Archie's saturation exponent for natural gas hydrate in coarse‐grained reservoirs

Author Posting. © American Geophysical Union, 2018. 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 123 (2018): 2069-2089, doi:10.1002/2017JB015138.Accurately quantifying the amount of naturally occurring gas hydrate in marine and permafrost environments is important for assessing its resource potential and understanding the role of gas hydrate in the global carbon cycle. Electrical resistivity well logs are often used to calculate gas hydrate saturations, Sh, using Archie's equation. Archie's equation, in turn, relies on an empirical saturation parameter, n. Though n = 1.9 has been measured for ice‐bearing sands and is widely used within the hydrate community, it is highly questionable if this n value is appropriate for hydrate‐bearing sands. In this work, we calibrate n for hydrate‐bearing sands from the Canadian permafrost gas hydrate research well, Mallik 5L‐38, by establishing an independent downhole Sh profile based on compressional‐wave velocity log data. Using the independently determined Sh profile and colocated electrical resistivity and bulk density logs, Archie's saturation equation is solved for n, and uncertainty is tracked throughout the iterative process. In addition to the Mallik 5L‐38 well, we also apply this method to two marine, coarse‐grained reservoirs from the northern Gulf of Mexico Gas Hydrate Joint Industry Project: Walker Ridge 313‐H and Green Canyon 955‐H. All locations yield similar results, each suggesting n ≈ 2.5 ± 0.5. Thus, for the coarse‐grained hydrate bearing (Sh > 0.4) of greatest interest as potential energy resources, we suggest that n = 2.5 ± 0.5 should be applied in Archie's equation for either marine or permafrost gas hydrate settings if independent estimates of n are not available.DOE Grant Number: DE‐FE0023919; Gas Hydrate Project of the U.S. Geological Survey's Coastal and Marine Geology Program2018-08-1

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

Methane hydrate formation in partially water-saturated Ottawa sand

This paper is not subject to U.S. copyright. The definitive version was published in American Mineralogist 89 (2004): 1202-1207.Bulk properties of gas hydrate-bearing sediment strongly depend on whether hydrate forms primarily in the pore fluid, becomes a load-bearing member of the sediment matrix, or cements sediment grains. Our compressional wave speed measurements through partially water-saturated, methane hydrate-bearing Ottawa sands suggest hydrate surrounds and cements sediment grains. The three Ottawa sand packs tested in the Gas Hydrate And Sediment Test Laboratory Instrument (GHASTLI) contain 38(1)% porosity, initially with distilled water saturating 58, 31, and 16% of that pore space, respectively. From the volume of methane gas produced during hydrate dissociation, we calculated the hydrate concentration in the pore space to be 70, 37, and 20% respectively. Based on these hydrate concentrations and our measured compressional wave speeds, we used a rock physics model to differentiate between potential pore-space hydrate distributions. Model results suggest methane hydrate cements unconsolidated sediment when forming in systems containing an abundant gas phase.This work was supported by the U.S. Geological Surveyʼs Coastal and Marine Geology and Eastern Region Gas Hydrate Programs, in addition to DOE contract DE-AI21-92MC29214

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

Xenon Hydrate as an Analog of Methane Hydrate in Geologic Systems Out of Thermodynamic Equilibrium

Methane hydrate occurs naturally under pressure and temperature conditions that are not straightforward to replicate experimentally. Xenon has emerged as an attractive laboratory alternative to methane for studying hydrate formation and dissociation in multiphase systems, given that it forms hydrates under milder conditions. However, building reliable analogies between the two hydrates requires systematic comparisons, which are currently lacking. We address this gap by developing a theoretical and computational model of gas hydrates under equilibrium and nonequilibrium conditions. We first compare equilibrium phase behaviors of the Xe·H₂O and CH₄·H₂O systems by calculating their isobaric phase diagram, and then study the nonequilibrium kinetics of interfacial hydrate growth using a phase field model. Our results show that Xe·H₂O is a good experimental analog to CH₄·H₂O, but there are key differences to consider. In particular, the aqueous solubility of xenon is altered by the presence of hydrate, similar to what is observed for methane; but xenon is consistently less soluble than methane. Xenon hydrate has a wider nonstoichiometry region, which could lead to a thicker hydrate layer at the gas‐liquid interface when grown under similar kinetic forcing conditions. For both systems, our numerical calculations reveal that hydrate nonstoichiometry coupled with hydrate formation dynamics leads to a compositional gradient across the hydrate layer, where the stoichiometric ratio increases from the gas‐facing side to the liquid‐facing side. Our analysis suggests that accurate composition measurements could be used to infer the kinetic history of hydrate formation in natural settings where gas is abundant

