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At least 37 records · Page 2

The solubility of ErPO 4 and Er speciation in hydrothermal fluids at varying pH and salinity between 350 and 450 °C

The rare earth elements (REE) are important for the green-energy transition and can be incorporated into the REE phosphates, such as xenotime-(Y), which also hosts heavy REE (Tb– Lu). Xenotime-(Y) is a common accessory mineral in metamorphic rocks and a range of mineral deposits where it controls the mobility of heavy REE, however, the impact of high temperature aqueous fluids on the behavior of heavy REE is largely unknown. Thermodynamic modeling can be utilized as a tool to predict the mobility of REE in hydrothermal aqueous fluids, but must be supported by accurate experimental data. Here, we measured the solubility of endmember synthetic xenotime-structured ErPO4 in NaCl-HCl-NaOH-bearing aqueous solutions at 350 °C and water vapor saturation pressure, at 400 and at 450 °C and 500 bar using batch-type Inconel reactors. Erbium speciation was investigated as a function of pH from 2.8 to 8, where Er chloride species are predominant at acidic conditions (pH <3) and Er hydroxyl complexes are predominant at near- neutral to alkaline conditions (pH >3). At pH 7–9, the measured ErPO 4 solubility (-9.8 to -7.5 log m Er ) is up to 2.5 orders of magnitude lower than thermodynamic predictions (-9.4 to -6.7 log m Er ) using existing thermodynamic databases. At pH 2–3, the predicted ErPO 4 solubility is ~0.5 orders of magnitude higher at 350 °C and ~1 order of magnitude lower at 450 °C compared to experimentally measured Er concentrations. The thermodynamic properties of aqueous Er species were therefore revised in this study. The partial molal Gibbs energy of formation (Δ f G 0 T,P ) for aqueous Er hydroxyl and chloride species are optimized using GEMSFITS and the logarithmic formation constants (logβ n ( Cl,OH) ) were derived at each experimental temperature and pressure. The updated thermodynamic properties for Er hydroxyl species (Er(OH) +2 , Er(OH) 2 + , and Er(OH) 3 0 ) show that their stability shifts to more acidic conditions at and below 400 °C. The Er chloride species (ErCl +2 and ErCl 2 + ) show increased stability compared to Er hydroxyl species at temperatures of 450 °C and 0.01 mol/kg NaCl. The updated thermodynamic properties are implemented into the GEM-Selektor modeling package to investigate the mobility of Er in saline hydrothermal fluids in equilibrium with alkaline rocks. Importantly, the updated properties for Er hydroxyl species result in low Er solubility at rock equilibrated pH conditions due to an expanded hydroxyl predominance zone, but lower aqueous complex stability overall, whereas previous models suggest greater stability for aqueous Er species. Furthermore, ErPO 4 solubility increases with decreasing temperature due to the deprotonation of HCl, which increases the acidity of hydrothermal fluids and the availability of Cl - to complex with the REE. These simulations highlight how fluid-rock reaction and temperature affect the mobility of REE in hydrothermal ore-forming systems.

58 GEOSCIENCES

Wildfire Produces Transient Minerals: Speciation, Reactivity, and Fate of Iron and Manganese in Surface Soils Post Wildfire

Wildfire leads to the deposition of an ash layer at the land surface. This material typically has alkaline properties, abundant pyrogenic carbon, and elevated metal concentrations compared to surface soils. Here, we compare ash and surface soils collected three weeks and two years after the Glass Fire (St. Helena, California, USA) to determine how wildfire affects the speciation and reactivity of iron (Fe) and manganese (Mn), two micronutrients that influence many soil processes. Synchrotron-based analyses revealed that wildfire generated stable Fe oxides like maghemite (γ-Fe 2 O 3 ) and hematite (α-Fe 2 O 3 ) that likely derived from surface soil or mineral dust rather than the vegetation, and Mn oxides such as hausmannite (Mn 3 O 4 ) and bixbyite (Mn 2 O 3 ) that derived primarily from aboveground biomass. However, these pyrogenic minerals were absent in soils collected two years after the fire. Their loss from the soil surface may result from a combination of erosion, translocation to deeper soil layers, and chemical weathering. The latter hypothesis is supported by the enhanced mobilization of Fe and Mn from ash upon the addition of pyoverdine, a model biogenic ligand. The increased mobility of micronutrients from fire-derived minerals in ash in response to microbial and root exudation may facilitate postfire soil and vegetation recovery.

