On the limitation of steady-state expressions as tests of photochemical theory of the stratosphere

Physics

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Atmospheric Chemistry, Atmospheric Models, Photochemical Reactions, Steady State, Stratosphere, Hydrochloric Acid, Nitric Acid, Nitrogen Dioxide

Scientific paper

The severe constraints on measurement accuracies required to test equilibrium expressions are examined for testing a number of steady-state expressions as a function of altitude. The work by Harries (1982) is extended by considering the applicability of the steady-state hypothesis with a photochemical diurnal model. The analysis shows that the steady-state expressions for NO2 and HNO3 can yield a test to +/- 20 percent if the observable parameters are measured to +/- 10 percent. HNO3 and HCl steady-state assumptions are shown to be untenable at some angles of solar zenith and some altitudes. The ratio of production rate to rate of loss of species is shown to be a good parameter for quantifying departures from the steady state. The approach is shown to provide a ClO mixing ratio that agrees with direct observations.

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