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LLNL Kimberlina 1.2 NUFT Simulations June 2018 (v2)

This dataset contains the output 6,000, 3-dimensional reactive multi-phase flow and transport aquifer simulations of brine and CO2 leakage into a protective aquiver in California’s San Joaquin Valley and input data files detailing the geologic mesh, aquifer physical properties and CO2 and brine injection rates. This data set was generated as an ongoing effort with the US DOE National Risk Assessment Partnership (NRAP) to evaluate the effectiveness of monitoring techniques to detect brine and CO2 leakage from legacy wells into underground sources of drinking water overlaying a CO2 storage reservoir. Each simulation contains a unique set of input parameters, generated stochastically. The outputs consist of these upper three geologic layers (from top): the Etchegoin, Macoma-Chanac, Santa Margarita-McLure formations. These simulations span the several distances (1, 3 and 6 km or wells W31-0.2, W31-0.5 and W31-1.0, respectively) from the CO2 injector, initiated from bottom hole pressure and saturation to calculate wellbore leakage from the storage reservoir, with low and high regional groundwater gradients and wellbore leakage into 5 leaky nodes. The dataset includes 1,000 unique simulations for each distance, which each contain a unique aquifer heterogeneity, aquifer and caprock permeability, and two model generations are included with a high permeability (prod07) and hybrid permeability (prod09). The range of permeability distributions is listed in Table 1. Each model generation consists of 3,000 simulations. Included in the dataset are the leakage rates determined from 2D wellbore models which utilize the pressure and CO2 saturation from LBL's reservoir simulations, NUFT mesh files with distributed lithology, NUFT rocktab files which describe the material properties for the geologic layers and the NUFT input files and post-processed output 'ntab' files. Each ntab file contains spatial (rows) and temporal (columns) model output tables for each model cell, the locations (x,y,z) and dimensions for each cells (dx, dy, dz). Table 1. Permeability distribution ranges for prod07 and prod09 model generations Geologic Layer: Permeability Range (log10 m^2) prod07 prod09 Etchegoin -12.92 to -10.92 -13.70 to -11.44 Macoma-Chanac -12.72 to -10.72 -13.50 to -11.24 Santa Margarita-McLure -12.70 to -10.70 -13.48 to -11.22 The input files used to generate the model include which are included in the dataset are: Time series of CO2 leakage input into the model (ex: Q_brn.W31-0.2.sim1000.layers123.tab) Time series of CO2 leakage input into the model (ex: Q_CO2.W31-0.2.sim1000.layers123.tab) Physical properties of the aquifer materials detailing the aquifer porosity, solid density, partitioning coefficients, permeabilities and van-Genuchten parameters detailed in a NUFT rocktab file: (ex: sim1000.usnt.rocktab) Numerical mesh and geologic data assigned to each model cell detailed in a NUFT genmsh format (ex: sim1000.mesh_k16.prod07.trans.genmsh) The primary output parameters are: pH (use absolute value) Change in TDS (mg/kg) Change in Pressure (Pa) Change CO2 gas saturation (fraction range 0.0-1.0) for example, the directory /p/lscratchh/mansoor1/nrap/kimberlina/prod09/mainfiles/sim1000/W31- 0.2 contains: sim1000.W31-0.2.trans.pH.red.ntab sim1000.W31-0.2.no_bg.trans.TDS.red.ntab sim1000.W31-0.2.usnt.P.deltabg.red.ntab sim1000.W31-0.2.usnt.CO2_sat.deltabg.red.ntab Each row in the NTAB files consist of model output per numerical grid cell. Each output file contains 33 columns (variables), including the information of numerical records, geologic location and sizes and the simulated parameter values over time. The first 13 variables are about numerical records and relative geologic information for a simulation grid: 1. index: simulation index 2. i: the ith grid of x-axis 3. j: the ith grid of y-axis 4. k: the ith grid of z-axis 5. element_ref: element reference 6. nuft_ind: nuft index 7. x: grid location in the x axis direction 8. y: grid location in the y axis direction 9. z: grid location in the z axis direction 10. dx: grid length in the x axis direction 11. dy: grid length in the y axis direction 12. dz: grid length in the z axis direction 13. volume: volume of the simulation grid The remainder (14, 15, 16...) variables are the simulated parameter values over time, take Pressure as an example, are: 14. 0.0y: initial pressure per cell. 15. 10.0y: simulated pressure at the end of the 10th year. 16. 20.0y: simulated pressure at the end of the 20th year. ... (repeated for every 10 years until 200 years)... The model extends 10,000 m, 5,000 m and 1,411 m in the x,y and z dimensions, respectively. The mesh consists of 164,832 cells with mesh dimensions of 101 x 51 x 32 (nx, ny, nz), with cell dimensions ranging from 100 m laterally (along x and y-axis) and model layers are as designated in the z-axis: Layer 1: atmosphere (1e-30 m thick) Layer 2: upper caprock (10 m thick) Layers 3-13: Etchegoin (536.23 m thck) Layers 14-27: Macoma-Chanac (679.04 m thick) Layers 28-32: Santa Margarita-McLure (185.94 m thick) The wellbore is placed along node i=51, j=26, and extends vertically along 5 nodes from the top to the bottom of the model. Special instructions when extracting files: Each Gzip archive (ex: prod07.sim1000-sim00099.tar.gz) contains 100 simulations. Gzip archives should be transferred into base directories (ie. In Linux: mkdir prod07; mv prod07.*.tar.gz prod07/.) before extracting, or files will be overwritten. Each sub-simulation tree should have the following file structure pattern (using the linux 'tree' command): |-- prod07 | |-- sim0001 | |-- W31-0.2 | | |-- Q_brn.W31-0.2.sim0001.layers123.tab | | |-- Q_co2.W31-0.2.sim0001.layers123.tab | | |-- sim0001.W31-0.2.no_bg.trans.TDS.red.ntab | | |-- sim0001.W31-0.2.trans.pH.red.ntab | | |-- sim0001.W31-0.2.usnt.CO2_sat.deltabg.red.ntab | | |-- sim0001.W31-0.2.usnt.P.deltabg.red.ntab | |-- W31-0.5 | | |-- Q_brn.W31-0.5.sim0001.layers123.tab | | |-- Q_co2.W31-0.5.sim0001.layers123.tab | | |-- sim0001.W31-0.5.no_bg.trans.TDS.red.ntab | | |-- sim0001.W31-0.5.trans.pH.red.ntab | | |-- sim0001.W31-0.5.usnt.CO2_sat.deltabg.red.ntab | | |-- sim0001.W31-0.5.usnt.P.deltabg.red.ntab | |-- W31-1.0 | | |-- Q_brn.W31-1.0.sim0001.layers123.tab | | |-- Q_co2.W31-1.0.sim0001.layers123.tab | | |-- sim0001.W31-1.0.no_bg.trans.TDS.red.ntab | | |-- sim0001.W31-1.0.trans.pH.red.ntab | | |-- sim0001.W31-1.0.usnt.CO2_sat.deltabg.red.ntab | | |-- sim0001.W31-1.0.usnt.P.deltabg.red.ntab | |-- sim0001.mesh_k16.prod07.trans.genmsh Disclaimer This document was prepared as an account of work sponsored by an agency of the United States government. Neither the United States government nor Lawrence Livermore National Security, LLC, nor any of their employees makes any warranty, expressed or implied, or assumes any legal liability or responsibility for the accuracy, completeness, or usefulness of any information, apparatus, product, or process disclosed, or represents that its use would not infringe privately owned rights. Reference herein to any specific commercial product, process, or service by trade name, trademark, manufacturer, or otherwise does not necessarily constitute or imply its endorsement, recommendation, or favoring by the United States government or Lawrence Livermore National Security, LLC. The views and opinions of authors expressed herein do not necessarily state or reflect those of the United States government or Lawrence Livermore National Security, LLC, and shall not be used for advertising or product endorsement purposes. Lawrence Livermore National Laboratory is operated by Lawrence Livermore National Security, LLC, for the U.S. Department of Energy, National Nuclear Security Administration under Contract DE-AC52-07NA27344. This report was reviewed and released as LLNL-MI-753464.

