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At least 271 records · Page 15
All sourcesNASA NTRSDOE OSTI
DOE OSTI2019

The effect of CO 2 -induced dissolution on flow properties in Indiana Limestone: An in situ synchrotron X-ray micro-tomography study

The injection of CO 2 -rich fluids in carbonate rocks results in an evolution of the pore space, with consequent changes in the hydraulic properties of the reservoir; how these properties evolve, particularly for parameters relevant to multiphase flow e.g. P c (s), remains a topic of active research despite several decades of study. We have carried out an in situ synchrotron X-ray microtomography experiment to monitor pore structure evolution during dissolution of an Indiana Limestone core; the experiment involved flowing CO 2 -saturated water through the core for 36 h and resulted in 10 volumes corresponding to different temporal stages of the dissolution process. The injection parameters corresponded to the flow velocities expected near the well-bore region of a shallow aqueous CO 2 injection; fast flow rates with high reactant availability. Analysis of the tomographic data shows flow-enhanced dissolution i.e. channeling, and provides a time-resolved map of pore space alteration. Using the resulting 4D pore space volume, we modeled the evolution of capillary-pressure curves; this exercise demonstrates how pore structure evolution could impact the invasion and remobilization of non-wetting fluids, dramatically decreasing the entry pressure and the P C in some parts of the sample. The modeling of permeability, using a Stokes solver approach, quantified the relationship of porosity vs. permeability; we found that a modest increase in porosity, especially when the channeling system is more developed, greatly affects permeability. Furthermore, these results demonstrate how movement of CO 2 saturated brine near injected plumes might alter drainage dynamics near the plume boundary, thus leading to mobilization across subtle capillary barriers.

58 GEOSCIENCES↗
DOE OSTI2024

Application of the immobilized low-activity waste glass corrosion model to the static dissolution of 24 statistically-designed alkali-borosilicate waste glasses

Glass corrosion models that capture the complex mechanisms of the glass-water reaction enable the prediction of nuclear waste glass durability in disposal scenarios. Parameterization of such models is challenging because of the need to capture changes in corrosion behavior with time, reaction conditions, and glass composition. In this report we describe and employ the immobilized low activity waste (ILAW) glass corrosion model (IGCM) in geochemical simulations of static dissolution tests, at two temperatures (40 °C and 90 °C), for a matrix of 24 enhanced low activity waste (eLAW) glasses statistically designed to cover a processable composition space defined by 8 major glass components (Al 2 O 3 , B 2 O 3 , CaO, Na 2 O, SiO 2 , SnO 2 , ZrO 2 , and Others as defined in the text). The IGCM includes a first-order chemical affinity term and an ion-exchange term that represents the net exchange of Na+ ions in the pristine glass with protons in aqueous solution. Constant, time-dependent, and time- and pH-dependent functional forms of the ion-exchange term are evaluated to reproduce the change in corrosion behavior with time in saturated, static dissolution tests. The agreement with measured aqueous concentrations of the main glass components (B, Na, and Si) improved significantly upon addition of a time-dependent term, which therefore constitutes a simple representation of the glass-water reaction progress. Due to the limited changes in pH in the static dissolution tests, past a short initial period of rapid increase, addition of a pH dependent term did not appreciably improve the fits, indicating that comprehensive model parameterization requires more than one type of glass corrosion test to capture a wide range of solution chemistries. IGCM parameters were found to be dependent on glass composition, and the parameter sets generated in this work will enable the development of composition–parameter correlation models that offer the promise of predicting IGCM parameters, and thus glass corrosion behavior, solely based on glass composition.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗
DOE OSTI2018

Inhibitory effect of Ti and La on Fe dissolution in Al–Zn–Si bath by in-situ SXRD, SXRF, TEM and DFT calculation

Highlights: • In-situ synchrotron X-rays diffraction was used to study the solid-liquid reaction. • The addition of Ti and La suppresses the dissolution of Fe in the reaction. • A new quaternary phase was found in the hot-dip coated sheets. • The formation of the quaternary phase needed an enrichment of Si from bath. • The continuous formation of dross probably caused by the initial dissolution - Abstract: During the hot-dipping process, there is always a desire to restrain the mutual diffusion between steel and alloy bath for suppressing the formation of bath dross. However, the dissolution of steel sheets is difficult to quantify by the traditional methods. In this work, in-situ X-ray diffraction was used to investigate the solid-liquid reaction between solid Fe and Al–Zn–Si liquid alloy for quantitatively analyzing the consumption of Fe and the formation of Fe–Al compounds. The results indicated that the addition of trace Ti or La could suppress the mutual diffusion. We also observed the microstructures of the Fe–Al intermetallic multilayers and the distribution of Ti or La in the multilayers. A new quaternary phase was identified. The inhibitory effects of Ti and La were also explained by calculating the diffusion barrier energies with density functional theory.

