Persistence and photochemical transformation of water soluble constituents from industrial crude oil and natural seep oil in seawater

The persistence and transformation of water soluble chemical constituents derived from surface oil from the 2015 Refugio Oil Spill and from a nearby natural seep were evaluated under simulated sunlight conditions. Photoirradiation resulted in enhanced oil slick dissolution, which was more pronounced in spill oil compared to seep oil. Nontargeted analysis based on GC × GC/TOF-MS revealed that photoirradiation promoted oil slick dissolution, and more water soluble compounds were released from spill oil (500 compounds) than from seep oil (180 compounds), most of them (488 in spill oil and 150 in seep oil) still persisting in solution after 67 days of photoirradiation. First-order degradation rate coefficients of humic-like water soluble constituents were found to be 0.26 day−1 and 0.29 day−1 for irradiated spill and seep samples, respectively. The decreases in humic-like fluorescence, specific UV absorbance, and aromatic compounds without corresponding decreases in DOC concentration support indirect photochemical transformation in addition to complete photomineralization. [Display omitted] •Oil from a spill and a natural seep were abiotically exposed to simulated sunlight.•Most soluble constituents detected were present after 67 d of sunlight exposure.•Photoirradiation promoted dissolution of surface oil-derived compounds.•Phototransformations occurred in addition to photooxidation.•A new, photolabile fluorescent component was identified in spill oil.