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At least 253 records · Page 14

Hydraulic Response to Thermal Stimulation Efforts at Raft River Based on Stepped Rate Injection Testing

The injection well stimulation project at the Raft River geothermal field tests the effect of long-term cold water injection and high pressure injection on well injectivity, improvements to which could reduce operating costs. The primary data for analysis and interpretation of the injection test are step-rate flow tests run before each new phase of the injection. These tests were analyzed using a combination of standard pump-test analytical solution methods and methods developed expressly for the observed conditions. The stepped rate injection tests, combined with long-term flow and pressure response data suggest that the well is located within a fractured formation of low transmissivity but high storativity. These calculated parameters appeared to increase with pressure during the first injection test and the higher values were reproduced during the second stepped rate test. Calculated transmissivity and storativity are on the order of 4E-5 m cm 2 and 1E-4 m Pa -1 , respectively. The apparent pressure dependence of fitted hydraulic parameters may reflect near-well fracture compliance that increased the effective radius of the wellbore during the first test. While the type curve fit analysis also suggests that the reservoir behaves as a uniformly fractured reservoir with a radial flow regime, the hydraulic parameters indicate that condition may exist only a very limited distance (<10 m) from the well. Longer-term pressure response suggests that flow in the system effectively reaches steady state in a period of less than a day, which may reflect pressure stabilization resulting from pressure-dependent permeability or a region of much higher permeability located with a few meters of the well. The transmissivity estimates obtained from this analysis, converted to approximate fracture density and aperture, provide useful constraints on the distance to which the thermal front may migrate from the well during the cold water injection phase of the stimulation project. We estimate that the cooling front will migrate less than a tenth of a kilometer over an approximately one-year injection period. Here, the effects of that cooling, however, may be substantial, because increases in permeability have maximum effect nearest the well.

cold water injection↗

Simulation of Reverse Osmosis Membrane Compaction Using Material Point Method

Reverse Osmosis (RO) is a promising technology to address the impending water-crisis in the upcoming decades. RO at high salinities and high pressures is challenging due to membrane compaction that changes its porosity and permeability. In this study, we present a simulation methodology for membrane structural mechanics to understand pore size distribution and permeability variations under high pressure. We use the material point method (MPM), that solves the solid mechanics equations in a Lagrangian framework. MPM provides many features that make it well-suited for simulating mesoporous membranes. The Lagrangian framework allows for large deformations, easy integration of constitutive models and direct import of complex geometries as particles. The spatial discretization in our MPM solver is achieved using linear or cubic-spline shape functions while the time integration is carried out using the explicit Euler method. A series of images containing detailed pore structures obtained from X-ray tomography is first converted to a collection of material points. Compressive loads are applied to the top layer of the membrane to simulate the application of pressure. The membrane deformation and pore size distribution before and after load application are reported and compared with the experimental measurements. The presentation discusses the numerical methods used, the performance of the solver on high-performance computing machines, and the results of membrane compact in detail.

compaction↗

Porous condensers can double the efficiency of membrane distillation

Among membrane distillation (MD) configurations, air gap MD (AGMD) has superior energy efficiency at high salinity. However, flooding of the gap prevents optimal thin gap depths as water removal is a challenge. To address these challenges, this work provides the first analysis of efficiency enhancement via porous wicking conductive condensers in MD. To do so, we examined performance with experiments and comprehensive thermo-fluid numerical models; we find that the porous wick condenser significantly improves thermal efficiency, gain output ratio (GOR), and flux. MD experiments show that the porous copper foam improves the thermal efficiency of air gap membrane distillation up to 40 % and water flux up to 144 %. Numerical modeling shows the porous copper foam improves the GOR of membrane distillation in high salinity by 98.7 %, outperforming air gap MD, permeate gap MD, and conductive gap MD. Furthermore, the optimized thickness and permeability of porous condensers significantly help eliminate the risk of flooding in AGMD.

