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All sourcesNASA NTRSDOE OSTI
DOE OSTI2023

Effects of crystallographic orientation on calcite dissolution under alkaline conditions

Here, this study investigates the dissolution of calcite’s (104) and (100) surfaces under alkaline conditions (pH 8.8–13.1) using vertical scanning interferometry under flow-through conditions. The dissolution rate of (100) surfaces decreases with increasing pH. For example, the dissolution rate at pH 8.8 is more than 20 times higher than that at pH 13.1. In contrast, the dissolution rate of (104) surfaces is far less sensitive to pH. We explain these observations as being on account of the preferential adsorption of [OH – ] on (100) surfaces, inhibiting their dissolution. Particularly, this is because Ca-surface sites on (100) surfaces are less coordinated and have a stronger tendency for [OH – ] adsorption. As a result, (100) surfaces dissolve nearly twice as fast as (104) surfaces at pH 8.8, whereas (104) surfaces dissolved ~4.5 times faster than (100) surfaces at pH 13.1; indicating an inversion in dissolution behavior. The dissolution rate of (104) surfaces at pH 13.1 is 60 % of the rate at pH 10–12 because of the formation of slow dissolving microfacets of other orientations. The rhombohedral dissolution etch-pits formed on (104) surfaces, at lower pH’s, disappeared upon exposure to solutions with pH > 12 and were replaced by protrusions. The addition of up to 4m (molality) NaCl enhances the dissolution of (104) surfaces at pH 8.8–13.1 and (100) surfaces at pH 8.8–11.0, and inhibited the dissolution of (100) surfaces at pH = 12.0–13.1. In addition, the competing adsorption between OH – and CO 3 2– species mitigates the inhibition effects of CO 3 2– on both surfaces at pH 13.1 compared to pH 11, and the dissolution of (100) surfaces is far less affected by CO 3 2– than (104) surfaces. These results provide new insights into the rates and mechanisms of how crystallographic orientations affect calcite’s dissolution at alkaline pH conditions.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2016

Dissolution of nontronite in chloride brines and implications for the aqueous history of Mars

Increasing evidence suggests the presence of recent liquid water, including brines, on Mars. Brines have therefore likely impacted clay minerals such as the Fe-rich mineral nontronite found in martian ancient terrains. So to interpret these interactions, we conducted batch experiments to measure the apparent dissolution rate constant of nontronite at 25.0 °C at activities of water (aH 2 O) of 1.00 (0.01 M CaCl 2 or NaCl), 0.75 (saturated NaCl or 3.00 mol kg -1 CaCl 2 ), and 0.50 (5.00 mol kg -1 CaCl 2 ). Experiments at aH 2 O = 1.00 (0.01 M CaCl 2 ) were also conducted at 4.0 °C, 25.0 °C, and 45.0 °C to measure an apparent activation energy for the dissolution of nontronite. Apparent dissolution rate constants at 25.0 °C in CaCl 2 -containing solutions decrease with decreasing activity of water as follows: 1.18 × 10 -12 ± 9 × 10 -14 mol mineral m -2 s -1 (aH 2 O = 1.00) > 2.36 × 10 -13 ± 3.1 × 10 -14 mol mineral m -2 s -1 (aH 2 O = 0.75) > 2.05 × 10 -14 ± 2.9 × 10 -15 mol mineral m -2 s -1 (aH 2 O = 0.50). Similar results were observed at 25.0 °C in NaCl-containing solutions: 1.89 × 10 -12 ± 1 × 10 -13 mol mineral m -2 s -1 (aH 2 O = 1.00) > 1.98 × 10 -13 ± 2.3 × 10 -14 mol mineral m -2 s -1 (aH 2 O = 0.75). This decrease in apparent dissolution rate constants with decreasing activity of water follows a relationship of the form: log k diss = 3.70 ± 0.20 × aH 2 O - 15.49, where k diss is the apparent dissolution rate constant, and aH 2 O is the activity of water. The slope of this relationship (3.70 ± 0.20) is within uncertainty of that of other minerals where the relationship between dissolution rates and activity of water has been tested, including forsteritic olivine (log R = 3.27 ± 0.91 × aH 2 O - 11.00) and jarosite (log R = 3.85 ± 0.43 × aH 2 O - 12.84), where R is the mineral dissolution rate. This result allows prediction of mineral dissolution as a function of activity of water and suggests that with decreasing activity of water, mineral dissolution will decrease due to the role of water as a ligand in the reaction. Apparent dissolution rate constants in the dilute NaCl solution (1.89 × 10 -12 ± 1 × 10 -13 mol mineral m -2 s -1 ) are slightly greater than those in the dilute CaCl 2 solutions (1.18 × 10 -12 ± 9 × 10 -14 mol mineral m -2 s -1 ). We attribute this effect to the exchange of Na with Ca in the nontronite interlayer. An apparent activation energy of 54.6 ± 1.0 kJ/mol was calculated from apparent dissolution rate constants in dilute CaCl 2 -containing solutions at temperatures of 4.0 °C, 25.0 °C, and 45.0 °C: 2.33 × 10 -13 ± 1.3 × 10 -14 mol mineral m -2 s -1 (4.0 °C), 1.18 × 10 -12 ± 9 × 10 -14 mol mineral m -2 s -1 (25.0 °C), and 4.98 × 10 -12 ± 3.8 × 10 -13 mol mineral m -2 s -1 (45.0 °C). The greatly decreased dissolution of nontronite in brines and at low temperatures suggests that any martian nontronite found to be perceptibly weathered may have experienced very long periods of water–rock interaction with brines at the low temperatures prevalent on Mars, with important implications for the paleoclimate and long-term potential habitability of Mars.