36 MATERIALS SCIENCE↗
DOE OSTI2026

Ion-Specific Effects on PuO 2 Nanoparticle Aggregation and Dissolution in Concentrated Electrolytes

Hydrolytic PuO 2 nanoparticles (NPs) are a dominant aqueous Pu-bearing phase in high ionic strength nuclear wastes, yet their reactivity in nonideal brines remains poorly constrained. We quantify how electrolyte identity and concentration control PuO 2 NP aggregation and ligand-assisted dissolution in acidic, high salinity solutions (NaCl, NaNO 3 , NaClO 4 , Na 2 SO 4 , Na 2 C 2 O 4 up to 5 M). A multitechnique workflow combining liquid scintillation counting (operationally defined aqueous [Pu]), scattering/electrokinetic measurements (aggregate size and zeta potential), and spectroscopy (UV–vis, XPS, Raman) resolves electrolyte-dependent partitioning between colloidal and molecular Pu species. Weakly coordinating anions (ClO 4 – , Cl – , NO 3 – ) largely preserve the (aggregated) nanoparticulate fraction but generate distinct dissolved species at high concentration, i.e., Pu(IV)–nitrato complexes in NaNO 3 and Pu(VI)–chloro complexes in NaCl. In contrast, stronger ligands substantially perturb PuO 2 NP stability: sulfate promotes partial dissolution to Pu(IV)–sulfate complexes at low concentration but reduces aqueous [Pu] at higher sulfate levels via secondary Pu(IV) sulfate formation, whereas oxalate drives strong dissolution to aqueous Pu–oxalate complexes. Aged NPs show similar trends with reduced aqueous fractions and more dominant aggregation mechanisms. In conclusion, these spectroscopically constrained speciation data provide a foundation for incorporating PuO 2 NP reactivity into thermodynamic and reactive transport models for high salinity waste and brine environments.

Aggregation↗
DOE OSTI2018

Dissolution Kinetics of Epitaxial Cadmium Carbonate Overgrowths on Dolomite

Thin films grown on mineral surfaces can immobilize toxic metals in natural systems, but the effects of epitaxy and film thickness on dissolution rates of the overgrowth are typically unknown. To explore these effects, otavite (CdCO 3 ) films were grown on dolomite (104) surfaces from aqueous solutions containing [Cd] = [Ca] = [CO 3 ] = 0.2 mM for 1–48 h and then dissolved in deionized water. Films of various thicknesses and strain states were obtained by varying the growth reaction time. Growth for up to 3 h produced strained thin films with Cd coverages of <4.3 ± 0.6 equivalent monolayers (ML) (corresponding to a thickness of up to 17 Å), whereas reaction times of up to 48 h produced thicker films with as many as 114 ± 14 equivalent ML of Cd. Intrinsic dissolution rates were measured as a function of otavite film thickness by a combination of synchrotron X-ray fluorescence, specular X-ray reflectivity, and atomic force microscopy. As a result, the initial dissolution rates for unstrained films were comparable to those reported for synthetic otavite powders, whereas the thinnest films (<3.1 ± 1.1 ML) dissolved at a 50% slower rate, indicating that epitaxial strain effectively enhanced their stability. We discuss potential reasons for this difference.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2022

Manipulating Interfacial Dissolution–Redeposition Dynamics to Resynthesize Electrode Surface Chemistry

The solid-liquid electrochemical interface offers a two-dimensional environment for geometrically confined interfacial reactions to tailor electrode surface chemistry under operating conditions. In this study, we demonstrate that the dissolution and redeposition kinetics of transition metal cations, a ubiquitous phenomenon at the electrochemical interface, can be manipulated to regulate the chemical composition and crystal structure of the electrode surface as well as the overall electrochemical performance. Foreign cations (e.g., Ti 4+ ), either added as electrolyte additives or dissolved from surface coatings, can rapidly participate in the electrode dissolution-redeposition process, and facilitate the establishment of the dissolution-redeposition equilibrium. Our work expands the control over the electrochemical reactions at the solid-liquid interface and provides new insights into interfacial studies in electrochemistry and surface science.

