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  • 1
    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 Geochemistry Geophysics Geosystems 20(5), (2019):2462-2472, doi:10.1029/2019GC008250.
    Description: 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.
    Description: 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.
    Description: 2019-11-06
    Keywords: Methane hydrates ; Xenon hydrates ; Phase behavior ; Growth kinetics ; Nonstoichiometry
    Repository Name: Woods Hole Open Access Server
    Type: Article
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  • 2
    Publication Date: 2022-10-27
    Description: © 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.
    Description: 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.
    Description: 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.
    Keywords: Gas and hydrate systems ; Oceanography: biological and chemical ; Carbon cycling ; Biogeochemical cycles, processes, and modeling
    Repository Name: Woods Hole Open Access Server
    Type: Article
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  • 3
  • 4
    Publication Date: 2020-03-23
    Description: Water infiltration and unsaturated flow through heterogeneous soil control the distribution of soil moisture in the vadose zone and the dynamics of groundwater recharge, providing the link between climate, biogeochemical soil processes and vegetation dynamics. Infiltration into dry soil is hydrodynamically unstable, leading to preferential flow through narrow wet regions (fingers). In this paper we use numerical simulation to study the interplay between fingering instabilities and soil heterogeneity during water infiltration. We consider soil with heterogeneous intrinsic permeability. Permeabilities are random, with point Gaussian statistics, and vary smoothly in space due to spatial correlation. The key research question is whether the presence of moderate or strong heterogeneity overwhelms the fingering instability, recovering the simple stable displacement patterns predicted by most simplified model of infiltration currently used in hydrological models from the Darcy to the basin scales. We perform detailed simulations of constant-rate infiltration into soils with isotropic and anisotropic intrinsic permeability fields. Our results demonstrate that soil heterogeneity does not suppress fingering instabilities, but it rather enhances its effect of preferential flow and channeling. Fingering patterns strongly depend on soil structure, in particular the correlation length and anisotropy of the permeability field. While the finger size and flow dynamics are only slightly controlled by correlation length in isotropic fields, layering leads to significant finger meandering and bulging, changing arrival times and wetting efficiencies. Fingering and soil heterogeneity need to be considered when upscaling the constitutive relationships of multiphase flow in porous media (relative permeability and water retention curve) from the finger to field and basin scales. While relative permeabilities remain unchanged upon upscaling for stable displacements, the inefficient wetting due to fingering leads to relative permeabilities at the field scale that are significantly different from those at the Darcy scale. These effective relative permeability functions also depend, although less strongly, on heterogeneity and soil structure.
    Electronic ISSN: 2073-4441
    Topics: Energy, Environment Protection, Nuclear Power Engineering
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  • 5
    Publication Date: 2020-03-24
    Description: Modeling water flow and solute transport in the vadose zone is essential to understanding the fate of soil pollutants and their travel times towards groundwater bodies. It also helps design better irrigation strategies to control solute concentrations and fluxes in semiarid and arid regions. Heterogeneity, soil texture and wetting front instabilities determine the flow patterns and solute transport mechanisms in dry soils. When water is already present in the soil, the flow of an infiltration pulse depends on the spatial distribution of soil water and on its mobility. We present numerical simulations of passive solute transport during unstable infiltration of water into sandy soils that are prone to wetting front instability. We study the impact of the initial soil state, in terms of spatial distribution of water content, on the infiltration of a solute-rich water pulse. We generate random fields of initial moisture content with spatial structure, through multigaussian fields with prescribed correlation lengths. We characterize the patterns of water flow and solute transport, as well as the mass fluxes through the soil column. Our results indicate a strong interplay between preferential flow and channeling due to fingering and the spatial distribution of soil water at the beginning of infiltration. Fingering and initial water saturation fields have a strong effect on solute diffusion and dilution into the ambient water during infiltration, suggesting an effective separation between mobile and inmobile transport domains that are controlled by the preferential flow paths due to fingering.
    Electronic ISSN: 2073-4441
    Topics: Energy, Environment Protection, Nuclear Power Engineering
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  • 6
    Publication Date: 2018-04-02
    Print ISSN: 0031-9007
    Electronic ISSN: 1079-7114
    Topics: Physics
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  • 7
    Publication Date: 2018-08-08
    Electronic ISSN: 2469-990X
    Topics: Physics
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  • 8
    Publication Date: 2017-10-09
    Electronic ISSN: 2469-990X
    Topics: Physics
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  • 9
    Publication Date: 2016-09-20
    Print ISSN: 2470-0045
    Electronic ISSN: 2470-0053
    Topics: Physics
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  • 10
    Publication Date: 2019-05-06
    Description: 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. ©2019. American Geophysical Union. All Rights Reserved.
    Electronic ISSN: 1525-2027
    Topics: Chemistry and Pharmacology , Geosciences , Physics
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