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  • 1
    Publication Date: 2022-05-25
    Description: Author Posting. © American Geophysical Union, 2010. 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 11 (2010): Q03007, doi:10.1029/2009GC002667.
    Description: Gas hydrate formation and dissociation in sediments are accompanied by changes in the bulk volume of the sediment and can lead to changes in sediment properties, loss of integrity for boreholes, and possibly regional subsidence of the ground surface over areas where methane might be produced from gas hydrate in the future. Experiments on sand, silts, and clay subject to different effective stress and containing different saturations of hydrate formed from dissolved phase tetrahydrofuran are used to systematically investigate the impact of gas hydrate formation and dissociation on bulk sediment volume. Volume changes in low specific surface sediments (i.e., having a rigid sediment skeleton like sand) are much lower than those measured in high specific surface sediments (e.g., clay). Early hydrate formation is accompanied by contraction for all soils and most stress states in part because growing gas hydrate crystals buckle skeletal force chains. Dilation can occur at high hydrate saturations. Hydrate dissociation under drained, zero lateral strain conditions is always associated with some contraction, regardless of soil type, effective stress level, or hydrate saturation. Changes in void ratio during formation-dissociation decrease at high effective stress levels. The volumetric strain during dissociation under zero lateral strain scales with hydrate saturation and sediment compressibility. The volumetric strain during dissociation under high shear is a function of the initial volume average void ratio and the stress-dependent critical state void ratio of the sediment. Other contributions to volume reduction upon hydrate dissociation are related to segregated hydrate in lenses and nodules. For natural gas hydrates, some conditions (e.g., gas production driven by depressurization) might contribute to additional volume reduction by increasing the effective stress.
    Description: This research was initially supported by the Chevron Joint Industry Project on Methane Hydrates under contract DE‐FC26‐01NT41330 from the U.S. Department of Energy to Georgia Tech. Additional support was provided to J. Y. Lee by KIGAM, GHDO, and MKE and J. C. Santamarina by the Goizueta Foundation.
    Keywords: Gas hydrate ; Hydrate-bearing sediment ; Phase transformation ; Strain
    Repository Name: Woods Hole Open Access Server
    Type: Article
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  • 2
    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
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  • 3
    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
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  • 4
    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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  • 5
    Publication Date: 2022-05-26
    Description: This paper is not subject to U.S. copyright. The definitive version was published in Marine and Petroleum Geology 25 (2008): 819-829, doi:10.1016/j.marpetgeo.2008.02.007.
    Description: The Gulf of Mexico Gas Hydrates Joint Industry Project (JIP) is a consortium of production and service companies and some government agencies formed to address the challenges that gas hydrates pose for deepwater exploration and production. In partnership with the U.S. Department of Energy and with scientific assistance from the U.S. Geological Survey and academic partners, the JIP has focused on studies to assess hazards associated with drilling the fine-grained, hydrate-bearing sediments that dominate much of the shallow subseafloor in the deepwater (〉500 m) Gulf of Mexico. In preparation for an initial drilling, logging, and coring program, the JIP sponsored a multi-year research effort that included: (a) the development of borehole stability models for hydrate-bearing sediments; (b) exhaustive laboratory measurements of the physical properties of hydrate-bearing sediments; (c) refinement of new techniques for processing industry-standard 3-D seismic data to constrain gas hydrate saturations; and (d) construction of instrumentation to measure the physical properties of sediment cores that had never been removed from in situ hydrostatic pressure conditions. Following review of potential drilling sites, the JIP launched a 35-day expedition in Spring 2005 to acquire well logs and sediment cores at sites in Atwater Valley lease blocks 13/14 and Keathley Canyon lease block 151 in the northern Gulf of Mexico minibasin province. The Keathley Canyon site has a bottom simulating reflection at not, vert, ~ 392 m below the seafloor, while the Atwater Valley location is characterized by seafloor mounds with an underlying upwarped seismic reflection consistent with upward fluid migration and possible shoaling of the base of the gas hydrate stability (BGHS). No gas hydrate was recovered at the drill sites, but logging data, and to some extent cores, suggest the occurrence of gas hydrate in inferred coarser-grained beds and fractures, particularly between 220 and 330 m below the seafloor at the Keathley Canyon site. This paper provides an overview of the results of the initial phases of the JIP work and introduces the 15 papers that make up this special volume on the scientific results related to the 2005 logging and drilling expedition.
    Description: Supported by the U.S. Department of Energy, under award DE-FC26-01NT41330
    Keywords: Gas hydrate ; Hazard ; Ocean drilling ; Borehole ; Gulf of Mexico
    Repository Name: Woods Hole Open Access Server
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  • 6
    Publication Date: 2022-05-26
    Description: Author Posting. © American Geophysical Union, 2014. 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 41 (2014): 96-101, doi:10.1002/2013GL058048.
