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At least 379 records · Page 21

Performance of the Fluidized Bed Steam Reforming Product Under Hydraulically Unsaturated Conditions

Currently, several candidates for secondary waste immobilization at the Hanford site in the State of Washington, USA are being considered. To demonstrate the durability of the product in the unsaturated Integrated Disposal Facility (IDF) at the site, a series of tests have been performed one of the candidate materials using the Pressurized Unsaturated Flow (PUF) system. The material that was tested was the Fluidized Bed Steam Reformer (FBSR) granular product and the granular product encapsulated in a geopolymer matrix. The FBSR product is composed primarily of an insoluble sodium aluminosilicate matrix with the dominant phases being feldspathoid minerals mostly nepheline, sodalite, and nosean. The PUF test method allows for the accelerated weathering of materials, including radioactive waste forms, under hydraulically unsaturated conditions, thus mimicking the open-flow and transport properties that most likely will be present at the IDF. The experiments show a trend of decreasing tracer release as a function of time for several of the elements released from the material including Na, Si, Al, and Cs. However, some of the elements, notably I and Re, show a steady release throughout the yearlong test. This result suggests that the release of these minerals from the sodalite cage occurs at a different rate compared with the dissolution of the predominant nepheline phase.

Durability testing↗

Electrochemical Behavior of Cerium at an Indium Tin-Doped Oxide Electrode in Acidic Media

The redox behavior and speciation of cerium at mesoporous thin films composed of nanoparticles of indium tin-doped oxide (nITO) electrodes were characterized in pH 4.8, 0.1 M acetate buffer and both 0.1 and 1 M HNO 3 using electrochemical techniques and X-ray photoelectron spectroscopy. Anodic deposition of ceria species from Ce(III) to the nITO electrode was achieved under all solvent conditions via spontaneous condensation of electrochemically generated ceric hydroxide species. In 1 M nitric acid, the rate of CeO 2 dissolution is on the same order as CeO 2 deposition, resulting in negligible amounts of CeO 2 electrodeposited at the nITO surface. The cathodic stripping of CeO 2 from the nITO substrate deposited in 0.1 M nitric acid or pH 4.8 acetate buffer follows a 2-step process where Ce(IV)-oxide is initially reduced to an unstable Ce(III)-oxide species that rapidly undergoes acid catalyzed dissolution to yield soluble Ce(III) (aq) . These findings provide a foundation for the pH and anodic potential controlled deposition of CeO 2 thin films to ITO substrates, which can aid in the development of materials composed of ceria. As a result, they can also be used to infer likely analogous actinide redox behavior and speciation at these electrodes.

Cerium↗

Developing Soret Transport Coefficients for Lanthanides from Experimental Results

Understanding the nature of lanthanide transport in metallic fuels and its relation to fuel clad chemical interaction (FCCI) has been has been a topic that is long on interest and short on data. Recent experiments have shown a strong temperature-gradient based diffusion (Soret diffusion) and have thus provided vitally important information for modelers. However, details about the actual coefficients and many of the relevant processes that crucially participate in the cerium migration and precipitation process have not yet been disclosed. Using a combination of computing tools (primarily python and BISON) we are exploring methods that may extract useful information from visual data. In this specific example, we are using what is formally called 'blob detection' algorithms to analyzed the precipitate distribution of cerium in a U-Zr metal that has had a fixed temperature gradient enforced upon it for a specified period of time. These algorithms, once properly adapted to the problem at hand, may be useful at extracting information from radial and axial scans of metallic fuels which are much more abundant than direct measurements of lanthanides. We have developed a model that qualitatively works to move mass along a temperature gradient and precipitate heavily in the cold regions. Additionally, we have observed that the solubility of cerium in U-Zr held under this kind of temperature gradient is subject to some amount of U-Zr constituent redistribution. Our results predict movement of the Zr toward the hot end of the rod followed by a U-rich layer with the cooler 3/5 of the rod staying close the the initial U-Zr distribution. A more complete analysis will define groups of correlated parameters that correctly simulate the resulting distribution of precipitates. This restricted parameters space will give smaller bounds to modelers and will expedite the analysis of future works as new and more accurate data are made available. A follow-up experiment that started with 1/10 of the initial concentration of cerium may provide valuable additional information with regard to the effect of the rates of precipitation and dissolution as well as demonstrating the potential rapidity of migration in a lower burnup scenario. (authors)

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗

Presence and Impact of Surface Films formed on Mg in Chloroaluminate Electrolytes.

