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  • 11
    Publication Date: 2022-05-25
    Description: This paper is not subject to U.S. copyright. The definitive version was published in Marine and Petroleum Geology 25 (2008): 942-951, doi:10.1016/j.marpetgeo.2008.01.016.
    Description: Pore waters extracted from 18 piston cores obtained on and near a salt-cored bathymetric high in Keathley Canyon lease block 151 in the northern Gulf of Mexico contain elevated concentrations of chloride (up to 838 mM) and have pore water chemical concentration profiles that exhibit extensive departures (concavity) from steady-state (linear) diffusive equilibrium with depth. Minimum δ13C dissolved inorganic carbon (DIC) values of −55.9‰ to −64.8‰ at the sulfate–methane transition (SMT) strongly suggest active anaerobic oxidation of methane (AOM) throughout the study region. However, the nonlinear pore water chemistry-depth profiles make it impossible to determine the vertical extent of active AOM or the potential role of alternate sulfate reduction pathways. Here we utilize the conservative (non-reactive) nature of dissolved chloride to differentiate the effects of biogeochemical activity (e.g., AOM and/or organoclastic sulfate reduction) relative to physical mixing in high salinity Keathley Canyon sediments. In most cases, the DIC and sulfate concentrations in pore waters are consistent with a conservative mixing model that uses chloride concentrations at the seafloor and the SMT as endmembers. Conservative mixing of pore water constituents implies that an undetermined physical process is primarily responsible for the nonlinearity of the pore water-depth profiles. In limited cases where the sulfate and DIC concentrations deviated from conservative mixing between the seafloor and SMT, the δ13C-DIC mixing diagrams suggest that the excess DIC is produced from a 13C-depleted source that could only be accounted for by microbial methane, the dominant form of methane identified during this study. We conclude that AOM is the most prevalent sink for sulfate and that it occurs primarily at the SMT at this Keathley Canyon site.
    Description: This work was supported by DOE’s National Energy Technology Laboratory, the Office of Naval Research, and the Naval Research Laboratory. J.W.P was supported by a USGS Mendenhall Postdoctoral Research Fellowship Program during preparation of this manuscript.
    Keywords: Gas hydrate ; Methane ; Anaerobic methane oxidation ; Sulfate ; Brine ; Gulf of Mexico
    Repository Name: Woods Hole Open Access Server
    Type: Article
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  • 12
    Publication Date: 2022-05-25
    Description: Author Posting. © American Geophysical Union, 2011. This article is posted here by permission of American Geophysical Union for personal use, not for redistribution. The definitive version was published in Geophysical Research Letters 38 (2011): L06408, doi:10.1029/2011GL046768.
    Description: Methane is a potent greenhouse gas, but its effects on Earth's climate remain poorly constrained, in part due to uncertainties in global methane fluxes to the atmosphere. An important source of atmospheric methane is the methane generated in organic-rich sediments underlying surface water bodies, including lakes, wetlands, and the ocean. The fraction of the methane that reaches the atmosphere depends critically on the mode and spatiotemporal characteristics of free-gas venting from the underlying sediments. Here we propose that methane transport in lake sediments is controlled by dynamic conduits, which dilate and release gas as the falling hydrostatic pressure reduces the effective stress below the tensile strength of the sediments. We test our model against a four-month record of hydrostatic load and methane flux in Upper Mystic Lake, Mass., USA, and show that it captures the complex episodicity of methane ebullition. Our quantitative conceptualization opens the door to integrated modeling of methane transport to constrain global methane release from lakes and other shallow-water, organic-rich sediment systems, and to assess its climate feedbacks.
    Description: This work was supported by the U.S. Department of Energy (grants DE‐FC26‐06NT43067 and DE‐AI26‐05NT42496), an NSF Doctoral Dissertation Research grant (0726806), a GSA Graduate Student Research grant, and MIT Martin, Linden and Ippen fellowships.
    Keywords: Greenhouse gas ; Methane flux ; Freshwater methane ; Gas conduits ; Effective stress ; Ebullition
    Repository Name: Woods Hole Open Access Server
    Type: Article
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  • 13
    Publication Date: 2022-05-25
    Description: Author Posting. © American Geophysical Union, 2011. This article is posted here by permission of American Geophysical Union for personal use, not for redistribution. The definitive version was published in Global Biogeochemical Cycles 25 (2011): GB2002, doi:10.1029/2010GB003845.