    Description: Identifying the spatial distribution of seabed fluid expulsion features is crucial for understanding the substrate plumbing system of any continental margin. A 1100 km stretch of the U.S. Atlantic margin contains more than 5000 pockmarks at water depths of 120 m (shelf edge) to 700 m (upper slope), mostly updip of the contemporary gas hydrate stability zone (GHSZ). Advanced attribute analyses of high-resolution multichannel seismic reflection data reveal gas-charged sediment and probable fluid chimneys beneath pockmark fields. A series of enhanced reflectors, inferred to represent hydrate-bearing sediments, occur within the GHSZ. Differential sediment loading at the shelf edge and warming-induced gas hydrate dissociation along the upper slope are the proposed mechanisms that led to transient changes in substrate pore fluid overpressure, vertical fluid/gas migration, and pockmark formation.
    Description: The U.S. Geological Survey and the U.S. Nuclear Regulatory Commission funded this research.
    Description: 2014-07-08
    Keywords: Seismic stratigraphy ; Pockmark ; Gas hydrate ; Fluid expulsion ; Submarine landslide ; Attribute analysis
    Repository Name: Woods Hole Open Access Server
    Type: Article
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  • 7
    Publication Date: 2022-10-27
    Description: © The Author(s), 2020. This article is distributed under the terms of the Creative Commons Attribution License. The definitive version was published in Ruppel, C. D., & Waite, W. F. Timescales and processes of methane hydrate formation and breakdown, with application to geologic systems. Journal of Geophysical Research: Solid Earth, 125(8), (2020): e2018JB016459, doi:10.1029/2018JB016459.
    Description: Gas hydrate is an ice‐like form of water and low molecular weight gas stable at temperatures of roughly −10°C to 25°C and pressures of ~3 to 30 MPa in geologic systems. Natural gas hydrates sequester an estimated one sixth of Earth's methane and are found primarily in deepwater marine sediments on continental margins, but also in permafrost areas and under continental ice sheets. When gas hydrate is removed from its stability field, its breakdown has implications for the global carbon cycle, ocean chemistry, marine geohazards, and interactions between the geosphere and the ocean‐atmosphere system. Gas hydrate breakdown can also be artificially driven as a component of studies assessing the resource potential of these deposits. Furthermore, geologic processes and perturbations to the ocean‐atmosphere system (e.g., warming temperatures) can cause not only dissociation, but also more widespread dissolution of hydrate or even formation of new hydrate in reservoirs. Linkages between gas hydrate and disparate aspects of Earth's near‐surface physical, chemical, and biological systems render an assessment of the rates and processes affecting the persistence of gas hydrate an appropriate Centennial Grand Challenge. This paper reviews the thermodynamic controls on methane hydrate stability and then describes the relative importance of kinetic, mass transfer, and heat transfer processes in the formation and breakdown (dissociation and dissolution) of gas hydrate. Results from numerical modeling, laboratory, and some field studies are used to summarize the rates of hydrate formation and breakdown, followed by an extensive treatment of hydrate dynamics in marine and cryospheric gas hydrate systems.
    Description: Both authors have received nearly two decades of support from the U.S. Geological Survey's (USGS's) Energy Resources Program and the Coastal/Marine Hazards and Resources Program and from numerous DOE‐USGS Interagency Agreements, most recently DE‐FE0023495. C. R. acknowledges support from NOAA's Office of Ocean Exploration and Research (OER) under NOAA‐USGS Interagency Agreement 16‐01118.
    Keywords: Gas hydrate ; Hydrate breakdown ; Hydrate formation ; Permafrost hydrate ; Geologic systems ; Marine hydrate
    Repository Name: Woods Hole Open Access Server
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  • 8
    Publication Date: 2022-10-27
    Description: Author Posting. © American Geophysical Union, 2019. 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-Solid Earth 124(8), (2019): 7525-7537, doi: 10.1029/2019JB018186.
    Description: The proliferation of drilling expeditions focused on characterizing natural gas hydrate as a potential energy resource has spawned widespread interest in gas hydrate reservoir properties and associated porous media phenomena. Between 2017 and 2019, a Special Section of this journal compiled contributed papers elucidating interactions between gas hydrate and sediment based on laboratory, numerical modeling, and field studies. Motivated mostly by field observations in the northern Gulf of Mexico and offshore Japan, several papers focus on the mechanisms for gas hydrate formation and accumulation, particularly with vapor phase gas, not dissolved gas, as the precursor to hydrate. These studies rely on numerical modeling or laboratory experiments using sediment packs or benchtop micromodels. A second focus of the Special Section is the role of fines in inhibiting production of gas from methane hydrate, controlling the distribution of hydrate at a pore scale, and influencing the bulk behavior of seafloor sediments. Other papers fill knowledge gaps related to the physical properties of hydrate‐bearing sediments and advance new approaches in coupled thermal‐mechanical modeling of these sediments during hydrate dissociation. Finally, one study addresses the long‐standing question about the fate of methane hydrate at the molecular level when CO2 is injected into natural reservoirs under hydrate‐forming conditions.
