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At least 343 records · Page 19

Helium effects on the surface and subsurface evolutions in single-crystalline tungsten

Tungsten (W) has been perceived as one of the most promising plasma facing materials (PFMs) for future fusion reactors. In the past decade, its behavior under irradiation and helium (He) plasma interaction has been extensively studied. However, some key knowledge gaps still exist, such as the influence of crystallographic orientation on the surface and subsurface evolutions. In this work, we focus on the He ion-beam irradiation damage effects in mirror-polished single-crystalline W samples with three different surface planes of {100}, {110} and {111}. Irradiation was performed at room temperature using 40 keV He+ to a fluence of 1 × 10 16 /cm 2 , followed by thermal desorption spectroscopy (TDS) up to ~1920 K. The microstructures of He-irradiated W before and after TDS heat treatment were characterized by scanning and transmission electron microscopy. Subsurface He bubbles were imaged in all irradiated samples, but newly formed <111>-oriented surface grains and surface blisters were only observed in W {100} and {110} starting orientations. These results reveal that radiation damage, He thermal desorption, and surface/subsurface evolution are all strongly dependent on crystallographic orientation. Underlying physical mechanisms are discussed based on ion channeling effects, He-vacancy interactions, and surface diffusion. In conclusion, these findings provide new insights into He effects in W.

36 MATERIALS SCIENCE↗

Small Penetrator Instrument Concept for the Advancement of Lunar Surface Science

Fundamental scientific objectives concerning the surface and subsurface material and dynamics of the Moon are the drivers for the use and advancement of penetrators, which emplace a suite of scientific instruments by impact into a planetary surface, typically at velocities of dozens to hundreds of meters per second. Small lunar penetrators are poised to become a valuable new tool for lunar science and exploration during the next decade. These low-cost ballistic probes can be deployed in large numbers from orbit, or from descending robotic or crewed vehicles, in order to explore and characterize the diversity of extreme lunar shallow subsurface environments. In this paper, we describe the general overview of penetrator objectives, potential instrumentation, and how these would benefit the advancement of lunar science at various extreme environments.

47 OTHER INSTRUMENTATION↗

Approaching a universal scaling relationship between fracture stiffness and fluid flow

A goal of subsurface geophysical monitoring is the detection and characterization of fracture alterations that affect the hydraulic integrity of a site. Achievement of this goal requires a link between the mechanical and hydraulic properties of a fracture. Here we present a scaling relationship between fluid flow and fracture-specific stiffness that approaches universality. Fracture-specific stiffness is a mechanical property dependent on fracture geometry that can be monitored remotely using seismic techniques. A Monte Carlo numerical approach demonstrates that a scaling relationship exists between flow and stiffness for fractures with strongly correlated aperture distributions, and continues to hold for fractures deformed by applied stress and by chemical erosion as well. This new scaling relationship provides a foundation for simulating changes in fracture behaviour as a function of stress or depth in the Earth and will aid risk assessment of the hydraulic integrity of subsurface sites.

42 ENGINEERING↗

Anisotropic seismic-waveform inversion: Application to a seismic velocity model from Eleven-Mile Canyon in Nevada

Accurate imaging and characterization of fracture zones is crucial for geothermal energy exploration. Aligned fractures within fracture zones behave as anisotropic media for seismic-wave propagation. The anisotropic properties in fracture zones introduce extra difficulties for seismic imaging and waveform inversion. We have recently developed a new anisotropic elastic-waveform inversion method using a modified total-variation regularization scheme and a wave-energy-base preconditioning technique. Our new inversion method uses the parameterization of elasticity constants to describe anisotropic media, and hence it can properly handle arbitrary anisotropy. We apply our new inversion method to a seismic velocity model along a 2D-line seismic data acquired at Eleven-Mile Canyon located at the Southern Dixie Valley in Nevada for geothermal energy exploration. Our inversion results show that anisotropic elastic-waveform inversion has potential to reconstruct subsurface anisotropic elastic parameters for imaging and characterization of fracture zones.

