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.

The surfactant Dioctyl Sodium Sulfosuccinate (DOSS) exposure causes adverse effects in embryos and adults of zebrafish (Danio rerio).

Dioctyl Sodium Sulfosuccinate (DOSS, CAS 577-11-7) is a chemical emulsifying surfactant that is widely used in the food and the cosmetic industry, and it is also the major component of the crude oil chemical dispersant Corexit™. Despite of its wide use, the studies related to its negative effect have been evaluated mainly in marine environments showing that DOSS is highly bioactive, extremely low volatile, and potential to persist in the environment longer than other dispersant components. Up to date, there is no available information of DOSS concentration in freshwater environments, little is known about its downstream fate after excretion and its effect on freshwater organisms. The objective of this study was to evaluate the effect of DOSS at different concentrations in embryos and adults of zebrafish Danio rerio in an acute-static bioassays of 96 h. The median lethal concentration in embryos was 33.3 mg/L. Malformations started to be observed at 10 mg/L. In adults, the gene expression analysis in gill tissues showed a deregulation in genes associated with the antioxidant system and the nucleotide excision repair mechanism. Additionally, Micronuclei (DNA damage) in erythrocytes, and fat degeneration in liver, hypertrophy and hyperplasia in gills, and hyaline drops in kidney tissues were also observed. In conclusion, the concentrations of DOSS evaluated here would be of health relevance to fish based on morphological alterations in embryos and changes in the gene expression profile, DNA damage and tissue impairment in adults.

Structure and conductivity of AOT solutions in n-hexadecane-chloroform mixtures.

The structure and conductivity of AOT (sodium bis(2-ethylhexyl) sulfosuccinate) solutions (2.5 × 10-4 -2.5 × 10-1 M) in n-hexadecane-chloroform mixture at the chloroform concentration from 50 to 100 vol% were studied. The diffusion ordered spectroscopy NMR study revealed that in the indicated range, the observed hydrodynamic diameter of micelles depends only on the AOT concentration and does not depend on the chloroform content. Molar fractions of free AOT molecules and those aggregated into micelles were calculated using the Lindman's law: at concentrations above 2.5 × 10-1 М, the solutions contain mostly the micelles, whereas at concentrations below 2.5 × 10-4 M, the solutions contain AOT molecules. The transition region contains both the AOT molecules and the micelles. Conductivity measurements were used to determine free charge carriers in the bulk of solutions and their contributions to conductivity.

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.

Antioxidant responses and oxidative stress in sheepshead minnow larvae exposed to Corexit 9500® or its component surfactant, DOSS.

Large-scale use of dispersants to remediate oil spills has raised concerns about their toxicity to marine organisms. Of particular concern is oxidative stress and resulting membrane damage due to exposure to surfactants in dispersant mixtures. We investigated the potential of the dispersant Corexit 9500® and one of its major components, the anionic surfactant dioctyl sodium sulfosuccinate (DOSS), to induce oxidative stress in larval sheepshead minnows after 24 and 96h exposures, at two sublethal concentrations, the lesser being environmentally realistic for each compound. Corexit exposures elicited only minimal antioxidant responses for most antioxidant components tested, with increased glutathione peroxidase (GPx) and glutathione S-transferase (GST) activities observed only after 96h and at the higher exposure concentration. In contrast, DOSS induced statistically significant increases in the levels of reactive oxygen species (ROS), GPx, and lipid peroxidation, as well as depleted reduced glutathione (GSH) levels at both time points and concentrations. These data indicate that short-term and environmentally realistic exposures to DOSS can impact antioxidant response capabilities, raising concern about its use in oil dispersants and other high volume use products where environmental releases are likely.

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.

Investigation of the stabilizer elimination during the washing step of charged PLGA microparticles utilizing a novel HPLC-UV-ELSD method.