42 ENGINEERING↗

Spatiotemporal Analyses of Groundwater and Shoreline Cr(VI) Concentrations in the 100 Areas at Hanford

Cleanup efforts have been ongoing since the late 1990s to remediate contaminated waste sites and groundwater in the 100 Areas at the U.S. Department of Energy (DOE) Hanford Site. One of the primary contaminants of concern is hexavalent chromium (Cr(VI)), which was used as a corrosion inhibitor in cooling water for nuclear reactors that formerly operated along the shoreline of the Columbia River. Cleanup efforts have included 1) removal, treatment (as needed), and disposal of contaminated sediments; 2) in situ redox manipulation as a permeable reactive barrier; 3) pump-and-treat; 4) soil flushing; and 5) monitored natural attenuation. DOE’s annual groundwater monitoring reports document the significant reductions in Cr(VI) plume areas that have occurred over the past 10 years or more as a result of these cleanup efforts. The Record of Decision for the 100-HR-3 operable unit specified a cleanup level (CUL) for Cr(VI) in groundwater of 48 µg/L to protect human receptors, and a surface water CUL of 10 µg/L to protect aquatic organisms in the Columbia River. The Record of Decision did not specify point-of-compliance locations for the surface water CUL. Data for 2019 from the six groundwater operable units (OUs) in the 100 Areas indicate that the 48 μg/L groundwater CUL has been achieved in 100% of the wells in the 100-BC and 100-NR OUs, and in 89- 97% of the wells in the other OUs (100-KR, 100-HR-D, 100-HR-H, 100-FR). Data for 2019 indicate that 100% of the aquifer tubes monitored for Cr(VI) in the 100 Areas have concentrations below the 48 μg/L groundwater CUL. However, the 10 μg/L standard has not yet been consistently achieved for both inland groundwater monitoring wells and shoreline aquifer tubes. This report describes a series of data analyses performed to identify consistent relationships, if any, between inland well and shoreline Cr(VI) concentrations within the 100 Areas. To this end, select monitoring data for Cr(VI) measured in groundwater and aquifer tubes at the 100 Areas were analyzed for a 10-year period—2010 to 2019. Relationships between inland groundwater plumes and surface-water points of discharge in and along the Columbia River were examined through several analyses that included inland well and aquifer tube concentrations as a function of distance from the shoreline, evaluation of cumulative probability plots, trend analysis, correlation analysis, cluster analysis, and identification of plume trajectories for each of the 100 Areas. The analyses did not identify consistent relationships between inland groundwater Cr(VI) concentrations and shoreline concentrations within the 100 Areas due to several confounding factors influencing groundwater flow directions and Cr(VI) concentrations. The proximity of groundwater Cr(VI) plumes to the river, and the highly dynamic nature of the river, influence the transport behavior of the plumes and create challenges for quantifying attenuation of Cr(VI) between the inland monitoring wells and shoreline concentrations. Other factors contributing to temporal and spatial Cr(VI) concentrations, as supported by some of the data analyses, include the presence of vadose zone sources, variable sorption behavior, and complexities associated with Cr(VI) mass transfer between the upper and lower aquifers and their interactions with the river. Hence, monitoring to assess compliance with target CULs will need to be determined for each area individually since several factors influence Cr(VI) concentrations in the 100 Areas.

54 ENVIRONMENTAL SCIENCES↗

Soft interface instability and gas flow channeling in low-permeability deformable media

Understanding gas percolation through a clay layer or a shale formation is of great importance for the development of a geologic repository for nuclear waste disposal, a subsurface system for gas storage, and an engineering approach for hydrocarbon extraction from unconventional reservoirs. Gas injection experiments have revealed complex dynamic behaviours of gas percolation through water saturated compacted bentonite, characterized by a high breakthrough pressure, rapid breakthrough, a pressure/stress decay after the breakthrough, a relatively high migration rate, high-frequency periodic/nonperiodic variations in flow rate, stepwise rate reductions during relaxation, and low gas saturation over the whole process, all indicating channelling nature of the processes. Using linear stability analyses, we show that this channelling can autonomously emerge from the instability of the deformable interface between the injected gas and the compacted bentonite matrix driven by local stress concentration, pore dilation, and hydrologic gradient. Channel patterns formed would possess a fractal geometry. We further show that, once a percolating channel is established, the gas injected would percolate through the channel in a chain of gas bubbles, also due to the interface instability, resulting in periodic/chaotic variations in gas flow rate. Our work provides a unified explanation for key features observed for gas percolation in low-permeability deformable media. The work also suggests a possibility of designing an engineered barrier system for a nuclear waste repository that can have controllable gas release while limit water transport.