58 GEOSCIENCES↗
DOE OSTI2025

In-Situ FTIR Detection of Transition Metal (TM)-Ion Dissolution From Cathodes in Li-Ion Batteries

Transition metal (TM) ions, commonly Ni and Mn, play a crucial role in Li-ion battery cathodes as the reaction centers for rapid redox reactions. A major challenge with TM-based cathodes is capacity degradation, particularly at higher operating voltages. This degradation is closely linked to the dissolution of TMs from the cathode materials and their subsequent deposition on the anode. This process not only modifies the surface structure of the cathode but, more significantly, alters the SEI composition on the anode [1-2]. The dissolution of TMs cations into a liquid electrolyte from cathode materials, such as Mn-ion dissolution from Mn-rich cathode (LMR), is detrimental to the cycling performance of Li-ion batteries [3-4]. Much attention has been paid to this issue but there remains a lack of characterization techniques which can detect the TM-ion dissolution from the cathode during electrochemical measurements. In our study, we use in-situ ATR-FTIR as an effective technique to probe the TM-ion dissolution from the cathode. We have first demonstrated the detrimental effects of TM ions on the electrochemical performance of Li-ion batteries by adding a small amount of TM salt (50 mM Mn(PF6)) to the electrolyte of a Li-ion coin cell with LFP and graphite electrode. We observed a rapid capacity fade after the first delithiation cycle. To investigate TM ion dissolution, we established a baseline IR spectrum for various TM solvation states (such as Mn and Ni) by measuring concentration-dependent IR spectra. This baseline spectrum helps us detect TM ion dissolution during battery cycling. In this work, we discuss in detail the effect of TM ions on the electrochemical performance of Li-ion batteries and the detection of TM ions during battery cycling using in-situ FTIR spectroscopy. We will compare TM dissolution between coated and uncoated cathodes to examine the effect of cathode coatings to mitigate degradation due to TM dissolution and cross-over from cathode to anode. References: (1) Zhan, C.; Wu, T.; Lu, J.; Amine, K. Dissolution, migration, anddeposition of transition metal ions in Li-ion batteries exemplified byMn-based cathodes - a critical review. Energy Environ. Sci. 2018, 11,243-257. (2) Jung, R.; Linsenmann, F.; Thomas, R.; Wandt, J.; Solchenbach,S.; Maglia, F.; Stinner, C.; Tromp, M.; Gasteiger, H. A. Nickel,Manganese, and Cobalt Dissolution from Ni-Rich NMC and TheirEffects on NMC622-Graphite Cells. J. Electrochem. Soc. 2019, 166,A378-A389. (3) Zhao, L.; Chenard, E.; Capraz, O. O.; Sottos, N. R.; White, S.R. Direct Detection of Manganese Ions in Organic Electrolyte by UV-Vis Spectroscopy. J. Electrochem. Soc. 2018, 165, A345-A348 (4) Zhang, Y.; Hu, A.; Xia, D.; Hwang, S.; Sainio, S.; Nordlund, D.;Michel, F. M.; Moore, R. B.; Li, L.; Lin, F. Operando characterization and regulation of metal dissolution and redeposition dynamics nearbattery electrode surface. Nat. Nanotechnol. 2023, 18, 790.