Xenon hydrate as an analog of methane hydrate in geologic systems out of thermodynamic equilibrium

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 Geochemistry Geophysics Geosystems 20(5), (2019):2462-2472, doi:10.1029/2019GC008250.Methane hydrate occurs naturally under pressure and temperature conditions that are not straightforward to replicate experimentally. Xenon has emerged as an attractive laboratory alternative to methane for studying hydrate formation and dissociation in multiphase systems, given that it forms hydrates under milder conditions. However, building reliable analogies between the two hydrates requires systematic comparisons, which are currently lacking. We address this gap by developing a theoretical and computational model of gas hydrates under equilibrium and nonequilibrium conditions. We first compare equilibrium phase behaviors of the Xe·H2O and CH4·H2O systems by calculating their isobaric phase diagram, and then study the nonequilibrium kinetics of interfacial hydrate growth using a phase field model. Our results show that Xe·H2O is a good experimental analog to CH4·H2O, but there are key differences to consider. In particular, the aqueous solubility of xenon is altered by the presence of hydrate, similar to what is observed for methane; but xenon is consistently less soluble than methane. Xenon hydrate has a wider nonstoichiometry region, which could lead to a thicker hydrate layer at the gas‐liquid interface when grown under similar kinetic forcing conditions. For both systems, our numerical calculations reveal that hydrate nonstoichiometry coupled with hydrate formation dynamics leads to a compositional gradient across the hydrate layer, where the stoichiometric ratio increases from the gas‐facing side to the liquid‐facing side. Our analysis suggests that accurate composition measurements could be used to infer the kinetic history of hydrate formation in natural settings where gas is abundant.This work was funded in part by the U.S. Department of Energy, DOE [awards DE‐FE0013999 and DE‐SC0018357 (to R. J.) and DOE Interagency Agreement DE‐FE0023495 (to W. F. W.)]. X. F. acknowledges support by the Miller Research Fellowship at the University of California Berkeley. W. F. W. acknowledges support from the U.S. Geological Survey's Gas Hydrate Project and the Survey's Coastal, Marine Hazards and Resources Program. L. C. F. acknowledges funding from the Spanish Ministry of Economy and Competitiveness (grants RYC‐2012‐11704 and CTM2014‐54312‐P). L. C. F. and R. J. acknowledge funding from the MIT International Science and Technology Initiatives, through a Seed Fund grant. The simulation data are available on the UC Berkeley Dash repository at https://doi.org/10.6078/D1G67B.2019-11-0

Hydrate morphology : physical properties of sands with patchy hydrate saturation

Author Posting. © American Geophysical Union, 2012. 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 117 (2012): B11205, doi:10.1029/2012JB009667.The physical properties of gas hydrate-bearing sediments depend on the volume fraction and spatial distribution of the hydrate phase. The host sediment grain size and the state of effective stress determine the hydrate morphology in sediments; this information can be used to significantly constrain estimates of the physical properties of hydrate-bearing sediments, including the coarse-grained sands subjected to high effective stress that are of interest as potential energy resources. Reported data and physical analyses suggest hydrate-bearing sands contain a heterogeneous, patchy hydrate distribution, whereby zones with 100% pore-space hydrate saturation are embedded in hydrate-free sand. Accounting for patchy rather than homogeneous hydrate distribution yields more tightly constrained estimates of physical properties in hydrate-bearing sands and captures observed physical-property dependencies on hydrate saturation. For example, numerical modeling results of sands with patchy saturation agree with experimental observation, showing a transition in stiffness starting near the series bound at low hydrate saturations but moving toward the parallel bound at high hydrate saturations. The hydrate-patch size itself impacts the physical properties of hydrate-bearing sediments; for example, at constant hydrate saturation, we find that conductivity (electrical, hydraulic and thermal) increases as the number of hydrate-saturated patches increases. This increase reflects the larger number of conductive flow paths that exist in specimens with many small hydrate-saturated patches in comparison to specimens in which a few large hydrate saturated patches can block flow over a significant cross-section of the specimen.Research support provided to Georgia Tech by the Department of Energy/JIP project for methane hydrate, administered by Chevron. Additional funding provided by the Goiuzeta Foundation, the Gas Hydrate Project of the U.S. Geological Survey’s Coastal and Marine Geology Program, and the Assistant Secretary for Fossil Energy, Office of Oil and Natural Gas, Gas Hydrate Program through the National Energy Technology Laboratory of the U.S. Department of Energy under contract DE-AC02-05CH11231.2013-05-1

