ClOOCl photolysis at high solar zenith angles: analysis of the RECONCILE self-match flight
The photolysis rate constant of dichlorine peroxide (ClOOCl, ClO dimer) JClOOCl is a critical parameter in catalytic cycles destroying ozone (O3) in the polar stratosphere. In the atmospherically relevant wavelength region (λ > 310 nm), significant discrepancies between laboratory measurements of...
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ftawi:oai:epic.awi.de:24671 2023-05-15T17:04:16+02:00 ClOOCl photolysis at high solar zenith angles: analysis of the RECONCILE self-match flight Suminska-Ebersoldt, O. Lehmann, Ralph Wegner, T. Grooß, J. U. Hösen, E. Weigel, R. Frey, W. Griessbach, S. Mitev, V. Emde, C. Volk, C. M. Borrmann, S. Rex, Markus Stroh, F. von Hobe, M. 2012 application/pdf https://epic.awi.de/id/eprint/24671/ https://epic.awi.de/id/eprint/24671/1/Suminska_2012.pdf https://hdl.handle.net/10013/epic.38829 https://hdl.handle.net/10013/epic.38829.d001 unknown https://epic.awi.de/id/eprint/24671/1/Suminska_2012.pdf https://hdl.handle.net/10013/epic.38829.d001 Suminska-Ebersoldt, O. , Lehmann, R. , Wegner, T. , Grooß, J. U. , Hösen, E. , Weigel, R. , Frey, W. , Griessbach, S. , Mitev, V. , Emde, C. , Volk, C. M. , Borrmann, S. , Rex, M. orcid:0000-0001-7847-8221 , Stroh, F. and von Hobe, M. (2012) ClOOCl photolysis at high solar zenith angles: analysis of the RECONCILE self-match flight , Atmospheric Chemistry and Physics., 12 , pp. 1353-1365 . hdl:10013/epic.38829 EPIC3Atmospheric Chemistry and Physics., 12, pp. 1353-1365 Article isiRev 2012 ftawi 2021-12-24T15:35:11Z The photolysis rate constant of dichlorine peroxide (ClOOCl, ClO dimer) JClOOCl is a critical parameter in catalytic cycles destroying ozone (O3) in the polar stratosphere. In the atmospherically relevant wavelength region (λ > 310 nm), significant discrepancies between laboratory measurements of ClOOCl absorption cross sections and spectra cause a large uncertainty in JClOOCl. Previous investigations of the consistency of published JClOOCl with atmospheric observations of chlorine monoxide (ClO) and ClOOCl have focused on the photochemical equilibrium between ClOOCl formation and photolysis, and thus could only constrain the ratio of JClOOCl over the ClOOCl formation rate constant krec. Here, we constrain the atmospherically effective JClOOCl independent of krec, using ClO measured in the same air masses before and directly after sunrise during an aircraft flight that was part of the RECONCILE field campaign in the winter 2010 from Kiruna, Sweden. Over sunrise, when the ClO/ClOOCl system comes out of thermal equilibrium and the influence of the ClO recombination reaction is negligible, the increase in ClO concentrations is significantly faster than expected from JClOOCl 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 not supported by our observations. The observed night-time ClO would not be consistent with a ClO/ClOOCl thermal equilibrium constant significantly higher than the one proposed by Plenge et al. (2005). Article in Journal/Newspaper Kiruna Alfred Wegener Institute for Polar- and Marine Research (AWI): ePIC (electronic Publication Information Center) Kiruna |
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Alfred Wegener Institute for Polar- and Marine Research (AWI): ePIC (electronic Publication Information Center) |
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ftawi |