The impact of surface film formation on Mg is explored during electrodeposition and electrodissolution in two high activity, aprotic electrolytes: the all phenyl complex (APC) and the magnesium aluminum chloride complex (MACC). Where past studies have argued such films are benign, results show that interfacial films are responsible for controlling the Mg deposit structure when deposition and dissolution are conducted at the rates required for practical Mg batteries. Chronopotentiometry is shown to provide clear signatures of the impact of interfacial films on deposition and dissolution. The particular combination of cycling punctuated by periods of open circuit equilibration is shown to yield a noticeable decrease in coulombic efficiency over a 50 cycle sequence. High resolution electron imaging shows that cycling results in porosity development and accumulation of electrolyte constituents within the deposit. Reduced coulombic efficiency signaling Mg loss appears related to progressive isolation of a fraction of the deposit. Mg and electrolyte loss must be compensated for in a practical cell through the introduction of excess inventory and resulting in a reduced energy density of the system.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Radiolysis and Radiation-Driven Dynamics of Boehmite Dissolution Observed by In Situ Liquid-Phase TEM

We report over the last several decades, there have been several studies examining the radiation stability of boehmite and other aluminum oxyhydroxides, yet less is known about the impact of radiation on boehmite dissolution. Here, we investigate radiation effects on the dissolution behavior of boehmite by employing liquid-phase transmission electron microscopy (LPTEM) and varying the electron flux on the samples consisting of either single nanoplatelets or aggregated stacks. We show that boehmite nanoplatelets projected along the [010] direction exhibit uniform dissolution with a strong dependence on the electron dose rate. For nanoplatelets that have undergone oriented aggregation, we show that the dissolution occurs preferentially at the particles at the ends of the stacks that are more accessible to bulk solution than at the others inside the aggregate. In addition, at higher dose rates, electrostatic repulsion and knock-on damage from the electron beam causes delamination of the stacks and dissolution at the interfaces between particles in the aggregate, indicating that there is a threshold dose rate for electron-beam enhancement of dissolution of boehmite aggregates.

54 ENVIRONMENTAL SCIENCES↗

Quantification of Kinetic Rate Law Parameters of Uranium Release from Sodium Autunite as a Function of Aqueous Bicarbonate Concentrations

ABSTRACT: Hydrogen carbonate is one of the most significant components within the uranium geochemical cycle. In aqueous solutions, hydrogen carbonate forms strong complexes with uranium. As such, aqueous bicarbonate may significantly increase the rate of uranium release from uranium minerals. Quantifying the relationship of aqueous hydrogen carbonate solutions to the rate of uranium release during dissolution is critical to understanding the long-term fate of uranium within the environment. Single-pass flow-through (SPTF) experiments were conducted to estimate the rate of uranium release from Na meta-autunite as a function of bicarbonate solutions (0.0005-0.003 M) under the pH range of 6-11 and temperatures of 5-60oC. Consistent with the results of previous investigation, the rate of uranium release from sodium autunite exhibited minimal dependency on temperature; but were strongly dependent on pH and increasing concentrations of bicarbonate solutions. Most notably at pH 7, the rate of uranium release exhibited 370 fold increases relative to the rate of uranium release in the absence of bicarbonate. However, the effect of increasing concentrations of bicarbonate solutions on the release of uranium was significantly less under higher pH conditions. It is postulated that at high pH values, surface sites are saturated with carbonate, thus the addition of more bicarbonate would have less effect on uranium release. Results indicate the activation energies were unaffected by temperature and bicarbonate concentration variations, but were strongly dependent on pH conditions. As pH increased from 6 to 11, activation energy values were observed to decrease from 29.94 kJ mol-1 to 13.07 kJ mol-1. The calculated activation energies suggest a surface controlled dissolution mechanism.

