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At least 811 records · Page 45

Low-Field Nuclear Magnetic Resonance Characterization of Carbonate and Sandstone Reservoirs From Rock Spring Uplift of Wyoming

Laboratory measurements including gas (N 2 ) porosity and permeability, time-domain nuclear magnetic resonance, thin section, and scanning electron microscopy analysis were conducted to obtain petrographical and petrophysical descriptions of the Weber Sandstone and Madison Limestone at the Rock Spring Uplift, a potential carbon dioxide storage site in Southwestern Wyoming. The relationships between pore structures, such as pore geometry, pore-size distribution, pore network, and porosity/permeability are investigated. First, using thin sections combined with scanning electron microscopy for pore structures description, all samples are described in detail from the geological, petrographysical, and diagenetic viewpoint. Results show that within the Madison Limestone, pore types include intercrystalline, vuggy, moldic, or mixed (combination of all other pore types). Both moldic and vuggy pore types are associated with samples of high porosity and permeability. Nuclear magnetic resonance relaxation time distributions show either bimodal or multimodal distributions. Large relaxation time components are associated with samples with large pores, whereas small components are dominated by small pores. The T 2 geometric mean correlates well with gas permeability. Additionally, short-time diffusion coefficients (D) were measured by pulsed field gradient method using a series of gradient strengths. We found that diffusion coefficient distributions correlate with the corresponding T 2 distributions for macropores. By comparing the dominant peak position of T 2 distributions and their corresponding diffusion coefficient distributions, we predicted the surface relaxivity of different rock types. We found that surface relaxivities of Weber Sandstone samples can be well predicted, while for Madison Limestone samples, surface relaxivities are overestimated due to diffusive pore coupling effect.

58 GEOSCIENCES↗

The Role of Mineral Composition on the Frictional and Stability Properties of Powdered Reservoir Rocks

The growing hazard of induced seismicity driven by the boom in unconventional resources exploitation is strongly linked to fault activation. We perform laboratory measurements on simulated fault gouges comprising powdered reservoir rocks from major oil and gas production sites in China, to probe the control of mineral composition on fault friction and stability responses during reservoir stimulation. Double direct shear experiments were conducted on gouges with phyllosilicate content ranging from 0 to 30 wt.% and grain sizes <150 μm, at constant normal stresses of 10–40 MPa and conditions of room temperature and water saturation. The velocity step and slide-hold-slide sequences were employed to evaluate frictional stability and static healing, respectively. Results indicate that the mineralogy of the gouges exhibit a strong control on the frictional strength, stability, and healing. Phyllosilicate-rich samples show lower frictional strength μ and higher values of (a – b ), promoting stable sliding. For the gouges studied, the frictional strength decreases monotonically with increasing phyllosilicate content, and a transition from velocity weakening to velocity strengthening behavior is evident at 15 wt.% phyllosilicates. Intermediate healing rates are common in gouges with higher content of phyllosilicates, with high healing rates predominantly in phyllosilicate-poor gouges. As an indispensable component in reservoir rocks, the carbonates are shown to affect both the frictional stability and healing response. These findings can have important implications for understanding the effects of mineralogy on fault behavior and induced seismic potential in geoengineering activities, particularly in reservoirs in China.

58 GEOSCIENCES↗

Deformation Precursors to Catastrophic Failure in Rocks

Forecasting the timing of catastrophic failure, such as crustal earthquakes, has been a central concern for centuries. Such forecasting requires identifying signals that evolve or accelerate in the precursory phase leading to failure, and the subset of signals that may be detected in the crust. We develop machine learning models to predict the proximity of catastrophic failure in synchrotron X-ray tomography triaxial compression experiments on rocks using characteristics of evolving fracture networks. We then examine the characteristics that most strongly influence the model results, and thus may be considered the best predictors of the proximity of macroscopic failure. Finally, the resulting suite of predictive parameters underscores the importance of dilation in the precursory phase leading to catastrophic failure. The results indicate that the evolution of the strain energy density field may provide more robust predictions of the proximity of failure than other existing metrics of rock deformation.

