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As part of the Spent Nuclear Fuel (SNF) processing campaign, H-Canyon is planning to begin dissolving High Flux Isotope Reactor (HFIR) fuel in late FY17 or early FY18. Each HFIR fuel core contains inner and outer fuel elements which were fabricated from uranium oxide (U 3 O 8 ) dispersed in a continuous Al phase using traditional powder metallurgy techniques. Fuels fabricated in this manner, like other SNF’s processed in H-Canyon, dissolve by the same general mechanisms with similar gas generation rates and the production of H 2 . The HFIR fuel cores will be dissolved and the recovered U will be down-blended into low-enriched U. HFIR fuel was previously processed in H-Canyon using a unique insert in both the 6.1D and 6.4D dissolvers. Multiple cores will be charged to the same dissolver solution maximizing the concentration of dissolved Al. The objective of this study was to identify flowsheet conditions through literature review and laboratory experimentation to safely and efficiently dissolve the HFIR fuel in H-Canyon. Laboratory-scale experiments were performed to evaluate the dissolution of HFIR fuel using both Al 1100 and Al 6061 T6 alloy coupons. The Al 1100 alloy was considered a representative surrogate which provided an upper bound on the generation of flammable (i.e., H 2 ) gas during the dissolution process. The dissolution of the Al 6061 T6 alloy proceeded at a slower rate than the Al 1100 alloy, and was used to verify that the target Al concentration in solution could be achieved for the selected Hg concentration. Mass spectrometry and Raman spectroscopy were used to provide continuous monitoring of the concentration of H 2 and other permanent gases in the dissolution offgas, allowing the development of H 2 generation rate profiles. The H 2 generation rates were subsequently used to evaluate if a full HFIR core could be dissolved in an H-Canyon dissolver without exceeding 60% of the calculated lower flammability limit (LFL) for H 2 at a given Hg concentration. Complete dissolution of the Al 1100 and Al 6061 T6 alloys up to a final Al concentration of 2 M was obtained using a 7 M HNO 3 solution containing a 0.002 M Hg catalyst. However, following the dissolutions, solids were observed in the solution. The solids were amorphous, but likely originated from the Si present in the alloys. No crystalline materials, such as Al(NO 3 ) 3 were observed. During the course of the dissolution experiments, it was determined that delaying the addition of Hg once the HNO 3 solution reached the boiling point can reduce the total offgas and H 2 generation rates. The delay in starting the Hg addition is not necessary for HFIR fuel dissolution, but could be useful in other research reactor dissolution campaigns. The potential to generate flammable concentrations of H 2 in the offgas during a HFIR fuel dissolution was evaluated using the experimental data. The predicted H 2 concentration in the dissolver offgas stream was compared with 60% of the calculated H 2 LFL at 200 °C using several prototypical experiments. The calculations showed that a full HFIR core can be dissolved using nominally 0.002 M Hg to catalyze the dissolution. The margin between the predicted H 2 concentration and the calculated LFL was greater when the solution was allowed to boil for 45 min prior to initiating the Hg addition. When the Hg was increased to 0.004 M, the predicted H 2 concentration exceeded the calculated LFL early in the dissolution. The dissolution experiments also demonstrated that additional Hg (beyond the initial 0.002 M) could be added as the Al concentration increases. The ability to add more Hg during a HFIR fuel dissolution could be beneficial if slow dissolution rates are observed at high Al concentrations. Experimental data were used to demonstrate that the predicted H 2 concentration in a dissolver was below 60% of the calculated LFL at 200 °C when 0.004 M Hg was used to catalyze the dissolution if the Al concentration is conservatively greater than 0.5 M. Data also show that the Hg concentration during a HFIR fuel dissolution can be increased from 0.002 to 0.008 M at an Al concentration of 1.3 M.
