Effect of dissolution kinetics on flotation response of calcite with oleate

Directory of Open Access Journals (Sweden)

D. G. Horta

Full Text Available Abstract Phosphate flotation performance can be influenced by the dissolution kinetics of the minerals that compose the ore. The purpose of this work was to investigate the effect of dissolution kinetics on flotation response with oleate (collector of calcites from different origins and genesis. The calcite samples were first purified and characterized by x-ray Fluorescence (XRF and the Rietveld method applied to x-ray Diffractometry data (RXD. Experiments of calcite dissolution and microflotationwere performed at pH 8 and pH 10.The pH effect on the calcite dissolution and flotation indicates the possible influence of the carbonate/bicarbonate ions provided by the CO2 present in the air. In addition, the flotation response is greater as the dissolution increases, making more Ca2+ ions available to interact with collector molecules. This result corroborates the surface precipitation mechanism proposed foroleate adsorption on the calcite surface.

Kinetics of Inorganic Calcite Dissolution in Seawater under Pressure

Science.gov (United States)

Dong, S.; Subhas, A.; Rollins, N.; Berelson, W.; Adkins, J. F.

2016-02-01

While understanding calcium carbonate dissolution is vital in constructing global carbon cycles and predicting the effect of seawater acidification as a result of increasing atmospheric CO2, there is still a major debate over the basic formulation of a dissolution rate law. The kinetics of calcium carbonate dissolution are typically described by the equation: Rate=k(1-Ω)n, while Ω=[Ca2+][CO32-]/Ksp. In this study, 13C-labeled calcite is dissolved in unlabeled seawater and the evolving d13C composition of the fluid is traced over time to establish dissolution rate. Instead of changing ion concentration to obtain varying Ω (as in our previous study; Subhas et al. 2015), we changed Ksp by conducting experiments under different pressures (described in theory as ∂lnKsp/∂P=-ΔV/RT, where ΔV is partial molal volume). This involved the construction of a pressure vessel that could hold our sample bag and provide aliquots while remaining pressurized. Pressure experiments were conducted between 0-2000PSI. Results support the conclusion in our previous study that near-equilibrium dissolution rates are highly nonlinear, but give a disparate relationship between undersaturation and dissolution rate if Ω is calculated assuming the specific ΔV embedded in CO2SYS. A revised ΔV from -37cm3 to -65cm3 would make the dissolution formulation equation agree, but clearly appears unreasonable. Our results are explained by a pressure effect on carbonate dissolution kinetics over and above the influence of pressure on Ω. If this is a phenomenon that occurs in nature, then we would predict that dissolution should be occurring shallower in the water column (as sometimes observed) than indicated by standard Ω calculations.

The kinetics of anodic dissolution of rhenium in aqueous electrolyte solutions

International Nuclear Information System (INIS)

Atanasyants, A.G.; Kornienko, V.A.

1986-01-01

The kinetics of anodic rhenium dissolution was investigated by means of potentiodynamic and potentiostatic polarization curves recorded at temperature from 293 to 333 K in different media (NaOH, KOH, NaCl, NaBr, HCl, H 2 SO 4 ) using the rotating disc technique. It is shown that the kinetics of anodic rhenium dissolution and effective activation energy depend not only on the composition and pH value of the solutions but also on the structure of the dissolving rhenium surface. The investigation of the anodic behaviour of the rhenium monocrystal revealed the existence of anisotropy of the monocrystal electrochemical properties. The experimental results point to an important role of adsorption processes in anodic rhenium dissolution. Rhenium dissolution proceeds with formation of intermediate surface adsorption complexes between the metal and the components of the solution

Dissolution kinetics of lead telluride in alkali solutions of hydrogen peroxide

International Nuclear Information System (INIS)

Danilova, M.G.; Sveshnikova, L.L.; Stavitskaya, T.A.; Repinskij, S.M.

1991-01-01

Dissolution kinetics of lead telluride in alkali solutions of hydrogen peroxide was investigated. Dependences of change of PbTe dissolution rate on concentration of hydrogen peroxide and alkali in the solution were obtained. It is shown that dissolution rate of lead telluride is affected by dissolution rate of lead oxide, representing the product of ReTe dissolution. The obtained regularities can be explained by change of solution structure with increase of KOH concentration and by the state of hydrogen peroxide in the solution

Peroxide formation and kinetics of sodium dissolution in alcohols

International Nuclear Information System (INIS)

Muralidaran, P.; Chandran, K.; Ganesan, V.; Periaswami, G.