15 GEOTHERMAL ENERGY↗

A ModEx Framework for Watershed Subsurface Investigation With Limited Geophysical Data Using Machine Learning and Hydrologic Modeling

Abstract Subsurface heterogeneity influences watershed hydrology strongly but remains difficult to characterize at catchment scales with sparse and costly field data. Geophysical surveys such as electromagnetic induction (EMI) provide local spatial subsurface images yet scaling them to watershed scales and converting EMI‐derived resistivity into hydraulic properties remains a challenge. We present a Model–Experiment (ModEx) framework that integrates limited EMI data with machine learning (ML) and hydrologic modeling to improve process representation and guide field investigations. Sparse EMI surveys were scaled to the catchment scale using a Random Forest model, and the resulting resistivity fields were combined with nearby borehole constraints to parameterize a hydrologic model. The EMI‐informed hydrological simulations improved predictions of streamflow sustained by subsurface flow and shallow saturation patterns. By combining EMI data and ML with hydrologic modeling, the ModEx framework guides future subsurface surveys, providing a transferable and efficient strategy for data–model integration across diverse watersheds. Plain Language Summary Mapping the underground network of soil and rock that controls water is essential for predicting floods and droughts, but seeing underground is difficult and expensive. We cannot drill everywhere, so scientists use geophysical tools to scan broad areas. There are two key challenges: these geophysical scans are often sparse across the whole watershed, and the geophysical data is hard to translate into water‐related properties. We used artificial intelligence to solve these problems. We taught a computer to find patterns linking the limited geophysical data to the land surface properties. This allowed it to fill in the gaps and create a complete, useful subsurface map for the entire watershed. This new map improves hydrologic simulations, leading to more accurate predictions of water movement in the watershed. It also helps scientists build better models with less data and generates a priority map showing where to measure next, making future investigations more efficient. Key Points Limited EMI scaled with ML improves catchment‐scale subsurface parameterization for hydrologic models The framework integrates hydrologic modeling with limited geophysical data to support subsurface investigation design ModEx framework offers a transferable data–model integration strategy that quantifies and reduces uncertainty guiding watershed studies

Chen, Hang↗

Thermal and Well Flow Performance of Closed-Loop Geothermal in the Wattenberg Area

Closed-loop geothermal systems provide an alternative to resource-constrained hydrothermal systems and stimulation-intensive enhanced geothermal systems. In this work, we apply the slender-body theory (SBT) model, to simulate the well flow and heat transfer performance of U-loop well designs in the Wattenberg area of the Denver-Julesburg Basin. Three U-loop well patterns are investigated, including a single-, double-, and multi-lateral design. The subsurface within the area of interest is characterized by deep, hot (> 200 degrees C) igneous/metamorphic basement rock underlying multiple sedimentary formations. The lateral section(s) of the U-loop lie(s) within a target depth of 6 km, where temperatures are estimated to approach 300 degrees C. As a base case, conduction-only heat transfer is investigated through simulations with the SBT model within U-loops with open-hole laterals that exchange heat directly with the hot, dry rock using water as a working fluid. The utilization of supercritical CO2 as a heat transfer fluid is also considered. For each scenario, the system performance in terms of annual heat production and temperature profile over a 20-year project lifetime are assessed. Also, the levelized costs of heat and electricity (LCOH and LCOE) are determined using a top-down techno-economic analysis model. The results show that the performance- and cost-optimized U-loop design is one having an injection-production well spacing of 1,000 meters with ten 50-meter-spaced laterals that traverse a subsurface system with a temperature gradient of 60 degrees C/km. By injecting 20 degrees C-water at a rate of 60 kg/s through this loop, an average heat production of 19 MWth (i.e., 2.2 MWe net plant output) can be achieved, resulting in an LCOE and LCOH of $136/MWhe and $1.53/GJ, respectively, over a 20-year project life.

closed-loop geothermal↗

CCUS 2024, Interpreting the strain tensor Larry Murdoch Interpreting strain tensor data to characterize and monitor reservoirs for CO2 storage and other applications