25 ENERGY STORAGE↗
DOE OSTI2024

Pore‐Scale Modeling of Reactive Transport with Coupled Mineral Dissolution and Precipitation

Abstract We present a new pore‐scale model for multicomponent advective‐diffusive transport with coupled mineral dissolution and precipitation. Both dissolution and precipitation are captured simultaneously by introducing a phase transformation vector field representing the direction and magnitude of the overall phase change. An effective viscosity model is adopted in simulating fluid flow during mineral dissolution‐precipitation that can accurately capture the velocity field without introducing any empirical parameters. The proposed approach is validated against analytical solutions and interface tracking simulations in simplified structures. After validation, the proposed approach is employed in modeling realistic rocks where mineral dissolution and precipitation are dominant at different locations. We have identified three regimes for mineral dissolution‐precipitation coupling: (a) compact dissolution‐precipitation where dissolution is dominant near the inlet and precipitation is dominant near the outlet, (b) wormhole dissolution with clustered precipitation where dissolution generates wormholes in the main flow paths and precipitation clogs the secondary flow paths, and (c) dissolution dominant where all solid grains are gradually dissolved. In the three regimes, the proposed approach provides reliable porosity‐permeability relationships that cannot be described well by traditional macroscale models. We find that the permeability can increase while the overall porosity decreases when the main flow paths are expanded by dissolution and adjacent pore spaces are clogged by precipitation.

58 GEOSCIENCES↗
DOE OSTI2020

Evaluation of the Dissolution Behavior of L-Bundle End Caps and HFIR Fuel Carriers

The H-Canyon facility is currently using the 6.1D dissolver for the dissolution of Material Test Reactor (MTR) fuel and the 6.4D dissolver for the dissolution of High Flux Isotope Reactor (HFIR) fuel using mercury-catalyzed HNO₃ dissolution flowsheets. The processing strategy for both dissolvers involves the dissolution of multiple charges of fuel per batch. After the designated heating cycle, the dissolvers are opened, and the charging wells are probed to determine if the MTR or HFIR fuel has dissolved. If undissolved fuel fragments are beyond a certain height, the dissolver must be closed and heated for an additional amount of time to dissolve the remaining material. In recent MTR fuel dissolutions, “high probes” (i.e., excessive undissolved material) were frequently observed, which resulted in extended dissolution times. The suspected cause of the high probes was the incomplete dissolution of the L-Bundle End Cap, rather than the fuel or fuel bundles. The End Cap is hypothesized to be binding in the insert well and not dropping into the acid as the L-Bundle and fuel dissolve. Once the End Cap is dislodged by the probe and drops into the acid, the dissolution rate of the End Cap appears to be significantly reduced compared to the dissolution rate of the fuel and other parts of the L-Bundle. A similar issue has also been observed with the lifting bail on the HFIR fuel carriers. During HFIR fuel dissolutions, the lifting bail on the outer carrier has resulted in high probes due to incomplete dissolution. In one case, a partially dissolved bail was caught in one of the insert well holes which prevented the probe from going to the bottom of the well.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗
DOE OSTI2021

High pressure experimental investigation of clinopyroxene dissolution in a K-basaltic melt

Dissolution of clinopyroxene (cpx) in a K-basaltic melt from the Campi Flegrei Volcanic District (Italy) has been investigated through dissolution and dissolution-crystallization experiments at pressure of 0.8 GPa, superliquidus temperature of 1350 °C, and dwell times between 0.5 and 1 h. The obtained dissolution rates range from 7.9·10 –6 cm s –1 to 6.1·10 –6 cm s –1 as a function of dwell time. In the dissolution-crystallization experiment (1300 °C; 0.8 GPa; 2 h), the formation of overgrowth rims accompanied by new cpx crystals suggests that the injection of recharge magmas in basaltic reservoir may lead to inverse or oscillatory zonation. The interaction between cpx and K-basaltic melt at ~1570 °C was studied by in situ radiography using synchrotron radiation combined with the Paris-Edinburgh press. Here, this resulted in cpx resorption to occur depending on the temperature conditions with respect to the liquidus temperature of the cpx (T cpxL ). The calculated cpx dissolution rates are ~5·10 –3 cm s –1 at T ≤ T cpxL and ~ 3·10 –2 cm s –1 at T ≥ T cpxL . The role of crystal dissolution in the estimation of magma residence times has been also tested for a natural magmatic system by interpolating the dissolution rates (~10 –5 –10 –6 cm s –1 ) with the textural data of cpx phenocrysts from the Agnano-Monte Spina pyroclastic deposit at Campi Flegrei caldera (Campanian region, Italy). Results from calculations indicate that the time required for partial or complete resorption of phenocrysts varies from ~0.5 to ~40 h, and that the effect of crystal dissolution may be relevant to estimate magma residence times whether significant dissolution occurs during magma mixing processes.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2023