25 ENERGY STORAGE↗
DOE OSTI2020

Probing the Radial Chemistry of Getter Components in Light Water Reactors via Controlled Electrochemical Dissolution

Getters are among the key functional components in the Tritium Producing Burnable Absorber Rods (TPBARs) of Light Water Reactors, and are used to capture the released tritium gas. They are cylindrical tubes comprised of the alloy zircaloy-4 which is coated with nickel plating both internally and externally. Their exposure to tritium as well as the irradiation environments in the light water reactors changes their structure, chemical composition and chemistry. Understanding the radial tritium distribution is key to gaining insight into the evolution of new chemistry upon irradiation in order to predict getter performance. Consequently, efforts are underway to devise a method that can allow selective probing into the getter core radially to probe the chemistry akin to carefully and selectively peeling of the layers of an onion. We have recently devised an electrochemical dissolution technique for controlled radial dissolution of zirconium based liners; this work describes the first proof-of-concept demonstration of the applicability of this technique on the controlled radial dissolution of nickel plated getters. The technique is complemented with periodic analysis of the electrolyte solution to measure the rates of release of the various elemental components and therefore glean information on their radial distribution across the getter; further complementary microscopy on the exposed surfaces allows us insight into the chemistry at the getter core.

38 RADIATION CHEMISTRY, RADIOCHEMISTRY, AND NUCLEA↗
DOE OSTI2022

A Geo‐Structurally Based Correction Factor for Apparent Dissolution Rates in Fractured Media

Abstract Field measurements of apparent geochemical weathering reaction rates in subsurface fractured porous media are known to deviate from laboratory measurements by multiple orders of magnitude. To date, there is no geologically based explanation for this discrepancy that can be used to predict reaction rates in field systems. Proposed correction factors are typically based on ad hoc characterizations related to geochemical kinetic models. Through a series of high‐fidelity reactive transport simulations of mineral dissolution within explicit 3D discrete fracture networks, we are able to link the geo‐structural attributes with reactive transport observations. We develop a correction factor to linear transition state theory for the prediction of the apparent dissolution rate based on measurable geological properties. The modified rate law shows excellent agreement with numerical simulations, indicating that geological structure could be a primary reason for the discrepancy between laboratory and field observations of apparent dissolution rates in fractured media.

58 GEOSCIENCES↗
DOE OSTI2016

Tandem dissolution of UO 3 in amide-based acidic ionic liquid and in situ electrodeposition of UO 2 with regeneration of the ionic liquid: a closed cycle

A closed cycle is demonstrated for the tandem dissolution and electroreduction of UO 3 to UO 2 with regeneration of the acidic ionic liquid. The dissolution is achieved by use of the acidic ionic liquid N,N-dimethylacetimidium bis(trifluoromethanesulfonimide) in 1-ethyl-3-methylimidazolium bis(trifluoromethanesulfonimide) serving as the diluent. Bulk electrolysis performed at 1.0 V vs. Ag reference yields a dark brown-black uranium deposit (UO 2 ) on the cathode. Anodic oxidation of water in the presence of dimethylacetamide regenerates the acidic ionic liquid. We have demonstrated the individual steps in the cycle together with a sequential dissolution, electroreduction, and regeneration cycle.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2013

A reductive dissolution study of magnetite

Magnetite dissolution tests using a hydrazine base solution were performed at a temperature range of 90 to 150 deg. C. The dissolution rate of magnetite increased with [N{sub 2}H{sub 4}], time, and temperature. The optimum solution pH in the experimental range was 3. The addition of copper ion to the hydrazine base solution greatly increased the magnetite dissolution rate. This was explained by the complex formation between N{sub 2}H{sub 4} and Cu ions, and the reducing power of the hydrazine-Cu complex to the ferric ions of magnetite. The reductive decontamination solution can be applied below 100 deg. C by the addition of copper ions. The chemical decontamination of a Type 304 stainless steel specimen using a hydrazine base reductive decontamination solution was also performed. The contact dose rate was greatly decreased by the repetitive application of NP and the hydrazine base solution. (authors)

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗
DOE OSTI2022

Dissolution Flowsheet for Skull Oxide Generated during U-Mo Alloy Casting for High Performance Research Reactor Fuel

