Are models of catalytic removal of O_3 by HO_x accurate? Constraints from in situ measurements of the OH to HO_2 ratio

Abstract

Measurements of the ratio OH/HO_2, NO, O_3, ClO, and BrO were obtained at altitudes from 15–20 km and latitudes from 15–60°N. A method is presented for interpreting these simultaneous in situ observations that constrains the rates of chemical transformations that 1) are responsible for over half the ozone removal rate in the lower stratosphere via reactions of HO_2 and 2) control the abundance of HO_2 through coupling to nitrogen and halogen radicals. The results show our understanding of the chemical reactions controlling the partitioning of OH and HO_2 is complete and accurate and that the potential effects of "missing chemistry" are strictly constrained in the region of the atmosphere encompassed by the observations. The analysis demonstrates that the sensitivity of the ratio OH/HO_2 to changes in NO is described to within 12% by current models. This reduces by more than a factor of 2 the effect of uncertainty in the coupling of hydrogen and nitrogen radicals on the analysis of the potential effects of perturbations to odd nitrogen in the lower stratosphere.

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