    Description: The magnitude and feedbacks of future methane release from the Arctic region are unknown. Despite limited documentation of potential future releases associated with thawing permafrost and degassing methane hydrates, the large potential for future methane releases calls for improved understanding of the interaction of a changing climate with processes in the Arctic and chemical feedbacks in the atmosphere. Here we apply a “state of the art” atmospheric chemistry transport model to show that large emissions of CH 4 would likely have an unexpectedly large impact on the chemical composition of the atmosphere and on radiative forcing (RF). The indirect contribution to RF of additional methane emission is particularly important. It is shown that if global methane emissions were to increase by factors of 2.5 and 5.2 above current emissions, the indirect contributions to RF would be about 250% and 400%, respectively, of the RF that can be attributed to directly emitted methane alone. Assuming several hypothetical scenarios of CH 4 release associated with permafrost thaw, shallow marine hydrate degassing, and submarine landslides, we find a strong positive feedback on RF through atmospheric chemistry. In particular, the impact of CH 4 is enhanced through increase of its lifetime, and of atmospheric abundances of ozone, stratospheric water vapor, and CO 2 as a result of atmospheric chemical processes. Despite uncertainties in emission scenarios, our results provide a better understanding of the feedbacks in the atmospheric chemistry that would amplify climate warming.
    Keywords: Methane ; Permafrost ; Radiative forcing
    Repository Name: Woods Hole Open Access Server
    Type: Article
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  • 14
    Publication Date: 2022-05-25
    Description: This paper is not subject to U.S. copyright. The definitive version was published in Chemical Geology 339 (2013): 242-250, doi:10.1016/j.chemgeo.2012.09.033.
    Description: As a consequence of contemporary or longer term (since 15 ka) climate warming, gas hydrates in some settings may presently be dissociating and releasing methane and other gases to the ocean–atmosphere system. A key challenge in assessing the impact of dissociating gas hydrates on global atmospheric methane is the lack of a technique able to distinguish between methane recently released from gas hydrates and methane emitted from leaky thermogenic reservoirs, shallow sediments (some newly thawed), coal beds, and other sources. Carbon and deuterium stable isotopic fractionation during methane formation provides a first-order constraint on the processes (microbial or thermogenic) of methane generation. However, because gas hydrate formation and dissociation do not cause significant isotopic fractionation, a stable isotope-based hydrate-source determination is not possible. Here, we investigate patterns of mass-dependent noble gas fractionation within the gas hydrate lattice to fingerprint methane released from gas hydrates. Starting with synthetic gas hydrate formed under laboratory conditions, we document complex noble gas fractionation patterns in the gases liberated during dissociation and explore the effects of aging and storage (e.g., in liquid nitrogen), as well as sampling and preservation procedures. The laboratory results confirm a unique noble gas fractionation pattern for gas hydrates, one that shows promise in evaluating modern natural gas seeps for a signature associated with gas hydrate dissociation.
    Description: Partial support for this research was provided by Interagency Agreements DE-FE0002911 and DE-NT0006147 between the U.S. Geological Survey Gas Hydrates Project and the U.S. Department of Energy's Methane Hydrates Research and Development Program.
    Keywords: Gas hydrate ; Noble gas ; Methane ; Stable isotopes ; Mass-fractionation
    Repository Name: Woods Hole Open Access Server
    Type: Article
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  • 15
    Publication Date: 2022-05-25
    Description: Author Posting. © American Geophysical Union, 2016. This article is posted here by permission of American Geophysical Union for personal use, not for redistribution. The definitive version was published in Geochemistry, Geophysics, Geosystems 17 (2016): 3882–3892, doi:10.1002/2016GC006421.
    Description: Methane seeps were investigated in Hudson Canyon, the largest shelf-break canyon on the northern U.S. Atlantic Margin. The seeps investigated are located at or updip of the nominal limit of methane clathrate hydrate stability. The acoustic identification of bubble streams was used to guide water column sampling in a 32 km2 region within the canyon's thalweg. By incorporating measurements of dissolved methane concentration with methane oxidation rates and current velocity into a steady state box model, the total emission of methane to the water column in this region was estimated to be 12 kmol methane per day (range: 6–24 kmol methane per day). These analyses suggest that the emitted methane is largely retained inside the canyon walls below 300 m water depth, and that it is aerobically oxidized to near completion within the larger extent of Hudson Canyon. Based on estimated methane emissions and measured oxidation rates, the oxidation of this methane to dissolved CO2 is expected to have minimal influences on seawater pH.
