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At least 271 records · Page 15

The solubility of titanite in silicate melt determined from growth and dissolution experiments

The solubility of titanite (CaTiSiO 5 ) in Si-rich melts was measured experimentally through growth experiments at 800–1000 °C, 0.5–1.0 GPa, log fO 2 ~ CCO–0.8, t = 72–168 h, and H 2 O = 0 to 4 wt.%, and in dissolution experiments at 925–1300 °C, 0.8 GPa, t = 18–118 h, and H 2 O = 1–10 wt.% in a piston-cylinder apparatus. Run product glasses in growth experiments were homogeneous, and iron loss suppressed ilmenite crystallization. Saturation concentrations in dissolution experiments were estimated by fitting measured diffusion profiles. Titanite solubility increases with increasing temperature and melt composition parameter \(M = {\text{ molar }}\left( {{\text{Na }} + {\text{ K }} + {\text{ 2Ca}}} \right)/\left( {{\text{Al }} \times {\text{ Si}}} \right)\) . Multiple linear regression of glass composition data from growth and dissolution experiments ( n = 29) plus 39 experiments from the LEPR database (Hirschmann et al. 2008 ) yielded the titanite solubility equation (adj. r 2 = 0.95): \(\left( {TiO_{2} } \right)^{melt} \left( {wt.\% } \right) = 0.978 \times M + 0.0048 \times T\left( K \right){-}5.90\) . This model correctly predicted undersaturation in 95% of 2344 experiments from the LEPR database that did not have titanite or rutile. Application to natural rocks yields saturation temperatures that are similar to independent temperature estimates. Finally, this equation should be useful for constraining the temperatures of titanite-saturated melts, for determining whether titanite saturation in magmatic source regions is likely, and for determining when titanite can crystallize and begin to exert an influence on melt geochemistry.

58 GEOSCIENCES↗

Dissolution of Nb(C,N) and (Ti,V)N in the Coarse-Grained Heat-Affected Zone of Electric Resistance Welded X65 Line Pipe

Nb-rich and Ti/V-rich precipitates were introduced into the X65 linepipe via thermomechanical controlled processing. Their dissolution kinetics were investigated in the coarse-grained heat-affected zone after electric resistance welding. Nb-rich precipitates were found to dissolve completely, whereas Ti/V-rich precipitates were found to dissolve partially, because of slower dissolution kinetics. In conclusion, a complete dissolution of Nb-rich precipitates was associated with significant austenite grain coarsening, which promoted bainite as a quench product, which might have reduced the impact toughness.

microstructure↗

The Dissolution of Fe in HCl from the Ilmenite Concentrate; Evaluating the Effect of Operating Parameters and Mutual Interactions

Selective HCl dissolution of ilmenite components for obtaining Ti or titanium dioxide (TiO{sub 2}) has been highly recognized due to its advantages, greater environmental friendliness, and simplicity, compared to H{sub 2}SO{sub 4} and Cl{sub 2} methods. The effect of numerous parameters has been studied with the one-factor-at-a-time method. The present study aimed to evaluate the effect of key operation parameters, such as acid-to-solid ratio (A/S: 5 to 20 mL/g), reaction temperature (T: 70 °C to 100 °C), and acid concentration (A pct: 15 to 30 wt pct), on the dissolution of Fe in HCl solution with the minimum Ti losses to the leachate from its abundant, domestic, and low-cost mineral source (Kahnooj ilmenite concentrate) using central composite design–response surface methodology. After 90 minutes of leaching, the Ti/Fe (pct) in terms of dissolved amounts was selected as the process assessment response function. Based on the conducted experimental and statistical analysis, increasing the levels of parameters in the studied domain leads to an increase in Ti/Fe (pct), in the order of A pct > T > A/S. Two statistically significant mutual interactions between A/S-T and T-A pct, with 95 pct confidence level, were revealed for the first time in this study. The optimization strategy was set to the minimization of Ti/Fe (pct) by considering the objective of study and the selected response function. The A/S, T, and A pct were determined to be 5 mL/g, 70 °C, and 15 pct, respectively, for maximum impurity dissolution and minimum Ti loss to the leachate.

