Ozone production rates in an oxygen-hydrogen-nitrogen oxide atmosphere


  • P. J. Crutzen


The distribution of the compounds NO, NO2, NO3, N2O5, and HNO3 has been calculated for different choices of relevant parameters, the values of which are uncertain. An appreciable part of the NO and NO2 is converted to NO3, N2O5, HNO3 and possibly HNO2 is the ozone layer. Reactions of odd oxygen with NO and NO2 may be the dominating reassociation processes for odd-oxygen particles in the region below 45 km which is very important for the global ozone budget. Several processes may lead to the presence of significant amounts of nitrogen oxides, nitrous acid, and nitric acid in the stratosphere. Reported variations during the solar cycle of ozone concentrations above 30 km (Dütsch, 1969) can be explained by corresponding variations in the stratospheric odd nitrogen oxide content. An artificial increase of the mixing ratio of the oxides of nitrogen in the stratosphere by about 1×10−8 may lead to observable changes in the atmospheric ozone level. Chains of reactions involving the constituents OH, H2O2, and HO2 also lead to the catalytic destruction of odd oxygen. The presence of nitric acid with a mixing ratio of about 3×10−9 in the ozone layer (Murcray et al., 1968; Rhine et al., 1969) indicates much larger OH and HO2 concentrations than can be explained solely by the reaction O(1D) + H2O → 2 OH. The reaction N2O5 + H2O → 2HNO3 followed by O + HNO3 → OH + NO3 may also be an important source of OH if the rate constants given by Jaffe and Ford (1967) are adopted. It is difficult to explain the measured nitric acid concentrations between 20 and 30 km with the reaction HO2 + NO + M → HNO3 + M. Laboratory data (Asquith and Tyler, 1969) indicate that the reaction H2O2 + NO2 → HNO3 + OH (Nicolet, 1970α) is unimportant in the atmosphere.