Integration of Biorelevant Pediatric Dissolution Methodology into PBPK Modeling to Predict In Vivo Performance and Bioequivalence of Generic Drugs in Pediatric Populations: a Carbamazepine Case Study

This study investigated the impact of gastro-intestinal fluid volume and bile salt (BS) concentration on the dissolution of carbamazepine (CBZ) immediate release (IR) 100 mg tablets and to integrate these in vitro biorelevant dissolution profiles into physiologically based pharmacokinetic modelling (PBPK) in pediatric and adult populations to determine the biopredictive dissolution profile. Dissolution profiles of CBZ IR tablets (100 mg) were generated in 50–900 mL biorelevant adult fasted state simulated gastric and intestinal fluid (Ad-FaSSGF and Ad-FaSSIF), also in three alternative compositions of biorelevant pediatric FaSSGF and FaSSIF medias at 200 mL. This study found that CBZ dissolution was poorly sensitive to changes in the composition of the biorelevant media, where dissimilar dissolution (F2 = 46.2) was only observed when the BS concentration was changed from 3000 to 89 μM (Ad-FaSSIF vs Ped-FaSSIF 50% 14 BS). PBPK modeling demonstrated the most predictive dissolution volume and media composition to forecast the PK was 500 mL of Ad-FaSSGF/Ad-FaSSIF media for adults and 200 mL Ped-FaSSGF/FaSSIF media for pediatrics. A virtual bioequivalence simulation was conducted by using Ad-FaSSGF and/or Ad-FaSSIF 500 mL or Ped-FaSSGF and/or Ped-FaSSIF 200 mL dissolution data for CBZ 100 mg (reference and generic test) IR product. The CBZ PBPK models showed bioequivalence of the product. This study demonstrates that the integration of biorelevant dissolution data can predict the PK profile of a poorly soluble drug in both populations. Further work using more pediatric drug products is needed to verify biorelevant dissolution data to predict the in vivo performance in pediatrics.

60 APPLIED LIFE SCIENCES↗
DOE OSTI2021

Lattice Boltzmann simulation of the dissolution of slag in alkaline solution using real-shape particles

Highlights: • A dissolution numerical model was proposed to capture the real dissolution kinetics of slag in alkaline solution. • The log forward dissolution rate of Si was described as a function of NBO/T and solution pH. • A threshold solid volume fraction of 0.688 was found for a voxel in 3D, 63.8% larger than that for a pixel in 2D. • The proposed dissolution numerical model provides a reliable alternative to study the dissolution kinetics of slag. A dissolution numerical model was proposed in this study to capture the real dissolution kinetics of slag in alkaline solution. It consists of three modules, i.e. (i) simulation of the initial particle parking structure of slag in alkaline solution using real-shape particles of slag, (ii) simulation of the chemical reactions between slag and solution based on the transition state theory, and (iii) simulation of the physical transport of aqueous ions using the lattice Boltzmann method. This dissolution numerical model was verified using experimental results, showing reasonable accuracy. After verification, the dissolution numerical model was implemented to study the influences of temperature and particle shape using a proper recipe of slag in alkaline solution. This recipe was designed to avoid solid phase precipitation or gel formation via thermodynamic analysis. The simulation results showed faster dissolution kinetics of slag when using higher temperatures and more irregular particle shapes.