Chemical decontamination is committed to giving safe decommissioning of nuclear facilities as well as maintenance during the normal operation under sufficiently reduced radiation field. The removal of radioisotopes from the primary coolant system of nuclear power plant takes place with the dissolution of metal oxide layer. Dissolution of metal oxides in aqueous acidic solutions is primarily controlled by the protonation of metal-oxygen bonding to release the metal ions from the oxide lattices but in the presence of reducing or chelating agents dissolution is often facilitated by the enhanced mass transfer of metal ions together with chelating reagents as well as metal reduction to soluble state such as insoluble ferric ions to soluble ferrous ions of hematite. The mechanisms and kinetics related to the metal oxides dissolution in varied acidic reagents have been reported for many decades even though a general picture of dissolution is not available due to the peculiarity of each oxide in structure, stability of metal ions, solubility, and reactivity. In a number of experimental results and practical reports, organic acids such as oxalic acid, citric acid, ascorbic acid, malonic acid, thioglycolic acid, etc. were used as solvent reagents and many other literatures reported the effectiveness of the chelating agents in dissolution rate such as iminodiacetic acid (IDA), diethylene triamine pentaacetic acid (DTPA), nitrilo triacetic acid (NTA), and ethylenediaminetetraacetic acid (EDTA) by the sorption of dissolved metal ions forming stable metal chelates. Also reductive dissolution by the addition of reducing reagents such as hydrazine, vanadium as well as organic acids was reported with effective experimental results. However, organic acids and chelating ligands are often problematic on the safety of radioactive wastes. Organic compounds in a repository potentially form a complex with radionuclides, which increases the mobility of radionuclides and consequently increases the probability of the radioactive contamination of groundwater. Furthermore oxalic acid can cause a severe intergranular attack (IGA) to the type 304 stainless steel. Therefore, the use of organic acids or chelating reagents even though those effects to the dissolution performance is much greater than other chemical components must be minimized or carefully determined with appropriate treatment processes. Alternatively dissolution accommodated by inorganic reducing reagents or catalysts in inorganic acid solutions have been extensively studied for the feasible dissolution outcomes. The mixture of sulfuric acid and sulfurous acids as a dissolution media was reported to increase dissolution rate due to the effect of protonation by H{sub 2}SO{sub 4} and reducing effect of H{sub 2}SO{sub 3}. The increased dissolution of magnetite was also found in sulfur dioxide solution containing copper ions because SO{sub 2} plays as a reducing catalyst to form FeHSO{sub 3}{sup +} with Fe(III) from iron oxides and accordingly the concentration of Fe(III) ions decreases to accelerate the iron oxide dissolution. The present study is concerned with the feasibility of not using the organic compounds for the dissolution of oxide layers. We propose an acidic solution containing sulfuric acid, hydrazine, and copper ions for the effective dissolution of magnetite powders. The effects of both hydrazine and copper ions as a reducing agent and a catalyst respectively to promote the reducing power, as well as temperature will be investigated on the dissolution of magnetite powder. (authors)
The Direct Feed High-Level Waste (DFHLW) strategy seeks to bypass the Hanford Waste Treatment and Immobilization Plant Pretreatment Facility while retaining some processing functions to maximize waste feed loading and minimize high-level waste (HLW) waste volume. The DFHLW flowsheet needs leaching, washing, and solids concentration operations either in new or existing tanks. The effectiveness and efficiency of sludge washing has a substantial impact on DST space, mission duration, and the evaporation and low-activity waste (LAW) treatment operations required by these large wash-water additions. One target species requiring washing is fluoride. The HLW glass composition limits for fluorine drive operations to dissolve fluoride-bearing salts into the LAW fraction and thereby maximize waste loading in HLW glass. The fluoride in many high-level wastes at Hanford is predominantly in the form of fluoride-salt precipitates: villiaumite (NaF), kogarkoite (Na 3 FSO 4 ), and natrophosphate (Na 7 F(PO 4 ) 2 ·19H 2 O). Fluoride produces melter off-gas that creates corrosion risk in the off-gas system piping, while the sulfate and phosphate in the fluoride double salts kogarkoite and natrophosphate can be detrimental to glass waste loading. Fluoride salts are sparingly soluble, with solubilities ranging from approximately 40 to 130 kg per kL of pure water, and the dissolution kinetics of the three fluoride salts are not well known. Unexpected delays in a tank dissolution process could be encountered as a result of the lack of information about dissolution rates. In addition, if the double salts show transient non-stoichiometric dissolution of fluoride versus phosphate or sulfate, unexpectedly high concentrations of one of these other constituents could be produced. Washington River Protection Solutions authorized Pacific Northwest National Laboratory to collect the available data for fluoride salt dissolution rate, provide a scoping estimate of dissolution time if possible, and identify gaps in the understanding and predictive capability for estimating dissolution time. Open literature and Hanford reports were reviewed to document, understand, and (where possible) evaluate limitations on fluoride salt equilibria and dissolution kinetics, including both mass transport and surface reaction rate. Scoping estimates of dissolution time were made for mass-transfer-controlled dissolution of spherical particles of fluoride salts suspended in liquid. This is not the only potential governing mechanism; dissolution could be substantially slower if the surface reaction rate (the rate of release of ions from the surface) is the controlling mechanism. When the minimum amount of water for complete dissolution is used and the slip velocity between the liquid and suspended particles is less than or equal to the terminal settling velocity, the estimated mass-transfer rates allow 0.1 mm particles of fluoride salt to dissolve in minutes at 25 °C in water containing no other dissolved salts. Much larger solids, such as the 6-mm chunks that have been seen in heels, could take a few hours to more than a week to dissolve. The actual dissolution times will depend strongly on the actual slip velocity, the extent of particle suspension, constraint by surface reaction rates, the ratio of solvent to solid, and the presence of common ions that shift the solubility equilibria to restrict dissolution of fluoride salts.