Quantification of stabilizer content in microparticles and other products is of great importance for formulation development, drug product quality control as well as for reproducible manufacturing. A fast and sensitive HPLC method with evaporative light scattering detection (ELSD) capable of detecting docusate sodium (DOSS), poly (lactic-co-glycolic acid) (PLGA; Resomer RG 503 H) and R-1,2-dioleoyloxy-3-trimethylammonium-propane (DOTAP) in a single run was successfully developed. In contrast to previously described methods, hydrolysis of PLGA as pretreatment is not necessary, thereby enabling accurate quantification of stabilizer next to the intact matrix polymer. This method was used to investigate the impact of washing procedures of polymeric microparticles manufactured either with anionic stabilizer DOSS or with cationic stabilizer DOTAP. High amounts of DOSS were detected in the washing water. This finding was consistent with the result that no DOSS could be detected in the washed and dried microparticles (

Sand patties provide evidence for the presence of Deepwater Horizon oil on the beaches of the West Florida Shelf.

The ecological consequences of the Deepwater Horizon (DWH) oil spill are both long-term and pervasive. The distribution of toxicity and mutagenicity in the Gulf of Mexico suggests oil from the DWH spill could have contaminated the West Florida Shelf (WFS). We utilized polycyclic aromatic hydrocarbon (PAH) analysis to determine presence and potential origin of oil contaminants in beach sand patty samples. PAH profiles from WFS beaches were statistically significantly similar to DWH contaminated samples from the Northeast Gulf of Mexico (Gulf Shores, AL; Ft. Pickens, FL). Dioctyl sodium sulfosuccinate (DOSS), a major component of Corexit 9500 dispersant was also detected in the sediments. DOSS concentrations ranged from 1.6 to 5.5ngg(-1) dry weight. Additionally, two samples from DWH oil contaminated beaches were acutely toxic and one WFS beach sediment sample was mutagenic. These observations provide support for the theory that DWH oil made its way onto beaches of the WFS.

Photochemical degradation of Corexit components in ocean water.

Due to the large quantities of dispersants used during the Deepwater Horizon spill in 2010, there were immediate concerns with regards to the fate and transport of the mixture in ocean waters. Direct and sensitized photolysis experiments were carried out for two compounds chosen as surrogates for the Corexit mixture (9500 and 9527) that were applied to surface waters during the oil spill in the Gulf of Mexico. The results showed that direct photolysis did not contribute significantly to the overall degradation (max ∼30%), therefore the focus shifted to sensitized photolysis, specifically the degradation stemming from the reaction rate with hydroxyl radical (HO). The direct photochemical degradation rates for two of the compounds, dioctyl sulfosuccinate (DOSS) and dipropylene glycol butyl ether (DGBE) were measured as 4.29×10(-6)s(-1) and 5.95×10(-6)s(-1), respectively; whereas the overall degradation rate in ocean water was 1.56×10(-5)s(-1) and 2.23×10(-5)s(-1). The formation rates and apparent quantum yields for HO formation were determined for six ocean water samples. The values ranged from 1.81×10(-5) near shore to 0.061×10(-5) for the open ocean. These degradation rates suggest the possibility for photolysis to play a role in the overall fate of Corexit.

Electrospray ion mobility mass spectrometry of positively charged sodium bis[2-ethythexyl)sulfosuccinate aggregates.

Collision cross-sections (CCS) of positively singly and multiply charged aggregates of the surfactant sodium bis(2-ethylhexyl)sulfosuccinate (AOTNa) in the gas phase have been measured by quadrupole ion mobility time-of-flight mass spectrometry. Calibration of the observed drift times to the CCS of the AOTNa non-covalent aggregates was achieved by collecting, under the same experimental conditions, the drift times of a range of singly and multiply charged polyalanine peptides whose CCS had been obtained by conventional ion mobility spectrometry. Together with an obvious increase of the aggregate cross-section with the aggregation number, it was found that the aggregate cross-section increases with the charge state due to the sodium counterions steric effect and the augmented electrostatic repulsion. This finding is consistent with the result of a previous molecular dynamics study on positively charged AOTNa aggregates in the gas phase showing that, by increasing the charge state, the aggregates become progressively more oblate; implying a rise of their CCS. Moreover, the occurrence at each aggregation number and extra charge of a unique value of cross section points toward aggregates whose conformations do not show discernible shape change in the experiment time scale.

