Parallel quantitation of salt dioctyl sodium sulfosuccinate (DOSS) and fingerprinting analysis of dispersed oil in aqueous samples.

In many jurisdictions, dispersants are included in contingency plans as a viable countermeasure that can help reduce the overall environmental impact of marine oil spills. When used, it is imperative to monitor the progression of dispersant and oil to assess their environmental fate and behaviour. Amphiphilic salt dioctyl sodium sulfosuccinate (DOSS) is the major effective component of the most commonly available dispersants, such as Corexit® EC9500A. Without proper sample preparation, dispersed oil in water samples could interfere with the accurate analysis of DOSS and easily contaminate the LC-MS system. In this work, solid phase extraction (SPE) weak anion exchange (WAX) cartridges were used to separate oil and DOSS in aqueous samples. DOSS was accurately determined by liquid chromatography coupled with a high resolution Orbitrap mass spectrometer (LC-HRMS). Oil fingerprinting analysis was conducted and total petroleum hydrocarbons (TPHs), polycyclic aromatic hydrocarbons (PAHs), and petroleum biomarkers were determined by gas chromatography-flame ionization detection (GC-FID) and mass spectrometry (GC-MS). This SPE-LC/GC-MS method was used for the analysis of oil-dispersant water samples containing a mixture of Corexit® EC9500A and a selection of crude oils and refined petroleum products. Nearly a 100% DOSS recovery was obtained for various oil-surfactant conditions. Parallel quantitation of oils with dispersants was achieved using this method. A portion of the TPH loss was possibly attributed to oil retained by the SPE column. Chemical fingerprints and diagnostic ratios of target compounds in recovered dispersed oil overall remain unchanged compared with those of all studied oils.

Enhanced marine monitoring and toxicity study of oil spill dispersants including Corexit EC9500A in the presence of diluted bitumen.

Observations made for the analysis of the oil spill dispersant tracer dioctyl sulfosuccinate (DOSS) during LC50 toxicity testing, highlighted a stability issue for this tracer compound in seawater. A liquid chromatography high-resolution quadrupole time-of-flight mass spectrometry (LC/QToF) was used to confirm monooctyl sulfosuccinate (MOSS) as the only significant DOSS breakdown product, and not the related isomer, 4-(2-ethylhexyl) 2-sulfobutanedioate. Combined analysis of DOSS and MOSS was shown to be applicable to monitoring of spill dispersants Corexit® EC9500A, Finasol OSR52, Slickgone NS, and Slickgone EW. The unassisted conversion of DOSS to MOSS occurred in all four oil spill dispersants solubilized in seawater, although differences were noted in the rate of MOSS formation. A marine microcosm study of Corexit EC9500A, the formulation most rapid to form MOSS, provided further evidence of the stoichiometric conversion of DOSS to MOSS under conditions relevant to real world dilbit spill. Results supported combined DOSS and MOSS analysis for the monitoring of spill dispersant in a marine environment, with a significant extension of sample collection time by 10 days or longer in cooler conditions. Implications of the unassisted formation of MOSS and combined DOSS:MOSS analysis are discussed in relation to improving dispersant LC50 toxicity studies.

Post-deepwater horizon blowout seafood consumption patterns and community-specific levels of concern for selected chemicals among children in Mobile County, Alabama.

PURPOSE: The goal of the study was to characterize risk pertaining to seafood consumption patterns following the Deepwater Horizon oil spill, among school children (K to 4th grade) residing in close proximity to the Gulf of Mexico in Mobile County, Alabama. METHODS: Responses on seafood consumption pattern including the type of seafood and intake rate during the pre and post oil spill periods, from parents of 55 school children from three schools located <20mile radius from the Gulf of Mexico shoreline (coastal group) were compared with those from parents of 55 children from three schools located ≥20miles away from the shoreline (inland group). We also estimated levels of concern (LOCs) in seafood for selected chemicals found in crude oil including heavy metals, and polycyclic aromatic hydrocarbons (PAH), and dioctyl sodium sulfosuccinate (DOSS), the primary compound in dispersants. RESULTS: The coastal group ate more seafood consisting primarily of crustaceans (62% vs. 42%, p=0.04) and fin fish (78% vs. 58%, p=0.02) from the Gulf of Mexico compared to the inland group, while the inland group ate more fin fish not found in the Gulf of Mexico (62% vs. 33%, p<0.01). In the post-oil spill time period, both groups substantially reduced their consumption of sea food. On average, the coastal group ate ≥2 seafood meals per week, while the inland group ate ≤1 meal per week; these frequency patterns persisted in the post oil-spill period. Comparison of the estimated LOCs with contaminant levels detected in the seafood tested by the Food and Drug Administration and National Oceanic and Atmospheric Administration, post-oil spill, found that the levels of PAHs, arsenic, and DOSS in seafood were 1-2 orders of magnitude below the LOCs calculated in our study. Levels of methyl mercury (MeHg) in the seafood tested pre- and post- oil spill were higher than the estimated LOCs suggesting presence of higher levels of MeHg in seafood independent of the oil spill. CONCLUSION: In sum, the study found higher than average seafood consumption among children along the Mobile coastal area when compared to the inland children and the National Health and Nutrition Examination Survey (NHANES) estimates. Risk characterization based on the LOCs indicated no increase in risk of exposure despite higher seafood consumption rates among the study population compared to the general population.