Aqueous Bicarbonate↗

Evaluation of Changes to the MTR Fuel Dissolution Flowsheet to Increase the Number of L-Bundles Charged to a Dissolver

Material Test Reactor (MTR) fuels are dissolved in the H-Canyon facility using a Hg-catalyzed, HNO₃ dissolution flowsheet. The flowsheet is based on experimental work in which laboratory-scale experiments were used to provide bounding values for both offgas and H₂ generation rates. The generation of H₂ gas, primarily from the dissolution of Al, is controlled by limiting the surface area exposed to the solution. The number of L-Bundles charged and their submergence level defines the exposed surface area which is directly proportional to the H₂ generation rate. For the MTR fuel dissolution flowsheet, the maximum number of L-Bundles which can be charged to a dissolver was specified as a function of the Al concentration in the solution and the submergence level of the bundle. The MTR fuels are currently dissolved in the 6.1D dissolver. To reach the desired terminal Al concentration, a total of 12 L-Bundles of fuel are dissolved per batch. Depending on the submergence level being used in the dissolver, the 12 bundles are dissolved in three charges of four bundles per charge or in a sequence of three, four, and five bundles. However, if six L-Bundles could be dissolved in the initial charge, a dissolver batch could be completed in two dissolutions instead of three. To assess the feasibility of dissolving six bundles in the first charge, the Savannah River National Laboratory evaluated changes to the MTR flowsheet which increase the number of bundles which can be charged to a dissolver. Since the development of the existing MTR fuel dissolution flowsheet, improved offgas measurement methods have been developed to more accurately calculate the offgas composition and generation rate during laboratory-scale dissolutions. In the first part of this study, improvements in the calibration model for the Raman spectrometer (used for offgas characterization) and a more effective data smoothing routine were applied to existing data. The uncertainty in the offgas composition data used to define the MTR fuel dissolution flowsheet were subsequently re-evaluated which resulted in an approximate 50% reduction in the uncertainty of the H₂ gas concentration measurements. The reduced uncertainty was used in new calculations to define the maximum number of L-Bundles which can be charged to either the 6.1D or 6.4D dissolver as a function of the Al concentration. With the reduced uncertainty in the H₂ concentration measurements, a flowsheet was defined which supported initially charging 6 bundles to a dissolver. This flowsheet is based on the use of 0.002 M Hg, an L-Bundle immersion depth of 54 in., an air sparge/purge flowrate of 40 scfm, an iodine reactor operating temperature of 200 °C, and not exceeding 60% of the H₂ LFL in the dissolver offgas. In the second phase of this study, calculations were performed to assess the impact of changing various operating parameters to increase the number of L-Bundles charged to an H-Canyon dissolver. Applying the improved offgas measurement techniques including the reduced uncertainty in the H₂ concentration measurements to the existing data, the number of bundles of MTR fuel which can be charged to either the 6.1D or 6.4D dissolver were calculated based on varying the bundle immersion depth (44-60 in.), air sparge/purge flowrate (40-60 scfm), iodine reactor operating temperature (150-200 °C), and the percentage of the H₂ LFL which must not be exceeded (60-76%). Qualitatively, the percentage of the LFL had the largest influence on the maximum number of bundles which can be charged to a dissolver followed by the air sparge/purge flowrate, L-Bundle immersion depth, and the iodine reactor operating temperature. During the evaluation of each variable, the other variables were held at the baseline flowsheet conditions.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗

