Heterogeneous oxidation products of branched and linear unsaturated hydrocarbons as characterized by two-dimensional gas chromatography with high-resolution time-of-flight mass spectrometry

Previous research has shown that molecular structure (e.g. degree of branching) can influence reaction rates and mechanisms in heterogeneous hydrocarbon oxidation. In this study, we provide new insights into the influence of molecular structure on product formation chemistry in the OH-initiated oxidation of unsaturated hydrocarbon aerosols. Submicron aerosol particles composed of either squalene (branched alkene) or linolenic acid (linear unsaturated fatty acid) were oxidized by OH radicals in the presence and absence of oxygen in a photochemical flow reactor. Oxidation products are collected on filters and analyzed using two-dimensional gas chromatography, with high-resolution time-of-flight mass spectrometric detection utilizing vacuum ultraviolet photoionization and electron impact ionization. The oxidation products were separated, identified, and quantified. We observed that in the absence of oxygen, the OH oxidation of squalene aerosol mainly leads to the formation of functionalization products with one alcohol functional group. These functionalization products are found to be a result of intermolecular hydrogen atom abstraction by the hydroxyalkyl radical (i.e. chain propagation) and are consistent with previously measured squalene effective uptake coefficients that are observed to be larger than one. Reaction pathways that cleave C-C bonds are observed to be strongly suppressed when oxygen is absent, but become more prevalent when oxygen is present in the oxidation of squalene aerosol. In contrast, the presence of oxygen generally does not influence the formation of functionalization and fragmentation products in the OH oxidation of linolenic acid aerosols. These results provide new molecular and mechanistic insights into the reaction pathways in the OH-initiated oxidation of branched and linear unsaturated hydrocarbon aerosols.