The Oxidation of Oleate in Submicron Aqueous Salt Aerosols: Evidence of a Surface Process

Abstract

We have studied the oxidation of submicron aqueous aerosols consisting of internal mixtures of sodium oleate (oleic acid proxy), sodium dodecyl sulfate, and inorganic salts by O3, NO3/N2O5, and OH. Experiments were performed using an aerosol flow tube and a continuous flow photochemical reaction chamber coupled to a chemical ionization mass spectrometer (CIMS). The CIMS was fitted with a heated inlet for volatilization and detection of organics in the particle phase simultaneously with the gas phase. A differential mobility analyzer/condensation particle counter was used for determining aerosol size distributions. The oxidation of oleate by O3 follows Langmuir-Hinshelwood kinetics, with gammaO3 approximately 10(-5) calculated from the observed loss rate of oleate in the particle phase. The best fit Langmuir-Hinshelwood parameters are kImax=0.05+/-0.01 s-1 and KO3=4(+/-3)x10(-14) cm3molec-1. These parameters showed no dependence on the ionic composition of the aerosols or on the presence of alkyl surfactants. Several ozone oxidation products were observed to be particle-bound at ambient temperature, including nonanoic acid. We observed efficient processing of oleate by OH (0.1<or=gammaOH<or=1), and we suggest an upper bound of gammaNuOmicron3<10(-3). We conclude that for the aerosol compositions studied, oxidation occurs near the gas-aerosol interface and that the 1 e-fold lifetime of unsaturated organics at the aerosol surface is approximately 10 min due to O3 oxidation under atmospheric conditions. In the context of a Langmuir-Hinshelwood mechanism, different underlying aerosol compositions may extend the lifetime of oleic acid at the surface by reducing KO3.