Bentonite↗

Rapid Mineral Precipitation During Shear Fracturing of Carbonate-Rich Shales

Target subsurface reservoirs for emerging low-carbon energy technologies and geologic carbon sequestration typically have low permeability and thus rely heavily on fluid transport through natural and induced fracture networks. Sustainable development of these systems requires deeper understanding of how geochemically mediated deformation impacts fracture microstructure and permeability evolution, particularly with respect to geochemical reactions between pore fluids and the host rock. Here, a series of triaxial direct shear experiments was designed to evaluate how fractures generated at subsurface conditions respond to penetration of reactive fluids with a focus on the role of mineral precipitation. Calcite-rich shale cores were directly sheared under 3.5 MPa confining pressure using BaCl 2 -rich solutions as a working fluid. Experiments were conducted within an X-ray computed tomography (xCT) scanner to capture 4-D evolution of fracture geometry and precipitate growth. Three shear tests evidenced nonuniform precipitation of barium carbonates (BaCO 3 ) along through-going fractures, where the extent of precipitation increased with increasing calcite content. Precipitates were strongly localized within fracture networks due to mineral, geochemical, and structural heterogeneities and generally concentrated in smaller apertures where rock:water ratios were highest. The combination of elevated fluid saturation and reactive surface area created in freshly activated fractures drove near-immediate mineral precipitation that led to an 80% permeability reduction and significant flow obstruction in the most reactive core. While most previous studies have focused on mixing-induced precipitation, this work demonstrates that fluid–rock interactions can trigger precipitation-induced permeability alterations that can initiate or mitigate risks associated with subsurface energy systems.

58 GEOSCIENCES↗

Biobased Poly(dodecylene Furanoate) with Inherent Advantages in Performance and Circularity

Biobased polymers are gaining traction toward more sustainable flexible-film packaging, yet overcoming trade-offs between their performance properties and end-of-life (EoL) options still remains a challenge. Here, it is shown that biobased poly(dodecylene 2,5-furanoate) (PDDF), synthesized via both step-growth polycondensation and chain-growth ring-opening polymerization methods, exhibits advantages not only in gas barrier properties but also in EoL options due to its biodegradability and closed-loop chemical circularity. Specifically, PDDF displays significantly lower oxygen and carbon dioxide permeability than commercial poly(butylene adipate-co-terephthalate) (PBAT) and linear low-density polyethylene , alongside a markedly higher modulus (by ≈3 ×) and reduced water vapor transmission rate compared to PBAT. This superior performance is attributed to the inherently rigid, polar, H-bonding furan rings that enhance chain interaction, packing and crystallinity and thus reduce free volume impeding gas diffusion, while the long hydrophobic dodecylene segments inhibit water permeation. Furthermore, PDDF can be recycled back to its cyclic monomer by base-catalyzed depolymerization or diester and diol monomers by simple methanolysis. These superior barrier properties, coupled with biodegradation and closed-loop circularity, highlight the potential of the biobased PDDF as a more sustainable alternative for packaging.

Poly(dodecylene 2,5-furanoate) (PDDF)↗

Cellulose acetate membranes exhibit exceptional monovalent to divalent cation selectivities

