Fallout plume of submerged oil from Deepwater Horizon.

The sinking of the Deepwater Horizon in the Gulf of Mexico led to uncontrolled emission of oil to the ocean, with an official government estimate of ∼ 5.0 million barrels released. Among the pressing uncertainties surrounding this event is the fate of ∼ 2 million barrels of submerged oil thought to have been trapped in deep-ocean intrusion layers at depths of ∼ 1,000-1,300 m. Here we use chemical distributions of hydrocarbons in >3,000 sediment samples from 534 locations to describe a footprint of oil deposited on the deep-ocean floor. Using a recalcitrant biomarker of crude oil, 17α(H),21ß(H)-hopane (hopane), we have identified a 3,200-km(2) region around the Macondo Well contaminated by ∼ 1.8 ± 1.0 × 10(6) g of excess hopane. Based on spatial, chemical, oceanographic, and mass balance considerations, we calculate that this contamination represents 4-31% of the oil sequestered in the deep ocean. The pattern of contamination points to deep-ocean intrusion layers as the source and is most consistent with dual modes of deposition: a "bathtub ring" formed from an oil-rich layer of water impinging laterally upon the continental slope (at a depth of ∼ 900-1,300 m) and a higher-flux "fallout plume" where suspended oil particles sank to underlying sediment (at a depth of ∼ 1,300-1,700 m). We also suggest that a significant quantity of oil was deposited on the ocean floor outside this area but so far has evaded detection because of its heterogeneous spatial distribution.

Compositional discrimination of decompression and decomposition gas bubbles in bycaught seals and dolphins.

Gas bubbles in marine mammals entangled and drowned in gillnets have been previously described by computed tomography, gross examination and histopathology. The absence of bacteria or autolytic changes in the tissues of those animals suggested that the gas was produced peri- or post-mortem by a fast decompression, probably by quickly hauling animals entangled in the net at depth to the surface. Gas composition analysis and gas scoring are two new diagnostic tools available to distinguish gas embolisms from putrefaction gases. With this goal, these methods have been successfully applied to pathological studies of marine mammals. In this study, we characterized the flux and composition of the gas bubbles from bycaught marine mammals in anchored sink gillnets and bottom otter trawls. We compared these data with marine mammals stranded on Cape Cod, MA, USA. Fresh animals or with moderate decomposition (decomposition scores of 2 and 3) were prioritized. Results showed that bycaught animals presented with significantly higher gas scores than stranded animals. Gas composition analyses indicate that gas was formed by decompression, confirming the decompression hypothesis.

Composition and fate of gas and oil released to the water column during the Deepwater Horizon oil spill.

Quantitative information regarding the endmember composition of the gas and oil that flowed from the Macondo well during the Deepwater Horizon oil spill is essential for determining the oil flow rate, total oil volume released, and trajectories and fates of hydrocarbon components in the marine environment. Using isobaric gas-tight samplers, we collected discrete samples directly above the Macondo well on June 21, 2010, and analyzed the gas and oil. We found that the fluids flowing from the Macondo well had a gas-to-oil ratio of 1,600 standard cubic feet per petroleum barrel. Based on the measured endmember gas-to-oil ratio and the Federally estimated net liquid oil release of 4.1 million barrels, the total amount of C(1)-C(5) hydrocarbons released to the water column was 1.7 10(11) g. The endmember gas and oil compositions then enabled us to study the fractionation of petroleum hydrocarbons in discrete water samples collected in June 2010 within a southwest trending hydrocarbon-enriched plume of neutrally buoyant water at a water depth of 1,100 m. The most abundant petroleum hydrocarbons larger than C(1)-C(5) were benzene, toluene, ethylbenzene, and total xylenes at concentrations up to 78 µg L(-1). Comparison of the endmember gas and oil composition with the composition of water column samples showed that the plume was preferentially enriched with water-soluble components, indicating that aqueous dissolution played a major role in plume formation, whereas the fates of relatively insoluble petroleum components were initially controlled by other processes.

Gas chromatograph-combustion system for 14C-accelerator mass spectrometry.

A gas chromatograph-combustion (GC-C) system is described for the introduction of samples as CO(2) gas into a (14)C accelerator mass spectrometry (AMS) system with a microwave-plasma gas ion source. Samples are injected into a gas chromatograph fitted with a megabore capillary column that uses H(2) as the carrier gas. The gas stream from the outlet of the column is mixed with O(2) and Ar gas and passed through a combustion furnace where the H(2) carrier gas and separated components are quantitatively oxidized to CO(2) and H(2)O. Water vapor is removed using a heated nafion dryer. The Ar carries the CO(2) to the ion source. The system is able to separate and oxidize up to 10 microg of compound and transfer the products from 7.6 mL/min of H(2) carrier gas into 0.2-1.0 mL/min of Ar carrier gas. Chromatographic performance and isotopic fidelity satisfy the requirements of the (14)C-AMS system for natural abundance measurements. The system is a significant technical advance for GC-AMS and may be capable of providing an increase in sensitivity for other analytical systems such as an isotope-ratio-monitoring GC/MS.

Compound-specific 81Br/79Br analysis by capillary gas chromatography/multicollector inductively coupled plasma mass spectrometry.

Brominated organic compounds (BOCs) are of great interest in atmospheric chemistry, natural products, geochemistry, and marine chemistry. The Br isotope ratios ((81)Br and (79)Br; average (81)Br/(79)Br = 0.97277) have significant potential for the study of the source, transport, and fate of these compounds. Currently, there is no published method for determining the Br isotopic content of BOCs in complex mixtures. To measure the ratios of stable Br in BOCs on a compound-specific basis, we assembled a gas chromatography/multicollector inductively coupled plasma mass spectrometry (GC/MCICPMS) system. Background signals, the formation of Ar dimers from organic hydrogen, and the solvent peak did not affect the results. The analysis of three brominated benzenes revealed that 0.3 per thousand precision can be attained when 0.3 nmol of Br are injected. For samples larger than 0.3 nmol Br, the isotopic precision was within a factor of 3 of the shot-noise limit, which is the best possible statistical precision attainable avoiding all other sources of noise.

Identification and quantification of alkene-based drilling fluids in crude oils by comprehensive two-dimensional gas chromatography with flame ionization detection.

Comprehensive two-dimensional gas chromatography with flame ionization detection (GC x GC-FID) was used to measure alkene-based drilling fluids in crude oils. Compared to one-dimensional gas chromatography, GC x GC-FID is more robust for detecting alkenes due to the increased resolution afforded by second dimension separations. Using GC x GC-FID to analyze four oil samples from one reservoir contaminated with the same drilling fluid, C(15), C(16), C(17), C(18) and C(20) alkenes were identified. The drilling fluid that contaminated these samples also differed from another commercially obtained fluid, which only contained C(16) and C(18) alkenes. These results should motivate the petroleum industry to consider GC x GC-FID for measuring drilling fluids.