bixbyite

Homoleptic An(IV) Dimethyl Sulfoxide Complexes of Th–Pu Enable Insight into Solution Speciation and Redox

A family of 8- and 9- coordinate homoleptic dimethyl sulfoxide An(IV) complexes is used to evaluate the solvation properties of tetravalent actinide ions in dimethyl sulfoxide (DMSO) vs aqueous media. These compounds are prepared from aqueous mixtures of DMSO and yield crystalline solids, whose solid-state electronic absorption spectra are compared to solution phase spectra, providing insight into the solution speciation. The thermodynamics of the equilibria between the 8- and 9-coordinate compounds were determined experimentally and computationally, showing a trend that correlates with ionic radius. Cyclic voltammetry data for the +IV/+III couples of Np and Pu in the DMSO electrolyte indicate that the +IV ions are significantly stabilized compared to aqueous media due to the more donating nature of DMSO compared to water. As a result, computational studies of these systems indicate that further reactivity may take place upon reduction to the +III oxidation state.

Actinides

Influence of Nd(II) and Nd(III) Ions on the Speciation and Kinetic Dynamics of Radiolytic Transients in Molten LiCl-KCl Eutectic Salt Mixtures

In the pyrochemical reprocessing of used nuclear fuel, understanding the effects of ionizing radiation on the chemical behavior of fission products in molten chloride eutectic salt is crucial. Here, this study investigates the impact of radiation on the chemical and kinetic speciation of Nd ions in molten LiCl-KCl eutectic, which are challenging to separate due to their multivalent oxidation states and comproportionation reactions. Electron pulse radiolysis techniques were used to determine transient absorption spectra, chemical kinetics, and activation parameters for the reaction of Nd ions with the primary products of molten LiCl-KCl eutectic radiolysis: the solvated electron (e S - ) and dichlorine radical anion (Cl 2 •- ). Initially, Nd(III) reacted rapidly with e S - , forming Nd(II) with a second-order rate coefficient of k = (4.54 ± 0.07) × 10 10 M -1 s -1 at 673 K. The resulting Nd(II) ions then reacted slowly with Cl 2 •- , regenerating Nd(III) with an estimated rate of k = (1.72 ± 0.04) × 10 10 M -1 s -1 at 673 K. Additionally, the comproportionation reaction of Nd(III) and Nd(s) to form Nd(II) was monitored chemically and electrochemically. This work suggests that the comproportionation reaction of Nd(III) with Nd(s) to form Nd(II) is unstable in molten LiCl-KCl eutectic.

36 - MATERIALS SCIENCE

Post-Mortem Characterization of Cerium Speciation in Molten Calcium Chloride

Abstract Advancing radiochemistry and nuclear materials science requires understanding actinide interactions with molten salts, which are used in next-generation nuclear reactors and for processing of actinides to recover useful fissile material. Understanding chemical interactions of actinides with molten salts has been limited by challenges in developing spectroscopic and X-ray techniques that are compatible with the high temperatures necessary to study molten salts. In this work, interactions of CeO2 (serving as a nonradioactive surrogate for uranium and plutonium) with CaCl2 are characterized following heating. Scanning electron microscopy indicates CeO2 morphological changes from small (<1 μm) particles to 3–5 μm sheets. Powder X-ray diffraction and infrared and Raman spectroscopies show the formation of CeOCl at higher (850–1050 °C) temperatures. In the absence of a chemical reducing agent, it was found that a high-temperature, low-oxygen environment is the key to the formation of oxychloride and that oxychloride formation is inhibited by annealing the CeO2 starting material. Lastly, thermal analysis revealed lowering of the melting point of CaCl2 after heating with CeO2. In all, this work identifies applicable spectroscopic techniques to target studies of heavy elements in molten salt environments and highlights the relationship between chemical speciation and melting behavior, a key thermophysical property.