36 MATERIALS SCIENCE↗

Dissolution and reprecipitation of amorphous silica in silica Rich shales induces Non-Monotonic evolution of porosity in acidic reactive environments

Advances in sustainable subsurface energy technologies are crucial for meeting our energy and resource needs for a climate-resilient future. Novel strategies to harness subsurface shale reservoirs for recovering valuable metals and for enabling CO 2 storage are influenced by the morphological and mineralogical heterogeneities of these materials. In this context, delineating the interactions of highly acidic solutions such as wet supercritical CO 2 on shales with varying mineralogy is crucial to inform the stability of caprock seal for CO 2 storage and enhancements in permeability for fluid transport, reactivity, and storage. The feedback chemical effects associated with the interactions of acidic solutions on the morphologies and mineralogies of shales have not been extensively investigated. These insights are crucial for assessing temporal changes in the reactivity and the fate of the fluids in subsurface environments. In this study, we investigate the effect of 1M HCl solution on the chemistry and morphology of three different shale samples with varying carbonate, clay and silica contents. An increase in the amorphous content, from 37% to 41.3%, of silica-rich and carbonate/clay lean shale is noted due to reactions with an acidic solution which is attributed to the dissolution of Si-bearing phases such as clays, accompanied by SiO 2 precipitation. In shales bearing high content of clays and carbonates, significant increase in the pore volumes and surface areas are noted. Non-monotonic changes in the micron-scale porosity of silica rich–carbonate/clay lean (e.g., Mowry shale) are noted using in-situ X-ray microtomography experiments. Due to the initial mobilization of silica and dissolution of carbonate/clay phases, the total porosity slightly increases from 6.7% to 10.7% followed by a decrease to similar to 4% caused by SiO 2 reprecipitation. In conclusion, these findings suggest that even though silica is less reactive in acidic environments, the changes in the amorphous and crystalline content due to dissolution and reprecipitation alter the porosity and fluid flow paths.

04 OIL SHALES AND TAR SANDS↗

Concurrent measurement of strain and chemical reaction rates in a calcite grain pack undergoing pressure solution: Evidence for surface-reaction controlled dissolution

Pressure solution is inferred to be a significant contributor to sediment compaction and lithification, especially in carbonate sediments. For a sediment deforming primarily by pressure solution, the compaction rate should be directly related to the rate of calcite dissolution, transport along grain contacts, and calcite reprecipitation. Previous experimental work has shown that there is evidence that deformation in wet calcite grain packs is consistent with control by pressure solution, but considerable ambiguity remains regarding the rate limiting mechanism. We present the results of laboratory compaction experiments designed to directly measure calcite dissolution and precipitation rates (recrystallization rates) concurrently with strain rate to test whether measured rates are consistent with predicted rates both in absolute magnitude and time evolution. Recrystallization rates are measured using trace element chemistry (Sr/Ca, Mg/Ca) and isotopes (87Sr/86Sr) of fluids flowing slowly through a compacting grain pack as it is being triaxially compressed. Imaging techniques are used to characterize the grain contacts and strain effects in the post-experiment grain pack. Our data show that calcite recrystallization rates calculated from all three geochemical parameters are in approximate agreement and that the rates closely track strain rate. The geochemically inferred rates are close to predicted rates in absolute magnitude. Uncertainty in grain contact dimensions makes distinguishing between surface reaction control and diffusion control difficult. Measured reaction rates decrease faster than predicted from standard pressure solution creep flow laws. This inconsistency may indicate that calcite dissolution rates at grain contacts are more complex, and more time-dependent, than suggested by geometric models designed to predict grain contact stresses.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Experimental determination of zirconium hydride precipitation and dissolution in zirconium alloy

In this study, synchrotron X-Ray transmission diffraction experiments were performed to study hydride precipitation and dissolution in the zirconium/zirconium-hydride system while it occurs. Evidence was found that the hysteresis between the terminal solid solubility for precipitation and dissolution is not observed when hydride particles are already present at the beginning of sample cooldown. Additionally, experimental results show that, during a temperature hold, the concentration of hydrogen in solid solution becomes lower than the terminal solid solubility for hydride precipitation and eventually reaches the terminal solid solubility for hydride dissolution, indicating that the latter is the actual thermodynamic solubility limit.

