Unimolecular decay strongly limits the atmospheric impact of Criegee intermediates

Abstract

Stabilized Criegee intermediates (SCI) are reactive oxygenated species formed in the ozonolysis of hydrocarbons. Their chemistry could influence the oxidative capacity of the atmosphere by affecting the HOx and NOx cycles, or by the formation of low-volatility oxygenates enhancing atmospheric aerosols known to have an important impact on climate. The concentration of SCI in the atmosphere has hitherto not been determined reliably, and very little is known about their speciation. Here we show that the concentration of biogenic SCI is strongly limited by their unimolecular decay, based on extensive theory-based structure-activity relationships (SARs) for the reaction rates for decomposition. Reaction with water vapor, H2O and (H2O)2 molecules, is the second most important loss process; SARs are also proposed for these reactions. For SCI derived from the most common biogenic VOCs, we find that unimolecular decay is responsible for just over half of the loss, with reaction with water vapor the main remaining loss process. Reactions with SO2, NO2, or acids have negligible impact on the atmospheric SCI concentration. The ambient SCI concentrations are further characterized by analysis of field data with speciated hydrocarbon information, and by implementation of the chemistry in a global chemistry model. The results show a highly complex SCI speciation, with an atmospheric peak SCI concentrations below 1 × 105 molecule cm-3, and annual average SCI concentrations less than 7 × 103 molecule cm-3. We find that SCI have only a negligible impact on the global gas phase H2SO4 formation or removal of oxygenates, though some contribution around the equatorial belt, and in select regions, cannot be excluded.