Atmospheric Intermediates at the Air-Water Interface.

The air-water interface (AWI) is a ubiquitous reaction field different from the bulk phase where unexpected reactions and physical processes often occur. The AWI is a region where air contacts cloud droplets, aerosol particles, the ocean surface, and biological surfaces such as fluids that line human epithelia. In Earth's atmosphere, short-lived intermediates are expected to be generated at the AWI during multiphase reactions. Recent experimental developments have enabled the direct detection of atmospherically relevant, short-lived intermediates at the AWI. For example, spray ionization mass spectrometric analysis of water microjets exposed to a gaseous mixture of ozone and water vapor combined with a 266 nm laser flash photolysis system (LFP-SIMS) has been used to directly probe organic peroxyl radicals (RO·) produced by interfacial hydroxyl radicals (OH·) + organic compound reactions. OH· emitted immediately after the laser flash photolysis of carboxylic acid at the gas-liquid interface have been directly detected by time-resolved, laser-induced florescence techniques that can be used to study atmospheric multiphase photoreactions. In this Featured Article, we show some recent experimental advances in the detection of atmospherically important intermediates at the AWI and the associated reaction mechanisms. We also discuss current challenges and future prospects for atmospheric multiphase chemistry.