Salt transport properties of cellulose acetate membranes are reported for a series of chloride salts with mono- valent and divalent cations (LiCl, NaCl, MgCl 2 , CaCl 2 ). Measurements include salt permeability and sorption, with diffusivity values calculated from the permeability and sorption results. We report an exceptionally high LiCl/MgCl 2 selectivity of 750:1. Salts with similar valence (LiCl and NaCl; MgCl 2 and CaCl 2 ) have similar transport properties. The high monovalent/divalent selectivity arises from differences in both sorption and diffusion, with a LiCl/MgCl 2 solubility selectivity of about 11 and a diffusivity selectivity of about 70. Atomistic molecular dynamics simulations show that ions tend to reside in isolated clusters of water. Increasing ion charge strengthens ion–water interactions relative to ion–polymer interactions, explaining the reduced sorption of divalent ions. Diffusion of ions through the membrane occurs via hop-like motion between water clusters. Lithium diffuses faster than magnesium due to weaker ion–water coordination for lithium, which allows for greater mobility within water clusters and more frequent hopping. Altogether, our atomistic simulations suggest that the high LiCl/MgCl 2 selectivity is linked to cellulose acetate’s high water/salt selectivity and is a consequence of low water content and relatively uniform water distribution.

36 MATERIALS SCIENCE↗

Porosity-Permeability Evolution During Simultaneous Mineral Dissolution and Precipitation

Permeability in reactive porous media evolves in complex ways that are hard to predict. Macroscopic empirical equations are often used to estimate permeability evolution but fail to reflect the impact of pore scale reactions on permeability. This work aims to understand the evolution of permeability in systems where mineral dissolution and precipitation occur simultaneously. Pore network models are used for permeability simulation of a Paluxy sandstone using pore and pore-throat size distributions from the analysis of X-ray CT images. Pore and pore-throat radii are increased and decreased to reflect the effects of dissolution and precipitation reactions. Varying spatial distributions of reactions are simulated and the resulting porosity and permeability values compared with commonly used macroscopic equations. It is observed that when dissolution occurs at the inlet and precipitation at the outlet, porosity increases while permeability decreases. Similar results are also observed in the respective opposite scenario where precipitation occurs at the inlet and dissolution at the outlet. When dissolution and precipitation reactions are randomly distributed throughout the network, porosity increases with little change in permeability that is not captured by the empirical equations. When reactions are controlled by pore and pore-throat sizes, such as dissolution occurring in pores and pore-throats of small size and precipitation in pores and pore-throats of larger size, porosity and permeability decrease. When precipitation occurs in pores and pore-throats of smaller size and dissolution in pores and pore-throats of larger size, porosity and permeability increase and is described relatively well by the Verma-Pruess porosity-permeability equation.

54 ENVIRONMENTAL SCIENCES↗

Multiscale petrophysical characterization and flow unit classification of the Minnelusa eolian sandstones

Integration of petrophysical and geological information is critical to simulation of subsurface carbon storage (GCS). In this sense, two depositional facies were identified from the core description and well-log interpretation, namely massive (MS) and cross-bedded (CB) facies groups. Additionally, pore-scale characteristics were studied by a combination of techniques, e.g. Nuclear Magnetic Resonance (NMR) and mercury intrusion capillary pressure (MICP). Scanning electron microscope (SEM) and petrographic analyses show that the pore structure is dominantly controlled by the depositional environment and dolomite cementation. NMR-T 2 distributions of MS and CB facies show triple and quadruple modes, respectively. In addition, MICP of high- and low-permeability MS facies samples, and their CB facies group mixtures were collected. The MS sample pore-throat size distribution is uni-modal, while the triple-modal characteristic of the mixtures indicates heterogeneous pore structures at the sub-core scale for CB facies. The reliably estimates of porosity and permeability for both facies groups via NMR techniques and the MLR (Multiple Linear Regression) approach demonstrate the applicability of these techniques to eolian sandstone. Moreover, irreducible water saturation via the T 2 -cutoff method correlates strongly with T 2LM instead of porosity. Finally, the rock quality index and flow zone indicator were calculated based on Combinable Magnetic Resonance (CMR) log interpretations. This provides direct connection to properties measured in the well. Four flow units were classified for both facies groups. Finally, results show that better reservoir quality with significant heterogeneities is observed in the CB facies. This study highlights the importance integrating multiscale petrophysical properties including facies, pore architecture and diagenesis analysis with core- to log-scale property characterization. The results herein validate our reservoir characterization and flow unit classification in eolian reservoirs.

