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Extraordinary isotopic fractionation in ozone photolysis
Jet Propulsion Laboratory, California Institute of Technology, Pasadena, California, USA
Department of Chemistry, University of California, Berkeley, Berkeley, California, USA
Division of Geological and Planetary Sciences, California Institute of Technology, Pasadena, California, USA
Division of Geological and Planetary Sciences, California Institute of Technology, Pasadena, California, USA
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 17O and 18O 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.
Received 6 April 2005; accepted 16 June 2005; published 23 July 2005.
Citation: (2005), Extraordinary isotopic fractionation in ozone photolysis, Geophys. Res. Lett., 32, L14814, doi:10.1029/2005GL023160.
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