36 MATERIALS SCIENCE↗
DOE OSTI2020

Grain boundary facilitated dissolution of nanocrystalline NpO 2 (s) from legacy waste processing

Dissolution of actinide dioxides, including neptunium dioxide (NpO 2 (s)), is paramount for the prediction of the environmental fate of nuclear materials. Quantifying dissolution rates, as well as understanding qualitative dissolution mechanisms, informs performance assessment for geologic disposal of spent nuclear fuel and management of legacy radioactive waste. The aim of this research was to measure the dissolution rate of nanocrystalline NpO 2 (s), produced through legacy nuclear waste processing, under oxidizing conditions, as well as to characterize surface alteration to the material. The solid phase was characterized using electron microscopy techniques (SEM/STEM) and X-ray photoelectron spectroscopy (XPS), indicating preferential dissolution of Np-hydroxide contained in the grain boundaries of NpO 2 (s) and fragmentation of grains from the matrix. The oxidative dissolution was monitored over 40 weeks, yielding a two-step kinetic dissolution model involving hydration of NpO 2 (s) and subsequent oxidation and dissolution of the hydroxide phase. Here, the proposed dissolution models for nanocrystalline NpO 2 (s) suggest that microstructural features such as grain boundaries are key factors affecting dissolution, including release of colloidal particles, and ultimately, environmental fate and transport of nuclear materials.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗
DOE OSTI2023

Understanding the mechanisms of anisotropic dissolution in metal oxides by applying radiolysis simulations to liquid-phase TEM

Iron-based redox-active minerals are ubiquitous in soils, sediments, and aquatic systems. Their dissolution is of great importance for microbial impacts on carbon cycling and the biogeochemistry of the lithosphere and hydrosphere. Despite its widespread significance and extensive prior study, the atomic-to-nanoscale mechanisms of dissolution remain poorly understood, particularly the interplay between acidic and reductive processes. Here, we use in situ liquid-phase-transmission electron microscopy (LP-TEM) and simulations of radiolysis to probe and control acidic versus reductive dissolution of akaganeite (β–FeOOH) nanorods. Informed by crystal structure and surface chemistry, the balance between acidic dissolution at rod tips and reductive dissolution at rod sides was systematically varied using pH buffers, background chloride anions, and electron beam dose. We find that buffers, such as bis-tris, effectively inhibited dissolution by consuming radiolytic acidic and reducing species such as superoxides and aqueous electrons. In contrast, chloride anions simultaneously suppressed dissolution at rod tips by stabilizing structural elements while promoting dissolution at rod sides through surface complexation. Dissolution behaviors were systematically varied by shifting the balance between acidic and reductive attacks. The findings show LP-TEM combined with simulations of radiolysis effects can provide a unique and versatile platform for quantitatively investigating dissolution mechanisms, with implications for understanding metal cycling in natural environments and the development of tailored nanomaterials.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2015

Effect of medium permeability anisotropy on the morphological evolution of two non-uniformities in a geochemical dissolution system

The morphological evolutions of chemical dissolution fronts have attracted increasing interest in the field of the geological sciences and in industrial applications. Extensive research based on numerical simulations has been conducted to understand how various mechanisms and processes influence the morphological evolution of chemical dissolution fronts within geological media. Most researchers in previous studies have assumed the medium permeability to be isotropic for developing numerical models, despite isotropic geological media being uncommon in the real world. This study investigates the effect of medium permeability anisotropy on the morphological evolutions of two non-uniformities with higher permeability in a geochemical dissolution system. A series of numerical simulations are performed to evaluate the effect of medium permeability anisotropy on the morphological evolution of a chemical dissolution front. The simulation results indicate that the patterns of the dissolution reaction front are substantially affected by medium permeability anisotropy. An increase in the permeability anisotropy ratio, which is defined as the ratio of the permeability in the transverse direction to that in the longitudinal direction, enhances the dominance of the flow-focusing effect over the stabilizing or merging effect induced by diffusion/dispersion mechanism. Therefore, an increase in the permeability anisotropy ratio can increase the fingering length of the dissolution front or cause the dissolution front to have a more unstable pattern. By contrast, a reduction in the permeability anisotropy ratio will weaken the flow-focusing effect, thereby reducing the fingering length of the dissolution front or changing the front morphology such that it has a more stable status. The effect of the permeability anisotropy ratio on the morphological evolution tends to decrease when the Zhao number (negative dimensionless upstream pressure gradient) of the system increases. The consideration of medium permeability anisotropy in the geochemical dissolution model renders the simulation of the morphological evolutions of dissolution reaction fronts more realistic.