58 GEOSCIENCES↗

Unusual Seismic Signals in the Sevier Desert, Utah Possibly Related to the Black Rock Volcanic Field

Abstract On September 12, 2018 and April 14, 2019 shallow (<2.5 km from the surface, <1 km relative to sea level) earthquakes ( M w 4.0 and 4.1, respectively) struck a relatively aseismic area in south‐central Utah, within the Black Rock Desert volcanic field. Seismic waveforms are dominated by long‐period energy, no clear direct S‐wave arrivals, and signal durations of ∼100 s. Using co‐seismic interferograms, we detect clear and distinguishable surface deformation confirming the shallowness of the two mainshocks, while full moment tensor solutions rule out an isotropic source, such as an explosion or collapse. For the April 2019 sequence, we build an earthquake catalog using a dense temporary geophone array. The enhanced earthquake catalog shows a rapidly decaying aftershock sequence, with 85% of aftershocks occurring during the first three hours. Combining these observations, we argue that these earthquake sequences are related to the Black Rock Desert volcanic field.

Mesimeri, Maria↗

Electrical Conductivity of Clayey Rocks and Soils: A Non-Linear Model

It is well-accepted that Archie's law is only applicable to “clean” rocks and soils but fails in “dirty” ones where clay minerals possess an additional component of surface conductivity. Although several models, for example, Waxman-Smits model, were presented to account for this phenomenon, surface conductivity is always inappropriately treated as constant, which actually only holds at high salinities. The essential non-linear characteristic differing over fluid salinities has not been physically or mathematically explained well in those models. Here, we scrutinize the conduction mechanism of clayey rocks and soils and ascribe this non-linear feature to (a) variation of the electrical double layer and (b) the intrinsic clay-and-water conduction pattern. With effective medium theory, we develop an easy-to-use non-linear model that both reflects electrochemical theories and explains the measurement data well. Our model can be used to produce more accurate results for laboratory- and field-scale petrophysical parameter evaluations than the previous models.

58 GEOSCIENCES↗

From Fluid Flow to Coupled Processes in Fractured Rock: Recent Advances and New Frontiers

Abstract Quantitative predictions of natural and induced phenomena in fractured rock is one of the great challenges in the Earth and Energy Sciences with far‐reaching economic and environmental impacts. Fractures occupy a very small volume of a subsurface formation but often dominate fluid flow, solute transport and mechanical deformation behavior. They play a central role in CO 2 sequestration, nuclear waste disposal, hydrogen storage, geothermal energy production, nuclear nonproliferation, and hydrocarbon extraction. These applications require predictions of fracture‐dependent quantities of interest such as CO 2 leakage rate, hydrocarbon production, radionuclide plume migration, and seismicity; to be useful, these predictions must account for uncertainty inherent in subsurface systems. Here, we review recent advances in fractured rock research covering field‐ and laboratory‐scale experimentation, numerical simulations, and uncertainty quantification. We discuss how these have greatly improved the fundamental understanding of fractures and one's ability to predict flow and transport in fractured systems. Dedicated field sites provide quantitative measurements of fracture flow that can be used to identify dominant coupled processes and to validate models. Laboratory‐scale experiments fill critical knowledge gaps by providing direct observations and measurements of fracture geometry and flow under controlled conditions that cannot be obtained in the field. Physics‐based simulation of flow and transport provide a bridge in understanding between controlled simple laboratory experiments and the massively complex field‐scale fracture systems. Finally, we review the use of machine learning‐based emulators to rapidly investigate different fracture property scenarios and accelerate physics‐based models by orders of magnitude to enable uncertainty quantification and near real‐time analysis.