In-Tank Processing Using Low Temperature Aluminum Dissolution: Year 1 Progress Report

The Hanford Site stores approximately 56 million gallons of radioactive legacy defense waste in underground tanks. This study investigates the feasibility of utilizing in-tank low-temperature aluminum dissolution to favorably alter the transport properties of aluminum-rich southeast quadrant waste sludges, thereby de-risking sludge delivery for Direct Feed of High-Level Waste. Specifically, this study aims to assess the rate and extent of gibbsite dissolution under various conditions, including different particle sizes (~10 to 90 µm), NaOH concentrations (1 to 6 M), and the presence of specific analytes such as NO 2 - , NO 3 - , and other aluminum-rich waste background analytes, using simulated waste solids and liquids. Experimental tests were designed to highlight the impact of aluminum leaching on simulated waste transport properties, quantified by the just-suspended mixing speed (NJS), and were conducted under well-mixed, turbulent conditions, ensuring full suspension of gibbsite particles using an overhead mixer. The results suggest that the presence of NO 2 - and NO 3 - , in conjunction with leaching at relatively low free hydroxide contents, improved transport requirements (i.e., lowered NJS) for pure gibbsite slurries. These findings will inform the design of potential in-tank processing systems, optimizing aluminum dissolution for improved waste management in the Hanford Tank Farms.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

A Novel High Energy Density Sorption-based Thermal Battery for Low-grade Thermal Energy Storage

Thermal energy storage (TES) can alleviate peak demand on the electricity grid by offsetting building thermal loads, increasing the grid’s reliability and resilience. However, low energy density and poor energy performance of existing TES technologies limit their applications. Sorption-based thermal battery (STB) system is thus developed using three-phase sorption technology to harvest low-temperature heat, store it with a much higher energy density than common TES systems and dehumidify air or provide space cooling in buildings. Although STB has been experimentally proved to be feasible, influencing factors on its performance are still unknown by far. Therefore, this paper conducted a parametric analysis on crystallization and crystal dissolution performance of a developed STB test rig. The crystallization results showed that the energy density of the STB increased with reducing the solution flow rate and the cooling water temperature. The dissolution results showed that a higher discharge rate of the STB can be achieved with increasing the flow rate and temperature of inlet diluted solution. The work in this study is helpful to the optimal design and operation of the STB system.

Wang, Lingshi↗

The role of local strains from prior cold work on stress corrosion cracking of α-brass in Mattsson's solution

The dynamic strain rate ahead of a crack tip formed during stress corrosion cracking (SCC) under a static load is assumed to arise from the crack propagation. The strain surrounding the crack tip would be redistributed as the crack grows, thereby having the effect of dynamic strain. Recently, several studies have shown cold work to cause accelerated crack growth rates during SCC, and the slip-dissolution mechanism has been widely applied to account for this via a supposedly increased crack-tip strain rate in cold worked material. While these interpretations consider cold work as a homogeneous effect, dislocations are generated inhomogeneously within the microstructure during cold work. The presence of grain boundaries results in dislocation pile-ups that cause local strain concentrations. The local strains generated from cold working α-brass by tensile elongation were characterized using electron backscatter diffraction (EBSD). The role of these local strains in SCC was studied by measuring the strain distributions from the same regions of the sample before cold work, after cold work, and after SCC. Though, the cracks did not always initiate or propagate along boundaries with pre-existing local strains from the applied cold work, the local strains surrounding the cracked boundaries had contributions from both the crack propagation and the prior cold work. - Highlights: • Plastic strain localization has a complex relationship with SCC susceptibility. • Surface relief created by cold work creates its own granular strain localization. • Cold work promotes crack growth but several other factors are involved.

