Long-term weathering and continued oxidation of oil residues from the Deepwater Horizon spill.

To investigate the long-term weathering of oil from the Deepwater Horizon (DWH) incident, oil-soaked sand patties were collected from Gulf of Mexico beaches from Florida to Alabama over a three-year period from 2012 to 2014. Analysis of oil residues by gas chromatography with flame ionization detection (GC-FID), thin-layer chromatography with flame ionization detection (TLC-FID), and Fourier transform infrared spectroscopy (FT-IR) indicated uniformity in their chemical composition. Some variability within and between samples was observed, arising from differences in exposure to light and water, which increase the amount of weathering. Oxygenated hydrocarbons (OxHC) produced by weathering processes dominate the majority of oil residues. These OxHC have continued recalcitrance in the environment, and increase in relative abundance over time. Analyses of the bulk characteristics of oil residues via TLC-FID and FT-IR should be continued as these techniques provide important insight into the weathering state of oil residues.

Resolving biodegradation patterns of persistent saturated hydrocarbons in weathered oil samples from the Deepwater Horizon disaster.

Biodegradation plays a major role in the natural attenuation of oil spills. However, limited information is available about biodegradation of different saturated hydrocarbon classes in surface environments, despite that oils are composed mostly of saturates, due to the limited ability of conventional gas chromatography (GC) to resolve this compound group. We studied eight weathered oil samples collected from four Gulf of Mexico beaches 12-19 months after the Deepwater Horizon disaster. Using comprehensive two-dimensional gas chromatography (GC × GC), we successfully separated, identified, and quantified several distinct saturates classes in these samples. We find that saturated hydrocarbons eluting after n-C22 dominate the GC-amenable fraction of these weathered samples. This compound group represented 8-10%, or 38-68 thousand metric tons, of the oil originally released from Macondo well. Saturates in the n-C22 to n-C29 elution range were found to be partly biodegraded, but to different relative extents, with ease of biodegradation decreasing in the following order: n-alkanes > methylalkanes and alkylcyclopentanes+alkylcyclohexanes > cyclic and acyclic isoprenoids. We developed a new quantitative index designed to characterize biodegradation of >n-C22 saturates. These results shed new light onto the environmental fate of these persistent, hydrophobic, and mostly overlooked compounds in the unresolved complex mixtures (UCM) of weathered oils.