The potential impact of ClO<sub>x</sub> radical complexes on polar stratospheric ozone loss processes
The importance of radical-molecule complexes for atmospheric chemistry has been discussed in recent years. In particular, the existence of a ClO·O<sub>2</sub> and ClO<sub>x</sub> water radical complexes like ClO·H<sub>2</sub>O, OClO&middo...
| Main Authors: | , , , |
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| Format: | Article |
| Language: | English |
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Copernicus Publications
2006-01-01
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| Series: | Atmospheric Chemistry and Physics |
| Online Access: | http://www.atmos-chem-phys.net/6/3099/2006/acp-6-3099-2006.pdf |
| _version_ | 1818177026021916672 |
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| author | B. Vogel W. Feng M. Streibel M. Streibel R. Müller |
| author_facet | B. Vogel W. Feng M. Streibel M. Streibel R. Müller |
| author_sort | B. Vogel |
| collection | DOAJ |
| description | The importance of radical-molecule complexes for atmospheric chemistry has been discussed in recent years. In particular, the existence of a ClO·O<sub>2</sub> and ClO<sub>x</sub> water radical complexes like ClO·H<sub>2</sub>O, OClO·H<sub>2</sub>O, OClO·(H<sub>2</sub>O)<sub>2</sub>, and ClOO·H<sub>2</sub>O could play a role in enhancing the ClO dimer (Cl<sub>2</sub>O<sub>2</sub>) formation and therefore may constitute an important intermediate in polar stratospheric ozone loss cycles. Model simulations performed with the Chemical Lagrangian Model of the Stratosphere (CLaMS) will be presented to study the role of radical complexes on polar stratospheric ozone loss processes. The model simulations are performed for the Arctic winter 2002/2003 at a level of 500 K potential temperature and the results are compared to observed ozone loss rates determined by the Match technique. Moreover, recently reported values for the equilibrium constant of the ClO dimer formation are used to restrict the number of possible model results caused by large uncertainties about radical complex chemistry. Our model simulations show that the potential impact of ClO·O<sub>2</sub> on polar ozone loss processes is small (dO<sub>3</sub>/dt≪0.5 ppb/sunlight h) provided that the ClO·O<sub>2</sub> complex is only weakly stable. Assuming that the binding energies of the ClO<sub>x</sub> water complexes are much higher than theoretically predicted an enhancement of the ozone loss rate by up to ≈0.5 ppb/sunlight h is simulated. Because it is unlikely that the ClO<sub>x</sub> water complexes are much more stable than predicted we conclude that these complexes have no impact on polar stratospheric ozone loss processes. Although large uncertainties about radical complex chemistry exist, our findings show that the potential impact of ClO<sub>x</sub> radical molecule complexes on polar stratospheric ozone loss processes is very small considering pure gas-phase chemistry. However the existence of ClO<sub>x</sub> radical-molecule complexes could possibly explain discrepancies for the equilibrium constant of the ClO dimer formation found between recent laboratory and stratospheric measurements. |
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| institution | Directory Open Access Journal |
| issn | 1680-7316 1680-7324 |
| language | English |
| last_indexed | 2024-12-11T20:25:32Z |
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| series | Atmospheric Chemistry and Physics |
| spelling | doaj.art-8ddd6b71739242cd9f71842e2e4b75de2022-12-22T00:51:57ZengCopernicus PublicationsAtmospheric Chemistry and Physics1680-73161680-73242006-01-0161030993114The potential impact of ClO<sub>x</sub> radical complexes on polar stratospheric ozone loss processesB. VogelW. FengM. StreibelM. StreibelR. MüllerThe importance of radical-molecule complexes for atmospheric chemistry has been discussed in recent years. In particular, the existence of a ClO·O<sub>2</sub> and ClO<sub>x</sub> water radical complexes like ClO·H<sub>2</sub>O, OClO·H<sub>2</sub>O, OClO·(H<sub>2</sub>O)<sub>2</sub>, and ClOO·H<sub>2</sub>O could play a role in enhancing the ClO dimer (Cl<sub>2</sub>O<sub>2</sub>) formation and therefore may constitute an important intermediate in polar stratospheric ozone loss cycles. Model simulations performed with the Chemical Lagrangian Model of the Stratosphere (CLaMS) will be presented to study the role of radical complexes on polar stratospheric ozone loss processes. The model simulations are performed for the Arctic winter 2002/2003 at a level of 500 K potential temperature and the results are compared to observed ozone loss rates determined by the Match technique. Moreover, recently reported values for the equilibrium constant of the ClO dimer formation are used to restrict the number of possible model results caused by large uncertainties about radical complex chemistry. Our model simulations show that the potential impact of ClO·O<sub>2</sub> on polar ozone loss processes is small (dO<sub>3</sub>/dt≪0.5 ppb/sunlight h) provided that the ClO·O<sub>2</sub> complex is only weakly stable. Assuming that the binding energies of the ClO<sub>x</sub> water complexes are much higher than theoretically predicted an enhancement of the ozone loss rate by up to ≈0.5 ppb/sunlight h is simulated. Because it is unlikely that the ClO<sub>x</sub> water complexes are much more stable than predicted we conclude that these complexes have no impact on polar stratospheric ozone loss processes. Although large uncertainties about radical complex chemistry exist, our findings show that the potential impact of ClO<sub>x</sub> radical molecule complexes on polar stratospheric ozone loss processes is very small considering pure gas-phase chemistry. However the existence of ClO<sub>x</sub> radical-molecule complexes could possibly explain discrepancies for the equilibrium constant of the ClO dimer formation found between recent laboratory and stratospheric measurements.http://www.atmos-chem-phys.net/6/3099/2006/acp-6-3099-2006.pdf |
| spellingShingle | B. Vogel W. Feng M. Streibel M. Streibel R. Müller The potential impact of ClO<sub>x</sub> radical complexes on polar stratospheric ozone loss processes Atmospheric Chemistry and Physics |
| title | The potential impact of ClO<sub>x</sub> radical complexes on polar stratospheric ozone loss processes |
| title_full | The potential impact of ClO<sub>x</sub> radical complexes on polar stratospheric ozone loss processes |
| title_fullStr | The potential impact of ClO<sub>x</sub> radical complexes on polar stratospheric ozone loss processes |
| title_full_unstemmed | The potential impact of ClO<sub>x</sub> radical complexes on polar stratospheric ozone loss processes |
| title_short | The potential impact of ClO<sub>x</sub> radical complexes on polar stratospheric ozone loss processes |
| title_sort | potential impact of clo sub x sub radical complexes on polar stratospheric ozone loss processes |
| url | http://www.atmos-chem-phys.net/6/3099/2006/acp-6-3099-2006.pdf |
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