36 MATERIALS SCIENCE↗

Morphological instability of aqueous dissolution of silicate glasses and minerals [Nonlinear dynamics of aqueous dissolution of silicate glasses and minerals: Morphological instability]

Understanding of aqueous dissolution of silicate glasses and minerals is of great importance to both Earth science and materials science. Silicate dissolution exhibits complex temporal evolution and spatial pattern formations. Recently, we showed how observed complexity could emerge from a simple self-organizational mechanism: dissolution of the silica framework in a material could be catalyzed by the cations released from the reaction itself. This mechanism enables us to systematically predict many key features of a silicate dissolution process including the occurrence of a sharp corrosion front (vs. a leached surface layer), oscillatory dissolution and multiple stages of the alteration process (e.g., an alteration rate resumption at a late stage of glass dissolution). Here, through a linear stability analysis, we show that this same mechanism can also lead to morphological instability of an alteration front, which, in combination with oscillatory dissolution, can potentially lead to a whole suite of patterning phenomena, as observed on archaeological glass samples, including wavy dissolution fronts, growth rings, incoherent bandings of alteration products, and corrosion pitting. Here, the result thus further demonstrates the importance of the proposed self-accelerating mechanism in silicate material degradation.

36 MATERIALS SCIENCE↗

2015 Progress Report/July 2016: Iron Oxide Redox Transformation Pathways: The Bulk Electrical Conduction Mechanism

Despite decades of research on the reactivity and stable isotope properties of Fe oxides, the ability to describe the redox behavior of Fe oxides in the environment is still quite limited. This is due, in large part, to the analytical and spatial complexities associated with studying microscopic processes at the Fe oxide-water interface. This project had the long-term vision of filling this gap by developing a detailed understanding of the relationship between interfacial ET processes, surface structure and charge, and mineral semiconducting properties. We focused on the Fe(III)-oxides and oxyhydroxides because of their geochemical preponderance, versatility in synthesis of compositionally, structurally, and morphologically tailored phases, and because they are amenable to a wide range of surface and bulk properties characterization. In particular, reductive transformation of phases such as hematite (α-Fe 2 O 3 ) and goethite (α-FeOOH) in aqueous solution can serve as excellent model systems for studies of electron conduction processes, as well as provide valuable insights into effect of nanoscale conductive materials on contaminant fate at DOE sites. More specifically, the goal of the Iowa component of this project was to use stable Fe isotope measurements to simultaneously measure isotope specific oxidation states and concentrations of Fe at the hematite-water and goethite-water interface. This work builds on our previous work where we used an innovative combination of 57 Fe Mössbauer spectroscopy and high precision isotope ratio measurements (MC-ICP-MS) to probe the dynamics of the reaction of aqueous Fe(II) with goethite. Mössbauer spectroscopy detects 57 Fe only among all other Fe isotopes and we have capitalized on this to spectroscopically demonstrate Fe(II)-Fe(III) electron transfer between sorbed Fe(II) and Fe(III) oxides (Handler, et al., 2009; Gorski, et al. 2010; Rosso et al., 2010). By combining the Mössbauer spectroscopy and stable isotopes measurements, we have been able to simultaneously track the oxidation state and isotope concentration of the bulk Fe oxide and aqueous Fe. One of our most compelling findings is that despite the apparent stability of the Fe(II)-goethite system, there is actually a tremendous amount of Fe atom cycling occurring between the aqueous phase and the bulk goethite as indicated by the isotopic composition of both phases approaching the mass balance average (Handler et al., 2009). How such extensive re-crystallization and Fe atom exchange can occur with no significant morphological change is a fascinating question. Based on previous work from PI Rosso’s group showing that a potential gradient across hematite crystal faces leads to conduction through hematite and growth and dissolution at separate crystal faces we proposed that a redox-driven recrystallization could be occurring that would explain the extensive mixing observed with the isotope data. From our previous studies utilizing Mössbauer spectroscopy, we know that sorption of Fe(II) onto goethite results in electron transfer between the sorbed Fe(II) and the structural Fe(III) in goethite. Oxidation of the sorbed Fe(II) produces growth of goethite on goethite (i.e., homoepitaxy), as well as injection of an electron into goethite. It is possible that electron transfer from sorbed Fe(II) occurs across a potential gradient, and that Fe(II) atoms are dissolved at a different location on the goethite surface. These newly-reduced Fe(II) atoms could then dissolve into the aqueous phase, exposing fresh Fe(III) goethite to the aqueous phase. Through a repeated series of these five steps of sorption–electron transfer–crystal growth–conduction– dissolution, a redox-driven conveyor belt, could be established that would allow all of the goethite to be eventually exposed to the aqueous phase and exchanged. This surface-mediated recrystallization process would result in similar Fe isotope distributions in the aqueous phase and goethite particle, as we have observed here. It would also result in a stable aqueous Fe(II) concentration, if there were equal rates of goethite growth and dissolution.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Unraveling Anisotropic and Pulsating Etching of ZnO Nanorods in Hydrochloric Acid via Correlative Electron Microscopy

