Formation of Toxic Unsaturated Multifunctional and Organosulfur Compounds From the Photosensitized Processing of Fluorene and DMSO at the Air-Water Interface

Polycyclic aromatic hydrocarbons and dimethyl sulfoxide (DMSO) are ubiquitous at the sea surface. Photochemistry at the air-sea interface is a potentially important source of volatile organic compounds, but the relevant chemical processes are currently not well known. When aqueous solutions containing a mixture of fluorene (FL) and DMSO are irradiated with actinic radiation, a large suite of unsaturated high molecular weight compounds appear in the aqueous phase; a broad variety of saturated and unsaturated oxygenated multifunctional compounds are also observed in the gas phase, most of which are more toxic than FL. A possible sequence of steps leading to some of the observed compounds in aqueous solution as well as in the gas phase is proposed. The reaction pathways initiated by excited triplet state of FL ((FL)-F-3*) are supported by theoretical calculations of the reaction Gibbs energies. The formation of organosulfur compounds has been observed to occur in the gas and the aqueous phases initiated by the reaction between (FL)-F-3* and DMSO. The aforementioned photosensitized chemistry at the water surface can have an important impact on the formation of secondary organic aerosol in marine boundary layer as polycyclic aromatic hydrocarbons and DMSO enriched at the water surface are ubiquitous.