1997-01-01

Suitable techniques for sodium removal and decontamination of sodium wetted components of Liquid Metal Fast Reactors (LMFRs) are necessary both for repair, reuse and decommissioning of such components. Among the methods followed for sodium removal, alcohol dissolution is usually employed for small components like bellow sealed valves, gripping tools to handle core components and sodium sampling devices (primary and secondary). One of the concerns in the alcohol dissolution method is the possible role of peroxide formation in the ethoxy group during storage and handling leading to explosion. This paper describes the study of peroxide formation in ethyl carbitol and butyl cellosolve as well as some of the results of dissolution kinetic studies carried out in our laboratory using different alcohols. The peroxide formation of ethyl carbitol and butyl cellosolve were studied by iodometric technique. It has been found that the peroxide formation is less in sodium containing alcohol than in pure one. Ethyl carbitol, butyl cellosolve and Jaysol-SS (mixture of ethyl alcohol, methyl alcohol, isopropyl alcohol and methyl isobutyl ketone) were used in dissolution kinetics studies. The effects due to area and orientation of the fresh sodium surface have also been investigated. The reaction rates were studied in the temperature range of 303-343 K. The rate of dissolution was estimated by measuring the sodium content of alcohol at periodic intervals. It is found that the reaction rate varies in the order of ethyl alcohol-water mixture > Jaysol-SS > butyl cellosolve > ethyl carbitol. While cleaning sodium using alcohol, the concentration of alcohol is held essentially constant throughout the process. The rate of reaction depends only on the amount of sodium and follows pseudo-first order kinetics. Increase in surface area has a marked impact on the dissolution rate at lower temperatures while at higher temperatures, the temperature factor overrides the effect due to surface area

Thorium oxide dissolution kinetics for hydroxide and carbonate complexation

International Nuclear Information System (INIS)

Jardin, R.; Curran, V.; Czerwinski, K.R.

2002-01-01

The purpose of this project was to determine the kinetics and thermodynamics of thorium oxide dissolution in the environment. Solubility is important because it establishes an upper concentration limit on the concentration of a dissolved radionuclide in solution L1. While understanding the behavior of thorium fuels in the proposed repository at Yucca Mountain is most applicable, a more rigorous study of thorium solubility over a wide pH range was performed so that the data could also be used to model the behavior of thorium fuels in any environmental system. To achieve this, the kinetics and thermodynamics of thorium oxide dissolution under both pure argon and argon with P CO2 of 0. 1 were studied under the full pH range available in each atmosphere. In addition, thorium oxide powder remnants were studied after each experiment to examine structural changes that may affect kinetics

The dissolution rate of silicate glasses and minerals: an alternative model based on several activated complexes

International Nuclear Information System (INIS)

Berger, G.

1997-01-01

Most of the mineral reactions in natural water-rock systems progress at conditions close to the chemical equilibrium. The kinetics of these reactions, in particular the dissolution rate of the primary minerals, is a major constrain for the numerical modelling of diagenetic and hydrothermal processes. In the case of silicates, recent experimental studies have pointed out the necessity to better understand the elementary reactions which control the dissolution process. This article presents several models that have been proposed to account for the observed dissolution rate/chemical affinity relationships. The case of glasses (R7T7), feldspars and clays, in water, in near neutral pH aqueous solutions and in acid/basic media, are reviewed. (A.C.)

Hydrothermal alteration of plagioclase and growth of secondary feldspar in the Hengill Volcanic Centre, SW Iceland

Science.gov (United States)

Larsson, D.; Grönvold, K.; Oskarsson, N.; Gunnlaugsson, E.

2002-05-01

Dissolution of igneous feldspar and the formation and occurrence of secondary feldspar in tholeiitic basalts from the Hengill volcanic centre, in SW Iceland was studied by microprobe analysis of cuttings from two ca. 2000 m deep geothermal wells. Well NG-7 in Nesjavellir represents a geothermal system in a rift zone where the intensity of young, insignificantly altered intrusions increases with depth. Well KhG-1 in Kolviðarhóll represents the margin of a rift zone where the intensity of intrusives is lower and the intensity of alteration higher. This marginal well represents altered basaltic crust in an early retrograde state. The secondary plagioclase in both wells is mainly oligoclase, occurring in association with K-feldspar and chlorite±actinolite. The texture of this assemblage depends on the lithology and intensity of alteration. In Nesjavellir (NG-7) the composition of secondary albite-oligoclase is correlated with the host-rock composition. This connection is not apparent in more intensely altered samples from Kolviðarhóll (KhG-1). The influence of temperature on composition of secondary Na-feldspar is unclear in both wells although Ca is expected to increase with temperature. Any temperature dependence may be suppressed by the influence of rock composition in Nesjavellir and by retrograde conditions at Kolviðarhóll. The absence of clear compositional gradients between igneous plagioclase and secondary feldspar and between Na-feldspar and K-feldspar suggests that secondary feldspars formed by dissolution precipitation reactions.

Kinetics of dissolution of calcium phosphate (Ca-P bioceramics

Directory of Open Access Journals (Sweden)

Lukas Brazda

2008-06-01

Full Text Available Hydroxyapatite (HAp and β-tricalcium phosphate (β-TCP are widely used bioceramics for surgical or dental applications. This paper is dealing with dissolution kinetics of synthetically prepared β-TCP and four types of HAp granules. Two groups of HAp, treated at different temperatures, each of them with two different granule sizes, were tested. Three corrosive solutions with different pH and simulated body fluid (SBF were used for immersing of the samples. Changes in concentrations of calcium and phosphate ions, pH level and weight changes of the samples were observed. It was found that presence of TRIS buffer enhanced dissolution rate of the β-TCP approximately two times. When exposed to SBF solution, calcium phosphate (most probably hydroxyapatite precipitation predominates over β-TCP dissolution. Results from HAp samples dissolution showed some unexpected findings. Neither heat treatment nor HAp particle size made any major differences in dissolution rate of the same mass of each HAp sample.

