Photochemical Degradation of Petroleum-Derived Water-Soluble Organics into the Background Dissolved Organic Carbon Pool

Water-soluble organic (WSO) photoproducts produced from Macondo crude oil (MC252) and a heavy fuel oil (HFO), a surrogate for that which was spilled into the San Francisco Bay by the M/V Cosco Busan, were isolated and irradiated with simulated sunlight to examine the photochemical fate of the products in aquatic ecosystems. Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR MS) reveals marked transformations in the elemental composition of WSOs at specific irradiation periods across a time series that correspond with shifts in bulk properties determined with optical measurements. Blue shifts in EEMs spectra correlate with an increase in formulas classified as unsaturated, high oxygen while the polyphenols and unsaturated, low oxygen compounds decrease. The characteristic A and C humic- and fulvic-like FDOM signatures begin to appear in the EEM spectra of WSOs that were irradiated for as little as 8 to 12 hours, the equivalent of 2 to 3 days of natural sunlight. The presence of the A and C signatures correlate to elemental compositions that exhibit a further decrease in the unsaturated, low oxygen and subsequent increase of unsaturated, high oxygen and highly oxygenated aliphatic compounds. Furthermore, van Krevelen plots reveal a shift toward the compositional space associated with carboxyl-rich aromatic moieties (CRAM) as a function of irradiation period and the appearance of the humic- and fulvic-like FDOM signatures in the EEM spectra. Although the photodegraded WSO products show similarities in FDOM and elemental composition to representative natural dissolved organic matter from their respective pools, persistent petroleum signatures that are not photoactive are still detected. Future studies are required to examine the bioavailability of these photodegraded WSO products to determine if they degrade or persist in the environment.