36 MATERIALS SCIENCE↗

Solvation-guided inhibition of manganese dissolution of lithium- and manganese- rich cathode via cyclic carbonate molecular engineering

Lithium and manganese-rich (LMR) layered oxides represent a leading class of high-energy cathode materials, but their practical realization is fundamentally limited by severe manganese (Mn) dissolution, a process that triggers structural degradation and rapid capacity fade. While mitigation efforts have predominantly focused on interfacial engineering, the intrinsic contribution of bulk electrolyte solvation to this degradation pathway remains largely unexplored, primarily due to the difficulty of deconvolving its effects from concurrent cathode-electrolyte interphase (CEI) formation. Here, we report an experimental design to isolate the role of solvation. We systematically varied the electrolyte solvent solvation power by substituting the strongly coordinating ethylene carbonate (EC) with its weaker coordinating fluorinated derivatives, fluoroethylene carbonate (FEC) and trans-4,5-Difluoro-1,3-dioxolan-2-one (DFEC), while maintaining a consistent interfacial chemistry. Remarkably, the electrolyte formulated with the weakest solvent, DFEC, exhibits superior cycling stability, suppressing Mn dissolution by up to 63% relative to the conventional EC-based system. Post-mortem analysis unequivocally attributes this performance enhancement to the preservation of the LMR cathode's structural integrity, a direct consequence of mitigated Mn dissolution. This work provides conclusive evidence that modulating bulk electrolyte solvation is a potent and direct strategy for stabilizing LMR cathodes, establishing a vital design principle for next-generation battery systems.

25 ENERGY STORAGE↗

Mineral dissolution and wormholing from a pore-scale perspective

A micro-continuum approach is proposed to simulate the dissolution of solid minerals at the pore scale under single-phase flow conditions. The approach employs a Darcy–Brinkman–Stokes formulation and locally averaged conservation laws combined with immersed boundary conditions for the chemical reaction at the solid surface. The methodology compares well with the arbitrary-Lagrangian–Eulerian technique. The simulation framework is validated using an experimental microfluidic device to image the dissolution of a single calcite crystal. The evolution of the calcite crystal during the acidizing process is analysed and related to the flow conditions. Macroscopic laws for the dissolution rate are proposed by upscaling the pore-scale simulations. Finally, the emergence of wormholes during the injection of acid in a two-dimensional domain of calcite grains is discussed based on pore-scale simulations.

bio-inspired, mechanical behavior, carbon sequestr↗

Speciation and Aqueous Dissolution of Macronutrients in Fire Ash: Variation across Ecosystems and the Effects on Nutrient Cycling

This study investigated the speciation and aqueous dissolution of macronutrients in fire ash from diverse ecosystems and speciation of ash and smoke from laboratory burning, exploring the variations and their causes. The speciation of phosphorus (P), calcium (Ca), and potassium (K) in fire ash from five globally distributed ecosystems was characterized by using X-ray absorption spectroscopy and sequential fractionation. Aqueous dissolution of the macronutrients was measured by batch experiments at acidic and alkaline pHs. The results showed that P existed mainly as Ca phosphates, Ca as double carbonates, calcite, and sulfates, and most K was associated with Ca carbonates. Mineralogy and the relative abundance of the species were primarily controlled by elemental stoichiometry and fire temperature. Differences in Ca and P speciation existed between ash and smoke from laboratory burning, possibly caused by the temperature difference and/or mass fractionation during burning. The rates, extents, and pH dependencies of macronutrient dissolution differed among macronutrients and depended on their speciation, with K being highly soluble and the P and Ca regulated by solution pH. The variability in ash macronutrient chemistry and ecosystemspecific fire ash loads resulted in varying loads and availability of individual macronutrient from fire among ecosystems. This study provides a mechanistic understanding of how fires transform the chemistry of macronutrients and affect macronutrient returns to soils across different ecosystems, which is essential for evaluating the disturbance to ecosystem nutrient cycling by fires.