58 GEOSCIENCES↗

GeoThermalCloud for EGS – An Open-source, User-friendly, Scalable AI Workflow for Modeling Enhanced Geothermal Systems

Enhanced Geothermal Systems (EGS) offer a vast potential to expand the use of geothermal energy. Heat is extracted from this engineered system by injecting relatively cold water into subsurface fractures, which are in contact with hot dry rock, and brought back to surface through production wells. Creating EGS requires improving the natural permeability of hot crystalline rocks. In this short conference paper, we present a reproducible workflow for modeling EGS. Our workflow called the GeoThermalCloud (GTC) for EGS, leverages recent advances in machine learning, deep learning, and high-performance computing. This GTC framework is currently being made open-source, user-friendly, and reproducible through python scripts as well as Google Colab/Jupyter Notebooks. This GTC for EGS modeling scripts are made available at https://github.com/SmartTensors/GeoThermalCloud.jl/tree/master/EGS and will constantly be updated to cater for geothermal community. Current GTC framework provides scripts to train deep learning (DL) models for techno-economics and data worth analysis. The Geothermal Design Tool (https://github.com/GeoDesignTool/GeoDT.git), a fast and simplified multi-physics solver, is used to develop a database for training DL models. This short paper provides details on the scripts to curate, process, and train DL models. The scripts can easily be modified to train on databases generated by other popular open-source simulators such as PFLOTRAN, STOMP, TOUGH, and GEOSX or commercial software such as ResFrac and COMSOL.

15 GEOTHERMAL ENERGY↗

Geothermal Play-Fairway Analysis of Washington State Prospects: Final Report

The Washington State Geothermal Play-Fairway Analysis overcomes the exploration challenges posed by dense vegetation, glacial deposits, and extreme precipitation. The geothermal play-fairways we target are locations where heat, permeability, and saturated porosity are present in sufficient volume to provide adequate heat exchange at depths accessible by modern drilling technology. The three study areas lie along the Cascade Range magmatic arc and are near Mount Baker, Mount St. Helens, and the Wind River Valley. The seven-year project is divided into three phases. In Phase 1 we build on a previous statewide assessment of geothermal resources and develop an initial modeling approach. The results are a series of favorability, uncertainty, and risk maps for three targeted study areas. Based on these initial results, we collect new geologic and geophysical data to further refine our modeling and reduce exploration uncertainty in Phase 2. We improve the modeling method to handle the new data and update the favorability, uncertainty, and risk maps. We also update the conceptual geothermal resource models. In Phase 3 we validate our modeling approach by drilling two temperature-gradient holes and collecting and analyzing core, image logs, and new geochemistry. Our modeling approach improves on an earlier statewide method through a more-rigorous and detailed assessment of heat and permeability. Permeability potential is assessed through geomechanical modeling of the deformation that can generate and maintain reservoir porosity and permeability. Metrics to inform heat potential include temperature-gradient wells, which are sparse in Washington; proximity of Quaternary volcanic vents and young intrusive rock; spring temperature; and reservoir temperature inferred from geothermometry. We weight the individual components using an expert-guided approach known as the Analytical Hierarchy Process. During Phase 2 we also develop a fluid-filled fracture model, and an infrastructure model that helps to delineate areas which are more favorable for geothermal development based on proximity to transmission lines, elevation, land ownership and use restrictions, and availability of process water. New geologic and geophysical data is collected during Phase 2 in each of our three main study areas. At Mount Baker and north of Mount St. Helens we conduct 1:24,000-scale geologic mapping and lidar analysis to better constrain the location and character of surface faults; detailed mapping in the Wind River Valley was completed just prior to the start of this project. Ages of intrusive rocks are determined with 40 Ar/ 39 Ar geochronology, though all of our samples are Miocene or older. We collect ground based gravity observations (a total of 1,580 new stations) in all of our study areas and ground-based magnetic lines (a total of 93 km) at Mount Baker. These data are combined with existing gravity and aeromagnetic data and used to constrain fault locations and geometry. Two to three cross sections are constructed at each study area using the mapped surface geology and forward-modeling of the gravity and magnetic data; these cross sections form the basis for our updated conceptual models. We collect magnetotelluric surveys at Mount Baker and Mount St. Helens and these data are inverted to form a resistivity model from the surface to about 10 km depth; each model shows conductive zones that can be interpreted as upwelling geothermal fluids. At Mount St. Helens we deploy a passive seismic array and use the newly detected events to refine the location of the Saint Helens seismic zone. We also employ ambient-noise tomography to develop a detailed seismic-velocity model for the study area and use this model to help constrain our cross sections and conceptual model. Based on the new data collected during Phase 2—and our updated models—we develop a campaign of temperature-gradient holes and core analysis to validate our modeling in Phase 3. Drill hole MB76-31 is located near Little Park Creek, 11 km west-southwest of the summit of Mount Baker, and is 1,471 ft deep. About 410 ft of core from the lower portion of the hole—and image logs from ~175 ft below ground surface to the bottom—are collected and analyzed. Water samples are collected and processed for geothermometry. Drill hole MSH17-24 is located along upper Schultz Creek, 16 km north-northeast of Mount St. Helens and has core from 470 ft to the bottom at 1,053 ft. We did not collect image logs due to borehole stability concerns, but water samples are collected and analyzed for geothermometry. Repeat temperature-gradient measurements are made at both sites and thermal conductivity is measured from core samples. At MB76-31, the equilibrated temperature gradient of 64°C/km and calculated heat flow of 141–159 mW/m 2 is more than twice the regional average. Detailed mapping and analysis of the core, coupled with correlation to the image logs, indicates a history of permeability generation consistent with our predictions of high permeability. Because the site has high favorability in the Phase 2 model, we consider the results a positive validation of the modeling. At site MSH17-24, the equilibrated temperature gradient of ~15°C/km and calculated heat flow of 41–43 mW/m 2 are similar to regional. Geochemical analysis of the water samples indicates a meteoric source without any geothermal component. Detailed outcrop-based mapping of fault exposures near the drill site and analysis of image logs from nearby boreholes indicates a history of permeability generation consistent with our predictions. Because the site has low favorability in the Phase 2 model, we consider the results a positive validation of the modeling. Together, the two sites provide a reasonably positive validation of the Phase 2 modeling and should encourage future use of this modeling approach.

