Organic aerosol formation from the oxidation of biogenic hydrocarbons

Abstract

A series of outdoor chamber experiments has been used to establish and characterize the significant atmospheric aerosol‐forming potentials of the most prevalent biogenic hydrocarbons emitted by vegetation. These compounds were also studied to elucidate the effect of structure on aerosol yield for these types of compounds. Because oxidation products partition between the gas and aerosol phases, the aerosol yields of the parent biogenic hydrocarbons depend on the concentration of organic aerosol into which these products can be absorbed. For organic mass concentrations between 5 and 40 μg m−3, mass‐based yields in photooxidation experiments range from 17 to 67% for sesquiterpenes, from 2 to 23% for cyclic diolefins, from 2 to 15% for bicyclic olefins, and from 2 to 6% for the acyclic triolefin ocimene. In these photooxidation experiments, hydroxyl and nitrate radicals and ozone can contribute to consumption of the parent hydrocarbon. For bicyclic olefins (α‐pinene, β‐pinene, Δ 3‐carene, and sabinene), experiments were also carried out at daytime temperatures in a dark system in the presence of ozone or nitrate radicals alone. For ozonolysis experiments, resulting aerosol yields are less dependent on organic mass concentration, when compared to full, sunlight‐driven photooxidation. Nitrate radical experiments exhibit extremely high conversion to aerosol for β‐pinene, sabinene, and Δ 3‐carene. The relative importance of aerosol formation from each type of reaction for bicyclic olefin photooxidation is elucidated.