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Published July 28, 2005 | Published
Journal Article Open

Extraordinary isotopic fractionation in ozone photolysis


Analysis of experimental ozone absorption spectra reveals that ultraviolet photolysis within the structured Huggins band yields extraordinary wavelength-dependent isotopic fractionation, oscillating between complete enrichment and complete depletion for changes of less than 2 nm in the excitation wavelength. Visible photolysis yields wavelength-dependent fractionation that varies from −300‰ to +300‰. Photochemical modeling demonstrates photolysis contributes fractionation up to +45‰ to the heavy ozone anomaly in the middle stratosphere with measurable ^(17)O and ^(18)O isotopologue-dependent variations as a function of altitude despite the fact that the extraordinary photolysis-induced isotopic fractionation effect is dampened in the atmosphere due to the integration over all excitation wavelengths.

Additional Information

© 2005 The American Geophysical Union. Received 6 April 2005; Revised 15 May 2005; Accepted 16 June 2005; Published 23 July 2005. The authors thank Drs. J. Brion and S. M. Anderson for sharing their ozone absorption spectra. The research at the Jet Propulsion Laboratory (JPL), California Institute of Technology was performed under contract with the National Aeronautics and Space Administration.

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