    Description: National Science Foundation Grant Number: OCE-1318102; U.S. Department of Energy award Grant Numbers: DE-FE0013999 and NSF OCE-1352301, DOE-USGS, DE-FE0002911 and DE-FE0005806
    Description: 2017-04-13
    Keywords: Methane seeps ; Methane flux ; Methane oxidation ; Hudson Canyon
    Repository Name: Woods Hole Open Access Server
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  • 16
    Publication Date: 2022-05-25
    Description: Author Posting. © American Geophysical Union, 2016. This article is posted here by permission of American Geophysical Union for personal use, not for redistribution. The definitive version was published in Geochemistry, Geophysics, Geosystems 17 (2016): 4333–4353, doi:10.1002/2016GC006582.
    Description: Borehole logging data from legacy wells directly constrain the contemporary distribution of subsea permafrost in the sedimentary section at discrete locations on the U.S. Beaufort Margin and complement recent regional analyses of exploration seismic data to delineate the permafrost's offshore extent. Most usable borehole data were acquired on a ∼500 km stretch of the margin and within 30 km of the contemporary coastline from north of Lake Teshekpuk to nearly the U.S.-Canada border. Relying primarily on deep resistivity logs that should be largely unaffected by drilling fluids and hole conditions, the analysis reveals the persistence of several hundred vertical meters of ice-bonded permafrost in nearshore wells near Prudhoe Bay and Foggy Island Bay, with less permafrost detected to the east and west. Permafrost is inferred beneath many barrier islands and in some nearshore and lagoonal (back-barrier) wells. The analysis of borehole logs confirms the offshore pattern of ice-bearing subsea permafrost distribution determined based on regional seismic analyses and reveals that ice content generally diminishes with distance from the coastline. Lacking better well distribution, it is not possible to determine the absolute seaward extent of ice-bearing permafrost, nor the distribution of permafrost beneath the present-day continental shelf at the end of the Pleistocene. However, the recovery of gas hydrate from an outer shelf well (Belcher) and previous delineation of a log signature possibly indicating gas hydrate in an inner shelf well (Hammerhead 2) imply that permafrost may once have extended across much of the shelf offshore Camden Bay.
    Description: 2017-05-04
    Keywords: Permafrost ; Arctic Ocean ; Climate change ; Borehole logging ; Gas hydrates
    Repository Name: Woods Hole Open Access Server
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  • 17
    Publication Date: 2022-05-25
    Description: Author Posting. © The Oceanography Society, 2018. This article is posted here by permission of The Oceanography Society for personal use, not for redistribution. The definitive version was published in Oceanography 31, no. 1, supplement (2018): 93.
    Repository Name: Woods Hole Open Access Server
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  • 18
    Publication Date: 2022-05-25
    Description: Author Posting. © American Geophysical Union, 2007. This article is posted here by permission of American Geophysical Union for personal use, not for redistribution. The definitive version was published in Geochemistry Geophysics Geosystems 8 (2007): Q12008, doi:10.1029/2007GC001722.
    Description: Analysis of new multibeam bathymetry data and seismic Chirp data acquired over the Cape Fear Slide complex on the U.S. Atlantic margin suggests that at least 5 major submarine slides have likely occurred there within the past 30,000 years, indicating that repetitive, large-scale mass wasting and associated tsunamis may be more common in this area than previously believed. Gas hydrate deposits and associated free gas as well as salt tectonics have been implicated in previous studies as triggers for the major Cape Fear slide events. Analysis of the interaction of the gas hydrate phase boundary and the various generations of slides indicates that only the most landward slide likely intersected the phase boundary and inferred high gas pressures below it. For much of the region, we believe that displacement along a newly recognized normal fault led to upward migration of salt, oversteepening of slopes, and repeated slope failures. Using new constraints on slide morphology, we develop the first tsunami model for the Cape Fear Slide complex. Our results indicate that if the most seaward Cape Fear slide event occurred today, it could produce waves in excess of 2 m at the present-day 100 m bathymetric contour.
    Description: Acquisition of new data was funded by NOAA Ocean Exploration grant NA03OAR4600100 to C.R., and we thank the National Science Foundation for contributing to transit costs for the ship.
    Keywords: Submarine slides ; Tsunami ; Gas hydrates ; Continental margins ; Salt tectonics
    Repository Name: Woods Hole Open Access Server
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  • 19
    Publication Date: 2022-05-25
    Description: Author Posting. © American Geophysical Union, 2009. This article is posted here by permission of American Geophysical Union for personal use, not for redistribution. The definitive version was published in Journal of Geophysical Research 114 (2009): B11103, doi:10.1029/2008JB006235.