The dissolution kinetics of magnetite under regenerative conditions

International Nuclear Information System (INIS)

Ranganathan, S.

2004-01-01

Dissolution studies of magnetite were carried out under regenerative conditions in dilute chemical decontamination formulations. During regeneration of the formulation, the H + from the strong acid cation exchange resin gets released and the metal is absorbed on the resin. The efficiency of the regenerative process depends on the stability constants of the complexes involved and the selectivity on the ion exchange column. The regenerative condition helps to maintain a constant chelating agent concentration and pH during the dissolution experiment. Such a condition is ideal for obtaining data on the dissolution behaviour of the corrosion products with special application to actual reactor decontamination. The ethylenediaminetetraacetic acid (EDTA) based formulation used was found to be ineffective due to the high stability constant of Fe(III)-EDTA complex, which is not easily cleaved by the cation exchange resin. Hence, knowledge of the kinetics of magnetite dissolution under regenerative condition is of primary importance. The 2,6-pyridinedicarboxylic acid formulation is found to be better for the dissolution of Fe 3 O 4 in both static and regenerative modes in the presence of reductants than nitrilotriacetic acid and EDTA. (orig.)

The dissolution kinetics of magnetite under regenerative conditions

Energy Technology Data Exchange (ETDEWEB)

Ranganathan, S. [New Brunswick Univ., Frederiction (Canada). Dept. of Chemical Engineering; Raghavan, P.S.; Gopalan, R.; Srinivasan, M.P.; Narasimhan, S.V. [Water and Steam Chemistry Lab. of Bhabha Atomic Research Centre (BARC) (India)

2004-07-01

Dissolution studies of magnetite were carried out under regenerative conditions in dilute chemical decontamination formulations. During regeneration of the formulation, the H{sup +} from the strong acid cation exchange resin gets released and the metal is absorbed on the resin. The efficiency of the regenerative process depends on the stability constants of the complexes involved and the selectivity on the ion exchange column. The regenerative condition helps to maintain a constant chelating agent concentration and pH during the dissolution experiment. Such a condition is ideal for obtaining data on the dissolution behaviour of the corrosion products with special application to actual reactor decontamination. The ethylenediaminetetraacetic acid (EDTA) based formulation used was found to be ineffective due to the high stability constant of Fe(III)-EDTA complex, which is not easily cleaved by the cation exchange resin. Hence, knowledge of the kinetics of magnetite dissolution under regenerative condition is of primary importance. The 2,6-pyridinedicarboxylic acid formulation is found to be better for the dissolution of Fe{sub 3}O{sub 4} in both static and regenerative modes in the presence of reductants than nitrilotriacetic acid and EDTA. (orig.)

Kinetics of carbonate mineral dissolution in CO2-acidified brines at storage reservoir conditions.

Science.gov (United States)

Peng, Cheng; Anabaraonye, Benaiah U; Crawshaw, John P; Maitland, Geoffrey C; Trusler, J P Martin

2016-10-20

We report experimental measurements of the dissolution rate of several carbonate minerals in CO 2 -saturated water or brine at temperatures between 323 K and 373 K and at pressures up to 15 MPa. The dissolution kinetics of pure calcite were studied in CO 2 -saturated NaCl brines with molalities of up to 5 mol kg -1 . The results of these experiments were found to depend only weakly on the brine molality and to conform reasonably well with a kinetic model involving two parallel first-order reactions: one involving reactions with protons and the other involving reaction with carbonic acid. The dissolution rates of dolomite and magnesite were studied in both aqueous HCl solution and in CO 2 -saturated water. For these minerals, the dissolution rates could be explained by a simpler kinetic model involving only direct reaction between protons and the mineral surface. Finally, the rates of dissolution of two carbonate-reservoir analogue minerals (Ketton limestone and North-Sea chalk) in CO 2 -saturated water were found to follow the same kinetics as found for pure calcite. Vertical scanning interferometry was used to study the surface morphology of unreacted and reacted samples. The results of the present study may find application in reactive-flow simulations of CO 2 -injection into carbonate-mineral saline aquifers.

Dissolution of crystalline ceramics

International Nuclear Information System (INIS)

White, W.B.