Recent advances in instrumentation have made it feasible to measure the transient strain tensor caused by small changes in fluid volume or pressure in the subsurface and this has opened the door to new opportunities for characterization and monitoring during CCUS. We have demonstrated this method by deploying strainmeters at shallow depths (30 to 40m) and then conducting injection well tests in an underlying reservoir at 530m depth. The resulting data indicated that the horizontal strain at shallow strainmeters was tensile and the vertical strain was compressive. The radial strain was less than the horizontal strain, and the strain rates decreased from 100 nanostrain/day to roughly 10 ne/d over a few days (1 nanostrain = 1 part per billion strain). We then used the strain data to estimate reservoir properties, geometry and pressure through inversion of poroelastic forward models using both numerical and novel analytical methods. The average horizontal strain in the caprock resembles the transient pressure in the underlying reservoir and classic type-curve methods from transient well testing can be used for preliminary interpretations of strain data. We have developed fast, closed-form analytical solutions to a pressurized poroelastic inclusion and inhomogeneity in a half-space. Numerical models developed using finite element methods allow more details of the subsurface to be included in the inversion, but they require much longer run times and this makes inversion cumbersome using standard methods. We have developed an inversion approach that uses a proxy model created using machine learning to do most of the forward calculations. This approach markedly reduces the computational requirements and makes it feasible to use Bayesian inversion with large numerical models. Bayesian inversion is important because it provides predictions with uncertainties, which makes the results useful for decision making. We have shown with field tests and simulations that the strain tensor in the caprock is sensitive to pressure in the reservoir, reservoir properties and boundaries, and pressure in the caprock caused by leaks. These results indicate that measuring and interpreting the shallow strain tensor could be a valuable tool for both initial reservoir characterization efforts and long-term monitoring during CCUS. Recent advances in instrumentation have made it feasible to measure the transient strain tensor caused by small changes in fluid volume or pressure in the subsurface and our objective was to evaluate opportunities for strain monitoring during characterization and monitoring for CCUS. Our approach was to deploy strainmeters at shallow depths (30 to 40m) and then conduct injection well tests in an underlying reservoir at 530m depth. The results indicate that the horizontal strain at shallow strainmeters was tensile and the vertical strain was compressive. The radial strain was less than the horizontal strain, and the strain rates decreased from 100 nanostrain/day to roughly 10 ne/d over a few days (1 nanostrain = 1 part per billion strain). We then used the strain data to estimate reservoir properties, geometry and pressure through inversion of poroelastic forward models using both numerical and novel analytical methods. The average horizontal strain in the caprock resembles the transient pressure in the underlying reservoir and classic type-curve methods from transient well testing can be used for preliminary interpretations of strain data. We have developed fast, closed-form analytical solutions to a pressurized poroelastic inclusion and inhomogeneity in a half-space. Numerical models developed using finite element methods allow more details of the subsurface to be included in the inversion, but they require much longer run times and this makes inversion cumbersome using standard methods. We have developed an inversion approach that uses a proxy model created using machine learning to do most of the forward calculations. This approach markedly reduces the computational requirements and makes it feasible to use Bayesian inversion with large numerical models. Bayesian inversion is important because it provides predictions with uncertainties, which makes the results useful for decision making. In conclusion, we have shown with field tests and simulations that the strain tensor in the caprock is sensitive to pressure in the reservoir, reservoir properties and boundaries, and pressure in the caprock caused by leaks. These results indicate that measuring and interpreting the shallow strain tensor could be a valuable tool for both initial reservoir characterization efforts and long-term monitoring during CCUS.

Murdoch, Larry↗

Bioindicator “fingerprints” of methane-emitting thermokarst features in Alaskan soils

Permafrost thaw increases the bioavailability of ancient organic matter, facilitating microbial metabolism of volatile organic compounds (VOCs), carbon dioxide, and methane (CH 4 ). The formation of thermokarst (thaw) lakes in icy, organic-rich Yedoma permafrost leads to high CH 4 emissions, and subsurface microbes that have the potential to be biogeochemical drivers of organic carbon turnover in these systems. However, to better characterize and quantify rates of permafrost changes, methods that further clarify the relationship between subsurface biogeochemical processes and microbial dynamics are needed. In this study, we investigated four sites (two well-drained thermokarst mounds, a drained thermokarst lake, and the terrestrial margin of a recently formed thermokarst lake) to determine whether biogenic VOCs (1) can be effectively collected during winter, and (2) whether winter sampling provides more biologically significant VOCs correlated with subsurface microbial metabolic potential. During the cold season (March 2023), we drilled boreholes at the four sites and collected cores to simultaneously characterize microbial populations and captured VOCs. VOC analysis of these sites revealed “fingerprints” that were distinct and unique to each site. Total VOCs from the boreholes included > 400 unique VOC features, including > 40 potentially biogenic VOCs related to microbial metabolism. Subsurface microbial community composition was distinct across sites; for example, methanogenic archaea were far more abundant at the thermokarst site characterized by high annual CH 4 emissions. The results obtained from this method strongly suggest that ∼10% of VOCs are potentially biogenic, and that biogenic VOCs can be mapped to subsurface microbial metabolisms. By better revealing the relationship between subsurface biogeochemical processes and microbial dynamics, this work advances our ability to monitor and predict subsurface carbon turnover in Arctic soils.