58 GEOSCIENCES↗

Using Radiogenic Noble Gas Nuclides to Identify and Characterize Rock Fracturing

Abstract Fracture‐released radiogenic noble gas nuclides are used to identify locations and constrain the volume of new fracture creation during subsurface detonations. Real‐time, in situ noble gases and reactive gases were monitored using a field‐deployed mass spectrometer and automated sampling system in a multilevel borehole array. Released gases were measured after two different detonations having distinct energy, pressure, and gas volume characteristics. Explosive‐derived gases (N 2 O, CO 2 ) and excess radiogenic 4 He and 40 Ar above atmospheric background are used to identify locations of gas transport and new fracture creation after each detonation. Fracture‐released radiogenic 4 He is used to constrain the volume of newly created fractures with a model of helium release from fracturing. Explosive by‐product gas was observed in multiple locations both near and distal to the shot locations for both detonations. Radiogenic 4 He and 40 Ar release from rock damage was observed in locations near the detonation after the second, more powerful detonation. Observed 4 He response is consistent with a model of diffusive release from newly created fractures. Volume of new fractures estimated from the 4 He release ranges from 1 to 5 m 2 with apertures ranging from 0.1 to 1 m. Our results provide evidence that radiogenic noble gases released during fracture creation can be identified at the field scale in real time and used to identify timing and location of fracture creation during deformation events. This technique could be useful in subsurface science and engineering problems where the location and amount of newly created rock fracturing is of interest including fault rupture, mine safety, subsurface detonation monitoring and reservoir stimulation.

58 GEOSCIENCES↗

Stabilization of high-performance rock-salt LiMnSbTe3 thermoelectrics with embedded van der Waals-like gaps

Rock-salt-structured compounds like lead chalcogenides are promising thermoelectrics, as their high symmetry, strong anharmonicity, and favorable phase behavior collectively lead to high performance by enabling large power factors and ultralow thermal conductivity. Here, we report LiMnSbTe 3 , a new rock-salt semiconductor stabilized through targeted chemical design by combining hexagonal MnTe with cubic LiSbTe 2 . Embedded in the highsymmetry matrix, van der Waals-like gaps form due to Sb 2 Te 3 nanoscale segregation, which acts as effective phonon-scattering centers, leading to a low lattice thermal conductivity of 0.37Wm- 1 K -1 at 873 K with alloy scattering from disordered cations. The ordered local structure of Sb2Te 3 -type vdW-like gaps and the cross-gap interaction facilitate the carrier transport. Aided by energyconverged valence bands and a paramagnon drag effect, high Seebeck coefficients and enhanced power factor can be achieved, leading to a high ZT of 1.2 at 873 K. Furthermore, introducing Mn deficiency increases ZT to 1.5, highlighting the potential for higher performance through optimized doping or alloying. A segmented single-leg thermoelectric module achieves an output power density of 0.52 Wcm -2 and an efficiency of 8.7% under ΔT of 478 K, further demonstrating its promising thermoelectric applications.

42 ENGINEERING↗

Cross-Scale Molecular Analysis of Chemical Heterogeneity in Shale Rocks

The organic and mineralogical heterogeneity in shale at micrometer and nanometer spatial scales contributes to the quality of gas reserves, gas flow mechanisms and gas production. Here, we demonstrate two molecular imaging approaches based on infrared spectroscopy to obtain mineral and kerogen information at these mesoscale spatial resolutions in large-sized shale rock samples. The first method is a modified microscopic attenuated total reflectance measurement that utilizes a large germanium hemisphere combined with a focal plane array detector to rapidly capture chemical images of shale rock surfaces spanning hundreds of micrometers with micrometer spatial resolution. The second method, synchrotron infrared nano-spectroscopy, utilizes a metallic atomic force microscope tip to obtain chemical images of micrometer dimensions but with nanometer spatial resolution. This chemically "deconvoluted" imaging at the nano-pore scale is then used to build a machine learning model to generate a molecular distribution map across scales with a spatial span of 1000 times, which enables high-throughput geochemical characterization in greater details across the nano-pore and micro-grain scales and allows us to identify co-localization of mineral phases with chemically distinct organics and even with gas phase sorbents. Finally, this characterization is fundamental to understand mineral and organic compositions affecting the behavior of shales.