15 GEOTHERMAL ENERGY↗

Geologic hydrogen: From natural occurrences to anthropogenic generation – A review of fundamentals, potential, challenges and prospects

Growing demand for hydrogen is exposing the environmental and economic limits of reforming-based and carbon-managed supply chains, while the scale-up of electrolytic capacity remains capital-constrained. Geologic hydrogen, defined as molecular H₂ generated and stored within the Earth's crust offers a complementary, potentially lower-cost resource, yet exploration is still ad hoc. This review (1) revisits a global inventory of confirmed hydrogen seeps and subsurface occurrences; (2) analyzes the controlling reactions, migration pathways, and trapping conditions governing these occurrences; (3) proposes a process-based geologic hydrogen system concept analogous to, yet distinct from, the petroleum system; and (4) evaluates potential geologic hydrogen systems within the United States as a representative case study. Here, we contrast natural systems powered by serpentinization, mantle degassing or radiolysis with anthropogenic systems that stimulate the same reactions or convert in-situ hydrocarbons. Stable hydrogen accumulations require generation rates that outpace combined physical, chemical and microbial losses; the Bourakébougou field (Mali) exemplifies a self-recharging, free-gas reservoir sustained by meteoric-water serpentinization beneath an efficient caprock. Prospective geologic hydrogen resources are likely to occur in regions where iron-rich lithologies, deep-seated faults, and low-permeability sealing formations coexist. Applying this principle, we highlight three promising hydrogen play types in U.S. geological terrains: ophiolite belts (Appalachian and Californian regions), the Midcontinent Rift and the Lake Superior banded‑iron formations. Multiphysics numerical models and positive-unlabeled machine-learning workflows help to accelerate play screening and de-risk future production; yet, reaction kinetics, stimulation strategies, and full techno-economic and life-cycle assessments remain pivotal knowledge gaps.

