Jeffrey S. Seewald

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 C1-C5 hydrocarbons released to the water column was 1.7 × 1011 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 C1-C5 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.

A reassessment of the potential for reduction of dissolved CO 2 to hydrocarbons during serpentinization of olivine

The concept that aqueous CO2 can be reduced to hydrocarbons abiotically during serpentinization of olivine has become widespread in the earth and planetary sciences. This process has been invoked to explain the occurrence of hydrocarbons in crystalline igneous rocks and proposed as a source of prebiotic organic compounds for the origin of life. We reevaluate this scenario through an experimental study of the reaction of dissolved CO2 in the presence of olivine under hydrothermal conditions (300°C, 350 bar). Reduction of CO2 to formate (HCOO−) was found to proceed rapidly, with H2 generated from hydrothermal alteration of olivine serving as the reductant. The reverse reaction, decomposition of formic acid to CO2 and H2, was also found to proceed rapidly. Although dissolved hydrocarbon concentrations increased throughout the experiments, isotopic labeling of dissolved CO2 with 13C indicated that these compounds were primarily generated from reduced carbon compounds already present in olivine at the beginning of the experiment rather than by reduction of CO2. The only hydrocarbon product from reduction of CO2 observed in the experiments was a small amount of methane (<0.04% conversion of dissolved CO2 in more than 2500 h of heating). Comparison of the reaction products with thermodynamic data indicates that reactions between dissolved CO2 and formate rapidly achieved metastable equilibrium at the experimental conditions, suggesting that similar reactions could control the concentration of formate in geologic fluids. The results indicate that the potential for abiotic formation of hydrocarbons during serpentinization may be much more limited than previously believed, and other mineral catalysts or vapor phase reactions may be required to explain many occurrences of abiotic hydrocarbons in serpentinites and igneous rocks.

Organic–inorganic interactions in petroleum-producing sedimentary basins

Petroleum deposits form as a consequence of the increased temperatures that accompany progressive burial of organic matter deep within sedimentary basins. Recent advances in petroleum geochemistry suggest that inorganic sedimentary components participate in organic transformations associated with this process. Water is particularly important because it facilitates reaction mechanisms not available in dry environments, and may contribute hydrogen and oxygen for the formation of hydrocarbons and oxygenated alteration products. These findings suggest that petroleum generation and stability is influenced by subsurface chemical environments, and is a simple function of time, temperature and the composition of sedimentary organic matter.

Chemical data quantify Deepwater Horizon hydrocarbon flow rate and environmental distribution

Detailed airborne, surface, and subsurface chemical measurements, primarily obtained in May and June 2010, are used to quantify initial hydrocarbon compositions along different transport pathways (i.e., in deep subsurface plumes, in the initial surface slick, and in the atmosphere) during the Deepwater Horizon oil spill. Atmospheric measurements are consistent with a limited area of surfacing oil, with implications for leaked hydrocarbon mass transport and oil drop size distributions. The chemical data further suggest relatively little variation in leaking hydrocarbon composition over time. Although readily soluble hydrocarbons made up ∼25% of the leaking mixture by mass, subsurface chemical data show these compounds made up ∼69% of the deep plume mass; only ∼31% of the deep plume mass was initially transported in the form of trapped oil droplets. Mass flows along individual transport pathways are also derived from atmospheric and subsurface chemical data. Subsurface hydrocarbon composition, dissolved oxygen, and dispersant data are used to assess release of hydrocarbons from the leaking well. We use the chemical measurements to estimate that (7.8 ± 1.9) × 106 kg of hydrocarbons leaked on June 10, 2010, directly accounting for roughly three-quarters of the total leaked mass on that day. The average environmental release rate of (10.1 ± 2.0) × 106 kg/d derived using atmospheric and subsurface chemical data agrees within uncertainties with the official average leak rate of (10.2 ± 1.0) × 106 kg/d derived using physical and optical methods.

Aqueous geochemistry of low molecular weight hydrocarbons at elevated temperatures and pressures: constraints from mineral buffered laboratory experiments