aquifer↗

Simple Statistical Models for Predicting Overpressure Due to CO2 and Low-Salinity Waste-Fluid Injection into Deep Saline Formations

Deep saline aquifers have been used for waste-fluid disposal for decades and are the proposed targets for large-scale CO2 storage to mitigate CO2 concentration in the atmosphere. Due to relatively limited experience with CO2 injection in deep saline formations and given that the injection targets for CO2 sometimes are the same as waste-fluid disposal formations, it could be beneficial to model and compare both practices and learn from the waste-fluid disposal industry. In this paper, we model CO2 injection in the Patterson Field, which has been proposed as a site for storage of 50 Mt of industrial CO2 over 25 years. We propose general models that quickly screen the reservoir properties and calculate pressure changes near and far from the injection wellbore, accounting for variable reservoir properties. The reservoir properties we investigated were rock compressibility, injection rate, vertical-to-horizontal permeability ratio, average reservoir permeability and porosity, reservoir temperature and pressure, and the injectant total dissolved solids (TDS) in cases of waste-fluid injection. We used experimental design to select and perform simulation runs, performed a sensitivity analysis to identify the important variables on pressure build-up, and then fit a regression model to the simulation runs to obtain simple proxy models for changes in average reservoir pressure and bottomhole pressure. The CO2 injection created more pressure compared to saline waste-fluids, when similar mass was injected. However, we found a more significant pressure buildup at the caprock-reservoir interface and lower pressure buildup at the bottom of the reservoir when injecting CO2 compared with waste-fluid injection.