Regioselective syntheses of [13C]4-labelled sodium 1-carboxy-2-(2-ethylhexyloxycarbonyl)ethanesulfonate and sodium 2-carboxy-1-(2-ethylhexyloxycarbonyl)ethanesulfonate from [13C]4-maleic anhydride.

The entitled monohydrolysis products, also known as α-ethylhexyl and ß-ethylhexyl sulfosuccinate (EHSS), of the surfactant diisooctyl sulfosuccinate (DOSS) were synthesized in stable isotope-labelled form from [(13)C]4 -maleic anhydride. Sodium [(13)C]4 -1-carboxy-2-(2-ethylhexyloxycarbonyl)ethanesulfonate (α-EHSS) was prepared by the method of Larpent by reaction of 2-ethylhexan-1-ol with [(13)C]4 -maleic anhydride followed by regioselective conjugate addition of sodium bisulfite to the resulting monoester (38% overall yield). The regiochemical outcome of bisulfite addition was confirmed by a combination of (13)C/(13)C (incredible natural abundance double quantum transfer) and (1)H/(13)C (heteronuclear multiple-bond correlation (HMBC)) NMR spectral correlation experiments. Sodium [(13)C]4 -2-carboxy-1-(2-ethylhexyloxycarbonyl)ethanesulfonate (ß-EHSS) was prepared in four steps by reaction of 4-methoxybenzyl alcohol with [(13)C]4 -maleic anhydride, regioselective sodium bisulfite addition, N,N'-dicyclohexylcarbodiimide-mediated esterification with 2-ethylhexan-1-ol, and p-methoxybenzyl ester deprotection with trifluoroacetic acid (13% overall yield). The regiochemical outcome of the second synthesis was confirmed by a combination of (1)JCC scalar coupling constant analysis and (1)H/(13)C (HMBC) NMR spectral correlation. The materials prepared are required as internal standards for the liquid chromatography-mass spectrometry (LC-MS)/MS trace analysis of the degradation products of DOSS, the anionic surfactant found in Corexit, the oil dispersant used during emergency response efforts connected to the Deepwater Horizon oil spill of April 2010.

Stability of dioctyl sulfosuccinate (DOSS) towards hydrolysis and photodegradation under simulated solar conditions.

Dioctyl sulfosuccinate (DOSS) is one of the main components of Corexit® EC9500A, a chemical dispersant formulation used at the surface and at depth during the response to the Deepwater Horizon incident. Despite being a high volume use chemical, data on its environmental stability are scarce. Hydrolysis and photodegradation of DOSS in both pure water and seawater were reported in the present study. DOSS photodegraded much faster under ultraviolet light source (254 nm, with half-life in hours) compared to relevant environmental light sources i.e., 350 nm and solar simulator (with half-lives in days). LC/MS-MS analysis of hydrolysis and photo-irradiated samples showed the presence of a common degradation product. MS/MS fragmentation of that product indicated a substitution of an octyl group by a hydroxyl group with a corresponding formula of C12H21O7S, which was confirmed by HRMS detection (Q-TOF, m/z 309.1017, +1.29 ppm).

Contaminant levels in Gulf of Mexico reef fish after the Deepwater Horizon oil spill as measured by a fishermen-led testing program.

The BP oil disaster posed a significant threat to the U.S. seafood industry. Invertebrates (shrimp, oyster, crab) and other nearshore species comprised the majority of postspill testing by federal and state agencies. Deeper water finfish were sampled less frequently, despite population ranges that overlapped with affected waters. We report on a voluntary testing program with Gulf of Mexico commercial fishermen to ensure the safety of their catch. Seven species of reef fish were tested for polycyclic aromatic hydrocarbons, several metals, and a constituent of Corexit 9500A and 9527A dispersants. Only two of 92 samples had detectable levels of benzo(a)pyrene-equivalents (a combined measure of carcinogenic potency across 7 different PAHs), which were still below federal safety thresholds. PAH ratios for these samples suggest pyrogenic (not petrogenic) contamination - indicating potential sources other than Deepwater Horizon. Metals were largely absent (cadmium, lead) or consistent with levels previously reported (mercury, arsenic). One notable exception was tilefish, which showed mercury concentrations lower than expected. We did not detect dispersant in any of our samples, indicating that it was not present in these species during the study period. Our findings suggest minimal risk to public health from these seafoods as a result of the disaster; however, the most contaminated areas were not sampled through this program.

