Timescales and processes of methane hydrate formation and breakdown, with application to geologic systems

© 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.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.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

Thermal-modelling of extensional tectonics

Thesis (M.S.)--Massachusetts Institute of Technology, Dept. of Earth, Atmospheric and Planetary Sciences, 1986.Microfiche copy available in Archives and Science.Bibliography: leaves 81-82.by Carolyn Denise Ruppel.M.S

Thermal structure, compensation mechanisms, and tectonics of actively-deforming continents : Baikal Rift Zone and large-scale overthrust and extensional terrains

Thesis (Ph. D.)--Massachusetts Institute of Technology, Dept. of Earth, Atmospheric, and Planetary Sciences, 1992.Includes bibliographical references (p. 277-292).by Carolyn Denise Ruppel.Ph.D

Scientific results from Gulf of Mexico Gas Hydrates Joint Industry Project Leg 1 drilling : introduction and overview

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.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.Supported by the U.S. Department of Energy, under award DE-FC26-01NT4133

Neural net detection of seismic features related to gas hydrates and free gas accumulations on the northern U.S. Atlantic margin

Bottom-simulating reflections (BSRs) that sometimes mark the base of the gas hydrate stability zone in marine sediments are often identified based on the reverse polarity reflections that cut across stratigraphic layering in seismic amplitude data. On the northern U.S. Atlantic margin (USAM) between Cape Hatteras and Hudson Canyon, legacy seismic data have revealed pronounced BSRs south of the deepwater extension of Hudson Canyon and more subtle ones from offshore Delaware south to Cape Hatteras, where the reflections sometimes follow stratigraphic layering. Using high-resolution seismic data acquired during the 2018 Mid-Atlantic Resource Imaging Experiment and a supervised neural net, we identify seismic features associated with gas hydrates and/or the top of gas between Hudson Canyon and Cape Hatteras. Using seismic attributes especially sensitive to the presence of gas, we train a neural network algorithm on seismic data from an area with strong BSRs and then apply the model to the rest of the data set. The results indicate that gas hydrate and/or shallow free gas are significantly more widespread on the northern part of the USAM than previously known. Seismic indicators of gas extend landward from the 2000 m isobath to the upper continental slope in sectors with (offshore Virginia) and, to a lesser extent, without (offshore New Jersey) pervasive upper slope methane seeps. Higher sand content and intermediate sediment thickness, factors related to the container size and gas charge in a petroleum systems framework, are associated with more robust gas indicators

Hydrate formation on marine seep bubbles and the implications for water column methane dissolution

© The Author(s), 2021. This article is distributed under the terms of the Creative Commons Attribution License. The definitive version was published in Fu, X., Waite, W. F., & Ruppel, C. D. Hydrate formation on marine seep bubbles and the implications for water column methane dissolution. Journal of Geophysical Research: Oceans, 126(9), (2021): e2021JC017363, https://doi.org/10.1029/2021JC017363.Methane released from seafloor seeps contributes to a number of benthic, water column, and atmospheric processes. At seafloor seeps within the methane hydrate stability zone, crystalline gas hydrate shells can form on methane bubbles while the bubbles are still in contact with the seafloor or as the bubbles begin ascending through the water column. These shells reduce methane dissolution rates, allowing hydrate-coated bubbles to deliver methane to shallower depths in the water column than hydrate-free bubbles. Here, we analyze seafloor videos from six deepwater seep sites associated with a diverse range of bubble-release processes involving hydrate formation. Bubbles that grow rapidly are often hydrate-free when released from the seafloor. As bubble growth slows and seafloor residence time increases, a hydrate coating can form on the bubble's gas-water interface, fully coating most bubbles within ∼10 s of the onset of hydrate formation at the seafloor. This finding agrees with water-column observations that most bubbles become hydrate-coated after their initial ∼150 cm of rise, which takes about 10 s. Whether a bubble is coated or not at the seafloor affects how much methane a bubble contains and how quickly that methane dissolves during the bubble's rise through the water column. A simplified model shows that, after rising 150 cm above the seafloor, a bubble that grew a hydrate shell before releasing from the seafloor will have ∼5% more methane than a bubble of initial equal volume that did not grow a hydrate shell after it traveled to the same height.X. Fu acknowledges support from the Miller Fellowship during her time at U.C. Berkeley. W. Waite and C. Ruppel are supported by the United States Geological Survey (USGS) Coastal/Marine Hazards and Resources Program and the Energy Resources Program, with research conducted under USGS-Department of Energy interagency agreements DE-FE0023495 and 89243320SFE000013

Minimum distribution of subsea ice-bearing permafrost on the U.S. Beaufort Sea continental shelf

This paper is not subject to U.S. copyright. The definitive version was published in Geophysical Research Letters 39 (2012): L15501, doi:10.1029/2012GL052222.Starting in Late Pleistocene time (~19 ka), sea level rise inundated coastal zones worldwide. On some parts of the present-day circum-Arctic continental shelf, this led to flooding and thawing of formerly subaerial permafrost and probable dissociation of associated gas hydrates. Relict permafrost has never been systematically mapped along the 700-km-long U.S. Beaufort Sea continental shelf and is often assumed to extend to ~120 m water depth, the approximate amount of sea level rise since the Late Pleistocene. Here, 5,000 km of multichannel seismic (MCS) data acquired between 1977 and 1992 were examined for high-velocity (>2.3 km s−1) refractions consistent with ice-bearing, coarse-grained sediments. Permafrost refractions were identified along <5% of the tracklines at depths of ~5 to 470 m below the seafloor. The resulting map reveals the minimum extent of subsea ice-bearing permafrost, which does not extend seaward of 30 km offshore or beyond the 20 m isobath.This research was sponsored by DOE-USGS Interagency Agreement DE-FE0002911. L.B. was supported by a DOE NETL/NRC Methane Hydrate Fellowship under DE-FC26-05NT42248

Volume change associated with formation and dissociation of hydrate in sediment

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.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.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

Introduction to special issue on gas hydrate in porous media: linking laboratory and field-scale phenomena

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.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.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

Surface methane concentrations along the mid-Atlantic bight driven by aerobic subsurface production rather than seafloor gas seeps.

Author Posting. © American Geophysical Union, 2020. 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: Oceans 125(5), (2020): e2019JC015989, doi:10.1029/2019JC015989.Relatively minor amounts of methane, a potent greenhouse gas, are currently emitted from the oceans to the atmosphere, but such methane emissions have been hypothesized to increase as oceans warm. Here, we investigate the source, distribution, and fate of methane released from the upper continental slope of the U.S. Mid‐Atlantic Bight, where hundreds of gas seeps have been discovered between the shelf break and ~1,600 m water depth. Using physical, chemical, and isotopic analyses, we identify two main sources of methane in the water column: seafloor gas seeps and in situ aerobic methanogenesis which primarily occurs at 100–200 m depth in the water column. Stable isotopic analyses reveal that water samples collected at all depths were significantly impacted by aerobic methane oxidation, the dominant methane sink in this region, with the average fraction of methane oxidized being 50%. Due to methane oxidation in the deeper water column, below 200 m depth, surface concentrations of methane are influenced more by methane sources found near the surface (0–10 m depth) and in the subsurface (10–200 m depth), rather than seafloor emissions at greater depths.This research was supported by DOE Grant (DE‐FE0028980) to J. K. and by DOE‐USGS Interagency Agreement DE‐FE0026195.2020-10-0