Anthropogenic hydrogen generation↗

Sodium diffusion in heterogeneous porous media: Connecting laboratory experiments and simulations

Sodium has been suggested as a tracer for brine in reservoir formations where a significant amount of sodium ion is found mainly in the aqueous phase. Fortunately, the most abundant sodium isotope, 23 Na, is Nuclear Magnetic Resonance (NMR) active, making it possible to study the structure and dynamical properties of both bulk and pore confined fluid systems. We investigated the diffusion of key dissolved sodium species in bulk solution and porous media as a function of composition, ionic strength, and permeability of the carbonate samples using NMR relaxometry and pulsed-field gradient (PFG) NMR techniques. We use Indiana limestone as an example of natural porous media and water as a freely diffusible tracer and carrier. We demonstrate apparent diffusion measurement of sodium based on changes in spin–spin relaxation time (T 2 ) signal in pore confinement. The diffusion rate of sodium decreases with increasing counter-ion size. This effect is greater at higher ionic strengths and lower chemical potentials in porous media. The reactive transport code, CrunchFlow, was used to complement the NMR experiments to simulate diffusion behavior in porous media. Combining these two methods provides a powerful approach to estimating effective diffusion coefficients in heterogeneous matrices. The modeling considers the influence of physical properties (porosity and tortuosity) and chemical properties (geochemical composition and chemical gradients). The results presented in this work highlight the advantage of measuring apparent diffusivity using NMR T 2 relaxometry in conjunction with numerical simulation to derive effective diffusivity and the corresponding matrix properties (i.e., tortuosity) of the system.

58 GEOSCIENCES↗

Reinventing CEMENT: Carbonation-Enabled Mineralization to Engender Novel Technology

Cement is the most important building material used in civil infrastructure but it is extremely energy intensive to produce. We developed novel ways to make cements at low temperatures by mimicking the chemistry of the calcium silicate mineral pseudowollastonite. Pseudowollastonite is interesting because when it is exposed to hot (90-150oC), alkaline conditions with CO2 and water it reacts to form mineral phases that are much stronger than commercial cements. The resulting phases are also much more resistant to acid attack and have lower permeability, which will make them last longer. Many of the mineral phases in our cements are similar to those that exist in ancient Roman cements that have lasted thousands of years. Our objective was to understand how waste materials from industrial processes (such as power production, municipal solid waste treatment, or power plants) can be used to replicate the conditions that give pseudowollastonite cement its remarkable properties. We worked to optimize our formulations and incorporate the cements into concrete blends that the industry can test and consider using in different applications. Our cements could be used in pre-cast cement structural elements, which makes up nearly 20% of the total cement market and is growing rapidly. This work supports ARPA-E program objectives to significantly improve the industrial efficiency of materials production.

36 MATERIALS SCIENCE↗

Direct Measurement of Crossover and Interfacial Resistance of Ion-Exchange Membranes in All-Vanadium Redox Flow Batteries

Among various components commonly used in redox flow batteries (RFBs), the separator plays a significant role, influencing resistance to current as well as capacity decay via unintended crossover. It is well-established that the ohmic overpotential is dominated by the membrane and interfacial resistance in most aqueous RFBs. The ultimate goal of engineering membranes is to improve the ionic conductivity while keeping crossover at a minimum. One of the major issues yet to be addressed is the contribution of interfacial phenomena in the influence of ionic and water transport through the membrane. In this work, we have utilized a novel experimental system capable of measuring the ionic crossover in real-time to quantify the permeability of ionic species. Specifically, we have focused on quantifying the contributions from the interfacial resistance to ionic crossover. The trade-off between the mass and ionic transport impedance caused by the interface of the membranes has been addressed. The MacMullin number has been quantified for a series of electrolyte configurations and a correlation between the ionic conductivity of the contacting electrolyte and the Nafion® membrane has been established. The performance of individual ion-exchange membranes along with a stack of various separators have been explored. We have found that utilizing a stack of membranes is significantly beneficial in reducing the electroactive species crossover in redox flow batteries compared to a single membrane of the same fold thickness. For example, we have demonstrated that the utilization of five layers of Nafion ® 211 membrane reduces the crossover by 37% while only increasing the area-specific resistance (ASR) by 15% compared to a single layer Nafion ® 115 membrane. Therefore, the influence of interfacial impedance in reducing the vanadium ion crossover is substantially higher compared to a corresponding increase in ASR, indicating that mass and ohmic interfacial resistances are dissimilar. We have expanded our analysis to a combination of commercially available ion-exchange membranes and provided a design chart for membrane selection based on the application of interest (short duration/high-performance vs. long-term durability). The results of this study provide a deeper insight into the optimization of all-vanadium redox flow batteries (VRFBs).