Kelly, Sheridon N. [Lawrence Livermore National La

Solution and Active Site Speciation Drive Selectivity for Electrocatalytic Reactive Carbon Capture in Diethanolamine over Ni–N–C Catalysts

Direct conversion of captured forms of carbon, or reactive carbon capture (RCC), presents an opportunity to reduce the energy intensity and cost of direct CO 2 utilization from dilute sources. While amine-based sorbents effectively capture CO 2 , their use for RCC presents numerous challenges with typical pure metal catalysts used for electrochemical CO 2 reduction (CO 2 R). Here, using both theory and experiments, we find that Ni–N–C single atom catalysts are effective for RCC conversion to CO using a diethanolamine sorbent, in contrast to pure metal catalysts. Computational analysis reveals that RCC can proceed directly through direct reduction of the sorbent-CO 2 adduct or indirectly by C–N bond breaking facilitating CO 2 adsorption and subsequent reduction. We find that the latter mechanism is most prevalent at low overpotentials where we experimentally observe RCC selectivity. We also find experimentally that the rate of CO production for RCC with Ni–N–C catalysts can exceed pure bicarbonate solutions at intermediate sorbent concentration (0.1–0.5 M DEA) under dilute (10–25%) streams of CO 2 at low overpotentials. The coordination environment of Ni sites and the solution speciation influence their RCC activity, with changes in protonation to coordinating N/C atoms resulting in changing the RCC mechanism and consequent activity. In situ X-ray absorption spectroscopy and computational analysis reveal restructuring under RCC conditions due to hydrogen coadsorption with DEA that limits the stability of Ni–N–C catalysts. This work highlights the importance of carefully controlling the catalyst and solution environment to achieve active and stable RCC electrocatalysis.

Chemistry

Strontium Speciation in Relevant Tank Waste Components Examined by Electrospray Ionization Mass Spectrometry

The identification of chemical species formed in complex nuclear waste is crucial for the development and employment of advanced separations technologies to remediate the Hanford site by processing tank waste. The current Tank Side Cesium Removal (TSCR) process deployed at Hanford utilizes crystalline silicotitanate (CST) ion exchange (IX) media to aid in the separation of low-activity waste for proper treatment and disposal. The inorganic IX media is highly selective for Cs but has been shown to also remove Sr from caustic simulants and small-scale IX processing of Hanford tank waste.(Fiskum, Rovira et al. 2019, Fiskum, Campbell et al. 2021, Westesen, Campbell et al. 2022) Quantitative Sr removal has not been observed in all tank waste supernates tested; thus, to better understand Sr removal and effectively predict processing behavior through TSCR, it is necessary to first investigate Sr speciation in tank waste. This work utilized electrospray ionization mass spectrometry (ESI-MS) to identify ionic Sr complexes that form in the presence of NO 3 –, NO 2 –, OH–, and Cl–. Although our results show that NO 3 –, NO 2 –, and OH– are competitive for Sr 2+ binding, previous data from IX studies indicate that [SrOH] + is not the dominant species of concern in tank waste processing schemes.(Fiskum, Campbell and Trang-Le 2020) Our results show that the [Sr(NO3)]+ species and the [Sr(NO2)] + species form in considerable abundances, which may affect the ability to separate Sr using CST in nuclear waste separation processes.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W

Speciation of Transition Metal Dissolution in Electrolyte from Common Cathode Materials

Significant capacity loss has been observed across extended cycling of lithium-ion batteries cycled to high potential. One of the sources of capacity fade is transition metal dissolution from the cathode active material, ion migration through the electrolyte, and deposition on the solid-electrolyte interphase on the anode. While much research has been conducted on the oxidation state of the transition metal in the cathode active material or deposited on the anode, there have been limited investigations of the oxidation state of the transition metal ions dissolved in the electrolyte. Here, in this work, X-ray absorption spectroscopy has been performed on electrolytes extracted from cells built with four different cathode active materials (LiMn 2 O 4 (LMO), LiNi 0.5 Mn 1.5 O 4 (LNMO), LiNi 0.8 Mn 0.1 Co 0.1 O 2 (NMC811), and (x Li 2 MnO 3 *(1-x) LiNi a Mn b Co c O 2 , with a+b+c=1) (LMRNMC)) that were cycled at either high or standard potentials to determine the oxidation state of Mn and Ni in solution. Inductively coupled plasma-mass spectrometry has been performed on the anodes from these cells to determine the concentration of deposited transition metal ions. While transition metal ions were found dissolved in all electrolytes, the oxidation state(s) of Mn and Ni were determined to be dependent on the cathode material and independent of cycling potential.