Abstract Organic matter, water, and minerals coexist at elevated temperatures and pressures in sedimentary basins and participate in a wide range of geochemical processes that includes the generation of oil and natural gas. A series of laboratory experiments were conducted at 300 to 350°C and 350 bars to examine chemical interactions involving low molecular weight aqueous hydrocarbons with water and Fe-bearing minerals under hydrothermal conditions. Mineral buffers composed of hematite-magnetite-pyrite, hematite-magnetite, and pyrite-pyrrhotite-magnetite were added to each experiment to fix the redox state of the fluid and the activity of reduced sulfur species. During each experiment the chemical system was externally modified by addition of ethene, ethane, propene, 1-butene, or n-heptane, and variations in the abundance of aqueous organic species were monitored as a function of time and temperature. Results of the experiments indicate that decomposition of aqueous n-alkanes proceeds through a series of oxidation and hydration reactions that sequentially produce alkenes, alcohols, ketones, and organic acids as reaction intermediaries. Organic acids subsequently undergo decarboxylation and/or oxidation reactions to form carbon dioxide and shorter chain saturated hydrocarbons. This alteration assemblage is compositionally distinct from that produced by thermal cracking under anhydrous conditions, indicating that the presence of water and minerals provide alternative reaction pathways for the decomposition of hydrocarbons. The rate of hydrocarbon oxidation decreases substantially under reducing conditions and in the absence of catalytically active aqueous sulfur species. These results represent compelling evidence that the stability of aqueous hydrocarbons at elevated temperatures in natural environments is not a simple function of time and temperature alone. Under the appropriate geochemical conditions, stepwise oxidation represents a mechanism for the decomposition of low molecular weight hydrocarbons and the production of methane-rich (“dry”) natural gas. Evaluation of aqueous reaction products generated during the experiments within a thermodynamic framework indicates that alkane-alkene, alkene-ketone, and alkene-alcohol reactions attained metastable thermodynamic equilibrium states. This equilibrium included water and iron-bearing minerals, demonstrating the direct involvement of inorganic species as reactants during organic transformations. The high reactivity of water and iron-bearing minerals suggests that they represent abundant sources of hydrogen and oxygen available for the formation of hydrocarbons and oxygenated alteration products. Thus, variations in elemental kerogen composition may not accurately reflect the timing and extent of hydrocarbon, carbon dioxide, and organic acid generation in sedimentary basins. This study demonstrates that the stabilities of aqueous hydrocarbons are strongly influenced by inorganic sediment composition at elevated temperatures. Incorporation of such interactions into geochemical models will greatly improve prediction of the occurrence of hydrocarbons in natural environments over geologic time.

Experimental constraints on the hydrothermal reactivity of organic acids and acid anions: I. Formic acid and formate

A series of hydrothermal experiments covering a range of temperatures from 175 to 260°C examined the decomposition of formic acid and formate and also investigated the production of formate from reduction of CO2. Decomposition rates measured in this study, which were conducted in gold-TiO2 reactors, were several orders of magnitude slower than those reported in previous studies conducted in steel and Ti-metal reactors, indicating the previous studies substantially overestimated the rate of the reaction owing to reactor catalysis. Although experiments were conducted with several different minerals present (hematite, magnetite, serpentinized olivine, NiFe-alloy), the decomposition rates were similar in each experiment once the effects of fluid pH were accounted for, suggesting that the minerals had no effect on the stability of formic acid or formate. At higher temperatures (>225°C), the rates of both the decomposition of formate and the reduction of CO2 to formate were sufficiently rapid that reactions between dissolved CO2 and formate rapidly attained a state of metastable thermodynamic equilibrium. The results suggest that the amount of formate in many subsurface and hydrothermal fluids is likely to be controlled by equilibrium with dissolved CO2 at the prevailing oxidation state and pH of the fluid. This may account for the high concentrations of formate observed in strongly reducing environments such as serpentinites, as well as the low concentrations relative to other organic acid anions in mildly reducing environments such as oil-filed brines and formation waters in sedimentary basins. Although formate has been suggested to be a reaction intermediate in the formation of abiotic hydrocarbons from reduction of aqueous CO2, production of hydrocarbons was not observed in any of the experiments, except for trace amounts of methane, despite high concentrations of formate and strongly reducing conditions.

Pathways for abiotic organic synthesis at submarine hydrothermal fields

Significance Arguments for an abiotic origin of organic compounds in deep-sea hot springs are compelling because of their potential role in the origin of life and sustaining microbial communities. Theory predicts that warm H2-rich fluids circulating through serpentinizing systems create a favorable thermodynamic drive for inorganic carbon reduction to organic compounds. We show that abiotic synthesis proceeds by two spatially and temporally distinct mechanisms. Abundant dissolved CH4 and higher hydrocarbons are likely formed in H2-rich fluid inclusions over geologic timescales. Conversely, formate production by ΣCO2 reduction occurs rapidly during subsurface mixing, which may support anaerobic methanogenesis. We confirm models for abiotic metastable organic compound formation and argue that alkanes in all ultramafic-influenced vents may form independently of actively circulating serpentinizing fluids. Arguments for an abiotic origin of low-molecular weight organic compounds in deep-sea hot springs are compelling owing to implications for the sustenance of deep biosphere microbial communities and their potential role in the origin of life. Theory predicts that warm H2-rich fluids, like those emanating from serpentinizing hydrothermal systems, create a favorable thermodynamic drive for the abiotic generation of organic compounds from inorganic precursors. Here, we constrain two distinct reaction pathways for abiotic organic synthesis in the natural environment at the Von Damm hydrothermal field and delineate spatially where inorganic carbon is converted into bioavailable reduced carbon. We reveal that carbon transformation reactions in a single system can progress over hours, days, and up to thousands of years. Previous studies have suggested that CH4 and higher hydrocarbons in ultramafic hydrothermal systems were dependent on H2 generation during active serpentinization. Rather, our results indicate that CH4 found in vent fluids is formed in H2-rich fluid inclusions, and higher n-alkanes may likely be derived from the same source. This finding implies that, in contrast with current paradigms, these compounds may form independently of actively circulating serpentinizing fluids in ultramafic-influenced systems. Conversely, widespread production of formate by ΣCO2 reduction at Von Damm occurs rapidly during shallow subsurface mixing of the same fluids, which may support anaerobic methanogenesis. Our finding of abiogenic formate in deep-sea hot springs has significant implications for microbial life strategies in the present-day deep biosphere as well as early life on Earth and beyond.