Despite much technical progress achieved so far, the exact surface and shape evolution during wet chemical etching is less unraveled, especially in ionically bonded ceramics. Herein, by using in situ liquid cell transmission electron microscopy, a repeated two-stage anisotropic and pulsating periodic etching dynamic is discovered during the pencil shape evolution of a single crystal ZnO nanorod in aqueous hydrochloric acid. Specifically, the nanopencil tip shrinks at a slower rate along [0001̅] than that along the $\langle$101̅0$\rangle$ directions, resulting in a sharper ZnO pencil tip. Afterward, rapid tip dissolution happens due to accelerated etching rates along various crystal directions. Concurrently, the vicinal base region of the original nanopencil tip emerges as a new tip followed by the repeated sequence of tip shrinking and removal. The high-index surfaces, such as {101̅m} (m = 0, 1, 2, or 3) and {21̅1̅n} (n = 0, 1, 2, or 3), are found to preferentially expose in different ratios. Our 3D electron tomography, convergent beam electron diffraction, middle-angle bright-field STEM, and XPS results indicate the dissociative Cl – species were bound to the Zn-terminated tip surfaces. Furthermore, DFT calculation suggests the preferential Cl – passivation over the {101̅1} and (0001) surfaces of lower energy than others, leading to preferential surface exposures and the oscillatory variation of different facet etching rates. The boosted reactivity due to high-index nanoscale surface exposures is confirmed by comparatively enhanced chemical sensing and CO 2 hydrogenation activity. In conclusion, these findings provide an in-depth understanding of anisotropic wet chemical etching of ionic nanocrystals and offer a design strategy for advanced functional materials.

36 MATERIALS SCIENCE↗

Characterizing precipitate evolution of an Al–Zn–Mg–Cu-based commercial alloy during artificial aging and non-isothermal heat treatments by in situ electrical resistivity monitoring

In situ electrical resistivity monitoring technique was employed to continuously evaluate the precipitate evolution of an Al–Zn–Mg–Cu-based commercial alloy during typical artificial aging treatments. The effects of artificial aging on the precipitates stability during non-isothermal heat treatments were also explored. Conventional hardness test, transmission electron microscopy and differential scanning calorimetry were also adopted to verify the electrical resistivity results. The results indicated that both the precipitation process and its timely rate could be followed by the monitored electrical resistivity during artificial aging treatments. The electrical resistivity results gave overall information on continuous precipitation and dissolution processes, especially under high heating rates. Samples artificial aging heat treated at 120 °C for 24 h followed by aging at 150 °C for 24 h presented more stable state and coarser precipitates than the samples only artificial aging heat treated at 120 °C for 24 h or triple artificial aging heat treated at 120 °C/24 h + 195 °C/15 min + 120 °/24 h. While the incoherent η precipitates in the samples artificial aging heat treated at 120 °C for 24 h followed by aging at 150 °C for 24 h were more easiness to coarsening and dissolve during non-isothermal heat treatments as well. - Highlights: • In situ electrical resistivity monitoring technique was employed on an Al-Zn-Mg-Cu alloy. • The precipitate evolution during typical artificial aging treatments was studied. • The precipitate stability during non-isothermal heat treatments was explored. • The electrical resistivity wonderfully monitored continuous precipitation and dissolution. • The alloy submitted to a T7 treatment presents a more stable state during heating due to incoherent η precipitates.