58 GEOSCIENCES↗
DOE OSTI2020

DFT-Based Calculation of Dissolution Activation Energy and Kinetics of Ni–Cr Alloys

A density functional theory investigation of the process of dissolution of Ni and Cr adatoms from model Ni–Cr(111) alloy surfaces is presented, both in vacuum and with explicit water molecules. The goal is to understand how the electronic structures solved using DFT can provide insights as to changes in valence, energy and coordination of the adatoms in the process of dissolving from the alloy surface. It is found that nearby Cr solute atoms increase the dissolution activation energy of Ni. Cr adatoms have a similar dissolution activation energy as Ni adatoms, except for one particular surface configuration that has a much smaller dissolution activation energy, which might promote selective dissolution of Cr in Ni–Cr alloys. To interpret the first-principles modeling results for the potential energy trajectory along the dissolution reaction coordinate, we provide a thermodynamic breakdown of the various terms that contribute to the dissolution activation and total reaction energy. The role of addition of Cr is explored on the dissolution kinetics of a Ni–Cr alloys of varying composition by constructing a model for the corrosion current density with DFT-based activation energies. Lastly, dissolution resistance index is proposed as a quantifiable descriptor of the dissolution resistance of corrosion resistant alloys.

36 MATERIALS SCIENCE↗
DOE OSTI2016

Aluminum Metal Dissolution for Mark-18A Target Processing

The Mark-18A Program was established to preserve the unique materials found in Mark-18A targets for future research and development activity within the Department of Energy or other U.S. government agencies. The Savannah River Site has 65 Mark-18A targets to be provided for the recovery of high valued isotopes. The majority of the recovery work will be performed in the Savannah River National Laboratory (SRNL) Shielded Cells due to dose concerns. The recovered product will be transported to the Oak Ridge National Laboratory (ORNL) for future research and development tasks. The Mark-18A target material will be removed from their current configuration, dissolved, chemically separated, and calcined to a stable oxide. The baseline flowsheet is patterned after the flowsheet ORNL has previously used to process both Mark-18A and Mark-42 targets. However, it is necessary for SRNL to adapt its facility and the ORNL flowsheet to identify process improvements to successfully recover the actinide materials within the constraints of the SRNL Shielded Cells. These studies evaluated and demonstrated a chemical method for cladding removal using a mixture of sodium nitrate (NaNO 3 ) and sodium hydroxide (NaOH). Experiments provided better insights into dissolution of the Mark-18A aluminum cladding. In particular, these studies measured the effects of temperature on dissolution rate, flammable gas generation, and nitrite formation. Using the lessons learned from batch dissolution testing at SRNL, a continuous dissolution flowsheet was successfully demonstrated using prototypic-shaped materials and chemically-conservative materials. The SRNL target dissolution flowsheet departs from the baseline ORNL flowsheet in small but significant ways as discussed in the following paragraphs. These flowsheet changes facilitate faster initial reaction rates at a given temperature, enable cladding removal at a lower process temperature, and yield a more uniform dissolution rate throughout cladding removal. Multiple tests indicate that the total time at the dissolution temperatures will be about six hours for one fourth of a target. The shorter dissolution time provides the benefit of a single-shift dissolver operation. Off gas sampling determined that the quantities of flammable hydrogen (H 2 ) and ammonia (NH 3 ) expected in the process off gas will meet allowable flammable gas generation rates for the Shielded Cells Facility. The SRNL approach enables NaOH to be added at a constant rate, which simplifies operations in the shielded cells. In all six continuous dissolution tests, the process was easy to control with minimal operator interface. Analyses of process solutions throughout the experiments provide a better understanding of system behavior. The data show consistent behavior across several similar but different test conditions. Between the batch-test and continuous-test data, if future changes to the flowsheet are required, sufficient data exist to adequately predict how the system will respond to those changes. Future work will focus on design, fabrication, and evaluation of a system for dissolution of one-fourth of a Mark-18A target, which will be full-scale operations for SRNL. Based on these results, the process parameters are adequately understood and the system can be operated safely.