25 ENERGY STORAGE

Spectrophotometric study of erbium (III) speciation in chloride solutions from 25 to 75 °C

In this study, UV-Vis spectrophotometric experiments were conducted from 25 to 75 °C using Er-HClO4-bearing solutions with varying NaCl concentrations. The molar absorbance coefficient of Er3+ decreases with temperature, and the absorbance intensity gradually decreases with increasing mCl/mEr ratios. The number of absorbing species include Er3+ and ErCl2+ even at the highest mCl/mEr ratio. The formation constant (β 1 ) for the ErCl 2+ species was derived and fitted between 50 and 250 °C with existing literature values, yielding the following equation: logβ 1 0 = −22.4315 + 0.0345T + 3.9379·10 3 /T, where T is temperature in Kevin.

58 GEOSCIENCES

Chemical speciation correlated with microstructural heterogeneity of interdicted uranium materials

Two uranium powders seized by law enforcement in Victoria, Australia, have been characterized by established nuclear forensic methods in a previously published study. Here, in this work, the results of further characterization by a scanning transmission x-ray microscope (STXM) operating in the soft x-ray regime are reported. STXM images are used to estimate the elemental distribution in micrometer-scale particles of each powder, and oxygen K-edge absorption spectra are used to determine the chemical state of uranium. The results of the current study are consistent with the previous analysis; the first powder is found to be a potassium-uranium hydrate, while the second powder is determined to be a mixture of uranium oxides primarily consisting of UO 3 .

38 RADIATION CHEMISTRY, RADIOCHEMISTRY, AND NUCLEA

Speciation and diffusive dynamics in hydrated grain boundaries of complex oxide Gd2Ti2O7

Abstract Grain boundaries in polycrystalline materials significantly affect their properties, such as ionic transport, corrosion, and chemical durability. The pyrochlore compound (Gd 2 Ti 2 O 7 ) is employed as a model for complex oxides and is known for its diverse applications, including nuclear waste immobilization. Density functional theory-based first-principles molecular dynamics simulations were performed at different temperatures on the hydrated grain boundary system. The results show extensive transformations within the grain boundaries among hydrous water species (OH − , H 2 O, and H 3 O + ). The temperature dependence of self-diffusion coefficients follows Arrhenius behavior, with an activation energy of 35.9 kJ/mol for hydrogen and 46.3 kJ/mol for oxygen. The lifetime of OH − is about three to four times longer than that of H 2 O at temperatures from 800 to 2100 K, suggesting the greater stability of OH − over H 2 O, a unique characteristic of the grain boundaries. The estimated lifetime of the hydrous species decreases as the temperature increases, with an activation energy of 9.9 kJ/mol for OH − and 13.4 kJ/mol for H 2 O. While Gd 3 + is more mobile than Ti 4+ , both the Gd 3 + and Ti 4+ cations are orders of magnitude less mobile than the water species. The results suggest that water species are much more mobile within grain boundaries than in the bulk crystal and have the potential to penetrate deep into polycrystalline materials through grain boundaries, leading to grain boundary degradation and dissolution. The different mobilities of cations in complex oxides can lead to leaching of certain cations and incongruent dissolution during the chemical weathering of Earth and industrial materials.

B. Ghosh, Dipta

NdPO 4 solubility and aqueous Neodymium speciation in supercritical fluids: An experimental study at 500–700 °C and 1.7 kbar

