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Extraordinary isotopic fractionation in ozone photolysis
Author(s) -
Miller Charles E.,
Onorato Robert M.,
Liang MaoChang,
Yung Yuk L.
Publication year - 2005
Publication title -
geophysical research letters
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 2.007
H-Index - 273
eISSN - 1944-8007
pISSN - 0094-8276
DOI - 10.1029/2005gl023160
Subject(s) - photodissociation , fractionation , stratosphere , mass independent fractionation , ozone , isotopologue , ultraviolet , wavelength , atmosphere (unit) , photochemistry , ozone depletion , isotope fractionation , chemistry , analytical chemistry (journal) , materials science , geology , environmental chemistry , atmospheric sciences , physics , chromatography , meteorology , molecule , optoelectronics , organic chemistry
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.