    Description: A thorough understanding of the thermal conductivity of hydrate-bearing sediments is necessary for evaluating phase transformation processes that would accompany energy production from gas hydrate deposits and for estimating regional heat flow based on the observed depth to the base of the gas hydrate stability zone. The coexistence of multiple phases (gas hydrate, liquid and gas pore fill, and solid sediment grains) and their complex spatial arrangement hinder the a priori prediction of the thermal conductivity of hydrate-bearing sediments. Previous studies have been unable to capture the full parameter space covered by variations in grain size, specific surface, degree of saturation, nature of pore filling material, and effective stress for hydrate-bearing samples. Here we report on systematic measurements of the thermal conductivity of air dry, water- and tetrohydrofuran (THF)-saturated, and THF hydrate–saturated sand and clay samples at vertical effective stress of 0.05 to 1 MPa (corresponding to depths as great as 100 m below seafloor). Results reveal that the bulk thermal conductivity of the samples in every case reflects a complex interplay among particle size, effective stress, porosity, and fluid-versus-hydrate filled pore spaces. The thermal conductivity of THF hydrate–bearing soils increases upon hydrate formation although the thermal conductivities of THF solution and THF hydrate are almost the same. Several mechanisms can contribute to this effect including cryogenic suction during hydrate crystal growth and the ensuing porosity reduction in the surrounding sediment, increased mean effective stress due to hydrate formation under zero lateral strain conditions, and decreased interface thermal impedance as grain-liquid interfaces are transformed into grain-hydrate interfaces.
    Description: This work was supported by the Chevron Joint Industry Project on Methane Hydrates under contract DE-FC26- 01NT41330 to Georgia Institute of Technology from the U.S. Department of Energy’s National Energy Technology Laboratory. J.C.S. received additional support from the Goizueta Foundation. C.R. thanks the Petroleum Research Fund of the American Chemical Society under AC8–31351 for early support of thermal conductivity research on hydrate-bearing sediments at Georgia Institute of Technology.
    Keywords: Gas hydrate
    Repository Name: Woods Hole Open Access Server
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  • 20
    Publication Date: 2022-05-25
    Description: © The Author(s), 2017. This article is distributed under the terms of the Creative Commons Attribution License. The definitive version was published in Reviews of Geophysics 55 (2017): 126–168, doi:10.1002/2016RG000534.
    Description: Gas hydrate, a frozen, naturally-occurring, and highly-concentrated form of methane, sequesters significant carbon in the global system and is stable only over a range of low-temperature and moderate-pressure conditions. Gas hydrate is widespread in the sediments of marine continental margins and permafrost areas, locations where ocean and atmospheric warming may perturb the hydrate stability field and lead to release of the sequestered methane into the overlying sediments and soils. Methane and methane-derived carbon that escape from sediments and soils and reach the atmosphere could exacerbate greenhouse warming. The synergy between warming climate and gas hydrate dissociation feeds a popular perception that global warming could drive catastrophic methane releases from the contemporary gas hydrate reservoir. Appropriate evaluation of the two sides of the climate-methane hydrate synergy requires assessing direct and indirect observational data related to gas hydrate dissociation phenomena and numerical models that track the interaction of gas hydrates/methane with the ocean and/or atmosphere. Methane hydrate is likely undergoing dissociation now on global upper continental slopes and on continental shelves that ring the Arctic Ocean. Many factors—the depth of the gas hydrates in sediments, strong sediment and water column sinks, and the inability of bubbles emitted at the seafloor to deliver methane to the sea-air interface in most cases—mitigate the impact of gas hydrate dissociation on atmospheric greenhouse gas concentrations though. There is no conclusive proof that hydrate-derived methane is reaching the atmosphere now, but more observational data and improved numerical models will better characterize the climate-hydrate synergy in the future.
    Description: U.S. Geological Survey (USGS); USGS and the U.S. Department of Energy Grant Numbers: DE-FE0002911, DE-FE0005806, DE-FE0023495, DE-FE0026195, DE-FE0028980; Department of Earth, Atmospheric and Planetary Sciences; U.S. National Science Foundation, Divisions of Ocean Sciences and Polar Programs Grant Numbers: OCE-0849246 [1300040], 1042650, 1139203, 1318102, PLR-1417149
    Keywords: Methane hydrate ; Climate ; Global warming ; Greenhouse gas
    Repository Name: Woods Hole Open Access Server
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