Uranyl oxyhydroxide minerals are important weathering products in uranium-contaminated surface and subsurface environments that regulate dissolved uranium concentrations. However, dissolution rates for this class of minerals and associated dissolution mechanisms have not been previously reported for circumneutral pH conditions, particularly for the case of flow through porous media. In this paper, the dissolution rates of K- and Na-compreignacite (K 2 (UO 2 ) 6 O 4 (OH) 6 ·8H 2 O and Na 2 (UO 2 ) 6 O 4 (OH) 6 ·8H 2 O respectively) were measured using flow-through columns reacted with two simulated background porewater (BPW) solutions of low and high dissolved total carbonate content (ca. 0.2 and 2.8 mmol L -1 ). Column materials were characterized before and after reaction with electron microscopy, bulk chemistry, and EXAFS to identify structural and chemical changes during dissolution and to obtain insight into molecular-scale processes. The reactive transport code CrunchFlow was used to calculate overall dissolution rates while accounting for fluid transport and changes in mineral volume and reactive surface area and results were compared to steady-state dissolution rate calculations. In low carbonate BPW systems, interlayer K and Na were initially leached from both minerals, and in Na-compreignacite, K and minor divalent cations from the input solution were incorporated into the mineral structure. Results of characterization analyses suggested that after reaction both K- and Na-compreignacite resembled a disordered K-compreignacite with altered surfaces. A 10-fold increase in dissolved carbonate concentration and corresponding increase in pH (from 6.65 to 8.40) resulted in a net removal of 58-87% of total uranium mass from the columns, compared to <1% net loss in low carbonate BPW systems. Steady-state release of dissolved uranium was not observed with high carbonate solutions and post-reaction characterizations indicated a lack of development of leached or altered surfaces. Dissolution rates (normalized to specific surface area) were about 2.5-3 orders-of-magnitude faster in high versus low carbonate BPW systems, with Na-compreignacite dissolving more rapidly than K-compreignacite under both BPW conditions, possibly due to greater ion exchange (1.57·10 -10 vs. 1.28·10 -13 mol m -2 s -1 [log R = -9.81 and -12.89] and 5.79·10 -10 vs. 3.71·10 -13 mol m -2 s -1 [log R = -9.24 and -12.43] for K- and Na-compreignacite respectively). Experimental and spectroscopic results suggest that the dissolution rate is controlled by bond breaking of a uranyl group and detachment from polyhedral layers of the mineral structure. With higher dissolved carbonate concentrations, this rate-determining step is accelerated by the formation of Ca-uranyl carbonate complexes (dominant species under these conditions), which resulted in an increase of the dissolution rates. Optimization of both dissolution rate and mineral volume fraction in the reactive transport model to account for uranium mass removal during dissolution more accurately reproduced effluent data in high carbonate systems, and resulted in faster overall rates compared with a steady-state dissolution assumption. Finally, this study highlights the importance of coupling reaction and transport processes during the quantification of mineral dissolution rates to accurately predict the fate of contaminants such as uranium in porous geomedia.
In this study, the degradation of CH 3 NH 3 PbI 3 (MAPbI 3 ) hybrid organic inorganic perovskite (HOIP) by water has been the major issue hampering its use in commercial perovskites solar cells (PSCs) as MAPbI 3 HOIP have been known to easily degrade in the presence of water molecules. However, even though there have been numerous studies investigating this phenomenon, there is still no consensus on the mechanisms of initial stages of dissolution. Here, we attempt to consolidate differing mechanistic interpretations previously reported in the literature through the use of the first-principles constrained ab-initio molecular dynamics (AIMD) to study the mechanisms, kinetics, and thermodynamics that accompany the degradation of MAPbI 3 HOIP in liquid water. We consider not only the dissolution of the species found on the pristine MAPbI 3 HOIP surfaces, but also the dissolution from defect sites to imitate the successive degradation steps, and propose a sequence of events in the initial phase of MAPbI 3 HOIP dissolution. By comparing the dissolution free energy barrier between surface species of different surficial types, we find that the dominant dissolution mechanisms of surface species varies widely based on the specific surface features adjacent to the dissolving ion. The high sensitivity of dissolution mechanism to surface features has contributed to the many dissolution mechanisms proposed in the literature. In contrast, the dissolution free energy barriers are mainly determined by the dissolving species rather than the type of surfaces, and the type of surfaces the ions are dissolving from are inconsequential toward the dissolution free energy barrier. However, the presence of surface defects such as vacancy sites are found to significantly lower the dissolution free energy barriers. Based on the estimated dissolution free energy barriers from different types of surfaces that we investigated in this study, we proposed that the dissolution of MAPbI 3 HOIP in liquid water originates from surface defect sites that propagate laterally along the surface layer of the MAPbI 3 HOIP crystal.
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.
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.
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.
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.
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.
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.
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.
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.
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.
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.
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.