The Savannah River National Laboratory was requested to develop dissolution flowsheets for high assay low enriched U scrap generated during the fabrication of high performance research reactor fuel. The scrap streams include U-10Mo and U-10Mo-Zr foils, rejected Al-clad fuel plates, and skull oxide from casting molds. Flowsheets for the dissolution of the U-10Mo-Zr foils and Al-clad U-10Mo-Zr mini-plates received from BWX Technologies, Inc were developed and demonstrated in the first phase of this project. In the second phase (this work), the skull oxide from a U-10Mo casting mold was obtained from the Y-12 National Security Complex (Y-12) and small-scale experiments were performed to demonstrate dissolution flowsheets.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗
DOE OSTI2015

A Study of autunite dissolution in the presence of Shewanella oneidensis MR1 and different bicarbonate concentrations - 15736

Remediation of uranium at Hanford Site 300 area via tripolyphosphate injections could sequester uranium (VI) in an insoluble form, creating different types of uranium phosphate minerals like autunite. The factors that influence the dissolution of such minerals come into question. Bacteria can play a significant role in the dissolution of minerals and the formation of secondary minerals. Formed autunite, as a phosphorus-containing mineral, can attract bacteria to liberate phosphorus, meeting their nutrient requirements and causing uranium release back into the environment. Previous studies have been conducted under aerobic conditions. This research was extended to investigate the stability of the autunite mineral under anaerobic conditions pertaining to the Hanford Site, and to study the effect of facultative anaerobic bacteria on the uranium (VI) release from autunite. Objectives: - Evaluate bacterial interactions with uranium (VI) by focusing on facultative anaerobic bacteria, Shewanella Oneidensis MR1. - Study the effect of bacteria on the dissolution of the uranyl phosphate solid phases created as a result of sodium tripolyphosphate injections into the subsurface at the Hanford 300 Area. - Evaluate the role of anaerobic bacteria as one of the factors affecting the outcome of environmental remediation. Experimental Approach: - 16 crimp-sealed bottles were prepared with 50 ml of media solution and 90 mg (4.4 mM of uranium VI) Ca-autunite mineral obtained from Hanford site. Bottles were inoculated with Shewanella Oneidensis MR1 strains when autunite was equilibrated with the media solutions. Bacteria was obtained from Pacific Northwestern National Laboratory (PNNL). - Solution media preparation: 20 mM NaHepes buffer: pH=7, 10 mM Lactate plus bicarbonate in four concentrations (0, 3, 5 and 10 of KHCO{sub 3}) and a bacteria-free control. Samples were taken from the supernatant solutions of the experimental and control bottles. Wet and dry digestion was performed until a white solid residue was acquired. Dilution was made on solid samples for KPA analysis to determine concentration of U (VI) as function of time. The results suggests that in the absence of HCO{sub 3}{sup -} there was a decrease in the of uranium (VI) concentration due to metal reducing bacteria Shewanella Oneidensis MR1, but for higher concentrations of HCO{sub 3}{sup -}, there is no significant difference in uranium (VI) reduction before and after inoculation with bacteria. - Although bottles were sealed, there is an hypothesis that it was oxygen restricted but not strictly performed under anaerobic conditions. For that matter there is a reason to repeat the experiment using the glove box to understand the uranium (VI) reduction mechanism and behavior of bacteria with oxic/anoxic interfaces. Conclusions: - Higher bicarbonate concentrations might interfere with uranium (VI) reduction by anaerobic bacteria. - It is necessary to reduce time of sampling before the inoculation and prolong sampling time after inoculation. - It might be necessary to increase concentration of lactate. Future Work: - Conduct experiment in strictly anaerobic conditions by using the glove box and evaluate if further reduction of uranium (VI) is obtained in the presence of carbonates (HCO{sub 3}{sup -}). - Finalize analysis of calcium and phosphorous via ICP instrument.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗
DOE OSTI2015

Experimental study on effects of geologic heterogeneity in enhancing dissolution trapping of supercritical CO 2