anaerobic degradation↗

Detecting Microbially Induced Calcite Precipitation in a Model Well-Bore Using Downhole Low-Field NMR

Microbially induced calcite precipitation (MICP) has been widely researched recently due to its relevance for subsurface engineering applications including sealing leakage pathways and permeability modification. These applications of MICP are inherently difficult to monitor nondestructively in time and space. Nuclear magnetic resonance (NMR) can characterize the pore size distributions, porosity, and permeability of subsurface formations. This investigation used a low-field NMR well-logging probe to monitor MICP in a sand-filled bioreactor, measuring NMR signal amplitude and T 2 relaxation over an 8 day experimental period. Following inoculation with the ureolytic bacteria, Sporosarcina pasteurii , and pulsed injections of urea and calcium substrate, the NMR measured water content in the reactor decreased to 76% of its initial value. T 2 relaxation distributions bifurcated from a single mode centered about approximately 650 ms into a fast decaying population ( T 2 less than 10 ms) and a larger population with T 2 greater than 1000 ms. The combination of changes in pore volume and surface minerology accounts for the changes in the T 2 distributions. Destructive sampling confirmed final porosity was approximately 88% of the original value. Here, these results indicate the low-field NMR well-logging probe is sensitive to the physical and chemical changes caused by MICP in a laboratory bioreactor.

54 ENVIRONMENTAL SCIENCES↗

Techno-economic feasibility of geothermal energy production using inactive oil and gas wells for district heating and cooling systems in Tuttle, Oklahoma

Oil and gas wells have been drilled in the United States and often encounter hot co-produced water possibly suitable for geothermal direct-use applications. Here this study evaluated geothermal resources, heating and cooling demand, and techno-economic potential of four oil and gas wells repurposed for geothermal energy production to serve two public schools and 250 nearby houses in Tuttle, Oklahoma, USA. Subsurface geology in the study area primarily consists of Permian to Mississippian sandstone and limestone formations approximately from 2 km to 3.5 km depth. With a geothermal gradient of 25.3 °C/km, the temperature of geothermal energy production was estimated as 68.2 °C at 2.1 km. The potential of calcite scaling within boreholes and pipes was minimal. Using the characterized reservoir properties, techno-economic analyses were conducted for evaluating levelized costs of geothermal energy production for direct-use heating and cooling and district heating systems with five different production scenarios. Heating and cooling demand in two schools and 250 houses and additional 0.3 MW and 0.6 MW base heating loads for potential geothermal direct-use applications in the study area were also incorporated in the modeling. Results indicated that the levelized cost of heating of geothermal district heating systems utilizing existing wells were significantly lower than those of conventional geothermal energy systems that include well drillings. The geothermal energy production with doublet and quartet configurations was generally sufficient to supply total annual heating demand in the district, while a peaking boiler was used to supply peak loads. Doublet configurations showed higher production temperature with a lower thermal drawdown than the quartet configurations. The doublet system at 2.1 km production depth with 9.3 kg/s flow rate represented the optimal levelized cost of $71/MWh and 91.2% utilization factor. These results imply that the Tuttle geothermal district heating system is techno-economically feasible and comparable to geothermal district heating systems in the United States and the regional natural gas rate for residentials by recycling inactive oil and gas wells with no drillings.

