Stratospheric ozone: An introduction to its study

Abstract

An analysis is made of the various reactions in which ozone and atomic oxygen are involved in the stratosphere. At the present time, hydrogen, nitrogen, and chlorine compounds in the ranges parts per million, parts per billion, and parts per trillion may have significant chemical effects. In the upper stratosphere, above the ozone peak, where there is no strong departure from photochemical equilibrium conditions, the action of hydroxyl and hydroperoxyl radicals of nitrogen dioxide and chlorine monoxide on atomic oxygen and of atomic chlorine on ozone can be introduced. A precise determination of their exact effects requires knowledge of (1) the vertical distribution of the H2O, CH4, and H2dissociation by reaction of these molecules with electronically excited oxygen atom O(¹D); (2) the ratio of the OH and HO2concentrations and their absolute values, which depend on insufficiently known rate coefficients; (3) the various origins of nitric oxide production, with their vertical distributions related to latitude and season; and (4) the various sources giving different chlorine compounds that may be dissociated in the stratosphere. In the lower stratosphere, below the ozone peak, there is no important photochemical production of O3, but there exist various possibilities of transport. The predictability of the action of chemical reactions depends strongly on important interactions between OH and HO2radicals with CO and NO, respectively, which affect the ration(OH)/n(HO2) at the tropopause level; between OH and NO2, which lead to the formation of nitric acid with its downward transport toward the troposphere; between NO and HO2, which lead to NO2and its subsequent photodissociation; between ClO and NO, which also lead to NO2and become more important than the reaction of ClO with O; and between Cl and various molecules, such as CH4and H2, which lead to HCl with its downward transport toward the troposphere. All these chemical processes are subject to many changes since they occur in the lower stratosphere where seasonal, latitudinal, and even day‐to‐day variations of the ozone concentrations are observed in association with advective and dynamic transports, which depend on meteorological conditions as indicated by variations of tropopause heights.