Influence of Atmospheric Carboxylic Acids on Catalytic Oxidation of Sulfur(IV)

The influence of some low weight mono- and di-carboxylic acids, which were selected on the basis of analysis of the water-soluble fraction of size segregated marine and urban aerosols collected in Slovenia, on the kinetics of S(IV) oxidation catalyzed by Mn(II) under conditions representative of tropospheric liquid water, was investigated. Mono-carboxylic acids inhibit the oxidation, with the strongest influence found for formic acid. Inhibition by glycolic and lactic acid was found to be very similar, while the lowest inhibition was caused by acetic acid. Our results are in agreement with the proposed mechanism, i.e. scavenging of sulfate radicals, since the inhibiting effect of the individual acid increases with higher dissociation constant. An exception is formic acid, where the additional inhibiting steps should be responsible for the induction period and thus for higher inhibition. Malic and malonic acids have practically no influence, while oxalic acid slows down the oxidation, although to a lesser extent than mono-carboxylic acids. An extended version of a previously derived generalized simple kinetic model was also derived and applied for predicting the reaction kinetics in the presence of all examined carboxylic acids at pH 3.5 and 4.5.