15 GEOTHERMAL ENERGY↗

Characterization of volcanic tuff pores pre- and post-underground nuclear detonation using ultra-small and small angle neutron scattering

The ability to accurately model the subsurface transport of radionuclides is fundamental to the remote detection and characterization of underground nuclear explosion (UNE) events. Developing more sophisticated transport models presents a significant opportunity to enhance monitoring capabilities, particularly in the reliable prediction of signature migration. Experimentally determined characterization of geologic materials associated with transport properties is the pertinent base information for such robust model development and calibration. Here, we report results from an unprecedented study demonstrating changes to the pore and fracture network structures in geological materials in response to UNEs over nanometer to micrometer length scales. Volcanic tuffs of five different lithological formations from pre- and post-UNE environments were collected from the Nevada National Security Site. Combined ultra-small and small-angle neutron scattering techniques were used to characterize the tuff pore structure. The results demonstrate measurable differences in the specific surface area and porosity of samples pre- and post-shot from texturally similar lithological formations, indicating that pore properties can serve as a direct physical signature of a UNE. The results also provide experimentally determined transport parameters in support of advanced model development through the integration of gas migration, hydrodynamic simulations, and geologic framework models.

54 ENVIRONMENTAL SCIENCES↗

Progress toward cleanup of operable unit 1 groundwater at the US DOE0 Mound, Ohio, site: success of a phased-combined remedy - 15310

Industrial solvents (primarily trichloroethene) and other volatile organic compounds (VOCs) that originated from the former solid waste landfill contaminated the groundwater in the Buried Valley Aquifer beneath the Mound, Ohio, Site. The landfill was used from 1948 to 1974 for the disposal of trash, debris, and liquid waste. In 1977, much of the waste was relocated and encapsulated onsite. The landfill site and surrounding area (Operable Unit 1 [OU-1]) occupy approximately 1.6 hectares (4 acres) in the southwestern portion of the site. The historical pathway of concern consisted of leaching of contaminants from site soils or disposed wastes down into the groundwater, entrainment in the flowing groundwater, and migration toward former Mound site water-production wells. A groundwater pump-and-treat (P and T) system was initiated in 1996 to interdict the plume and a soil vapor extraction system was installed and operated from 1997 to 2003 to remove the bulk of the VOC sources from the vadose zone. Physical removal of the landfill waste and contaminated soil was performed between 2006 and 2010. Approximately 76,000 cubic meters (99,400 cubic yards) of material were removed from the OU-1 landfill area; the remaining soils in the OU-1 area meet the site cleanup objectives for future industrial or commercial use. Operation of the groundwater P and T system continued throughout this period. During the remediation time frame, groundwater monitoring and a number of innovative characterization campaigns were completed to assess the contaminant and biogeochemical conditions in the subsurface at OU-1. For example, in 2013 an integral pumping test was performed to characterize the amount (mass) of the low-level VOCs in groundwater. Soil and groundwater were also collected to obtain site-specific data to identify if geochemical conditions support natural attenuation reactions. Contaminant and hydrogeologic data collected from this test, as well as historical data, were evaluated to identify the distribution and potential sources of VOCs, refine the hydrogeologic description, update the conceptual model of VOC fate and transport, and determine if monitored natural attenuation remains a viable option to address VOCs in groundwater. To date, the performance of the phased-combined remedy has resulted in significant reductions in the concentrations of VOCs in the groundwater. For example, in 2013 the trichloroethene in all wells was less than 40 micrograms per liter, with a plurality of the wells near or below maximum contaminant levels. The generally observed declining concentration trends and the low concentrations for 2013 represent the net impact of source removal actions, P and T operation, and natural attenuation. In accordance with the current conditions, the joint US DOE and regulator Core Team is proceeding with a field demonstration of enhanced attenuation-an engineering and regulatory strategy that was recently developed by the Interstate Technology and Regulatory Council. Enhanced attenuation strategies focus on altering a target site in such a way that it can transition to natural attenuation. The combination of technologies to be deployed includes neat (pure) vegetable oil deployment in the deep vadose zone of the former landfill area and emulsified vegetable oil deployment within the footprint of the groundwater plume. In the first part of the deployment, neat oil spreads laterally and forms a thin layer on the water table beneath residual soil sources to intercept and reduce future VOC loading and to reduce oxygen inputs to the local groundwater. In the second part of the deployment, emulsified oil forms active bioremediation treatment zones within the plume footprint to degrade existing groundwater contaminants (via reductive dechlorination, co-metabolism, or both) and stimulates long-term attenuation capacity in the down-gradient plume (via co-metabolism). If the proposed activities are successful, they will accelerate the progress of the Mound OU-1 toward remedial goals and convert the current active P and T remedy into a passive attenuation-based remedy that represents a cost-effective final step in a phased remediation. (authors)

