Observations of OH, HO<sub>2</sub>, H<sub>2</sub>O, and O<sub>3</sub> in the upper stratosphere: Implications for HO<sub><i>x</i></sub> photochemistry

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Abstract

<jats:p>Balloon‐borne observations of concentrations of OH, HO<jats:sub>2</jats:sub>, H<jats:sub>2</jats:sub>O, and O<jats:sub>3</jats:sub> in the middle and upper stratosphere are used to test our understanding of HO<jats:sub><jats:italic>x</jats:italic></jats:sub> photochemistry. Assuming our photochemical model is complete, the measured [OH] and [HO<jats:sub>2</jats:sub>] above 38 km (where HO<jats:sub><jats:italic>x</jats:italic></jats:sub> partitioning is no longer dependent on [NO]) are modeled best by calculations that use a 25% reduction in the ratio of the reaction rate constants for O+HO<jats:sub>2</jats:sub> and O+OH as well as either a 25% reduction of the rate constant of OH+HO<jats:sub>2</jats:sub> (the primary HO<jats:sub><jats:italic>x</jats:italic></jats:sub> sink) or a 25% increase in HO<jats:sub><jats:italic>x</jats:italic></jats:sub> production. All of these changes are consistent with the uncertainties in the recommended rate constants. The kinetic parameters required to explain our observations of [OH] and [HO<jats:sub>2</jats:sub>] do not lead to a resolution of the long‐standing “ozone deficit problem” above 45 km.</jats:p>

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