Presence of the Corexit component dioctyl sodium sulfosuccinate in Gulf of Mexico waters after the 2010 Deepwater Horizon oil spill.

Between April 22 and July 15, 2010, approximately 4.9 million barrels of oil were released into the Gulf of Mexico from the Deepwater Horizon oil well. Approximately 16% of the oil was chemically dispersed, at the surface and at 1500 m depth, using Corexit 9527 and Corexit 9500, which contain dioctyl sodium sulfosuccinate (DOSS) as a major surfactant component. This was the largest documented release of oil in history at substantial depth, and the first time large quantities of dispersant (0.77 million gallons of approximately 1.9 million gallons total) were applied to a subsurface oil plume. During two cruises in late May and early June, water samples were collected at the surface and at depth for DOSS analysis. Real-time fluorimetry data was used to infer the presence of oil components to select appropriate sampling depths. Samples were stored frozen and in the dark for approximately 6 months prior to analysis by liquid chromatography/tandem mass spectrometry with isotope-dilution quantification. The blank-limited method detection limit (0.25 µg L(-1)) was substantially less than the U.S. Environmental Protection Agency's (USEPA) aquatic life benchmark of 40 µg L(-1). Concentrations of DOSS exceeding 200 µg L(-1) were observed in one surface sample near the well site; in subsurface samples DOSS did not exceed 40 µg L(-1). Although DOSS was present at high concentration in the immediate vicinity of the well where it was being continuously applied, a combination of biodegradation, photolysis, and dilution likely reduced persistence at concentrations exceeding the USEPA aquatic life benchmark beyond this immediate area.

Dioctyl sulfosuccinate analysis in near-shore Gulf of Mexico water by direct-injection liquid chromatography-tandem mass spectrometry.

Dioctyl sulfosuccinate (DOSS) was a major component of the dispersants most used in the 2010 Deepwater Horizon Oil Spill incident response. This analytical method quantifies salt water DOSS concentrations to a reporting limit of 20 µg/L, which was below the United States Environmental Protection Agency's (U.S. EPA) 40 µg/L DOSS Aquatic Life Benchmark. DOSS in Gulf of Mexico water samples were analyzed by direct-injection reversed-phase liquid chromatography-tandem mass spectrometry (LC-MS/MS). Sample preparation with 50% acetonitrile (ACN) enabled quantitative transfer of DOSS and increased DOSS response 20-fold by reducing aggregation. This increased sensitivity enabled the detection of a confirmatory transition over the calibration range of 10-200 µg/L. U.S. EPA Region 5 and Region 6 laboratories analyzed hundreds of near-shore surface Gulf of Mexico water samples, none contained more than the 20 ppb reporting limit. The matrix spike DOSS/deuterated surrogate (DOSS-D34) correlation of determination varied with mobile phase modifier (ammonium formate R(2)=0.95 and formic acid R(2)=0.27). Using ammonium formate, DOSS-D34 accurately measured DOSS matrix effect. The near-shore sodium concentrations varied more than 10,000-fold, but were not strongly correlated with DOSS recovery. DOSS detection by LC-MS/MS enabled rapid analysis which was valuable in guiding incident response.

Fate of dispersants associated with the deepwater horizon oil spill.