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

Imaging and quantification of spreading and trapping of carbon dioxide in saline aquifers using meter-scale laboratory experiments

The role of capillary forces during buoyant migration of CO 2 is critical toward plume immobilization within the postinjection phase of a geological carbon sequestration operation. However, the inherent heterogeneity of the subsurface makes it very challenging to evaluate the effects of capillary forces on the storage capacity of these formations and to assess in situ plume evolution. To overcome the lack of accurate and continuous observations at the field scale and to mimic vertical migration and entrapment of realistic CO 2 plumes in the presence of a background hydraulic gradient, we conducted two unique long-term experiments in a 2.44 m × 0.5 m tank. X-ray attenuation allowed measuring the evolution of a CO 2 -surrogate fluid saturation, thus providing direct insight into capillarity-dominated and buoyancy-dominated flow processes occurring under successive drainage and imbibition conditions. The comparison of saturation distributions between two experimental campaigns suggests that layered-type heterogeneity plays an important role on nonwetting phase (NWP) migration and trapping, because it leads to (i) longer displacement times (3.6 months versus 24 days) to reach stable trapping conditions, (ii) limited vertical migration of the plume (with center of mass at 39% versus 55% of aquifer thickness), and (iii) immobilization of a larger fraction of injected NWP mass (67.2% versus 51.5% of injected volume) as compared to the homogenous scenario. Finally, while these observations confirm once more the role of geological heterogeneity in controlling buoyant flows in the subsurface, they also highlight the importance of characterizing it at scales that are below seismic resolution (1–10 m).

54 ENVIRONMENTAL SCIENCES↗

Estimating posterior quantity of interest expectations in a multilevel scalable framework

Scalable approaches for uncertainty quantification are necessary for characterizing prediction confidence in large-scale subsurface flow simulations with uncertain permeability. To this end we explore a multilevel Monte Carlo approach for estimating posterior moments of a particular quantity of interest, where we employ an element-agglomerated algebraic multigrid (AMG) technique to generate the hierarchy of coarse spaces with guaranteed approximation properties for both the generation of spatially correlated random fields and the forward simulation of Darcy's law to model subsurface flow. In both these components (sampling and forward solves), we exploit solvers that rely on state-of-the-art scalable AMG. To illustrate the applicability of this approach, numerical tests are performed on two 3D examples-a unit cube and an egg-shaped domain with an irregular boundary-where the scalability of each simulation as well as the scalability of the overall algorithm are demonstrated.

97 MATHEMATICS AND COMPUTING↗

Extraordinary phylogenetic diversity and metabolic versatility in aquifer sediment

Microorganisms in the subsurface represent a substantial but poorly understood component of the Earth’s biosphere. Subsurface environments are complex and difficult to characterize; thus, their microbiota have remained as a ‘dark matter’ of the carbon and other biogeochemical cycles. Here we deeply sequence two sediment-hosted microbial communities from an aquifer adjacent to the Colorado River, CO, USA. No single organism represents more than ~1% of either community. Remarkably, many bacteria and archaea in these communities are novel at the phylum level or belong to phyla lacking a sequenced representative. The dominant organism in deeper sediment, RBG-1, is a member of a new phylum. On the basis of its reconstructed complete genome, RBG-1 is metabolically versatile. Its wide respiration-based repertoire may enable it to respond to the fluctuating redox environment close to the water table. We document extraordinary microbial novelty and the importance of previously unknown lineages in sediment biogeochemical transformations.