04 OIL SHALES AND TAR SANDS↗

Enhanced terrestrial Fe(II) mobilization identified through a novel mechanism of microbially driven cave formation in Fe(III)-rich rocks

Most cave formation requires mass separation from a host rock in a process that operates outward from permeable pathways to create the cave void. Given the poor solubility of Fe(III) phases, such processes are insufficient to account for the significant iron formation caves (IFCs) seen in Brazilian banded iron formations (BIF) and associated rock. Here in this study we demonstrate that microbially-mediated reductive Fe(III) dissolution is solubilizing the poorly soluble Fe(III) phases to soluble Fe(II) in the anoxic zone behind cave walls. The resultant Fe(III)-depleted material (termed sub muros) is unable to maintain the structural integrity of the walls and repeated rounds of wall collapse lead to formation of the cave void in an active, measurable process. This mechanism may move significant quantities of Fe(II) into ground water and may help to explain the mechanism of BIF dissolution and REE enrichment in the generation of canga. The role of Fe(III) reducing microorganism and mass separation behind the walls (outward-in, rather than inward-out) is not only a novel mechanism of speleogenesis, but it also may identify a previously overlooked source of continental Fe that may have contributed to Archaean BIF formation.

54 ENVIRONMENTAL SCIENCES↗

The environmental controls on efficiency of enhanced rock weathering in soils

Abstract Enhanced rock weathering (ERW) in soils is a promising carbon removal technology, but the realistically achievable efficiency, controlled primarily by in situ weathering rates of the applied rocks, is highly uncertain. Here we explored the impacts of coupled biogeochemical and transport processes and a set of primary environmental and operational controls, using forsterite as a proxy mineral in soils and a multiphase multi-component reactive transport model considering microbe-mediated reactions. For a onetime forsterite application of ~ 16 kg/m 2 , complete weathering within five years can be achieved, giving an equivalent carbon removal rate of ~ 2.3 kgCO 2 /m 2 /yr. However, the rate is highly variable based on site-specific conditions. We showed that the in situ weathering rate can be enhanced by conditions and operations that maintain high CO 2 availability via effective transport of atmospheric CO 2 (e.g. in well-drained soils) and/or sufficient biogenic CO 2 supply (e.g. stimulated plant–microbe processes). Our results further highlight that the effect of increasing surface area on weathering rate can be significant—so that the energy penalty of reducing the grain size may be justified—only when CO 2 supply is nonlimiting. Therefore, for ERW practices to be effective, siting and engineering design (e.g. optimal grain size) need to be co-optimized.

54 ENVIRONMENTAL SCIENCES↗

Li–Mn–O Li-rich cation disordered rock-salt cathode materials do not undergo reversible oxygen redox during cycling

An in-depth study of “Li 4 Mn 2 O 5 ”, a nanocomposite of Li 2 O and Li 4-x Mn 2 O 5 with a disordered rock salt structure (LMO), was conducted to determine the origins of the observed anomalously high charge and discharge capacity in lithium cells, which can exceed 350 mA h g -1 . Using soft and hard X-ray absorption spectroscopy (XAS), mapping of resonant inelastic X-ray scattering (mRIXS), and X-ray Raman spectroscopy (XRS), it was determined that electrochemical decomposition of Li 2 O upon charge and reduction of Mn to below 3+ during discharge is responsible for the capacities that are observed, with no evidence of contributions from reversible oxygen redox. Here, the over-reduction is exacerbated when charging limits of 4.5–4.8 V are used due to side reactions between electrolytic solution and the highly oxidized active material. These side reactions result in dissolution of Mn at room temperature and release of oxygen and other gases during initial cycles, which, in turn, cause rapid capacity fading. This is accompanied by evolution of the voltage profile upon cycling towards one that resembles that of manganese oxide spinels. The cycling behavior can be improved somewhat by reducing the upper voltage limit, although this results in a diminishment of the discharge capacities below 200 mA h g -1 . By adding various amounts of spinel LiMn 2 O 4 during synthesis, it was possible to produce LMOs with rock salt structures having significantly improved cycling behavior but still having capacities in excess of 250 mA h g -1 . An optimized modified material also exhibits better rate capability and much less gas evolution during initial cycles than the unmodified LMO. Interestingly, as-made modified materials generally exhibited lower than expected average Mn oxidation states attributable to oxygen loss during the synthesis process, as well as higher capacities than expected based on their manganese contents. The oxygen loss during processing may reduce the activity of the remaining oxygen and account for the lower reactivity of the spinel-modified material.