Ansari, Esmail↗

Design of a Meso-Scale Test of a Fracture Thermal Energy Storage (FTES) System

This paper will present the characterization, scaling, and design of an intermediate-scale field test of a fracture thermal energy storage system (FTES). Seasonal storage of thermal energy has the potential to both significantly reduce the total energy requirements for heating and cooling of buildings, but also allow for the flexibility to store thermal energy from intermittent sources. With approximately half of global energy consumption currently being used for heating and cooling, this represents an important path to reducing greenhouse gas (GHG) emissions. The concept of FTES is to drill two or more wells into a low permeability formation, generally at a depth of less than a few hundred meters, and then generate hydraulic fractures to create flow paths for water to circulate between the wells. Hot or cold thermal energy can then be stored in the surrounding rock mass by circulating hot or cold water through the fractures, which will heat or cool the rock mass. To recover the stored energy, ambient temperature water can be then circulated through the fractures, which will then be heated or cooled by the rock mass. Fractures inherently have a very large ratio of surface area to volume. This allows for very high heat fluxes to and from the rock mass to be achieved despite the relatively low thermal conductivity of most geologic formations. Because large fractures can be made with low-cost equipment and with only inexpensive and environmentally safe materials such as water and sand, the cost to construct even large FTES systems is expected to be quite low. This paper will present what the performance requirements, size, and operating conditions of a full-scale system to operate a commercial building. The paper will describe how these full-scale system characteristics will be used as a design basis for an intermediate-scale FTES test to be conducted at the Sanford Underground Research Facility (SURF) in Lead, SD.

Burghardt, Jeffrey A.↗

Normal Gravity Testing of a Microchannel Phase Separator for In Situ Resource Utilization

A microchannel separator, with 2.7 millimeters as the smallest dimension, was tested, and a pore throat structure captured and removed liquid from a gas-liquid stream. The microchannel device was tested over a of gas and liquid flow rates ranging from 0.0005 up to 0. 14 volume fraction of liquid. Four liquids were tested with air. The biggest factor affecting the throughput is the capacity of liquid flow through the pore throat, which is dictated by permeability, liquid viscosity, flow area, pore throat thickness, and pressure difference across the pore throat. Typically, complete separation of gas and liquid fractions was lost when the liquid flow rate reached about 40 to 60% of the pore throat capacity. However, this could occur over a range of 10 to 90% utilization of pore throat capacity. Breakthrough occurs in the microchannel phase separator at conditions similar to the annular to plug flow transition of two-phase microgravity pipe flow implying that operating in the proper flow regime is crucial. Analysis indicates that the Bond number did not affect performance, supporting the premise that hydrodynamic, interfacial, and capillary forces are more important than gravity. However, the relative importance of gravity is better discerned through testing under reduced gravity conditions.

TeGrotenhuis, Ward E.↗

Advances in 3D Geologic Modeling of Alluvial Basins with a Focus on Facies and Property Modeling

The unsaturated zone alluvium reference case is one of several geologic systems under consideration by the U.S. Department of Energy Office of Nuclear Energy for hosting repositories for spent nuclear fuel and associated waste (Sevougian et al., 2019). As noted by Mariner et al. (2018), the generic alluvial basin offers positive attributes that merit its consideration as a reference case by the Spent Fuel and Waste Science and Technology (SFWST) campaign. There are hundreds of alluvial basins and sub-basins scattered across the arid western United States (Figure 1-1). Precipitation and infiltration rates are relatively low with high evapotranspiration, resulting in vertical separation between repository and water table and thus longer transport paths to an aquifer. Accumulations of alluvial sediments within these basins are typically on the order of hundreds of meters, and locally may exceed 1,000 m in thickness, as is the case for the Deming sub-basin in southern New Mexico. A thick geologic host medium, which serves as the natural barrier system (NBS) in the conceptual model framework of a geologic disposal system, isolates the waste packages from receptors in the biosphere. Further, alluvial basin fill is typically comprised of stacked playa and lacustrine deposits along the basin axis (Perry et al., 2018). Characterized by low permeability, these layers protect the biosphere above the repository and the groundwater resources below the repository.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

Using onset times from frequent seismic surveys to understand fluid flow at the Peace River Field, Canada

