Derivation of the reduced reaction mechanisms of ozone depletion events in the Arctic spring by using concentration sensitivity analysis and principal component analysis

Abstract

Abstract. The ozone depletion events (ODEs) in the springtime Arctic have been investigated since the 1980s. It is found that the depletion of ozone is highly associated with an auto-catalytic reaction cycle, which involves mostly the bromine-containing compounds. Moreover, bromide stored in various substrates in the Arctic such as the underlying surface covered by ice and snow can be also activated by the absorbed HOBr. Subsequently, this leads to an explosive increase of the bromine amount in the troposphere, which is called the “bromine explosion mechanism”. In the present study, a reaction scheme representing the chemistry of ozone depletion and halogen release is processed with two different mechanism reduction approaches, namely, the concentration sensitivity analysis and the principal component analysis. In the concentration sensitivity analysis, the interdependence of the mixing ratios of ozone and principal bromine species on the rate of each reaction in the ODE mechanism is identified. Furthermore, the most influential reactions in different time periods of ODEs are also revealed. By removing 11 reactions with the maximum absolute values of sensitivities lower than 10 %, a reduced reaction mechanism of ODEs is derived. The onsets of each time period of ODEs in simulations using the original reaction mechanism and the reduced reaction mechanism are identical while the maximum deviation of the mixing ratio of principal bromine species between different mechanisms is found to be less than 1 %. By performing the principal component analysis on an array of the sensitivity matrices, the dependence of a particular species concentration on a combination of the reaction rates in the mechanism is revealed. Redundant reactions are indicated by principal components corresponding to small eigenvalues and insignificant elements in principal components with large eigenvalues. Through this investigation, aside from the 11 reactions identified as unimportant in the concentration sensitivity analysis, additionally nine reactions were indicated to contribute only little to the total response of the system. Thus, they can be eliminated from the original reaction scheme. The results computed by applying the reduced reaction mechanism derived after the principal component analysis agree well with those by using the original reaction scheme. The maximum deviation of the mixing ratio of principal bromine species is found to be less than 10 %, which is guaranteed by the selection criterion adopted in the simplification process. Moreover, it is shown in the principal component analysis that O(1D) in the mechanism of ODEs is in quasi-steady state, which enables a following simplification of the reduced reaction mechanism obtained in the present study.