25 ENERGY STORAGE↗

Understanding the Mn dissolution mechanism in rock salt-type Li 4 Mn 2 O 5 cathodes

For the first time, a detailed exploration of Mn dissolution in disordered rock salt (DRX) Li 4 Mn 2 O 5 is presented. Herein, we apply a suite of synchrotron and lab scale X-ray techniques to both the cathode and the separator harvested from pristine, charged, or cycled lithium half-cells containing the disordered rock salt (DRX) material Li 4 Mn 2 O 5 , in order to understand Mn dissolution processes throughout charging and discharging. Previous research has hypothesized two concurrent effects that may drive Mn dissolution in cells during cycling: acid-induced disproportionation of Jahn–Teller active Mn 3+ and structural rearrangement of the cathode lattice. Through depth probing of the Mn oxidation state in both the cathode and separator via soft X-ray absorption spectroscopy (XAS), hard XAS, and X-ray photoelectron spectroscopy (XPS) in progressive states-of-charge, as well as extended X-ray absorption fine structure (EXAFS) analysis of the local Mn environment, the primary driving force of Mn dissolution is determined to be high-voltage structural rearrangement above 4.2 V. Mn dissolution is, additionally, a main source of capacity fade in Li 4 Mn 2 O 5 DRX cells, which retain only 59% capacity after 20 cycles.

Theibault, Monica↗

Half-metallicity and stability of the rock salt BaC and SrC (111) surfaces: A density functional study

The electronic structure and magnetic properties of relaxed (111) surfaces of the alkaline-earth monocarbides BaC and SrC in the stable rock salt structure, are calculated on the basis of first principle density functional theory within the framework of self-consistent field plane wave pseudo-potential method, using the generalized gradient approximation for the exchange-correlation functional. The results of this study reveal that the C-terminated (111) surfaces retain the bulk half-metallic property in both BaC and SrC. The half-metallicity of the C-terminated BaC surface is found to be more robust compared to the bulk BaC due to the larger half-metallic energy gap. In contrast, the half-metallic energy gap of the C-terminated SrC surface is found to be smaller than that of the bulk. The Ba-terminated surface of BaC and the Sr-terminated surface of SrC, however, lose their bulk half-metallicity due to the formation of surface states in the majority spin band gap. The calculations also show that the atomic magnetic moments at the half-metallic C-terminated surfaces in both BaC and SrC increase considerably with respect to the corresponding bulk values, which is explained in terms of an increase in the number of unpaired 2p electrons of the carbon atom at the surface. We also discuss the stability of the surfaces via the calculated bulk formation energies. The bulk formation energies for both BaC and SrC in the rock salt structure are found to be positive, which indicate that the surfaces are not stable at normal pressure and temperature conditions, and non-equilibrium growth techniques may be required for the realization of BaC and SrC thin films.