With our limited knowledge of the relationship between changes in the state of an aquifer or reservoir and the corresponding changes in the elastic moduli, that is the rock physics model, hampers the effective use of time-lapse seismic observations for estimating flow properties within the Earth. A central problem is the complicated dependence of the magnitude of time-lapse changes on the saturation, pressure, and temperature changes within an aquifer or reservoir. We describe an inversion methodology for reservoir characterization that uses onset times, the calendar time of the change in seismic attributes, rather than the magnitude of the changes. We find that onset times are much less sensitive than magnitudes to the rock physics model used to relate time-lapse observations to changes in saturation, temperature and fluid pressure. We apply the inversion scheme to observations from daily monitoring of enhanced oil recovery at the Peace River field in Canada. An array of 1492 buried hydrophones record seismic signals from 49 buried sources. Time-shifts for elastic waves traversing the reservoir are extracted from the daily time-lapse cubes. In our analysis 175 images of time-shifts are transformed into a single map of onset times, leading to a substantial reduction in the volume of data. These observations are used in conjunction with bottom hole pressure data to infer the initial conditions prior to the injection, and to update the reservoir permeability model. The combination of a global and local inversion scheme produces a collection of reservoir models that are best described by three clusters. The updated model leads to a nearly 70 percent reduction in seismic data misfit. The final set of solutions successfully predict the observed normalized pressure history during the soak and flow-back into the wells between 82 and 175 days into the cyclic steaming operation.

58 GEOSCIENCES↗

Tritium Transport Phenomena in Molten-Salt Reactors: Molten Salt Tritium Transport Experiment Design

Tritium is produced from neutron interactions with both lithium and beryllium. Large quantities of tritium are generated in Molten Salt Reactors (MSRs) which use LiF/BeF2 (FLiBe) as the fuel salt. Tritium is unique among the radionuclide hazards as it readily permeates through metal structural materials at high temperatures. All metal surfaces are potential release paths for tritium. For adequate safety analysis and eventual licensing of new reactors, predictive models for tritium transport and release from MSRs must be developed. These models must account for the multiple transport phenomena involved with tritium: fuel salt phase mass transport, dissociation/recombination reactions on metal surfaces, interstitial diffusion through the metal structure, and salt or gas phase mass transport in the downstream fluid. These models also must also be validated with representative experiments. Our previous report outlined tritium transport phenomena involved in MSRs, made suggestions on gaps in the transport dataset, and proposed an experimental test stand to test combined transport effects – tritium transport through pipe walls in a convective salt flow. In this report, we summarize an updated analysis framework for tritium transport in MSRs, report our results on hydrogen and deuterium permeation through Hastelloy N, and describe the final design of the Molten Salt Tritium Transport Experiment (MSTTE, pronounced “misty”). The MSRE provides the only wholistic experimental data set for tritium transport in MSRs and understanding the transport phenomena involved in the MSRE is crucial for future model development. One set of parameters in our analysis framework was unknown for the MSRE—surface reaction rates for tritium on Hastelloy N. This warranted our hydrogen and deuterium permeation campaign to assess the permeability, diffusivity, and solubility of hydrogen isotopes in clean Hastelloy N. Surface reaction rate constants were probed by low pressure measurements, however, no surface effects were observed in the limits of our permeation apparatus. Permeation experiments on oxidized Hastelloy N were not performed for this report but are planned in future work. The experimental test stand, MSTTE, measures combined transport properties of the salt-metal system. MSTTE is a forced convection FLiBe loop with custom designed test section to measure tritium transport through candidate structural materials. We use MSRE relevant dimensionless numbers to design and scale the test section. Hastelloy N is a candidate loop and test section material due to the relevance for the MSRE and related designs, however, other metals are being considered (e.g. 316H SS) which may better align with current vendor concepts.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

Rotational stabilization of the resistive wall modes in tokamaks with a ferritic wall

The dynamics of the rotating resistive wall modes (RWMs) is analyzed in the presence of a uniform ferromagnetic resistive wall with μ{sup ^}≡μ/μ{sub 0}≤4 (μ is the wall magnetic permeability, and μ{sub 0} is the vacuum one). This mimics a possible arrangement in ITER with ferromagnetic steel in test blanket modules or in future experiments in JT-60SA tokamak [Y. Kamada, P. Barabaschi, S. Ishida, the JT-60SA Team, and JT-60SA Research Plan Contributors, Nucl. Fusion 53, 104010 (2013)]. The earlier studies predict that such a wall must provide a destabilizing influence on the plasma by reducing the beta limit and increasing the growth rates, compared to the reference case with μ{sup ^}=1. This is true for the locked modes, but the presented results show that the mode rotation changes the tendency to the opposite. At μ{sup ^}>1, the rotational stabilization related to the energy sink in the wall becomes even stronger than at μ{sup ^}=1, and this “external” effect develops at lower rotation frequency, estimated as several kHz at realistic conditions. The study is based on the cylindrical dispersion relation valid for arbitrary growth rates and frequencies. This relation is solved numerically, and the solutions are compared with analytical dependences obtained for slow (s/d{sub w}≫1) and fast (s/d{sub w}≪1) “ferromagnetic” rotating RWMs, where s is the skin depth and d{sub w} is the wall thickness. It is found that the standard thin-wall modeling becomes progressively less reliable at larger μ{sup ^}, and the wall should be treated as magnetically thick. The analysis is performed assuming only a linear plasma response to external perturbations without constraints on the plasma current and pressure profiles.

