significantly faster than expected from <i>J</i><sub>ClOOCl</sub> based on the absorption spectrum proposed by Pope et al. (2007), but does not warrant cross sections larger than recently published values by Papanastasiou et al. (2009). In particular, the existence of a significant ClOOCl absorption band longwards of 420 nm, is effectively ruled out by our observations. Additionally, the night-time ClO observations show that the ClO/ClOOCl thermal equilibrium constant can not be significantly higher than the one proposed by Plenge et al. (2005).

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