Impact of pore fluid chemistry on fine‐grained sediment fabric and compressibility

Author Posting. © American Geophysical Union, 2018. 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 123 (2018): 5495-5514, doi:10.1029/2018JB015872.Fines, defined here as grains or particles, less than 75 μm in diameter, exist nearly ubiquitously in natural sediment, even those classified as coarse. Macroscopic sediment properties, such as compressibility, which relates applied effective stress to the resulting sediment deformation, depend on the fabric of fines. Unlike coarse grains, fines have sizes and masses small enough to be more strongly influenced by electrical interparticle forces than by gravity. These electrical forces acting through pore fluids are influenced by pore fluid chemistry changes. Macroscopic property dependence on pore fluid chemistry must be accounted for in sediment studies involving subsurface flow and sediment stability analyses, as well as in engineered flow situations such as groundwater pollutant remediation, hydrocarbon migration, or other energy resource extraction applications. This study demonstrates how the liquid limit‐based electrical sensitivity index can be used to predict sediment compressibility changes due to pore fluid chemistry changes. Laboratory tests of electrical sensitivity, sedimentation, and compressibility illustrate mechanisms linking microscale and macroscale processes for selected pure, end‐member fines. A specific application considered here is methane extraction via depressurization of gas hydrate‐bearing sediment, which causes a dramatic pore water salinity drop concurrent with sediment being compressed by the imposed effective stress increase.DOI U.S. Geological Survey (USGS); U.S. Department of Energy (DOE) Grant Numbers: DE‐FE00‐28966, DE‐FE00‐261662019-01-1

Hydro-bio-geomechanical properties of hydrate-bearing sediments from Nankai Trough

This paper is not subject to U.S. copyright. The definitive version was published in Marine and Petroleum Geology 66 (2015): 434-450, doi:10.1016/j.marpetgeo.2015.02.033.Natural hydrate-bearing sediments from the Nankai Trough, offshore Japan, were studied using the Pressure Core Characterization Tools (PCCTs) to obtain geomechanical, hydrological, electrical, and biological properties under in situ pressure, temperature, and restored effective stress conditions. Measurement results, combined with index-property data and analytical physics-based models, provide unique insight into hydrate-bearing sediments in situ. Tested cores contain some silty-sands, but are predominantly sandy- and clayey-silts. Hydrate saturations Sh range from 0.15 to 0.74, with significant concentrations in the silty-sands. Wave velocity and flexible-wall permeameter measurements on never-depressurized pressure-core sediments suggest hydrates in the coarser-grained zones, the silty-sands where Sh exceeds 0.4, contribute to soil-skeletal stability and are load-bearing. In the sandy- and clayey-silts, where Sh < 0.4, the state of effective stress and stress history are significant factors determining sediment stiffness. Controlled depressurization tests show that hydrate dissociation occurs too quickly to maintain thermodynamic equilibrium, and pressure–temperature conditions track the hydrate stability boundary in pure-water, rather than that in seawater, in spite of both the in situ pore water and the water used to maintain specimen pore pressure prior to dissociation being saline. Hydrate dissociation accompanied with fines migration caused up to 2.4% vertical strain contraction. The first-ever direct shear measurements on never-depressurized pressure-core specimens show hydrate-bearing sediments have higher sediment strength and peak friction angle than post-dissociation sediments, but the residual friction angle remains the same in both cases. Permeability measurements made before and after hydrate dissociation demonstrate that water permeability increases after dissociation, but the gain is limited by the transition from hydrate saturation before dissociation to gas saturation after dissociation. In a proof-of-concept study, sediment microbial communities were successfully extracted and stored under high-pressure, anoxic conditions. Depressurized samples of these extractions were incubated in air, where microbes exhibited temperature-dependent growth rates.PCCTs were developed with funding to Georgia Tech from the DOE/Chevron Joint Industry Project (JIP), with additional funds from the Joint Oceanographic Institutions, Inc. The JIP also funded the Georgia Tech participation in Sapporo. USGS participation in Sapporo was funded through a technical assistance agreement with Chevron (TAA-12-2135/CW928359). Some USGS developments on the IPTC were funded under Interagency Agreement DE-FE0002911 with the U.S. Department of Energy, with additional support from the U.S. Geological Survey. Core acquisition and Japanese participation in this study was supported by the Research Consortium for Methane Hydrate Resources in Japan (MH21 Research Consortium) to carry out Japan's Methane Hydrate R&D Program conducted by the Ministry of Economy, Trade and Industry (METI)