36 MATERIALS SCIENCE↗
DOE OSTI2016

Effect of the size of nanoparticles on their dissolution within metal-glass nanocomposites under sustained irradiation

We investigate the dissolution law of metallic nanoparticles (NPs) under sustained irradiation. The system is composed of isolated spherical gold NPs (4–100 nm) embedded in an amorphous silica host matrix. Samples are irradiated at room temperature in the nuclear stopping power regime with 4 MeV Au ions for fluences up to 8 × 10{sup 16 }cm{sup −2}. Experimentally, the dependence of the dissolution kinetics on the irradiation fluence is linear for large NPs (45–100 nm) and exponential for small NPs (4–25 nm). A lattice-based kinetic Monte Carlo (KMC) code, which includes atomic diffusion and ballistic displacement events, is used to simulate the dynamical competition between irradiation effects and thermal healing. The KMC simulations allow for a qualitative description of the NP dissolution in two main stages, in good agreement with the experiment. Moreover, the perfect correlation obtained between the evolution of the simulated flux of ejected atoms and the dissolution rate in two stages implies that there exists an effect of the size of NPs on their dissolution and a critical size for the transition between the two stages. The Frost-Russell model providing an analytical solution for the dissolution rate, accounts well for the first dissolution stage but fails in reproducing the data for the second stage. An improved model obtained by including a size-dependent recoil generation rate permits fully describing the dissolution for any NP size. This proves, in particular, that the size effect on the generation rate is the principal reason for the existence of two regimes. Finally, our results also demonstrate that it is justified to use a unidirectional approximation to describe the dissolution of the NP under irradiation, because the solute concentration is particularly low in metal-glass nanocomposites.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗
DOE OSTI2021

Parametric Study of Used Nuclear Oxide Fuel Constituent Dissolution in Molten LiCl-KCl-UCl 3

Prior work identified dissolution of used nuclear oxide fuel constituents from a uranium oxide matrix into molten LiCl-KCl-UCl 3 at 500°C, prompting a subsequent series of three progressive studies (including an initial scoping study, an electrolytic dissolution study, and a chemical-seeded dissolution study) to further investigate associated parameters and mechanisms. Thermodynamic calculations were performed to identify possible reaction mechanisms and their propensities in used oxide fuel constituent dissolution. Used nuclear oxide fuels with varying preconditions from fast and thermal test reactors were separately immersed in the subject salt system to assess fuel constituent migration from the bulk fuel matrix to the salt phase in an initial scoping study. Dissolution of expected fuel constituents, including alkali, alkaline earth, lanthanide, and transuranium oxides, into the chloride salt phase varied widely, ranging from 12% to 99% in the initial study. Uranium isotope blending between the salt phase and bulk fuel matrix was also observed, which was attributed to reducing conditions in the fuel matrix. Electrolytic and chemical-seeded dissolution studies were subsequently performed to effect reducing conditions in the fuel. Other parameters, including temperature (at 500°C, 650°C, 725°C, and 800°C) and uranium trichloride concentrations (at 6, 9, and 19 wt% uranium), were investigated in the latter two studies, resulting in fuel constituent dissolution above 90%. Extents of dissolution were based on initial and final fuel constituent concentrations in the oxide fuels following operations in the salt and subsequent removal of the salt via distillation. Finally, in this series of progressive studies, oxide fuel preconditioning and in situ reducing conditions, along with elevated temperature and uranium trichloride concentrations, were the primary parameters promoting used nuclear oxide fuel constituent dissolution in accordance with identified reaction mechanisms.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗
DOE OSTI2026

Comparative Dissolution of Iron-Bearing Minerals by Catecholate and Hydroxamate Siderophores under Oxic and Anoxic Conditions