59 BASIC BIOLOGICAL SCIENCES↗

Probing multiscale dissolution dynamics in natural rocks through microfluidics and compositional analysis

Mineral dissolution significantly impacts many geological systems. Carbon released by diagenesis, carbon sequestration, and acid injection are examples where geochemical reactions, fluid flow, and solute transport are strongly coupled. The complexity in these systems involves interplay between various mechanisms that operate at timescales ranging from microseconds to years. Current experimental techniques characterize dissolution processes using static images that are acquired with long measurement times and/or low spatial resolution. These limitations prevent direct observation of how dissolution reactions progress within an intact rock with spatially heterogeneous mineralogy and morphology. We utilize microfluidic cells embedded with thin rock samples to visualize dissolution with significant temporal resolution (100 ms) in a large observation window (3 × 3 mm). Here we injected acidic fluid into eight shale samples ranging from 8 to 86 wt % carbonate. The pre- and postreaction microstructures are characterized at the scale of pores (0.1 to 1 µm) and fractures (1 to 1,000 µm). We observe that nonreactive particle exposure, fracture morphology, and loss of rock strength are strongly dependent on both the relative volume of reactive grains and their distribution. Time-resolved images of the rock unveil the spatiotemporal dynamics of dissolution, including two-phase flow effects in real time and illustrate the changes in the fracture interface across the range of compositions. Moreover, the dynamical data provide an approach for characterizing reactivity parameters of natural heterogeneous samples when porous media effects are not negligible. The platform and workflow provide real-time characterization of geochemical reactions and inform various subsurface engineering processes.

58 GEOSCIENCES↗

On negative induced polarization in frequency domain measurements

SUMMARY Induced polarization (IP) has been widely used to non-invasively characterize electrical conduction and polarization in the subsurface resulting from an applied electric field. Earth materials exhibit a lossy capacitance defined by a negative intrinsic phase in frequency-domain IP (FDIP) or a positive intrinsic chargeability in time-domain IP (TDIP). However, error-free positive apparent phase or negative apparent chargeability (i.e. negative IP effects) can occur in IP measurements over heterogeneous media. While negative IP effects in TDIP data sets have been discussed, no studies have addressed this topic in detail for FDIP measurements. We describe theory and numerical modelling to explain the origin of negative IP effects in FDIP measurements. A positive apparent phase may occur when a relatively high polarizability feature falls into negative sensitivity zones of complex resistivity measurements. The polarity of the apparent phase is determined by the distribution of subsurface intrinsic phase and resistivity, with the resistivity impacting the apparent phase polarity via its control on the sensitivity distribution. A physical explanation for the occurrence of positive apparent phase data is provided by an electric circuit model representing a four-electrode measurement. We also show that the apparent phase polarity will be frequency dependent when resistivity changes significantly with frequency (i.e. in the presence of significant IP effects). Consequently, negative IP effects manifest themselves in the shape of apparent phase spectra recorded with multifrequency (spectral IP) data sets. Our results imply that positive apparent phase measurements should be anticipated and should be retained during inversion and interpretation of single frequency and spectral IP data sets.

Geochemistry & Geophysics↗

Computational and Experimental Characterization of Intermediate Amorphous Phases in Geological Materials

In the subsurface, MgO engineered barriers are employed at the Waste Isolation Pilot Plant (WIPP), a transuranic waste repository near Carlsbad, NM. During service, the MgO will be exposed to high concentration brine environments and may form stable intermediate phases that can alter the barriers effectiveness. Here, MgO was aged in water and three different brine solutions. X-ray diffraction (XRD) and 1 H nuclear magnetic resonance (NMR) analysis were performed to identify the formation of secondary phases. After aging, ~4% of the MgO was hydrated and fine-grained powders resulted in greater loss of crystallinity than hard granular grains. 1 H magic angle spinning (MAS) NMR spectra resolved minor phases not visible in XRD, indicating that diverse 1 H environments are present along with Mg(OH) 2 . Density functional theory (DFT) simulations for several proposed Mg-O-H, Mg-CI-O-H, and Na-O-H containing phases were performed to index peaks in the experimental 1 H MAS NMR spectra. While proposed intermediate crystal structures exhibited overlapping 1 H NMR peaks, Mg-O-H intermediates were attributed to the growth of the 1.0-0.0ppm peak while the Mg-CI-O-H structures contributed to the 2.5- 5.0ppm peak in the chloride containing brines. Overall, NMR analysis of aged MgO indicates the formation of a range of possible intermediate structures that cannot be resolved with XRD analysis alone.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