70 PLASMA PHYSICS AND FUSION TECHNOLOGY↗

Multiscale Characterization of the Caney Shale — An Emerging Play in Oklahoma

From a hydrocarbon perspective, the Caney Shale has historically been evaluated as a sealing unit, which resulted in limited studies characterizing the rock properties of the Caney Shale and its suitability for hydraulic fracturing. The objective of our research is to help bridge the current knowledge gap through the integration of multiscale laboratory techniques and to characterize the macro- and microscale rock properties of the Caney Shale. We employed an integrated approach for the characterization of the Caney using 200 ft (61 m) of Caney core from a target well in southern Oklahoma. Core observation and petrographic analysis of thin sections were combined to characterize the general rock types and associated fabrics and textures. Mineralogical composition, pore system architecture, and rock fabric were analyzed using x-ray diffraction (XRD), scanning electron microscopy/energy dispersive x-ray spectroscopy (SEM/EDS), and focused ion beam (FIB)-SEM. In addition, rebound hardness and indentation testing were carried out to determine rock hardness (brittleness) and elasticity, respectively. With the integrated multiscale characterization, three mixed carbonate-siliciclastic rock types were identified — mudstone, calcareous siltstone, and silty carbonate — likely representing a spectrum of deposition from low to relatively high energy environments in the distal portions of a ramp system. Silty carbonate contains mostly interparticle pores. The calcareous siltstones and silty mudstones contain a combination of organic matter pores and interparticle pores. Each of the rock types shows unique mineralogical compositions based on XRD. The mudstone lithofacies has the highest clay content and the least carbonate content. Calcareous siltstones show moderate carbonate and clay content. Silty carbonate indicates the highest carbonate content with the least clay content. In an order of mudstone, calcareous siltstone, and silty carbonate, rebound hardness and Young’s modulus show an increasing trend. As a result of rock-fluid interactions, there are potential scaling reactions during completion and production that could ultimately affect permeability and production rates. Overall, the proposed multiscale integration approach is critical for the geologic characterization of most rocks. However, in shale reservoirs dominated by microporosity and microstructure where engineered fractures are expected to provide permeability at a reservoir scale, successful integration is essential. An optimized, integrated geological characterization of the Caney Shale that is well aligned with the engineering designs in drilling, completing, and producing wellbores will ultimately lead to optimal production while providing safe and environmentally responsible operations.

Wang, Yulun↗

A Passive Magnetoelastic Radiation Sensor

A passive gamma detection technology, consisting of a fielded sensor and a separate analysis system, is described. The sensor is a small cylinder, about 2.5 mm in diameter and 15 mm in length. It requires no onboard power sources or physical connections for power or data transfer, and retains its cumulative response to radiation. The sensor consists of an amorphous magnetoelastic wire held in a longitudinally-stressed state by a radiation-sensitive material. When the radiation-sensitive material is subjected to gamma radiation, it mechanically degrades, relaxing the stress on the wire and lowering the wire’s magnetic permeability. The changes in permeability are observed by switching the magnetic domains in the wire and measuring the reduction in the Faraday voltage as the stress is diminished. The analysis package is built around an excitation-detection coil set and can communicate wirelessly with the sensor through a metallic or nonmetallic barrier at distances up to about 25 mm. The sensor response is linear up to a dose of at least 7 kGy.