    Description: C. R. was supported by the U.S. Geological Survey's Energy Resources Program and the Coastal/Marine Hazards and Resources Program, as well as by DOE Interagency Agreement DE‐FE0023495. C. R. thanks W. Waite and J. Jang for discussions and suggestions that improved this paper and L. Stern for a helpful review. J. Y. Lee was supported by the Ministry of Trade, Industry, and Energy (MOTIE) through the Project “Gas Hydrate Exploration and Production Study (19‐1143)” under the management of the Gas Hydrate Research and Development Organization (GHDO) of Korea and the Korea Institute of Geoscience and Mineral Resources (KIGAM). Any use of trade, firm, or product name is for descriptive purposes only and does not imply endorsement by the U.S. Government.
    Keywords: Gas hydrate ; Methane ; Reservoir properties ; Multiphase flow
    Repository Name: Woods Hole Open Access Server
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  • 9
    Publication Date: 2022-05-26
    Description: Author Posting. © American Geophysical Union, 2014. 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: Solid Earth 119 (2014): 8594–8609, doi:10.1002/2014JB011290.
    Description: The most climate-sensitive methane hydrate deposits occur on upper continental slopes at depths close to the minimum pressure and maximum temperature for gas hydrate stability. At these water depths, small perturbations in intermediate ocean water temperatures can lead to gas hydrate dissociation. The Arctic Ocean has experienced more dramatic warming than lower latitudes, but observational data have not been used to study the interplay between upper slope gas hydrates and warming ocean waters. Here we use (a) legacy seismic data that constrain upper slope gas hydrate distributions on the U.S. Beaufort Sea margin, (b) Alaskan North Slope borehole data and offshore thermal gradients determined from gas hydrate stability zone thickness to infer regional heat flow, and (c) 1088 direct measurements to characterize multidecadal intermediate ocean warming in the U.S. Beaufort Sea. Combining these data with a three-dimensional thermal model shows that the observed gas hydrate stability zone is too deep by 100 to 250 m. The disparity can be partially attributed to several processes, but the most important is the reequilibration (thinning) of gas hydrates in response to significant (~0.5°C at 2σ certainty) warming of intermediate ocean temperatures over 39 years in a depth range that brackets the upper slope extent of the gas hydrate stability zone. Even in the absence of additional ocean warming, 0.44 to 2.2 Gt of methane could be released from reequilibrating gas hydrates into the sediments underlying an area of ~5–7.5 × 103 km2 on the U.S. Beaufort Sea upper slope during the next century.
    Description: This work was supported by the U.S. Department of Energy (DOE), grant DE-FE0010180 to SMU and a USGS-DOE interagency agreement DE-FE0005806.
    Description: 2015-06-09
    Keywords: Gas hydrate ; Heat flow ; Seismic reflection ; Ocean temperature ; Modeling ; Beaufort Sea
    Repository Name: Woods Hole Open Access Server
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  • 10
    Publication Date: 2022-05-26
    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 Journal of Geophysical Research 112 (2007): B04106, doi:10.1029/2006JB004484.
    Description: The mechanical behavior of hydrate-bearing sediments subjected to large strains has relevance for the stability of the seafloor and submarine slopes, drilling and coring operations, and the analysis of certain small-strain properties of these sediments (for example, seismic velocities). This study reports on the results of comprehensive axial compression triaxial tests conducted at up to 1 MPa confining pressure on sand, crushed silt, precipitated silt, and clay specimens with closely controlled concentrations of synthetic hydrate. The results show that the stress-strain behavior of hydrate-bearing sediments is a complex function of particle size, confining pressure, and hydrate concentration. The mechanical properties of hydrate-bearing sediments at low hydrate concentration (probably 〈 40% of pore space) appear to be determined by stress-dependent soil stiffness and strength. At high hydrate concentrations (〉50% of pore space), the behavior becomes more independent of stress because the hydrates control both stiffness and strength and possibly the dilative tendency of sediments by effectively increasing interparticle coordination, cementing particles together, and filling the pore space. The cementation contribution to the shear strength of hydrate-bearing sediments decreases with increasing specific surface of soil minerals. The lower the effective confining stress, the greater the impact of hydrate formation on normalized strength.
    Description: This research was sponsored by a contract to C.R. and J.C.S. from the Joint Industry Project for Methane Hydrate, administered by ChevronTexaco with funding from award DE-FC26- 01NT41330 from DOE’s National Energy Technology Laboratory. The Goizueta Foundation at Georgia Tech also provided support for this work. The research was completed while C.R. was on assignment at and wholly supported by the National Science Foundation (NSF).
    Keywords: Gas hydrate ; Sediment strength ; Elasticity ; Mechanical behavior ; Stiffness
    Repository Name: Woods Hole Open Access Server
    Type: Article
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