Macondo oil in northern Gulf of Mexico waters - Part 1: Assessments and forensic methods for Deepwater Horizon offshore water samples.

Forensic chemistry assessments documented the presence of Macondo (MC252) oil from the Deepwater Horizon (DWH) spill in offshore water samples collected under Natural Resource Damage Assessment (NRDA) protocols. In ocean depths, oiled water was sampled, observed, photographed, and tracked in dissolved oxygen (DO) and fluorometry profiles. Chemical analyses, sensor records, and observations confirmed the shifting, rising oil plume above the wellhead while smaller, less buoyant droplets were entrapped in a layer at ~1000-1400 m and advected up to 412 km southwest. Near-surface oil samples showed substantial dissolution weathering from oil droplets rising through the water column, as well as enhanced evaporative losses of lighter n-alkanes and aromatic hydrocarbons. Dispersant effects from surface applications and injected at the wellhead were seen in oil profiles as enhanced weathering patterns (increased dissolution), thus implying dispersants were a functionally effective mediation treatment. Forensic assessment methods are detailed in the Supplemental information (SI).

Macondo oil in northern Gulf of Mexico waters - Part 2: Dispersant-accelerated PAH dissolution in the Deepwater Horizon plume.

During the Deepwater Horizon blowout, unprecedented volumes of dispersant were applied both on the surface and at depth. Application at depth was intended to disperse the oil into smaller microdroplets that would increase biodegradation and also reduce the volumes buoyantly rising to the surface, thereby reducing surface exposures, recovery efforts, and potential stranding. In forensically examining 5300 offshore water samples for the Natural Resource Damage Assessment (NRDA) effort, profiles of deep-plume oil droplets (from filtered water samples) were compared with those also containing dispersant indicators to reveal a previously hypothesized but undocumented, accelerated dissolution of the polycyclic aromatic hydrocarbons (PAH) in the plume samples. We interpret these data in a fate-and-transport context and conclude that dispersant applications were functionally effective at depth.

Footprint, weathering, and persistence of synthetic-base drilling mud olefins in deep-sea sediments following the Deepwater Horizon disaster.

Olefin-based synthetic-based drilling mud (SBM) was released into the Gulf of Mexico as a result of the Deepwater Horizon (DWH) disaster in 2010. We studied the composition of neat SBM and, using conventional GC-FID, the extent, concentration, and chemical character of SBM-derived olefins in >3600 seafloor sediments collected in 2010/2011 and 2014. SBM-derived (C14-C20) olefins occurred (up to 10cm deep) within a 6.5km2 "footprint" around the well. The olefin concentration in most sediments decreased an order of magnitude between 2010/2011 and 2014, at least in part due to biodegradation, evidenced by the preferential loss C16 and C18 linear (α- and internal) versus branched olefins. Based on their persistence for 4-years in sediments around the Macondo well, and 13-years near a former unrelated drill site (~62km away), weathered SBM-derived olefins released during the DWH disaster are anticipated to persist in deep-sea sediment for (at least) a comparable duration.

Weathering of field-collected floating and stranded Macondo oils during and shortly after the Deepwater Horizon oil spill.

Chemical analysis of large populations of floating (n=62) and stranded (n=1174) Macondo oils collected from the northern Gulf of Mexico sea surface and shorelines during or within seven weeks of the end of the Deepwater Horizon oil spill demonstrates the range, rates, and processes affecting surface oil weathering. Oil collected immediately upon reaching the sea surface had already lost most mass below n-C8 from dissolution of soluble aliphatics, monoaromatics, and naphthalenes during the oil's ascent with further reductions extending up to n-C13 due to the onset of evaporation. With additional time, weathering of the floating and stranded oils advanced with total PAH (TPAH50) depletions averaging 69±23% for floating oils and 94±3% for stranded oils caused by the combined effects of evaporation, dissolution, and photo-oxidation, the latter of which also reduced triaromatic steroid biomarkers. Biodegradation was not evident among the coalesced floating oils studied, but had commenced in some stranded oils.