1982-01-01

The present program objectives are to lay out the fundamentals of crystalline waste form dissolution. Nuclear waste ceramics are polycrystalline. An assumption of the work is that to the first order, the release rate of a particular radionuclide is the surface-weighted sum of the release rates of the radionuclide from each crystalline form that contains it. In the second order, of course, there will be synergistic effects. There will be also grain boundary and other microstructural influences. As a first approximation, we have selected crystalline phases one at a time. The sequence of investigations and measurements is: (i) Identification of the actual chemical reactions of dissolution including identification of the solid reaction products if such occur. (ii) The rates of these reactions are then determined empirically to give what may be called macroscopic kinetics. (iii) Determination of the rate-controlling mechanisms. (iv) If the rate is controlled by surface reactions, the final step would be to determine the atomic kinetics, that is the specific atomic reactions that occur at the dissolving interface. Our concern with the crystalline forms are in two areas: The crystalline components of the reference ceramic waste form and related ceramics and the alumino-silicate phases that appear in some experimental waste forms and as waste-rock interaction products. Specific compounds are: (1) Reference Ceramic Phases (zirconolite, magnetoplumbite, spinel, Tc-bearing spinel and perovskite); (2) Aluminosilicate phases (nepheline, pollucite, CsAlSi 5 O 12 , Sr-feldspar). 5 figures, 1 table

Surface controlled dissolution rates of gypsum in aqueous solutions exhibit nonlinear dissolution kinetics

Science.gov (United States)

Jeschke, Alexander A.; Vosbeck, Katrin; Dreybrodt, Wolfgang

2001-01-01

The effective dissolution rates of gypsum are determined by mixed kinetics, where the rate constants of dissolution at the surface and the transport constant of molecular diffusion of dissolved material are similar. To obtain the surface reaction rate law it is necessary to know the transport constant. We have determined the surface rate law for monocrystalline selenite by using a rotating disc set-up, where the transport coefficients are well known. As a result, up to a calcium concentration of 0.6 · ceq, we find a nearly linear rate law Rs = ksl (1- cs/ ceq) n1, where cs is the total calcium concentration at the surface and ceq the equilibrium concentration with respect to gypsum, n1 = 1.2 ± 0.2, and ksl = 1.1 · 10 -4 mmol cm -2 s -1 ± 15%. We also employed batch-experiments for selenite, alabaster and gypsum rock samples. The result of these experiments were interpreted by using a transport constant determined by NaCl dissolution experiments under similar physical conditions. The batch experiments reveal a dissolution rate law Rs = ksl (1- cs/ ceq) n1, ksl = 1.3 · 10 -4 mmol · cm -2 s -1, n1 = 1.2 ± 0.2 for c ≤ 0.94 · ceq. Close to equilibrium a nonlinear rate law, Rs = ks2 (1- cs/ ceq) n2, is observed, where ks2 is in the order of 10 mmol · cm -2 s -1 and n2 ≈ 4.5. The experimentally observed gypsum dissolution rates from the batch experiments could be accurately fitted, with only minor variations of the surface reaction constant obtained from the rotating disk experiment and the transport coefficient from the NaCl dissolution batch experiment. Batch experiments on pure synthetic gypsum, reveal a linear rate law up to equilibrium. This indicates inhibition of dissolution in natural samples close to equilibrium, as is known also for calcite minerals.

The Use of Artificial Neural Network for Prediction of Dissolution Kinetics

Directory of Open Access Journals (Sweden)

H. Elçiçek

2014-01-01

Full Text Available Colemanite is a preferred boron mineral in industry, such as boric acid production, fabrication of heat resistant glass, and cleaning agents. Dissolution of the mineral is one of the most important processes for these industries. In this study, dissolution of colemanite was examined in water saturated with carbon dioxide solutions. Also, prediction of dissolution rate was determined using artificial neural networks (ANNs which are based on the multilayered perceptron. Reaction temperature, total pressure, stirring speed, solid/liquid ratio, particle size, and reaction time were selected as input parameters to predict the dissolution rate. Experimental dataset was used to train multilayer perceptron (MLP networks to allow for prediction of dissolution kinetics. Developing ANNs has provided highly accurate predictions in comparison with an obtained mathematical model used through regression method. We conclude that ANNs may be a preferred alternative approach instead of conventional statistical methods for prediction of boron minerals.

Dissolution kinetics of schwertmannite and ferrihydrite in oxidized mine samples and their detection by differential X-ray diffraction (DXRD)

International Nuclear Information System (INIS)

Dold, Bernhard

2003-01-01

A dissolution test with 9 natural and synthetic schwertmannite and ferrihydrite samples was performed by reaction with 0.2 M ammonium oxalate at pH 3.0 in the dark. The method was coupled with differential X-ray diffraction (DXRD) to successfully detect schwertmannite at low concentrations in oxidized mine tailings. Rapid dissolution was observed for all schwertmannites (> 94% in 60 min) and natural 2-line ferrihydrites (> 85% in 60 min); however, synthetic 2-line and 6-line ferrihydrite dissolved slower (42 and 16% after 60 min, respectively). The results showed that it was not possible to distinguish between natural schwertmannites and ferrihydrites on the basis of their dissolution kinetics. Modeling of the schwertmannite dissolution curves, examinations of mineral shape by scanning electron microscopy, and Fe/S mole ratios of the dissolved fractions indicated that two different schwertmannite particle morphologies (spherical and web-like) occurred. Collapse of spherical (sea-urchin) schwertmannite aggregates seemed to control the dissolution kinetics according to a shrinking core model. In the case of web-like schwertmannite, dissolution could be modeled with a simple first order equation, and structural SO 4 2- may have affected the dissolution kinetics. No relationship was found between ferrihydrite particle shape and dissolution behavior in acid NH 4 -oxalate. A 1-h extraction with 0.2 M NH 4 -oxalate at pH 3.0 in the dark should be adequate to dissolve schwertmannite and natural 2-line ferrihydrite in most samples. In some cases, a fraction of secondary jarosite or goethite may also be dissolved, although at a slower rate. If only schwertmannite is of interest (e.g., determination by DXRD), a 15 min attack should be used to increase selectivity. A truly selective leach of schwertmannite and ferrihydrite should be based on dissolution tests, as a broad variety of dissolution kinetics can be observed in this mineral group