54 ENVIRONMENTAL SCIENCES↗

Reconstruction and Dissolution of Copper Catalysts during Electrocatalytic Nitrate Reduction

Copper-based electrocatalysts are widely explored for electrochemical nitrate remediation, yet their stability under operating conditions remains poorly understood. While nanoscale and subnanoscale Cu motifs are known to restructure during the nitrate reduction reaction (NO 3 RR), how these transformations translate into irreversible material loss remains unclear. Here, we quantify Cu dissolution during NO 3 RR as a function of catalyst architecture and electrolyte chemistry using two model systems: single-atom Cu (Cu 1 ) and Cu nanoparticles (Cu NP ). Time-resolved leaching measurements, integrated with in situ X-ray absorption spectroscopy (XAS), reveal measurable Cu loss for both catalysts during NO 3 RR. Dissolution is concentrated at the initiation of electrolysis, coinciding with rapid restructuring, and depends strongly on morphology, with Cu NP consistently exhibiting greater Cu loss than Cu 1 . In situ XAS reveals that Cu 1 forms transient metallic clusters under reduction that largely redisperse upon returning to open-circuit voltage, whereas Cu NP undergoes reduction of an oxidized surface layer accompanied by sustained Cu loss during electrolysis. Notably, the presence of nitrate significantly intensifies restructuring and Cu loss, highlighting the critical role of electrolyte composition. Furthermore, these findings establish a direct link between electrochemical restructuring and Cu dissolution, unveiling electrolyte-dependent interactions as key determinants of catalyst durability in electrochemical nitrate conversion.

36 MATERIALS SCIENCE↗

Electrolyte-induced surface transformation and transition-metal dissolution of fully delithiated LiNi 0.8 Co 0.15 Al 0.05 O 2

Here, enabling practical utilization of layered R $\bar{3}$ m positive electrodes near full delithiation requires an enhanced understanding of the complex electrode–electrolyte interactions that often induce failure. Using Li[Ni 0.8 Co 0.15 Al 0.05 ]O 2 (NCA) as a model layered compound, the chemical and structural stability in a strenuous thermal and electrochemical environment was explored. Operando microcalorimetry and electrochemical impedance spectroscopy identified a fingerprint for a structural decomposition and transition-metal dissolution reaction that occurs on the positive electrode at full delithiation. Surface-sensitive characterization techniques, including X-ray absorption spectroscopy and high-resolution transmission electron microscopy, measured a structural and morphological transformation of the surface and subsurface regions of NCA. Despite the bulk structural integrity being maintained, NCA surface degradation at a high state of charge induces excessive transition-metal dissolution and significant positive electrode impedance development, resulting in a rapid decrease in electrochemical performance. Additionally, the impact of electrolyte salt, positive electrode surface area, and surface Li 2 CO 3 content on the magnitude and character of the dissolution reaction was studied.

25 ENERGY STORAGE↗

Effects of Dissolution Regimes on Flow Channelization and Solute Transport in 3D Fracture Networks: Insights From Graph‐Based Reactive Transport Modeling

We investigate how mineral dissolution reshapes flow pathways and solute transport in three‐dimensional discrete fracture networks using a computationally efficient graph‐based reactive transport model. The DFNs are inspired by field‐site observations of fractured carbonate and represent realistic connectivity and structural heterogeneity. Flow is simulated with the Reynolds equation, and dissolution follows first‐order kinetics with diffusive limitations captured through an effective mass‐transfer coefficient. By systematically varying two key dimensionless parameters, the effective Damköhler number (Da), governing reaction versus advection rates, and a transport parameter (Da), analogous to the Thiele modulus, distinct flow channelization regimes emerge: mildly channelized at low G, highly channelized at intermediate Da, and extreme wormhole formation at high Da and low G. Eulerian and Lagrangian analyses, including breakthrough curves, particle tortuosity, dispersivity, and flow channeling indicators quantitatively characterize the progression of dissolution‐driven network restructuring. Across all regimes, initial fracture heterogeneity persists. The results underscore how the interplay between this initial structure, advection, reaction, and diffusion critically shapes subsurface flow pathways, with implications for applications ranging from groundwater remediation to enhanced geothermal systems.

