Aldehyde and Ketone Photoproducts from Solar-Irradiated Crude Oil-Seawater Systems Determined by Electrospray Ionization-Tandem Mass Spectrometry.

Aldehyde and ketone photoproducts were observed in the aqueous phase under oil exposed to simulated sunlight by using 2,4-dinitrophenylhydrazine (DNPH) derivatization and electrospray ionization-tandem mass spectrometry (ESI-MS/MS). Oil samples were spread over seawater in a jacketed beaker held at 27.0 °C and exposed to simulated sunlight. The aqueous phase was collected after irradiation and derivatized with DNPH, which selectively reacts with aldehydes and ketones. The derivatized hydrazones (aldehyde- and ketone-DNPH derivatives) were washed and enriched with a solid-phase extraction cartridge prior to analysis by ESI-MS/MS in negative ion mode. Over 80 aldehyde and ketone photoproducts were observed from scan range 200-1000 atomic mass units (amu) in the aqueous phase after irradiation but were absent in dark controls. Based on the MS/MS fragmentation of the aldehyde- and ketone-DNPH derivatives, most of the aldehyde and ketone photoproduct mass spectra observed from the aqueous phase were determined to be consistent with dicarbonyls, hydroxycarbonyls, and oxo-carboxylic acids. The formation of the photoproducts can be attributed to photoinduced oxidation of oil. The approach in this study allows the easy identification of molar mass and other structural features of aldehyde and ketone photoproducts without interference from the many tens of thousands of parent compounds in the oil. These results will provide insight into the impact of photochemistry on the fate of oil in environmental systems and will have implications for oil-spill response decisions.