UV/Vis spectroscopy↗

Interfacial and Confinement-Mediated Organization of Gas Hydrates, Water, Organic Fluids, and Nanoparticles for the Utilization of Subsurface Energy and Geological Resources

Harnessing the subsurface geologic environments in an efficient and environmentally sustainable manner is challenged by uncertainties associated with predicting the fate of fluids and sustaining porosity and permeability in subsurface geologic environments. Some of these uncertainties arise from confined and interfacially induced structures of fluids in subsurface geologic environments. The formation of gas hydrates, phase transitions of confined fluids, assembly and deposition of heavy hydrocarbons, and the agglomeration and fate of nanoparticles in confined environments are summarized in this review. Nanoscale confinement contributes to anisotropic structures and dynamics of fluids, which is the basis for anomalous phase transition thermodynamics, reactivity, transport, and geomechanical behavior. In this review, we discuss the structures of confined fluids and deviation in observed properties from bulk fluids. The factors influencing the structures of confined fluids can be generally divided into two groups: (a) pore characteristics including pore size, pore surface chemistry, and pore geometry and (b) confined fluid/solid characteristics such as molecular structure, concentrations, charges, pore filling, and presence of additives. Scientific advancements and knowledge gaps in our understanding of the structures of confined fluids and the associated differences in observed properties compared to bulk fluids are discussed. Here, the phenomena discussed in this review are of particular relevance to our efforts in harnessing the subsurface environments for a low carbon future by increasing the utilization of geothermal energy, using CO 2 as a working fluid, and storing CO 2 in subsurface geologic environments.

42 ENGINEERING↗

Assessment of chemo-mechanical impacts of CO 2 sequestration on the caprock formation in Farnsworth oil field, Texas

This study evaluates the chemo-mechanical influence of injected CO 2 on the Morrow B sandstone reservoir and the upper Morrow shale caprock utilizing data from the inverted 5-spot pattern centered on Well 13-10A within the Farnsworth unit (FWU). This study also seeks to evaluate the integrity of the caprock and the long-term CO 2 storage capability of the FWU. The inverted 5-spot pattern was extracted from the field-scale model and tuned with the available field observed data before the modeling work. Two coupled numerical simulation models were utilized to continue the study. First, a coupled hydro-geochemical model was constructed to simulate the dissolution and precipitation of formation minerals by modeling three intra-aqueous and six mineral reactions. In addition, a coupled hydro-geomechanical model was constructed and employed to study the effects of stress changes on the caprock’s porosity, permeability, and ground displacement. The Mohr–Coulomb circle and failure envelope were used to determine caprock failure. In this work, the CO 2 -WAG injection is followed by the historical field-observed strategy. During the forecasting period, a Water Alternating Gas (WAG) injection ratio of 1:3 was utilized with a baseline bottom-hole pressure constraint of 5500 psi for 20 years. A post-injection period of 1000 years was simulated to monitor the CO 2 plume and its effects on the CO 2 storage reservoir and caprock integrity. The simulation results indicated that the impacts of the geochemical reactions on the porosity of the caprock were insignificant as it experienced a decrease of about 0.0003% at the end of the 1000-year post-injection monitoring. On the other hand, the maximum stress-induced porosity change was about a 1.4% increase, resulting in about 4% in permeability change. It was estimated that about 3.3% of the sequestered CO 2 in the formation interacted with the caprock. Despite these petrophysical property alterations and CO 2 interactions in the caprock, the caprock still maintained its elastic properties and was determined to be far from its failure.

04 OIL SHALES AND TAR SANDS↗