36 MATERIALS SCIENCE↗

Calcium nitrate: A chemical admixture to inhibit aggregate dissolution and mitigate expansion caused by alkali-silica reaction

Alkali-silica reaction (ASR) is a significant cause of the degradation of concrete structures. ASR results from the dissolution of reactive silicate aggregates and the subsequent formation of damaging, expansive ASR gels. Despite the prevalence of ASR, so far only lithium-based chemical admixtures have been shown to be successful in mitigating its deleterious effects. Herein, dissolved calcium nitrate (Ca(NO 3 ) 2 : CN) is demonstrated to reduce ASR-induced expansion caused by the use of sodium borosilicate (NBS) glass as a model reactive aggregate. The significance of reductions of NBS-glass dissolution and mortar-bar expansion rates is discussed, with special focus on highlighting the mechanism by which calcium nitrate mitigates ASR, i.e., by the inhibition of aggregate dissolution. This study reveals a new and cost-effective pathway to suppress aggregate dissolution and ASR in concrete based on the dosage of soluble alkaline-earth additives.

36 MATERIALS SCIENCE↗

Final Report: Optimal Model Complexity in Geological Carbon Sequestration: A Response Surface Uncertainty Analysis

The critical component of a risk assessment study in evaluating GCS is an analysis of uncertainty in CO2 modeling. In such analyses, direct numerical simulation of CO2 flow and leakage requires many time-consuming model runs. Alternatively, analytical methods have been developed which allow fast and efficient estimation of CO2 storage and leakage, although restrictive assumptions on formation rock and fluid properties are employed. In this study, an intermediate approach is proposed based on the Design of Experiment and Response Surface methodology, which consists of using a limited number of numerical simulations to estimate a prediction outcome as a combination of the most influential uncertain site properties. The methodology can be implemented within a Monte Carlo framework to efficiently assess parameter and prediction uncertainty while honoring the accuracy of numerical simulations. The choice of the uncertain properties is flexible and can include geologic parameters that influence reservoir heterogeneity, engineering parameters that influence gas trapping and migration, and reactive parameters that influence the extent of fluid/rock reactions. The method was tested and verified on modeling long-term CO2 flow, non-isothermal heat transport, and CO2 dissolution storage by coupling two-phase flow with explicit miscibility calculation using an accurate equation of state that gives rise to convective mixing of formation brine variably saturated with CO2. All simulations were performed using three-dimensional high-resolution models including a target deep saline aquifer, overlying caprock, and a shallow aquifer. To evaluate the uncertainty in representing reservoir permeability, sediment hierarchy of a heterogeneous digital stratigraphy was mapped to create multiple irregularly shape stratigraphic models of decreasing geologic resolutions: heterogeneous (reference), lithofacies, depositional environment, and a (homogeneous) geologic formation. To ensure model equivalency, all the stratigraphic models were successfully upscaled from the reference heterogeneous model for bulk flow and transport predictions (Zhang & Zhang, 2015). GCS simulation was then simulated with all models, yielding insights into the level of parameterization complexity that is needed for the accurate simulation of reservoir pore pressure, CO2 storage, leakage, footprint, and dissolution over both short (i.e., injection) and longer (monitoring) time scales. Important uncertainty parameters that impact these key performance metrics were identified for the stratigraphic models as well as for the heterogeneous model, leading to the development of reduced/simplified models at lower characterization cost that can be used for the reservoir uncertainty analysis. All the CO2 modeling was conducted using PFLOTRAN – a massively parallel, multiphase, multi-component, and reactive transport simulator developed by a multi-laboratory DOE/SciDAC (Scientific Discovery through Advanced Computing) project (Zhang et al., 2017, in review). Within the uncertainty analysis framework, increasing reservoir depth were investigated to explore its effect on the uncertainty outcomes and the potential for developing gravity-stable injection with increased storage security (Dai et al., 20126; Dai et al., 2017, in review). Finally, to accurately model CO2 fluid-rock reactions and resulting long-term storage as secondary carbonate minerals, a modified kinetic rate law for general mineral dissolution and precipitation was proposed and verified that is invariant to a scale transformation of the mineral formula weight. This new formulation will lead to more accurate assessment of mineral storage over geologic time scales (Lichtner, 2016).

