Abstract
Hydrocarbons released during the Deepwater Horizon (DWH) oil spill weathered due to exposure to oxygen, light, and microbes. During weathering, the hydrocarbons’ reactivity and lability was altered, but it remained identifiable as “petrocarbon” due to its retention of the distinctive isotope signatures (14C and 13C) of petroleum. Relative to the initial estimates of the quantity of oil-residue deposited in Gulf sediments based on 2010–2011 data, the overall coverage and quantity of the fossil carbon on the seafloor has been attenuated. To analyze recovery of oil contaminated deep-sea sediments in the northern Gulf of Mexico we tracked the carbon isotopic composition (13C and 14C, radiocarbon) of bulk sedimentary organic carbon through time at 4 sites. Using ramped pyrolysis/oxidation, we determined the thermochemical stability of sediment organic matter at 5 sites, two of these in time series. There were clear differences between crude oil (which decomposed at a lower temperature during ramped oxidation), natural hydrocarbon seep sediment (decomposing at a higher temperature; Δ14C = -912‰) and our control site (decomposing at a moderate temperature; Δ14C = -189‰), in both the stability (ability to withstand ramped temperatures in oxic conditions) and carbon isotope signatures. We observed recovery toward our control site bulk Δ14C composition at sites further from the wellhead in ~4 years, whereas sites in closer proximity had longer recovery times. The thermographs also indicated temporal changes in the composition of contaminated sediment, with shifts towards higher temperature CO2 evolution over time at a site near the wellhead, and loss of higher temperature CO2 peaks at a more distant site.
Highlights
The results of a number of field studies indicate unambiguously that oil residues from the Deepwater Horizon (DWH) oil spill were deposited on the seafloor [1,2,3,4,5,6,7]
In 2015, the surface sediment Δ14C signatures of the 4 high polycyclic aromatic hydrocarbons (PAHs) sites ranged from -187.1 to -467.5‰ (Fig 2E) indicating that not all sites in the northern Gulf of Mexico had fully recovered to baseline values by 2015
We further explored the isotopic recovery at these sites by using ramped pyrolysis oxidation (RPO) to analyze the potential evolution of the sedimented petrocarbon from the time series and the high PAH sites
Summary
The results of a number of field studies indicate unambiguously that oil residues from the Deepwater Horizon (DWH) oil spill were deposited on the seafloor [1,2,3,4,5,6,7]. Studies by Stout and Payne [5] and Bagby et al [9] analyzed biodegradation rates of multiple hydrocarbons in the sediment, showing that biodegradation continued on the seafloor after the deposition of the sedimented oil-residues. In contrast to focusing on specific petroleum compounds, studies by Pendergraft et al [11] and Pendergraft and Rosenheim [12] employed ramped pyrolysis/oxidation paired with carbon isotope analysis on bulk coastal sediments. We applied their approach to the deep-sea floor
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