A key aspect in the formation of rare earth elements (REE) deposits is the role of REE transport as aqueous REE complexes in supercritical hydrothermal solutions, where the nature of the aqueous complex is controlled by solution composition, temperature and pressure. Despite chloride being considered as one of the most abundant transporting ligands in magmatic-hydrothermal fluids, experimental investigations on the stability of aqueous REE chloride complexes are scarce above 300 °C. In this study, synthetic NdPO 4 crystals were reacted with non-saline and saline (0, 0.05 and 0.5 mNaCl), acidic (0.01 mHCl) aqueous solutions in a series of solubility experiments conducted at 500–700 °C and 1.7 kbar, where the solubilities were determined using a stable Nd isotope ( 145 Nd isotope spike) dilution technique. NdPO 4 solubility ranges between 28 ppm and 10,858 ppm, where solubility increases with both temperature and salinity. At 500 °C, log mNdPO 4 increases from –3.93 to –1.60 and there is a strong correlation between NdPO 4 solubility and NaCl concentrations (slope of 1.2 ± 0.3), indicating stabilization of the Nd chloride aqueous complexes with a stoichiometry corresponding to NdCl 2+ . At 600 °C, this correlation is weaker (slope of 0.4, log mNdPO 4 increases from –2.63 to –1.88) indicating the stabilization of both Nd chloride and hydroxyl species controlling solubility. At 700 °C, NdPO 4 solubility is largely independent of NaCl concentration indicating that solubility is controlled by Nd hydroxyl complexes, where stoichiometry suggests the neutral Nd(OH) 3 0 species is dominant. The solubility product (Ksp) of NdPO4 is derived from experimental data with the relation: log K sp = -41.81 – 0.057T – 20987/T, with T temperature in Kelvin. Comparison of the measured Nd phosphate solubility to thermodynamic predictions using the available Helgeson-Kirkham-Flowers equation of state parameters for aqueous Nd complexes indicate that predictions are up to three orders of magnitude lower compared to experimental observations. This discrepancy is most pronounced in saline solutions, suggesting that thermodynamic properties of the REE chloride species in supercritical fluids require revision. Numerical simulations of fluid-rock interaction between acidic, saline fluids and a Strange Lake felsic mineral assemblage demonstrates that NdPO 4 solubility predictions from models are four to six orders of magnitude lower than those calculated based on empirical fits from experiments, which suggests that acidic, saline fluids may play an important role in mobilizing large amounts of light REE from 450 to 700 °C.

58 GEOSCIENCES

An experimental study of synthetic Hydroxybastnäsite-(La) solubility and speciation in carbonate bearing aqueous solutions at 175–250 °C

The transport and enrichment of rare earth element (REE) ore bodies are dependent on the stability of aqueous metal ligand complexes and the solubility of REE bearing minerals. REE ores are commonly associated with igneous systems having aqueous fluids with high carbonate concentrations and REE solubilities have been shown to be dependent on temperature and associate anion aqueous ligands present in solution. Furthermore, this work presents solubility experiments of hydroxybastnäsite-(La) at elevated temperatures in aqueous solutions of varying carbonate concentrations. At lower temperatures, hydroxybastnäsite-(La) solubility is controlled by neutral mono-carbonate LaCO 3 OH° but at higher temperatures and activities of carbonate species, charged di-carbonate La(CO 3 ) 2 - increases and predominates. This divergence, and the difference in solubility products of other hydroxybastnäsite-(REE) phases, provides a potential mechanism for REE fractionation in carbonate dominated aqueous solutions. To illustrate one such mechanism the solubility data of hydroxybastnäsite-(La) is compared with previously reported data of hydroxybastnäsite-(Nd) at elevated temperatures.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH

Speciation mapping of the oxidation layer on aged uranium dioxide using scanning transmission x-ray spectromicroscopy

In this study, UO 2 was aged in humid air and prepared as a thin section using a focused ion beam (FIB) instrument. The specimen was measured using synchrotron radiation spectromicroscopy techniques at the Beamline 11.0.2 STXM end station of the Advanced Light Source (ALS). Non-negative matrix factorization (NMF) methods were used to identify and map three component x-ray absorption near-edge structure (XANES) spectra in the oxygen K-edge data, revealing a surface layer of U 4 O 9 with a thickness of 206 ± 21 nm, and the bulk of the sample remaining as UO 2 . Uranium N 4,5 -edge XANES spectromicroscopy supports these results. The diffusion-controlled parabolic rate constant for UO 2 oxidation to U 4 O 9 was calculated from the observed layer thickness and compared to literature values. Complementary transmission electron microscopy (TEM) was used to image the sample and identify the phases present in various regions, confirming the STXM results.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS

Versatile Cell Design for Molten Fluoride Salt Spectroscopy: Investigating Metal-Ion Speciation in Molten Fluoride Salts