58 GEOSCIENCES↗

Dynamic development of geochemical reaction fronts during hydraulic stimulation of shale

Injection of acidic hydraulic fracture fluid (HFF) into shale formations for unconventional oil/gas production results in chemical reactions in the shale matrix that can alter fluid transport. Here, we report the results of set of experiments designed to evaluate the impact of calcite dissolution as a function of carbonate mineral content on matrix chemical reactivity and pore-space modification concomitant with imbibition. In this study, we tracked acidic HFF transport in four samples of Wolfcamp shale with calcite contents varying from 4% to 59% by monitoring the rate and spatial extent of bromide tracer transport using synchrotron-based X-ray fluorescence microprobe (XFM) imaging. Concurrently, we also carried out XFM imaging of the spatial distribution of Ca in the Wolfcamp shale cores (as a proxy of calcite distribution). Our approach thus yields a direct record of time-resolved selective ion transport resulting from the penetration of acidic HFF and the associated mineral transformations in the shale cores. We show that the variability in calcite content of Wolfcamp shale samples can directly affect the rate and spatial extent of imbibition. Although reaction of the acidic HFF with carbonates in shales enhances calcite dissolution and increases porosity, the spatial extent of calcite dissolution in the shale matrix is limited due to a rapid neutralization of pH. The relative abundance and spatial distribution of calcite control the chemical saturation state of the HFF progressing into the matrix. As a result, calcite has a major impact on the spatial extent and rate of matrix alteration and thus on HFF transport during subsurface reservoir stimulation. Consequently, increased calcite content in the shale matrix inhibits the spatial extent of the pore-volume increase and, by extension, the spatial extent and rate of imbibition. Our results thus show that the overall rates of calcite dissolution approach the rates of acidic HFF transport (i.e., Damköhler number ~1), which could contribute to the efficiency of subsurface reservoir stimulation. A better understanding of HFF-calcite reaction rates is crucial for improving the prediction and optimization of fluid transport across HFF-shale interfaces during hydraulic fracturing.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Kinetics of lime/bentonite pozzolanic reactions at 20 and 50 °C: Batch tests and modeling

The effects of duration (1–100 days) and temperature (20 and 50 °C) were assessed from batch tests for Ca-bentonite mixed with 10 wt.% lime. The pozzolanic processes were monitored over time by {sup 29}Si NMR (Cement Concr. Res. 42, 2012), TGA-DTA, XRD and chemical analysis. Modeling considered kinetics and thermodynamics of mineralogical transformations and cation exchange. Kinetic laws were dependent on pH and temperature (Arrhenius energy). Lime hydration occurs within hours, modifying the bentonite exchangeable population and increasing the pH. These alkaline conditions initiate the pozzolanic reactions in a second stage. The rate-limiting step is the dissolution kinetics of the bentonite minerals, i.e. a relatively fast and total consumption of cristobalite in parallel to a long-term slower dissolution of montmorillonite. First C–S–H and then C–A–S–H are formed consequently. Temperature speeds up the pozzolanic reaction kinetics by a factor 5 from 20 to 50 °C, corresponding to an apparent activation energy of 40–50 kJ/mol.

36 MATERIALS SCIENCE↗