Dissolution of kinetics of nanoscale liquid Pb/Bi inclusions at a grain boundary in aluminium

DEFF Research Database (Denmark)

Prokofjev, Sergei I.; Johnson, Erik; Zhilin, Victor M.

2008-01-01

of the inclusions was observed until their complete disappearance. Digitized video recordings of the process of dissolution were used to obtain the dependence of the inclusion size with time. The kinetics of the dissolution of the grain boundary inclusions can be described with a model where it is assumed...

A method for phenomenological and chemical kinetics study of autocatalytic reactive dissolution by optical microscopy. The case of uranium dioxide dissolution in nitric acid media

Science.gov (United States)

Marc, Philippe; Magnaldo, Alastair; Godard, Jérémy; Schaer, Éric

2018-03-01

Dissolution is a milestone of the head-end of hydrometallurgical processes, as the stabilization rates of the chemical elements determine the process performance and hold-up. This study aims at better understanding the chemical and physico-chemical phenomena of uranium dioxide dissolution reactions in nitric acid media in the Purex process, which separates the reusable materials and the final wastes of the spent nuclear fuels. It has been documented that the attack of sintering-manufactured uranium dioxide solids occurs through preferential attack sites, which leads to the development of cracks in the solids. Optical microscopy observations show that in some cases, the development of these cracks leads to the solid cleavage. It is shown here that the dissolution of the detached fragments is much slower than the process of the complete cleavage of the solid, and occurs with no disturbing phenomena, like gas bubbling. This fact has motivated the measurement of dissolution kinetics using optical microscopy and image processing. By further discriminating between external resistance and chemical reaction, the "true" chemical kinetics of the reaction have been measured, and the highly autocatalytic nature of the reaction confirmed. Based on these results, the constants of the chemical reactions kinetic laws have also been evaluated.

A method for phenomenological and chemical kinetics study of autocatalytic reactive dissolution by optical microscopy. The case of uranium dioxide dissolution in nitric acid media

Directory of Open Access Journals (Sweden)

Marc Philippe

2018-01-01

Full Text Available Dissolution is a milestone of the head-end of hydrometallurgical processes, as the stabilization rates of the chemical elements determine the process performance and hold-up. This study aims at better understanding the chemical and physico-chemical phenomena of uranium dioxide dissolution reactions in nitric acid media in the Purex process, which separates the reusable materials and the final wastes of the spent nuclear fuels. It has been documented that the attack of sintering-manufactured uranium dioxide solids occurs through preferential attack sites, which leads to the development of cracks in the solids. Optical microscopy observations show that in some cases, the development of these cracks leads to the solid cleavage. It is shown here that the dissolution of the detached fragments is much slower than the process of the complete cleavage of the solid, and occurs with no disturbing phenomena, like gas bubbling. This fact has motivated the measurement of dissolution kinetics using optical microscopy and image processing. By further discriminating between external resistance and chemical reaction, the “true” chemical kinetics of the reaction have been measured, and the highly autocatalytic nature of the reaction confirmed. Based on these results, the constants of the chemical reactions kinetic laws have also been evaluated.

Montmorillonite dissolution kinetics: Experimental and reactive transport modeling interpretation

Science.gov (United States)

Cappelli, Chiara; Yokoyama, Shingo; Cama, Jordi; Huertas, F. Javier

2018-04-01

The dissolution kinetics of K-montmorillonite was studied at 25 °C, acidic pH (2-4) and 0.01 M ionic strength by means of well-mixed flow-through experiments. The variations of Si, Al and Mg over time resulted in high releases of Si and Mg and Al deficit, which yielded long periods of incongruent dissolution before reaching stoichiometric steady state. This behavior was caused by simultaneous dissolution of nanoparticles and cation exchange between the interlayer K and released Ca, Mg and Al and H. Since Si was only involved in the dissolution reaction, it was used to calculate steady-state dissolution rates, RSi, over a wide solution saturation state (ΔGr ranged from -5 to -40 kcal mol-1). The effects of pH and the degree of undersaturation (ΔGr) on the K-montmorillonite dissolution rate were determined using RSi. Employing dissolution rates farthest from equilibrium, the catalytic pH effect on the K-montmorillonite dissolution rate was expressed as Rdiss = k·aH0.56±0.05 whereas using all dissolution rates, the ΔGr effect was expressed as a non-linear f(ΔGr) function Rdiss = k · [1 - exp(-3.8 × 10-4 · (|ΔGr|/RT)2.13)] The functionality of this expression is similar to the equations reported for dissolution of Na-montmorillonite at pH 3 and 50 °C (Metz, 2001) and Na-K-Ca-montmorillonite at pH 9 and 80 °C (Cama et al., 2000; Marty et al., 2011), which lends support to the use of a single f(ΔGr) term to calculate the rate over the pH range 0-14. Thus, we propose a rate law that also accounts for the effect of pOH and temperature by using the pOH-rate dependence and the apparent activation energy proposed by Rozalén et al. (2008) and Amram and Ganor (2005), respectively, and normalizing the dissolution rate constant with the edge surface area of the K-montmorillonite. 1D reactive transport simulations of the experimental data were performed using the Crunchflow code (Steefel et al., 2015) to quantitatively interpret the evolution of the released cations