46 INSTRUMENTATION RELATED TO NUCLEAR SCIENCE AND ↗

Technical Requirements for Geothermal Resource Confirmation

In 2017-2018, the Bureau of Land Management's Renewable Energy Coordination Office, through its Geothermal Program, funded the National Renewable Energy Laboratory (NREL) to analyze technical and environmental considerations related to geothermal resource confirmation drilling. NREL solicited input from a group of technical and environmental experts in the geothermal industry, along with analyzing National Environmental Policy Act of 1969 (NEPA) documentation for previously approved projects. The collected data and analysis will be used by the Bureau of Land Management to examine the possibility of developing a new classification of wells and/or expediting the NEPA compliance process, which could potentially reduce permitting and regulatory compliance timelines when compared to the current process for obtaining a geothermal drilling permit for resource confirmation drilling activities. This paper provides a summary of the technical requirements for confirming a geothermal resource. The analysis showed that confirming a geothermal resource requires confirming reservoir temperature, chemistry, permeability, and flow rate. Obtaining these data requires drilling at least two-preferably three-successful wells into the resource to conduct the necessary tests, including an interference test. Bottom-hole well diameters of at least 6'' to 8'' (0.15 to 0.2 m) are needed to limit the wellbore frictional pressure drop to effectively perform well flow and interference tests. Drilling these wells requires a drill rig with a mud pump and derrick capable of holding three drill pipes. This type of rig requires a minimum well-pad size of 2.5 acres (104 m2) including surface area for a 1 million-gallon (3.8 million-liter) pit. Up to 15 acres (5x104 m2) of total surface disturbance are needed for developing access roads and well pads to drill a total of three to five wells.

15 GEOTHERMAL ENERGY↗

Integrated Experimental and Modeling Studies of Mineral Carbonation as a Mechanism for Permanent Carbon Sequestration in Mafic/Ultramafic Rocks

A program of laboratory experiments, modeling and fieldwork was carried out at Yale University, University of Maryland, and University of Hawai‘i, under a DOE Award (DE-FE0004375) to study mineral carbonation as a practical method of geologic carbon sequestration. Mineral carbonation, also called carbon mineralization, is the conversion of (fluid) carbon dioxide into (solid) carbonate minerals in rocks, by way of naturally occurring chemical reactions. Mafic and ultramafic rocks, such as volcanic basalt, are natural candidates for carbonation, because the magnesium and iron silicate minerals in these rocks react with brines of dissolved carbon dioxide to form carbonate minerals. By trapping carbon dioxide (CO 2 ) underground as a constituent of solid rock, carbonation of natural basalt formations would be a secure method of sequestering CO 2 captured at power plants in efforts to mitigate climate change. Geochemical laboratory experiments at Yale, carried out in a batch reactor at 200°C and 150 bar (15 MPa), studied carbonation of the olivine mineral forsterite (Mg 2 SiO 4 ) reacting with CO 2 brines in the form of sodium bicarbonate (NaHCO 3 ) solutions. The main carbonation product in these reactions is the carbonate mineral magnesite (MgCO 3 ). A series of 32 runs varied the reaction time, the reactive surface area of olivine grains and powders, the concentration of the reacting fluid, and the starting ratio of fluid to olivine mass. These experiments were the first to study the rate of olivine carbonation under passive conditions approaching equilibrium. The results show that, in a simple batch reaction, olivine carbonation is fastest during the first 24 hours and then slows significantly and even reverses. A natural measure of the extent of carbonation is a quantity called the carbonation fraction, which compares the amount of carbon removed from solution, during a run, to the maximum amount that could have been removed if the olivine initially present had fully dissolved and the cations released had subsequently precipitated in carbonate minerals. The carbonation fractions observed in batch experiments with olivine grains and powders varied significantly, from less than 0.01 (1%) to more than 0.5 (50%). Over time, the carbonation fractions reached an upper limit after about 24 to 72 hours of reaction, then stayed constant or decreased. The peak Final Scientific/Technical Report DE-FE0004275 | Mineral Carbonation | 4 coincided with the appearance of secondary magnesium-bearing silicate minerals, whose formation competes for magnesium ions in solution and can even promote conditions that dissolve magnesite. The highest carbonation fractions resulted from experiments with low ratios of concentrated solution to olivine, during which amorphous silica spheres or meshes formed, instead of secondary silicate minerals. The highest carbonation fractions appear to result from competing effects. Precipitation of silica layers on olivine reduces the reactive surface area and, thus, the rate of olivine dissolution (which ultimately limits the carbonation rate), but these same silica layers can also inhibit the formation of secondary silicate minerals that consume magnesite formed in earlier stages of carbonation. Simulation of these experiments with simple geochemical models using the software program EQ3/6 reproduces the general trends observed—especially the results for the carbonation fraction in short-run experiments. Although further experimentation and better models are needed, this study nevertheless provides a framework for understanding the optimal conditions for sequestering carbon dioxide by reacting CO 2 -bearing fluids with rocks containing olivine minerals. A series of experiments at the Rock Physics Laboratory at the University of Maryland studied the carbonation process during deformation of thermally cracked olivine-rich rock samples (dunite) saturated with CO 2 brines of varying compositions. A goal of these geomechanical experiments was to see if flow and deformation processes, which accompany natural carbonation reactions in underground settings, work to enhance or inhibit the reactions. The experiments involved hydrostatic compaction, followed by deformation at a constant rate of strain. Sample permeability was monitored during the reactions. Comparison of the samples’ volume changes to their axial strains (shortening) during deformation indicates that samples reacted with CO 2 -saturated brines accommodate more axial compaction, before the onset of dilation (a swelling that precedes rock failure), than samples reacted with distilled water. Analyses of the reacted samples with scanning electron microscope (SEM) images indicate, first, that dissolution of olivine occurring in the initial stages of carbonation can provide pathways to fluid flow that sustain the reaction, and, second, that carbonate minerals precipitated along existing fractures in the rocks may serve as asperities, or roughness on a crack’s surface that restricts its closure. Final Scientific/Technical Report DE-FE0004275 | Mineral Carbonation | 5 In a related study undertaken by one of the principal investigators as a spin-off of the main project, a simple model of (magnesite) crystal growth in the pore space of basalts undergoing carbonation was developed. The model suggests that, under a carefully controlled program of CO 2 injection, carbonate mineral growth can harden the rock formation against earthquakes that might otherwise be induced by the injection of large fluid volumes (Yarushina and Bercovici, 2013). The overall conclusion of the research project is that mineral carbonation of underground mafic and ultramafic rock formations is a viable candidate for long-term sequestration of man-made carbon dioxide. No results obtained during the project indicate that the method is inherently intractable in its implementation; moreover, enormous volumes of basalt near Earth’s surface are candidate locations for large-scale injection programs. The geochemical experiments do indicate, however, that there will be significant engineering challenges in maintaining high rates of carbonation, by delaying the onset of chemical conditions that promote formation of secondary silicate minerals and, therefore, slow down, or even reverse, the carbonation process. It remains an open question as to whether carbonation processes can be sustained for many years in an engineered system operating on a large scale—a scale capable of accommodating millions of tons of CO 2 annually. The development of realistic theoretical models that can systematically describe the combined effects of reactive flow, precipitation and geomechanical deformation is a major barrier to further understanding of the practical viability of mineral carbonation as large-scale method of carbon sequestration.