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The photolysis rate constant of dichlorine peroxide (ClOOCl, ClO dimer) JClOOCl is a critical parameter in catalytic cycles destroying ozone (O3) in the polar stratosphere. In the atmospherically relevant wavelength region (λ > 310 nm), significant discrepancies between laboratory measurements of ClOOCl absorption cross sections and spectra cause a large uncertainty in JClOOCl. Previous investigations of the consistency of published JClOOCl with atmospheric observations of chlorine monoxide (ClO) and ClOOCl have focused on the photochemical equilibrium between ClOOCl formation and photolysis, and thus could only constrain the ratio of JClOOCl over the ClOOCl formation rate constant krec. Here, we constrain the atmospherically effective JClOOCl independent of krec, using ClO measured in the same air masses before and directly after sunrise during an aircraft flight that was part of the RECONCILE field campaign in the winter 2010 from Kiruna, Sweden. Over sunrise, when the ClO/ClOOCl system comes out of thermal equilibrium and the influence of the ClO recombination reaction is negligible, the increase in ClO concentrations is significantly faster than expected from JClOOCl 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 not supported by our observations. The observed night-time ClO would not be consistent with a ClO/ClOOCl thermal equilibrium constant significantly higher than the one proposed by Plenge et al. (2005). |
format |
Article in Journal/Newspaper |
author |
Suminska-Ebersoldt, O. Lehmann, Ralph Wegner, T. Grooß, J. U. Hösen, E. Weigel, R. Frey, W. Griessbach, S. Mitev, V. Emde, C. Volk, C. M. Borrmann, S. Rex, Markus Stroh, F. von Hobe, M. |
spellingShingle |
Suminska-Ebersoldt, O. Lehmann, Ralph Wegner, T. Grooß, J. U. Hösen, E. Weigel, R. Frey, W. Griessbach, S. Mitev, V. Emde, C. Volk, C. M. Borrmann, S. Rex, Markus Stroh, F. von Hobe, M. ClOOCl photolysis at high solar zenith angles: analysis of the RECONCILE self-match flight |
author_facet |
Suminska-Ebersoldt, O. Lehmann, Ralph Wegner, T. Grooß, J. U. Hösen, E. Weigel, R. Frey, W. Griessbach, S. Mitev, V. Emde, C. Volk, C. M. Borrmann, S. Rex, Markus Stroh, F. von Hobe, M. |
author_sort |
Suminska-Ebersoldt, O. |
title |
ClOOCl photolysis at high solar zenith angles: analysis of the RECONCILE self-match flight |
title_short |
ClOOCl photolysis at high solar zenith angles: analysis of the RECONCILE self-match flight |
title_full |
ClOOCl photolysis at high solar zenith angles: analysis of the RECONCILE self-match flight |
title_fullStr |
ClOOCl photolysis at high solar zenith angles: analysis of the RECONCILE self-match flight |
title_full_unstemmed |
ClOOCl photolysis at high solar zenith angles: analysis of the RECONCILE self-match flight |
title_sort |
cloocl photolysis at high solar zenith angles: analysis of the reconcile self-match flight |
publishDate |
2012 |
url |
https://epic.awi.de/id/eprint/24671/ https://epic.awi.de/id/eprint/24671/1/Suminska_2012.pdf https://hdl.handle.net/10013/epic.38829 https://hdl.handle.net/10013/epic.38829.d001 |
geographic |
Kiruna |
geographic_facet |
Kiruna |
genre |
Kiruna |
genre_facet |
Kiruna |
op_source |
EPIC3Atmospheric Chemistry and Physics., 12, pp. 1353-1365 |
op_relation |
https://epic.awi.de/id/eprint/24671/1/Suminska_2012.pdf https://hdl.handle.net/10013/epic.38829.d001 Suminska-Ebersoldt, O. , Lehmann, R. , Wegner, T. , Grooß, J. U. , Hösen, E. , Weigel, R. , Frey, W. , Griessbach, S. , Mitev, V. , Emde, C. , Volk, C. M. , Borrmann, S. , Rex, M. orcid:0000-0001-7847-8221 , Stroh, F. and von Hobe, M. (2012) ClOOCl photolysis at high solar zenith angles: analysis of the RECONCILE self-match flight , Atmospheric Chemistry and Physics., 12 , pp. 1353-1365 . hdl:10013/epic.38829 |
_version_ |
1766058339474604032 |