Heterogeneous Formation of Organonitrates (ON) and Nitroxy-Organosulfates (NOS) from Adsorbed α-Pinene-Derived Organosulfates (OS) on Mineral Surfaces.

Abstract

Organonitrates (ON) and nitroxy-organosulfates (NOS) are important components of secondary organic aerosols (SOAs). Gas-phase reactions of α-pinene (C10H16), a primary precursor for several ON compounds, are fairly well understood although formation pathways for NOS largely remain unknown. NOS formation may occur via reactions of ON and organic peroxides with sulfates as well as through radical-initiated photochemical processes. Despite the fact that organosulfates (OS) represent a significant portion of the organic aerosol mass, ON and NOS formation from OS is less understood, especially through nighttime heterogeneous and multiphase chemistry pathways. In the current study, surface reactions of adsorbed α-pinene-derived OS with nitrogen oxides on hematite and kaolinite surfaces, common components of mineral dust, have been investigated. α-Pinene reacts with sulfated mineral surfaces, forming a range of OS compounds on the surface. These OS compounds when adsorbed on mineral surfaces can further react with HNO3 and NO2, producing several ON and NOS compounds as well as several oxidation products. Overall, this study reveals the complexity of reactions of prevalent organic compounds leading to the formation of OS, ON, and NOS via heterogeneous and multiphase reaction pathways on mineral surfaces. It is also shown that this chemistry is mineralogy-specific.