54 ENVIRONMENTAL SCIENCES↗

Reductive dissolution of pyrite by methanogenic archaea

Abstract The formation and fate of pyrite (FeS2) modulates global iron, sulfur, carbon, and oxygen biogeochemical cycles and has done so since early in Earth’s geological history. A longstanding paradigm is that FeS2 is stable at low temperature and is unavailable to microorganisms in the absence of oxygen and oxidative weathering. Here, we show that methanogens can catalyze the reductive dissolution of FeS2 at low temperature (≤38 °C) and utilize dissolution products to meet cellular iron and sulfur demands associated with the biosynthesis of simple and complex co-factors. Direct access to FeS2 is required to catalyze its reduction and/or to assimilate iron monosulfide that likely forms through coupled reductive dissolution and precipitation, consistent with close associations observed between cells and FeS2. These findings demonstrate that FeS2 is bioavailable to anaerobic methanogens and can be mobilized in low temperature anoxic environments. Given that methanogens evolved at least 3.46 Gya, these data indicate that the microbial contribution to the iron and sulfur cycles in ancient and contemporary anoxic environments may be more complex and robust than previously recognized, with impacts on the sources and sinks of iron and sulfur and other bio-essential and thiophilic elements such as nickel and cobalt.

59 BASIC BIOLOGICAL SCIENCES↗

Imaging the kinetics of anisotropic dissolution of bimetallic core–shell nanocubes using graphene liquid cells

Chemical design of multicomponent nanocrystals requires atomic-level understanding of reaction kinetics. Here, we apply single-particle imaging coupled with atomistic simulation to study reaction pathways and rates of Pd@Au and Cu@Au core-shell nanocubes undergoing oxidative dissolution. Quantitative analysis of etching kinetics using in situ transmission electron microscopy (TEM) imaging reveals that the dissolution mechanism changes from predominantly edge-selective to layer-by-layer removal of Au atoms as the reaction progresses. Dissolution of the Au shell slows down when both metals are exposed, which we attribute to galvanic corrosion protection. Morphological transformations are determined by intrinsic anisotropy due to coordination-number-dependent atom removal rates and extrinsic anisotropy induced by the graphene window. Our work demonstrates that bimetallic coreshell nanocrystals are excellent probes for the local physicochemical conditions inside TEM liquid cells. Furthermore, single-particle TEM imaging and atomistic simulation of reaction trajectories can inform future design strategies for compositionally and architecturally sophisticated nanocrystals.

77 NANOSCIENCE AND NANOTECHNOLOGY↗

Atomic-scale understanding of oxide growth and dissolution kinetics of Ni-Cr alloys

Aqueous corrosion of metals is governed by formation and dissolution of a passivating, multi-component surface oxide. Unfortunately, a detailed atomistic description is challenging due to the compositional complexity and the need to consider multiple kinetic factors simultaneously. To this end, we combine experiments with a first-principles-derived, multiscale computational framework that transcends thermodynamic descriptions to explicitly simulate the kinetic evolution of surface oxides of Ni-Cr alloys as a function of composition, temperature, pH, and applied voltage. In the absence of pitting, we identify three distinct voltage regimes, which are kinetically dominated by oxide growth, dissolution, and competitive dissolution and reprecipitation. Evolving compositional gradients and oxide thickness are revealed, including a transition between a metastable Ni-Cr mixed oxide and a thick, porous Ni-dominated oxide. Beyond elucidating the underlying physics, we highlight the need for competing kinetics in models to properly predict the transition from passivation to corrosion. Our results provide a key step towards co-design of alloy composition alongside environmental conditions for sustainable use across a variety of critical energy and infrastructure applications.

36 MATERIALS SCIENCE↗

Can a simple topological-constraints-based model predict the initial dissolution rate of borosilicate and aluminosilicate glasses?