Dissolution kinetics of purified and synthetic smectites at 25°C and PH∼9

International Nuclear Information System (INIS)

Marty, Nicolas C.M.; Tournassat, Christophe; Gaucher, Eric C.; Chino, Daisuke; Sato, Tsutomu; Villieras, Frederic; Giffaut, Eric; Cama, Jordi; Soler, J.M.

2010-01-01

Document available in extended abstract form only. Mineral rate laws that account for the kinetics of dissolution/precipitation of clays and other minerals are used in reactive transport codes to simulate and evaluate the evolution of geochemical conditions in the near-field of high level radioactive waste (HLW) in deep geological repositories. Smectite is the main component in the compacted bentonite used in the Multi-barrier system to lower permeability. As a consequence, molecular diffusion becomes the main mechanism of mass transport, and dissolution and precipitation reactions take place in close-to-equilibrium conditions. Nonetheless, in the reactive transport codes, databases utilized mainly incorporate rate laws derived at far-from- equilibrium conditions, which are not representative of near-field and far-field conditions of concrete-clay or iron-clay interfaces. Hence, there is an important need to derive kinetic rate laws that allow extrapolation of mineral dissolution/precipitation as a function of the solution saturation state (i.e., Gibbs free energy, ΔG r ). Once the effect of the environmental variables, such as pH, T and ΔG r , etc. exert on smectite dissolution is discerned, evaluation of the evolution of geochemical conditions in the HLW repository is carried out using reactive transport codes that couple the rate laws with transport equations. Several studies related dissolution of natural smectites with pH, and just a few dealt with the rate dependency on Gibbs free energy. The present study aims at estimating dissolution rates of montmorillonite in conditions as close as possible to those expected in the Callovo-Oxfordian formation, i.e. pH∼7.2 and 25 deg. C. Dissolution kinetics of two montmorillonites (natural Na-montmorillonite purified from MX80 and synthetic smectite) were investigated by means of flow-through experiments and solution-chemistry data obtained. The calculated rates were based on release of Si, Al and Mg and normalized

Study of the dissolution velocity of dispersed solid particles. Development of a calculation method for analyzing the kinetic curves. Extension to the study of composed kinetics

International Nuclear Information System (INIS)

Jorda, Michel.

1976-01-01

The dissolution of a solid in an aqueous phase is studied, the solid consisting of dispersed particles. A continuous colorimetric analysis method is developed to study the dissolution process and a two-parameter optimization method is established to investigate the kinetic curves obtained. This method is based on the differential equation dx/dt=K(1-x)sup(n). (n being the decrease in the dissolution velocity when the dissolved part increases and K a velocity parameter). The dissolution of SO 4 Cu and MnO 4 K in water and UO 3 in SO 4 H 2 is discussed. It is shown that the dissolution velocity of UO 3 is proportional to the concentration of the H + ions in the solution as far as this one is not higher than 0.25N. The study of the temperature dependence of the UO 3 dissolution reaction shows that a transition phase takes place from 25 to 65 0 C between a phase in which the dissolution is controlled by the diffusion of the H + ions and the chemical reaction at the interface and a phase in which the kinetics is only controlled by the diffusion [fr

[Energy related studies utilizing K-feldspar thermochronology

International Nuclear Information System (INIS)

1992-01-01

In our second year of current funding cycle, we have investigated the Ar diffusion properties and microstructures of K-feldspars and the application of domain theory to natural K-feldspars. We completed a combined TEM and argon diffusion study of the effect of laboratory heat treatment on the microstructure and kinetic properties of K-feldspar. We conclude in companion papers that, with one minor exception, no observable change in the diffusion behavior occurs during laboratory extraction procedures until significant fusion occurs at about 1100 degrees C. The effect that is observed involves a correlation between the homogenization of cryptoperthite lamelle and the apparent increase in retentivity of about 5% of the argon in the K-feldspar under study. We can explain this effect of both as an artifact of the experiment or the loss of a diffusion boundary. Experiments are being considered to resolve this question. Refinements have been made to our experimental protocol that appears that greatly enhance the retrieval of multi-activation energies from K-feldspars. We have applied the multi-domain model to a variety of natural environments (Valles Caldera, Red River fault, Appalachian basin) with some surprising results. Detailed 40 Ar/ 39 Ar coverage of the Red River shear zone, thought to be responsible for the accommodation of a significant fraction of the Indo-Asian convergence, strongly suggests that our technique can precisely date both the termination of ductile strike-slip motion and the initiation of normal faulting. Work has continued on improving our numerical codes for calculating thermal histories and the development of computer based graphing tools has significantly increased our productivity