58 GEOSCIENCES↗

Galfenol Tactile Sensor Array and Visual Mapping System

The smart material, Galfenol, is being explored for its uses as a magnetostrictive material. This project seeks to determine if Galfenol can be used as a tactile sensor in a 2-D grid array, magnetic circuit system. When used within a magnetic circuit, Galfenol indicates induced stress and force as a change in flux, due to a change in permeability of the material. The change in flux is detected by Giant MagnetoResistive (GMR) Sensors, which produce a voltage change proportional to the field change. By using Galfenol in an array, this research attempts to create a sensory area. Galfenol is an alloy made of Iron and Gallium. FexGax, where 15 less than or equal to x less than or equal to 28, creates a material with useful mechanical and transduction attributes (Clark et al and Kell). Galfenol is also distinguished by the crystalline structure of the material. Two types currently exist: single crystal and polycrystalline. Single crystal has higher transduction coefficients than polycrystalline, but is more costly. Polycrystalline Galfenol is currently available as either production or research grade. The designations are related to the sample growth rate with the slower rate being the research grade. The slower growth rate more closely resembles the single crystal Galfenol properties. Galfenol 17.5- 18% research grade is used for this experiment, provided by Etrema Products Inc. The magnetic circuit and sensor array is first built at the macro scale so that the design can be verified. After the macro scale is proven, further development will move the system to the nano-level. Recent advances in nanofabrication have enabled Galfenol to be grown as nanowires. Using the nanowires, research will seek to create high resolution tactile sensors with spatial resolutions similar to human finger tips, but with greater force ranges and sensitivity capabilities (Flatau & Stadler). Possible uses of such systems include robotics and prosthetics.

Hale, Kathleen↗

Clean and Secure Energy from Domestic Oil Shale and Oil Sands Resources

This report summarizes the significant findings from the Clean and Secure Energy from Domestic Oil Shale and Oil Sands Resources program sponsored by the Department of Energy through the National Energy Technology Laboratory. There were four principle areas of research: Environmental, legal, and policy issues related to development of oil shale and oil sands resources, Economic and environmental assessment of domestic unconventional fuels industry, Basin-scale assessment of conventional and unconventional fuel development impacts, and Liquid fuel production by in situ thermal processing of oil shale. Multiple research projects were conducted in each area and the results have been communicated via sponsored conferences, conference presentations, invited talks, interviews with the media, numerous topical reports, journal publications, and a book that summarizes much of the oil shale research relating to Utah’s Uinta Basin. In addition, a repository of materials related to oil shale and oil sands has been created within the University of Utah’s Institutional Repository, including the materials generated during this research program.