Laboratory and theoretical constraints on the generation and composition of natural gas

Hydrous pyrolysis experiments were conducted at 125 to 375°C and 350 bars to constrain factors that regulate the generation and relative abundance of hydrocarbon and nonhydrocarbon gases during thermal maturation of Monterey, Eutaw, and Smackover shale. Thermogenic gas was generated at temperatures as low as 125°C and increased in abundance with increasing temperature. The relative abundance of individual hydrocarbons varied substantially in response to increasing time and temperature reflecting the chemical processes responsible for their formation. The hydrocarbon fraction of low maturity gas produced via primary cracking of kerogen was composed predominantly of methane. With increasing thermal maturity, the onset of bitumen generation produced longer-chain hydrocarbons causing a decrease in the relative abundance of methane. At high levels of thermal maturity, the absolute and relative abundance of methane increased due to decomposition of bitumen. In all experiments at all temperatures, carbon dioxide was the most abundant volatile organic alteration product. Carbon dioxide was produced directly from kerogen at low thermal maturity and via the decomposition of bitumen and/or kerogen at high thermal maturity. During early stage alteration, kerogen likely represents the dominant source of oxygen in carbon dioxide while at high thermal maturities water may represent an abundant and reactive oxygen source. Hydrogen released during the disproportionation of water is likely consumed during hydrocarbon generation. Theoretical reaction path modeling suggests that the precipitation of calcite may effectively remove carbon dioxide from natural gas if a source of Ca is available within the rock. Thus, carbon dioxide-rich natural gas may be relatively pristine while methane-rich natural gas may reflect the occurrence of secondary reactions involving inorganic sedimentary components. Kinetic analysis of the experimental data indicates a narrow range of activation energies for the generation of C1-C4 hydrocarbons from the Monterey, Smackover, and Eutaw shales. Carbon dioxide generation from the Monterey and Eutaw shales is accounted for by a substantially broader range of activation energies. Application of these data to predict gas formation at temperatures and time scales typical of subsiding sedimentary basins suggests that C1-C4 generation is restricted to relatively high temperatures while carbon dioxide generation occurs at both low and high thermal maturities. Thus, in contrast to the bulk of C1-C4 generation which is predicted to occur after peak bitumen generation, production of carbon dioxide will occur before, during, and after the generation of liquid hydrocarbons.

A new gas-tight isobaric sampler for hydrothermal fluids

A new gas-tight isobaric sampler for the collection of hydrothermal fluids venting at the seafloor has been designed, constructed, and tested at a ridge-crest vent site. The new device is constructed of chemically inert titanium, is gas-tight to 450 bar and can be used to sample fluids with temperatures up to 400°C. Compressed gas is used to maintain the sample at seafloor pressure before and during sample withdrawal onboard ship, allowing subsampling without degassing the fluid remaining in the sampler. This feature eliminates the need to collect separate gas-tight and major element samples since a single fluid sample can be analyzed quantitatively for major, trace, semi-volatile, and volatile components. The sampler fill rate is regulated to minimize entrainment of ambient seawater during collection of fluids from environments characterized by low fluid flow such as diffuse hydrothermal vents. In addition to deployment at the ridge-crest, the samplers can be used to collect gas-tight samples from other subseasurface environments such as hydrocarbon seeps, areas of methane-gas hydrate formation, cold seeps associated with serpentinites, regions of groundwater egress to the oceans, and the water column.

Acoustic measurement of the Deepwater Horizon Macondo well flow rate

On May 31, 2010, a direct acoustic measurement method was used to quantify fluid leakage rate from the Deepwater Horizon Macondo well prior to removal of its broken riser. This method utilized an acoustic imaging sonar and acoustic Doppler sonar operating onboard a remotely operated vehicle for noncontact measurement of flow cross-section and velocity from the well’s two leak sites. Over 2,500 sonar cross-sections and over 85,000 Doppler velocity measurements were recorded during the acquisition process. These data were then applied to turbulent jet and plume flow models to account for entrained water and calculate a combined hydrocarbon flow rate from the two leak sites at seafloor conditions. Based on the chemical composition of end-member samples collected from within the well, this bulk volumetric rate was then normalized to account for contributions from gases and condensates at initial leak source conditions. Results from this investigation indicate that on May 31, 2010, the well’s oil flow rate was approximately 0.10 ± 0.017 m3 s-1 at seafloor conditions, or approximately 85 ± 15 kg s-1 (7.4 ± 1.3 Gg d-1), equivalent to approximately 57,000 ± 9,800 barrels of oil per day at surface conditions. End-member chemical composition indicates that this oil release rate was accompanied by approximately an additional 24 ± 4.2 kg s-1 (2.1 ± 0.37 Gg d-1) of natural gas (methane through pentanes), yielding a total hydrocarbon release rate of 110 ± 19 kg s-1 (9.5 ± 1.6 Gg d-1).