Pressure dependent mechanistic branching in the formation pathways of secondary organic aerosol from cyclic-alkene gas-phase ozonolysis.

The gas-phase ozonolysis of cyclic-alkenes (1-methyl-cyclohexene, methylene-cyclohexane, α-pinene, β-pinene) is studied with respect to the pressure dependent formation of secondary organic aerosol (SOA). We find that SOA formation is substantially suppressed at lower pressures for all alkenes under study. The suppression coincides with the formation of ketene (α-pinene, 1-methyl-cyclohexene), ethene (1-methyl-cyclohexene) and the increased formation of CO (all alkenes) at lower reaction pressures. The formation of these products is independent of the presence of an OH scavenger and explained by an increased chemical activation of intermediate species in the hydroperoxide channel after the OH elimination. These findings underline the central role of the hydroperoxide pathway for SOA formation and give insight into the gas-phase ozonolysis mechanism after the stage of the Criegee intermediate chemistry.