Response actions to the Deepwater Horizon oil spill included the injection of ∼771,000 gallons (2,900,000 L) of chemical dispersant into the flow of oil near the seafloor. Prior to this incident, no deepwater applications of dispersant had been conducted, and thus no data exist on the environmental fate of dispersants in deepwater. We used ultrahigh resolution mass spectrometry and liquid chromatography with tandem mass spectrometry (LC/MS/MS) to identify and quantify one key ingredient of the dispersant, the anionic surfactant DOSS (dioctyl sodium sulfosuccinate), in the Gulf of Mexico deepwater during active flow and again after flow had ceased. Here we show that DOSS was sequestered in deepwater hydrocarbon plumes at 1000-1200 m water depth and did not intermingle with surface dispersant applications. Further, its concentration distribution was consistent with conservative transport and dilution at depth and it persisted up to 300 km from the well, 64 days after deepwater dispersant applications ceased. We conclude that DOSS was selectively associated with the oil and gas phases in the deepwater plume, yet underwent negligible, or slow, rates of biodegradation in the affected waters. These results provide important constraints on accurate modeling of the deepwater plume and critical geochemical contexts for future toxicological studies.

Dynamics of water confined on a nanometer length scale in reverse micelles: ultrafast infrared vibrational echo spectroscopy.

The dynamics of water, confined on a nanometer length scale (1.7 to 4.0 nm) in sodium bis-(2-ethylhexyl) sulfosuccinate reverse micelles, is directly investigated using frequency resolved infrared vibrational echo experiments. The data are compared to bulk water and salt solution data. The experimentally determined frequency-frequency correlation functions show that the confined water dynamics is substantially slower than bulk water dynamics and is size dependent. The fastest dynamics (approximately 50 fs) is more similar to bulk water, while the slowest time scale dynamics is much slower than water, and, in analogy to bulk water, reflects the making and breaking of hydrogen bonds.

The dependence of the lipolytic activity of Rhizopus arrhizus lipase on surfactant concentration in Aerosol-OT/isooctane reverse micelles and its relationship to enzyme structure.

Aerosol OT, bis(2-ethylhexyl)sodium sulfosuccinate/isooctane reverse micelles were used to investigate the dependence of the lipolytic activity of Rhizopus arrhizus lipase on surfactant concentration. Kinetic constants for the lipolytic reaction were measured in parallel with structural studies using protein fluorescence and circular dichroism (CD) spectroscopy. Km values remained constant throughout the range of AOT concentrations studied. The kcat values decreased with increasing surfactant concentration at constant water-to-surfactant ratio (wo = 11) from 50 mM to 100 mM AOT, but remained constant from 100 to 200 mM AOT. These data suggested an association of the lipase with the micellar membrane. An inflection in the time-course of the reaction was found to be a function of both surfactant and substrate concentrations and was likely an indication of the interfacial nature of the hydrolysis reaction. Structure prediction based on far-UV CD spectral data demonstrated structural reorganization of R. arrhizus lipase upon incorporation into reverse micelles which was characterized by a dramatic increase in beta-sheet and overall accountable secondary structure. Other spectral changes of the lipase upon incorporation into reverse micelles included appearance of fine structure in the near-UV CD spectrum and a blue shift in the fluorescence emission maximum from 336 to 326 nm.

High-performance liquid chromatographic analysis of docusate sodium in soft gelatin capsules.

A rapid and simple high-performance liquid chromatographic (HPLC) method for the analysis of docusate sodium in soft gelatin capsules was developed with progesterone as the internal standard. The method requires a reversed-phase column and a paired-ion technique to separate docusate sodium from other components. A C22 column was used with a mobile phase of acetonitrile:water (70:30) containing 0.005 M tetrabutylammonium phosphate. The flow rate was 1.8 mL/min, and the effluent was monitored at 214 nm. Docusate sodium and progesterone had retention times of 4.5 and 6.8 min, respectively. The proposed HPLC method is linear, accurate, and precise. A mean assay value of 99.6% was obtained by the proposed method when five samples, each containing a composite of 10 capsules, were analyzed. The results obtained by the proposed HPLC, tetra-n-butylammonium iodide titration, and USP XXII HPLC methods are compared.