Abstract Dissolution trapping is one of the primary mechanisms that enhance the storage security of supercritical carbon dioxide (scCO 2 ) in saline geologic formations. When scCO 2 dissolves in formation brine produces an aqueous solution that is denser than formation brine, which leads to convective mixing driven by gravitational instabilities. Convective mixing can enhance the dissolution of CO 2 and thus it can contribute to stable trapping of dissolved CO 2 . However, in the presence of geologic heterogeneities, diffusive mixing may also contribute to dissolution trapping. The effects of heterogeneity on mixing and its contribution to stable trapping are not well understood. The goal of this experimental study is to investigate the effects of geologic heterogeneity on mixing and stable trapping of dissolved CO 2 . Homogeneous and heterogeneous media experiments were conducted in a two‐dimensional test tank with various packing configurations using surrogates for scCO 2 (water) and brine (propylene glycol) under ambient pressure and temperature conditions. The results show that the density‐driven flow in heterogeneous formations may not always cause significant convective mixing especially in layered systems containing low‐permeability zones. In homogeneous formations, density‐driven fingering enhances both storage in the deeper parts of the formation and contact between the host rock and dissolved CO 2 for the potential mineralization. On the other hand, for layered systems, dissolved CO 2 becomes immobilized in low‐permeability zones with low‐diffusion rates, which reduces the risk of leakage through any fault or fracture. Both cases contribute to the permanence of the dissolved plume in the formation.

Agartan, Elif↗
DOE OSTI2019

Enhanced Drug Delivery by Dissolution of Amorphous Drug Encapsulated in a Water Unstable Metal–Organic Framework (MOF)

Abstract Encapsulating a drug molecule into a water‐reactive metal–organic framework (MOF) leads to amorphous drug confined within the nanoscale pores. Rapid release of drug occurs upon hydrolytic decomposition of MOF in dissolution media. Application to improve dissolution and solubility for the hydrophobic small drug molecules curcumin, sulindac, and triamterene is demonstrated. The drug@MOF composites exhibit significantly enhanced dissolution and achieves high supersaturation in simulated gastric and/or phosphate buffer saline media. This combination strategy where MOF inhibits crystallization of the amorphous phase and then releases drug upon MOF irreversible structural collapse represents a novel and generalizable approach for drug delivery of poorly soluble compounds while overcoming the traditional weakness of amorphous drug delivery: physical instability of the amorphous form.

Suresh, Kuthuru↗
DOE OSTI2019

Enhanced Drug Delivery by Dissolution of Amorphous Drug Encapsulated in a Water Unstable Metal–Organic Framework (MOF)

Encapsulating a drug molecule into a water-reactive metal–organic framework (MOF) leads to amorphous drug confined within the nanoscale pores. Rapid release of drug occurs upon hydrolytic decomposition of MOF in dissolution media. Application to improve dissolution and solubility for the hydrophobic small drug molecules curcumin, sulindac, and triamterene is demonstrated. The drug@MOF composites exhibit significantly enhanced dissolution and achieves high supersaturation in simulated gastric and/or phosphate buffer saline media. This combination strategy where MOF inhibits crystallization of the amorphous phase and then releases drug upon MOF irreversible structural collapse represents a novel and generalizable approach for drug delivery of poorly soluble compounds while overcoming the traditional weakness of amorphous drug delivery: physical instability of the amorphous form.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2024

Incorporation of trace metals in Hanford waste boehmite mineral phases and dissolution rate impacts

Abstract Data from radioactive Hanford tank waste samples was analyzed to assess whether trace metals present were incorporated into the bulk boehmite matrix or were simply intermingled with the bulk material and subsequent impacts to the boehmite dissolution rate. Results suggest that chromium is primarily blended into the bulk boehmite, with a small fraction present on the surface of the solids. However, increasing the level of chromium incorporation 30‐fold decreased the dissolution rate of boehmite by only 8%, suggesting incorporation of chromium into these samples had a minimal impact on the dissolution rate. Iron was also found to be incorporated in the boehmite solids. Silicon appears to be simply intermingled and not blended into the boehmite crystals.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗
DOE OSTI2013

Buoyant currents arrested by convective dissolution

[1] When carbon dioxide (CO 2 ) dissolves into water, the density of water increases. This seemingly insubstantial phenomenon has profound implications for geologic carbon sequestration. In this work we show, by means of laboratory experiments with analog fluids, that the up–slope migration of a buoyant current of CO 2 is arrested by the convective dissolution that ensues from a fingering instability at the moving CO 2 –groundwater interface. We consider the effectiveness of convective dissolution as a large–scale trapping mechanism in sloping aquifers, and we show that a small amount of slope is beneficial compared to the horizontal case. We review the development and coarsening of the fingering instability along the migrating current and predict the maximum migration distance of the current with a simple sharp–interface model. We show that convective dissolution exerts a powerful control on CO 2 plume dynamics and, as a conclusion, on the potential of geologic carbon sequestration.

54 ENVIRONMENTAL SCIENCES↗
DOE OSTI2022

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↗