Dissolution kinetics of magnesium hydroxide for CO{sub 2} separation from coal-fired power plants

Energy Technology Data Exchange (ETDEWEB)

Bharadwaj, Hari Krishna [Chemical Engineering Program, School of Energy, Environmental, Biological, and Medical Engineering, University of Cincinnati, Cincinnati, OH 45221-0012 (United States); Lee, Joo-Youp, E-mail: joo.lee@uc.edu [Chemical Engineering Program, School of Energy, Environmental, Biological, and Medical Engineering, University of Cincinnati, Cincinnati, OH 45221-0012 (United States); Li, Xin; Liu, Zhouyang [Chemical Engineering Program, School of Energy, Environmental, Biological, and Medical Engineering, University of Cincinnati, Cincinnati, OH 45221-0012 (United States); Keener, Tim C. [Environmental Engineering Program, School of Energy, Environmental, Biological, and Medical Engineering, University of Cincinnati, Cincinnati, OH 45221-0012 (United States)

2013-04-15

Highlights: ► Magnesium hydroxide dissolution was found to be controlled by chemical reaction. ► The intrinsic kinetics has a fractional order between 0.20 and 0.31. ► The true activation energy value was found to have 76 ± 11 kJ/gmol. ► A shrinking-core model predicted experimental data with good accuracy. -- Abstract: The dissolution of magnesium hydroxide in water for the release of magnesium and hydroxyl ions into the solution to maintain suitable alkalinity is a crucial step in the Mg(OH){sub 2}-based CO{sub 2} absorption process. In this study, the rate of dissolution of Mg(OH){sub 2} was investigated under different operating conditions using a pH stat apparatus. The dissolution process was modeled using a shrinking core model and the overall Mg(OH){sub 2} dissolution process was found to be controlled by the surface chemical reaction of Mg(OH){sub 2} with H{sup +} ions. Under the chemical reaction control regime, the dissolution of Mg(OH){sub 2} in alkaline conditions was found not to follow a first-order reaction, and the fractional order of reaction was estimated to lie between 0.20 and 0.31. This suggests that the dissolution reaction is a non-elementary reaction, consisting of a sequence of elementary reactions, via most likely forming a surface magnesium complex. The true activation energy value of 76 ± 11 kJ/gmol was found to be almost twice as much as the observed activation energy value of 42 ± 6 kJ/gmol determined at pH 8.6, and was comparable with the previously reported values. The particle sizes predicted from the intrinsic kinetics determined from the model were in good agreement with the experimentally measured particle sizes during the dissolution process.

Mechanism and Kinetics for the Dissolution of Apatitic Materials in Acid Solutions

Directory of Open Access Journals (Sweden)

Calmanovici C.E.

1997-01-01

Full Text Available Abstract - This work concerns the study of the digestion step in the production process of phosphoric acid. Some qualitative experiments indicate that the difference between the pH at the surface of the phosphate and that in the bulk of the solution is negligible and that the dissolution is controlled by diffusion of products away from the phosphate particle. In further experiments, to isolate the dissolution phenomenon from the formation of calcium sulfate, the sulfuric acid normally used industrially is replaced by hydrochloric acid. The phosphate material used in our experiments is a model apatitic material: synthetic hydroxyapatite (HAP. The dissolution of calcium hydroxyapatite was studied with increasing amounts of calcium and phosphate at different temperatures. A simple method was developed for this observation based on the time required for complete dissolution of the HAP powder. The results confirm that the dissolution is controlled by a diffusional process through an interface of calcium and phosphate ions released from the solid surface. A kinetic model for the dissolution of apatitic materials is proposed which assumes a shrinking particle behaviour controlled by diffusion of calcium ions. The experimental results are fitted to this model to determine the mass transfer constant for HAP dissolution in acid solutions. The activation energy of the reaction is about 14kJ/mol. This study was carried on in conditions similar to the industrial ones for the production of phosphoric acid by the dihydrate-process

Non-equilibrium Thermodynamic Dissolution Theory for Multi-Component Solid/Liquid Surfaces Involving Surface Adsorption and Radiolysis Kinetics

International Nuclear Information System (INIS)