Siderophores play a crucial role in biological iron (Fe) acquisition and mobilization by promoting Fe mineral and rock weathering. While the effects of the hydroxamate siderophore desferrioxamine B (DFOB) have been extensively studied, the role of catecholates in the dissolution of Fe mineral and rock under varying redox conditions remain limited. Moreover, despite Fe being one of the most redox-active metals, the siderophore-mediated redox transformations of solid-phase Fe and their impact on mineral dissolution are not well understood. Herein, this study systematically investigated dissolution behavior of both Fe(II) and Fe(III)-bearing minerals and rocks (Fe(II)- bearing basalt and olivine, and Fe(III)- bearing nontronite and goethite), by two structurally distinct biological siderophores, catecholate protochelin and hydroxamate DFOB, under both oxic and anoxic conditions. Batch experiments quantified Fe and transition metals (Mn, Ni, Zn, Mo) released from the tested minerals in the presence of siderophores. Throughout the dissolution experiments, siderophore concentrations and Fe-siderophore complexation in solutions were measured using UV-vis spectrometry. Fe redox changes under oxic and anoxic conditions by siderophores were determined, and mineral surface alterations following siderophore treatments were characterized through scanning electron microscopy (SEM) and time-of-flight secondary ion mass spectroscopy (ToF-SIMS). Results revealed distinct interplays of dissolution mechanisms, including ligand-exchange promoted dissolution and reductive dissolution, along with Fe(III) reduction and Fe(II) oxidation, contributing to the Fe(II)- and Fe(III)-rich mineral weathering under varying redox conditions. Under oxic conditions, both protochelin and DFOB enhanced Fe release from Fe(II)-rich basalt and olivine more effectively than from Fe(III)-rich minerals. DFOB induced greater Fe(II)-mineral dissolution than protochelin. This difference was attributed to a higher level of Fe(II) oxidation by DFOB in contrast to protochelin, as well as the protochelin oxidation with the loss of Fe binding groups (catechols). Under anoxic conditions, both siderophores significantly reduced Fe(III) in nontronite and goethite, with protochelin demonstrating substantially stronger Fe(III) reduction capacity than DFOB. However, Fe(III) reduction negatively impacted Fe release from Fe(III)-rich minerals. Instead, Fe release from Fe(II)-rich minerals was enhanced under anoxic conditions due to the absence of Fe(II) oxidation and labile Fe(II). Variations in siderophore adsorption also contributed to dissolution differences. Beyond iron, the release of transition metals from tested minerals was influenced by elemental contents, mineral compositions, and siderophore types, revealing distinct metal- and siderophore-dependent patterns. This systematic investigation highlights the roles of siderophores in Fe redox cycling and metal mobilization, enhancing our understanding of different siderophore behaviors in siderophore-mediated microbial metal acquisition within redox-dynamic environments, with implications for bioleaching industries and applications in agriculture and climate change mitigation.

Guo, Dongyi↗
DOE OSTI2018

Effects of Na + and K + Exchange in Interlayers on Biotite Dissolution under High-Temperature and High-CO 2 -Pressure Conditions

Cations in formation brine can affect CO 2 -induced dissolution of minerals during geologic CO 2 sequestration (GCS), affecting the GCS performance. This study investigated the dissolution of biotite with 0–4 M Na + and 0–10 mM K + under high temperature and high CO 2 pressure (i.e., 95 °C and 100 bar CO 2 ). At <0.5 M Na + concentration, Na + replaced K + in the biotite interlayer and enhanced the biotite dissolution. In >0.5 M Na + , however, the enhancing effect of Na + was mitigated by an inhibition caused by competing sorption between Na + and protons. With 0.5 M Na + concentration, coexisting K + significantly inhibited the biotite dissolution with high sensitivity at even lower K + concentrations, such as 0.1–0.5 mM. In this study, we also reported the dissolution of Na-treated biotite, mimicking biotite naturally equilibrated with Na + -abundant brine. Na-treated biotite dissolved faster than natural K-containing biotite, and during the dissolution, it transformed to vermiculite. Aqueous Na + inhibited the dissolution of Na-treated biotite by suppressing the release of interlayer Na + , and aqueous K + inhibited the dissolution of Na-treated biotite by replacing the interlayer Na + . In conclusion, these findings contribute to better understanding of biotite dissolution in the presence of potassium-containing clay-swelling inhibitors and different salinities at GCS sites.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2016

Nonlinear dynamics and instability of aqueous dissolution of silicate glasses and minerals

Aqueous dissolution of silicate glasses and minerals plays a critical role in global biogeochemical cycles and climate evolution. The reactivity of these materials is also important to numerous engineering applications including nuclear waste disposal. The dissolution process has long been considered to be controlled by a leached surface layer in which cations in the silicate framework are gradually leached out and replaced by protons from the solution. This view has recently been challenged by observations of extremely sharp corrosion fronts and oscillatory zonings in altered rims of the materials, suggesting that corrosion of these materials may proceed directly through congruent dissolution followed by secondary mineral precipitation. Here we show that complex silicate material dissolution behaviors can emerge from a simple positive feedback between dissolution-induced cation release and cation-enhanced dissolution kinetics. This self-accelerating mechanism enables a systematic prediction of the occurrence of sharp dissolution fronts (vs. leached surface layers), oscillatory dissolution behaviors and multiple stages of glass dissolution (in particular the alteration resumption at a late stage of a corrosion process). In conclusion, our work provides a new perspective for predicting long-term silicate weathering rates in actual geochemical systems and developing durable silicate materials for various engineering applications.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