On the OH initiated oxidation of C2-C5 aliphatic aldehydes in the presence of mineral aerosols

Clay particles are present in large quantities in mineral dust of atmospheric aerosols, and their interaction with organic species may influence atmospheric reactions and the prediction of environmental risks. However, the kinetics and mechanisms of adsorption and reaction of atmospheric volatile organic compounds on aerosol surfaces are not well understood.In this work, quantum chemical methods are used to study the adsorption of C2-C5 aliphatic aldehydes on silicate clusters active sites, and their subsequent reaction with OH radicals. It is shown that adsorption may occur in two different ways, and that the adsorption complex structure determines the subsequent path of its reaction with OH. The initial step in the OH reaction with acetaldehyde occurs according to the same mechanism as in the gas phase, i.e., the aldehydic hydrogen abstraction. Starting from propanal, another abstraction channel becomes increasingly important, involving mainly the abstraction of a β-hydrogen of the aliphatic chain. In the presence of a silica monomer model surface, the reaction rate of aldehydes with OH free-radicals is smaller than in the gas phase. Furthermore silicates are good sinks for trapping these aldehydes. Thus, our results may have implications in the study of tropospheric chemistry and cosmochemistry.