74 ATOMIC AND MOLECULAR PHYSICS↗

Estimation of anisotropy parameters in organic-rich shale: Rock physics forward modeling approach

Anisotropy analysis becomes an important step in processing and interpretation of seismic data. One of the most important things in anisotropy analysis is anisotropy parameter estimation which can be estimated using well data, core data or seismic data. In seismic data, anisotropy parameter calculation is generally based on velocity moveout analysis. However, the accuracy depends on data quality, available offset, and velocity moveout picking. Anisotropy estimation using seismic data is needed to obtain wide coverage of particular layer anisotropy. In anisotropic reservoir, analysis of anisotropy parameters also helps us to better understand the reservoir characteristics. Anisotropy parameters, especially ε, are related to rock property and lithology determination. Current research aims to estimate anisotropy parameter from seismic data and integrate well data with case study in potential shale gas reservoir. Due to complexity in organic-rich shale reservoir, extensive study from different disciplines is needed to understand the reservoir. Shale itself has intrinsic anisotropy caused by lamination of their formed minerals. In order to link rock physic with seismic response, it is necessary to build forward modeling in organic-rich shale. This paper focuses on studying relationship between reservoir properties such as clay content, porosity and total organic content with anisotropy. Organic content which defines prospectivity of shale gas can be considered as solid background or solid inclusion or both. From the forward modeling result, it is shown that organic matter presence increases anisotropy in shale. The relationships between total organic content and other seismic properties such as acoustic impedance and Vp/Vs are also presented.

58 GEOSCIENCES↗

Magnetic coupling at perovskite and rock-salt structured interfaces

We study magnetic coupling between hole-doped manganite layers separated by either a perovskite or a rock-salt barrier of variable thickness. Both the type and the quality of the interface have a strong impact on the minimum critical barrier thickness where the manganite layers become magnetically decoupled. A rock-salt barrier layer only 1 unit cell (0.5 nm) thick remains insulating and is able to magnetically de-couple the electrode layers. The technique can therefore be used for developing high-performance planar oxide electronic devices such as magnetic tunnel junctions and quantum well structures that depend on magnetically and electronically sharp heterointerfaces.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗

A Physical Basis for M s -Yield Scaling in Hard Rock and Implications for Late-Time Damage of the Source Medium

Surface wave magnitude M s for a compilation of 72 nuclear tests detonated in hard rock media for which yields and burial depths have been reported in the literature is shown to scale with yield W as a + b × log[W], where a = 2.50 ± 0.08 and b = 0.80 ± 0.05. While the exponent b is consistent with an M s scaling model for fully coupled, normal containment-depth explosions, the intercept a is offset 0.45 magnitude units lower than the model. The cause of offset is important to understand in terms of the explosion source. Hard rock explosions conducted in extensional and compressional stress regimes show similar offsets, an indication that the tectonic setting in which an explosion occurs plays no role causing the offset. The scaling model accounts for the effects of source medium material properties on the generation of 20-s period Rayleigh wave amplitudes. Aided by thorough characterizations of the explosion and tectonic release sources, an extensive analysis of the 1963 October 26 Shoal nuclear test detonated in granite 27 miles southeast of Fallon NV shows that the offset is consistent with the predictions of a material damage source model related to non-linear stress wave interactions with the free surface. This source emits Rayleigh waves with polarity opposite to waves emitted by the explosion. The Shoal results were extended to analyse surface waves from the 1962 February 15 Hardhat nuclear test, the 1988 September 14 Soviet Joint Verification Experiment, and the anomalous 1979 August 18 northeast Balapan explosion which exhibits opposite polarity, azimuth-independent source component U1 compared to an explosion. Modelling these tests shows that Rayleigh wave amplitudes generated by the damage source are nearly as large as or larger than amplitudes from the explosion. As such, destructive interference can be drastic, introducing metastable conditions due to the sensitivity of reduced amplitudes to Rayleigh wave initial phase angles of the explosion and damage sources. This meta-stability is a likely source of scatter in M s -yield scaling observations. The agreement of observed scaling exponent b with the model suggests that the damage source strength does not vary much with yield, in contrast to explosions conducted in weak media where Ms scaling rates are greater than the model predicts, and the yield dependence of the damage source strength is significant. This difference in scaling behaviour is a consequence of source medium material properties.

58 GEOSCIENCES↗