04 OIL SHALES AND TAR SANDS↗

Electrochemical Measurement of Water Transport Numbers in Anion-Exchange Membranes

Anion-exchange membranes (AEMs) are a possible replacement for perfluorosulfonic-acid membranes in energy-conversion devices, primarily due to the hydroxide mobile ion allowing the devices to operate in alkaline conditions with less expensive electrocatalysts. However, the transport properties of AEMs remain understudied, especially electro-osmosis. In this work, an electrochemical technique, where the open-circuit voltage is measured between two ends of a membrane maintained at different relative humidities, is used to determine the water transport number of various ionomers, including Versogen and Sustainion AEMs and Nafion cation-exchange membrane (CEM), as a function of water content and temperature. In addition, the CEMs and AEMs are examined in differing single-ion forms, specifically proton and sodium (CEM) and hydroxide and carbonate (AEM). Carbonate-form AEMs have the highest transport number (∼11), followed by sodium-form CEMs (∼8), hydroxide-form AEMs (∼6), and proton-form CEMs (∼3). Finally, a multicomponent transport model based on the Stefan-Maxwell-Onsager framework of binary interactions is used to develop a link between water transport number and water-transport properties, extracting a range for the unmeasured membrane water permeability of Versogen as a function of water content.

30 DIRECT ENERGY CONVERSION↗

Real Time Degassing of Rock during Deformation

An experimental system we developed combines triaxial rock deformation and mass spectrometry to measure noble gas flow before, during, and after rock fracture. Geogenic noble gas is released during triaxial deformation (real time) and is related to volume strain and acoustic emissions. The noble gas release then represents a signal of deformation during its stages of development. Noble gases are contained in most crustal rock at inter and intra granular sites. Their release during natural and man-made stress and strain changes represents a signal of deformation in brittle and semi-brittle conditions. The noble gas composition depends on lithology, geologic history, age of the rock, and fluids present. Uranium, thorium and potassium-40 concentrations in the rocks also affect the production of radiogenic noble gases (4He, Ar). Noble gas emission and its relationship to crustal processes have been studied for many years in the geologic community including correlations to tectonic velocities and qualitative estimates of deep permeability from surface measurements, finger prints of nuclear weapon detonation, and as a potential precursory signal to earthquakes attributed to gas release due to pre-seismic stress, dilatancy and/or fracturing of the rock. Helium emission has been shown as a precursor of volcanic activity. We present empirical results/relationships of specimen strain, microstructural evolution, acoustic emissions, and noble gas release from laboratory triaxial experiments performed upon a granite and a young basalt, bedded salt, and a marine shale.

58 GEOSCIENCES↗

Integrated Modeling Report for CO 2 Storage with Enhanced Oil Recovery in Northern Michigan

The Midwest Regional Carbon Sequestration Partnership (MRCSP) was founded in 2003 as part of the U.S. Department of Energy’s (DOE’s) Regional Carbon Sequestration Partnership initiative. Since its founding, MRCSP has made significant strides toward making CCUS a viable option for states in the region. The public/private consortium, funded through the DOE Regional Carbon Sequestration Initiative, brings together nearly 40 industry partners and 10 states. Battelle, as the project lead, oversees research, development and operations and coordinates activities among the partners. The incremental, phased approach has built a valuable knowledge base for the industry and paved the way for commercial-scale adoption of CCUS technologies. From 2008 to 2020, MRCSP Phase III focused on the development of large-scale injection projects. This report is part of a series of reports prepared under the Midwestern Regional Carbon Sequestration Partnership (MRCSP) Phase III (Development Phase). These reports summarize and detail the findings of the work conducted under the Phase III project. MRCSP has been investigating various reservoir characterization and modeling technologies related to Carbon Capture, Utilization, and Storage (CCUS) in conjunction with carbon dioxide enhanced oil recovery (CO 2 -EOR) operations in multiple Silurian-age (Niagaran), oil-bearing, carbonate pinnacle reefs in northern Michigan, USA. This report provides a comprehensive discussion of reservoir modeling studies that were conducted for tracking oil production, forecasting CO 2 plume migration, and estimating associated storage in a number of reefs that were at different stages of their CO 2 -EOR life cycle. The modeling process for simulating oil production, CO 2 injection, and associated storage in these reefs entails two phases. The first phase, geologic framework modeling, integrates all pertinent geological and geophysical data (from logs, cores and seismic surveys) about reservoir structure, geometry, rock types, and property distributions (porosity, permeability, water saturation) into a 3-D distributed grid-based static earth model (SEM). The second phase, dynamic reservoir modeling, uses the SEM as a platform to simulate the movement of oil, gas, water, and CO 2 within the reservoir during primary hydrocarbon production, as well as during subsequent phases such as CO 2 -injection assisted EOR, plume migration, and associated storage. In addition, an assessment of coupled process effects is also carried out, where the impacts of geochemical and geo-mechanical processed induced by CO 2 injection are studied.

01 COAL, LIGNITE, AND PEAT↗