Criegee Chemistry on Aqueous Organic Surfaces.

In the troposphere, the fate of gas-phase Criegee intermediates (CIs) is deemed to be determined by their reactions with water molecules. Here it is shown that CIs produced in situ on the surface of water/acetonitrile (W/AN) solutions react competitively with millimolar carboxylic acids. Present experiments probe, via online electrospray mass spectrometry, CIs' chemistry on the surface of α-humulene and β-caryophyllene in W/AN microjets exposed to O3(g) for <10 μs. Mass-specific identification lets us establish the progeny of products and intermediates generated in the early stages of CIs' reactions with H2O, D2O, H218O, and n-alkyl-COOH (n = 1-7). It is found that n-alkyl-COOH competes for CIs with interfacial water, their competitiveness being an increasing function of n. Present findings demonstrate that CIs can react with species other than H2O on the surface of aqueous organic aerosols due to the low water concentrations prevalent in the outermost interfacial layers.