Instantaneous photochemical rates in the global stratosphere

Abstract

Starting with the average actual distribution of ozone (Dütsch [15]) and temperature in the stratosphere, we have calculated the solar intensity as a function of wavelength and the instantaneous rates (molecules cm⁻³ sec⁻¹) for each Chapman reaction and for each of several reactions of the oxides of nitrogen. The calculation is similar to that ofBrewer andWilson [5]. These reaction rates were calculated independently in each volume element in spherical polar coordinates defined by ΔR=1 km from zero to 50, δϑ=5° latitude, and δø=15° longitude (thus including day and night conditions). Calculations were made for two times: summer-winter (January 15) and spring-fall (March 22). As input data we take observed solar intensities (Ackerman [1]) and observed, critically evaluated. constants for elementary chemical and photochemical reactions; no adjustable parameters are employed. (These are not ‘photochemical equilibrium’ calculations.) According to the Chapman model, the instantaneous, integrated, world-wide rate of formation of ozone from sunlight is about five times faster than the rate of ozone destruction, and locally (lower tropical stratosphere) the rate of ozone formation exceeds the rate of destruction by a factors as great as 1000. The global rates of increase of ozone are more than 50 times faster thanBrewer andWilson's [5] estimate of the average annual transfer rate of ozone to the troposphere. The rate constants of the Chapman reactions are believed to be well-enough known that it is highly improbable that these discrepancies are, due to erroneous rate constants. It is concluded that something else besides neutral oxygen species is very important in stratospheric ozone photochemistry. The inclusion of a uniform concentration of the oxides of nitrogen (NO_x as, NO and NO₂) averaging 6.6×10⁻⁹ mole fraction gives a balance between global ozone formation and destruction rates. The inclusion of a uniform mole fraction of NO_x at 28×10⁻⁹ also gives a global balance. These calculations support the hypethesis (Crutzen [10],Johnston [24]) that the oxides of nitrogen are the most important factor in the global, natural ozone balance. Several authors have recently evaluated the natural source strength of NO_x in the stratosphere; the projected fleets of supersonic transports would constitute an artificial source of NO_x about equal to the natural value, thus promising more or less to double an active natural stratospheric ingredient.