Transfer of mass-independent fractionation in ozone to other oxygen-containing radicals in the atmosphere

Details Transfer of mass-independent fractionation in ozone to other oxygen-containing radicals in the atmosphere Transfer of mass-independent fractionation in ozone to other oxygen-containing radicals in the atmosphere

Sep 2001

adsabs.harvard.edu/cgi-bin/nph-data_query?bibcode=2001georl..28.3231l&link_type=abstract

Geophysical Research Letters, Volume 28, Issue 17, p. 3231-3234

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50

Atmospheric Composition And Structure: Chemical Kinetic And Photochemical Properties, Atmospheric Composition And Structure: Middle Atmosphere-Composition And Chemistry, Atmospheric Composition And Structure: Troposphere-Composition And Chemistry, Geochemistry: Isotopic Composition/Chemistry

Scientific paper

Mass-independent fractionation (MIF) of ozone has been observed in both the troposphere and stratosphere. Because ozone is a photochemically active species, its MIF signature can be imparted to other atmospheric molecules. Using a photochemical equilibrium model for short-lived radical species, I have computed the expected MIF for typical mid-latitude conditions. The model accounts for about ~70% of recent measurements of Δ17O for H2O2 in rainwater, and predicts large MIF for NOx and ClO species (~40-70‰), and their products (ClONO2 and HNO3). Furthermore, in the stratosphere oxygen exchange reactions between OH and NOx yield OH with Δ17O from 2 to 45‰. Stratospheric water produced during H abstraction by OH would be similarly mass-independently fractionated. In the troposphere rapid exchange between OH and H2O erases any MIF signature in OH. These model results depend on several O exchange reactions with unknown activation energies or with rate coefficients known only as upper limits.

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