Tuning glass composition to obtain targeted properties generally relies on empirical approaches. However, a deep understanding of the physical and chemical mechanisms linking glass composition to its structure and properties would enable developing reliable predictive models. Indeed, although empirical models are usually able to interpolate composition–property relationships within a given compositional envelope, they often fail at extrapolating predictions far from their training domain. Here, as an alternative route to empirical models, we show that a structural descriptor based on the number of topological constraints per atom can be used to predict the initial dissolution rate of aluminosilicate and borosilicate glasses after being parameterized on different families of glasses (specific series of borosilicate glasses). Sixteen glasses belonging to these families were studied and their initial dissolution rates were determined at 90 °C and pH 90 °C = 9, covering rates spanning over 5 orders of magnitude. The model based on topological constraints was trained based on seven select borosilicate glasses (R 2 = 0.997) and used to predict the dissolution rate of nine additional borosilicate and aluminosilicate glasses. We show that, provided that corrections are made for high alkali content glasses that dissolve incongruently (preferential release of Na), the model gives reasonable predictions, even far from its training domain.

36 MATERIALS SCIENCE↗

Toward the performance assessment of advanced nuclear waste forms: temperature dependence of lanthanide borosilicate glass dissolution

Lanthanide borosilicate (LaBS) glasses are among the most promising waste forms for the immobilization of high-level radioactive waste generated from advanced nuclear fuel cycles. However, the temperature dependence of their dissolution kinetics remains poorly understood and constrained, limiting the integration of these materials into established performance assessment models. Here, we investigate the dissolution behavior of the legacy AmCm2-19 LaBS glass and the benchmark alkali aluminoborosilicate ISG-1 in deionized water between 50 °C and 250 °C using ASTM C1285 (Product Consistency Test-B) protocols. For AmCm2-19 LaBS glass, normalized elemental release rates for boron and silicon increase with temperature before plateauing near 150 °C, consistent with solubility-limited behavior. From data obtained at 50 °C and 100 °C, Arrhenius analysis yields activation energies of E a (B) = 24.8 ± 0.3 kJ mol⁻¹ and E a (Si) = 14.4 ± 0.2 kJ mol⁻¹, similar or slightly lower than those previously reported for two other compositions of LaBS glasses. No secondary phases or alteration layers were detected by SEM-EDX or pXRD. These results establish one of the first temperature-dependent kinetic datasets for LaBS glass dissolution, providing quantitative parameters to inform mechanistic corrosion models and predictive simulations of glass degradation in geological disposal environments.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

Insights on the dissolution of water in an albite melt at high pressures and temperatures from a direct structural analysis

The water dissolution mechanism in silicate melts under high pressures is not well understood. Here we present the first direct structure investigation of a water-saturated albite melt to monitor the interactions between water and the network structure of silicate melt at the molecular level. In situ high-energy X-ray diffraction was carried out on the NaAlSi 3 O 8 -H 2 O system at 800 °C and 300 MPa, at the Advanced Photon Source synchrotron facility. The analysis of the X-ray diffraction data was augmented with classical Molecular Dynamics simulations of a hydrous albite melt, incorporating accurate water-based interactions. The results show that metal–oxygen bond breaking at the bridging sites occurs overwhelmingly at the Si site upon reaction with H 2 O, with subsequent Si–OH bond formation and negligible Al–OH formation. Furthermore, we see no evidence for the dissociation of the Al 3+ ion from the network structure upon breaking of the Si–O bond in the hydrous albite melt. The results also indicate that the Na + ion is an active participant in the modifications of the silicate network structure of the albite melt upon water dissolution at high P–T conditions. We do not find evidence for the Na + ion dissociating from the network structure upon depolymerization and subsequent formation of NaOH complexes. Instead, our results show that the Na + ion persists as a structure modifier with a shift away from Na–BO bonding to an increase in the extent of Na-NBO bonding, in parallel with pronounced depolymerization of the network. Our MD simulations show that the Si–O and Al–O bond lengths are expanded by about 6% in the hydrous albite melt compared to those of the dry melt at high P–T conditions. The changes in the network silicate structure of a hydrous albite melt at high pressure and temperature, as revealed in this study, must be considered in the advancement of water dissolution models of hydrous granitic (or alkali aluminosilicate) melts.

36 MATERIALS SCIENCE↗