Fluoride-based molten salts are widely used in industrial applications including aluminum production, thermal energy storage, optical crystal growth, and advanced nuclear reactor designs. Despite the wide range of uses, fundamental understandings of coordination chemistry and methods for probing molten fluorides are scarce, likely due to the difficulty of probing fluoride melts with spectroscopic techniques. Performing spectroscopic measurements of fluoride-based salts is challenging due to the highly corrosive nature of these salts, which can degrade many common optical materials. Here, in this work, we present a versatile optical cell design that enables spectroscopic measurements of corrosive melts. This innovative cell design overcomes the challenges posed by the corrosive nature of the salts, allowing for an accurate and consistent spectroscopic analysis. This work reports temperature-dependent absorption measurements for Co 2+ , Ni 2+ , and Cr 3+ analytes in LiF-NaF-KF eutectic salt (i.e., FLiNaK), which are common corrosion products originating from structural alloys in molten-fluoride handling. Absorption spectra were used to understand interactions of these analytes with FLiNaK, particularly ligand field coordination. The analysis of absorption spectra was complemented by structural analyses using ab initio molecular dynamics (AIMD) simulations, providing deeper insights into the behavior of the analytes in FLiNaK. Our findings indicate that the analytes studied in this work exist in octahedral or near-octahedral coordination states that remain stable across the temperature range of 500–600 °C. This work not only highlights an applied solution to performing optical spectroscopy in corrosive, high-temperature melts but also provides important fundamental insight on coordination behavior of transition-metal species in molten fluorides.

Fluoride salt spectroscopy

La 3+ Networks and Speciation in the Molten State: Impact of Spacer Salt Selection on Structural Heterogeneity

We recently introduced the concept of a “spacer salt” that creates structural heterogeneity and intermediate range order. Put simply, a fully networked salt melt, such as LaCl 3 or UCl 3 , becomes disrupted by the introduction of ions that do not participate in the network. One of the results of this disruption is the experimental observation of two characteristic distances between the multivalent cations: the shorter “in-network” distance and the longer “across-network” distance spaced by the lowvalency salt. The longer characteristic distance, absent if there is no spacer salt, is the culprit for a new first sharp diffraction peak in scattering experiments. Intuitively, it would appear to follow from this analysis that higher concentrations of the lower-valency salt would further separate multivalent cations, resulting in a shift to lower q values of this first sharp diffraction peak. We will show experimentally and computationally that this is not always the case because multiple other factors enter into play.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH

Imaging and speciation of intracellular metallic implant debris using synchrotron-based X-ray fluorescence micro-spectroscopy: a study of two cases

Debris generated from total hip arthroplasty (THA) components made from metal alloys can cause, in some cases, inflammatory cell (e.g., macrophages) responses that lead to adverse local tissue reactions (ALTR) and implant failure. The lack of information on intracellular chemical alterations of metal debris has hindered the understanding of the pathogenesis of ALTR. The goal of this study was to characterize intracellular debris within macrophages using Synchrotron imaging and spectroscopy. We studied periprosthetic tissues of two retrieved THAs with (1) a metal-on-metal (MoM) articulation and (2) a metal-on-polyethylene (MoP) articulation exhibiting corrosion of the metal femoral head. The MoM-THA exhibited different valence states of chromium- and cobalt-containing debris, suggesting three different moieties: Cr 2 O 3 , CrPO 4 , and an alloy-oxide mixture. The findings further suggest that Cr 2 O 3 formed in the tribological interfaces of the implant, while CrPO 4 is a by-product of the phagocytosis process of cobalt alloy-containing debris. Titanium debris appeared to occur in a mixed crystalline/amorphous oxide state. It remains unclear if this chemical state results from the tribochemical processes at the implant surface or intracellular alterations. The MoP-THA specimen exhibited no intracellular particulate debris associated with macrohpages, indicating that the ALTR may be entirely triggered by metal ionic species in this case. A better understanding of in vivo chemical alteration of implant debris will aid in assessing the risk for ALTR during implant design and material choice. However, various techniques are needed to accurately determine the interaction between metal particles and the inta- and extra-cellular environment.

60 APPLIED LIFE SCIENCES