Mapping spatial and temporal variation of seafloor organic matter Δ14C and δ13C in the Northern Gulf of Mexico following the Deepwater Horizon Oil Spill.

Following the Deepwater Horizon oil spill of 2010, large amounts of biodegraded oil (petrocarbon) sank to the seafloor. Our objectives were to 1) determine post-spill isotopic values as the sediments approached a new baseline and 2) track the recovery of affected sediments. Sediment organic carbon δ13C and Δ14C reached a post-spill baseline averaging -21.2 ± 0.9‰ (n = 129) and -220 ± 66‰ (n = 95). Spatial variations in seafloor organic carbon baseline isotopic values, 13C and 14C, were influenced by river discharge and hydrocarbon seepage, respectively. Inverse Distance Weighting of surface sediment Δ14C values away from seep sites showed a 50% decrease in the total mass of petrocarbon, from 2010 to 2014. We estimated a rate of loss of -2 × 109 g of petrocarbon-C/year, 2-11% of the degradation rates in surface slicks. Despite the observed recovery in sediments, lingering residual material in the surface sediments was evident seven years following the blowout.

The southern Gulf of Mexico: A baseline radiocarbon isoscape of surface sediments and isotopic excursions at depth.

The southern Gulf of Mexico (sGoM) is home to an extensive oil recovery and development infrastructure. In addition, the basin harbors sites of submarine hydrocarbon seepage and receives terrestrial inputs from bordering rivers. We used stable carbon, nitrogen, and radiocarbon analyses of bulk sediment organic matter to define the current baseline isoscapes of surface sediments in the sGoM and determined which factors might influence them. These baseline surface isoscapes will be useful for accessing future environmental impacts. We also examined the region for influence of hydrocarbon deposition in the sedimentary record that might be associated with hydrocarbon recovery, spillage and seepage, as was found in the northern Gulf of Mexico (nGoM) following the Deepwater Horizon (DWH) oil spill in 2010. In 1979, the sGoM experienced a major oil spill, Ixtoc 1. Surface sediment δ13C values ranged from -22.4‰ to -19.9‰, while Δ14C values ranged from -337.1‰ to -69.2‰. Sediment δ15N values ranged from 2.8‰ to 7.2‰, while the %C on a carbonate-free basis ranged in value of 0.65% to 3.89% and %N ranged in value of 0.09% to 0.49%. Spatial trends for δ13C and Δ14C were driven by water depth and distance from the coastline, while spatial trends for δ15N were driven by location (latitude and longitude). Location and distance from the coastline were significantly correlated with %C and %N. At depth in two of twenty (10%) core profiles, we found negative δ13C and Δ14C excursions from baseline values in bulk sedimentary organic material, consistent with either oil-residue deposition or terrestrial inputs, but likely the latter. We then used 210Pb dating on those two profiles to determine the time in which the excursion-containing horizons were deposited. Despite the large spill in 1979, no evidence of hydrocarbon residue remained in the sediments from this specific time period.

Petrocarbon evolution: Ramped pyrolysis/oxidation and isotopic studies of contaminated oil sediments from the Deepwater Horizon oil spill in the Gulf of Mexico.

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.