Stout, R B

2001-01-01

A theoretical expression is developed for the dissolution rate response for multi-component radioactive materials that have surface adsorption kinetics and radiolysis kinetics when wetted by a multi-component aqueous solution. An application for this type of dissolution response is the performance evaluation of multi-component spent nuclear fuels (SNFs) for long term interim storage and for geological disposition. Typically, SNF compositions depend on initial composition, uranium oxide and metal alloys being most common, and on reactor burnup which results in a wide range of fission product and actinide concentrations that decay by alpha, beta, and gamma radiation. These compositional/burnup ranges of SNFs, whether placed in interim storage or emplaced in a geologic repository, will potentially be wetted by multi-component aqueous solutions, and these solutions may be further altered by radiolytic aqueous species due to three radiation fields. The solid states of the SNFs are not thermodynamically stable when wetted and will dissolve, with or without radiolysis. The following development of a dissolution theory is based on a non-equilibrium thermodynamic analysis of energy reactions and energy transport across a solid-liquid phase change discontinuity that propagates at a quasi-steady, dissolution velocity. The integral form of the energy balance equation is used for this spatial surface discontinuity analysis. The integral formulation contains internal energy functional of classical thermodynamics for both the SNFs' solid state and surface adsorption species, and the adjacent liquid state, which includes radiolytic chemical species. The steady-state concentrations of radiolytic chemical species are expressed by an approximate analysis of the decay radiation transport equation. For purposes of illustration a modified Temkin adsorption isotherm was assumed for the surface adsorption kinetics on an arbitrary, finite area of the solid-liquid dissolution interface. For

Kinetics and thermodynamics of the dissolution of Th1-xMxO2 solid solutions (M = U, Pu)

International Nuclear Information System (INIS)

Hubert, S.; Heisbourg, G.; Dacheux, N.; Moisy, Ph.; Purans, J.

2004-01-01

Kinetics of the dissolution of Th 1-x M x O 2 (M = U, Pu) solid solutions was investigated as a function of several chemical parameters such as pH, substitution ratio, temperature, ionic strength, and electrolyte. Several compositions of Th 1-x U x O 2 and Th 1-x Pu x O 2 were synthesized and characterized before and after leaching by using several methods such as XRD, EXAFS, BET, PIXE, SEM, and XPS. Leaching tests were performed in nitric, hydrochloric or sulfuric media and groundwater. The normalized dissolution rates were evaluated for Th 1-x U x O 2 , and Th 0.88 Pu 0.12 O 2 leading to the determination of the partial order related to the proton concentration, n, and to the corresponding normalized dissolution rate constant at pH = 0, k'T. While for Th enriched solids, the solid solutions Th 1-x U x O 2 have the same dissolution behaviour than ThO 2 with a partial order n ∼ 0.3, in the case of uranium enriched solids, Th 1-x U x O 2 has the same dissolution behaviour than UO 2 with a partial order of n = 1, indicating that uranium oxidation rate becomes the limiting step of the dissolution process. The stoichiometry of the release of both actinides (U or Pu, Th) was verified until the precipitation of thorium occurred in the leachate for pH > 2, while uranium was released in the solution as an uranyl form. For uranium enriched solid solutions, thermodynamic equilibrium was reached after 100 days, and solubility constant of secondary phase was determined. In the case of Th 1-x Pu x O 2 , the dissolution behaviour is similar to that of ThO 2 , but only kinetic aspect of the dissolution can be studied. From the analysis of XPS and EXAFS data on leached and un-leached Th 1-x U x O 2 samples, the dissolution mechanism of solid solutions was explained and will be discussed. The role of the electrolytes on the dissolution of the solid solutions is discussed. Kinetics parameters of dissolution are also given in groundwater and in neutral media

Kinetics of UO2(s) dissolution under reducing conditions: Numerical modelling

International Nuclear Information System (INIS)

Puigdomenech, I.; Casas, I.; Bruno, J.

1990-05-01

A numerical model is presented that describes the dissolution and precipitation of UO 2 (s) under reducing conditions. For aqueous solutions with pH>4, main reaction is: UO 2 (s)+2H 2 O↔U(OH) 4 (aq). The rate constant for the precipitation reaction is found to be log(k p )=-1.2±0.2 h -1 m -2 , while the value for the rate constant of the dissolution reaction is log(k d )=-9.0±0.2 mol/(1 h m 2 ). Most of the experiments reported in the literature show a fast initial dissolution of a surface film of hexavalent uranium oxide. Making the assumption that the chemical composition of the surface coating is U 3 O 7 (s), we have derived a mechanism for this process, and its rate constants have been obtained. The influence of HCO 3 - and CO 3 2- on the mechanism of dissolution and precipitation of UO 2 (s) is still unclear. From the solubility measurements reported, one may conclude that the identity of the aqueous complexes in solution is not well known. Therefore it is not possible to make a mechanistic interpretation of the kinetic data in carbonate medium. (orig.)

Kinetics of carbonate dissolution in CO2-saturated aqueous system at reservoir conditions

Science.gov (United States)

Peng, Cheng; Crawshaw, John P.; Maitland, Geoffrey; Trusler, J. P. Martin

2014-05-01

results of the study indicate that the rotating disc technique can allow accurate measurement of the carbonate dissolution rate under surface-reaction-controlled conditions, and that the carbonate dissolution rate typically increases with the increase of temperature, CO2 partial pressure and solution acidity. The study shows that the dissolution of carbonate in CO2-free acidic solutions can be described as a first order heterogeneous reaction; however, this model is not sufficient to describe the reaction kinetics of carbonate minerals in the (CO2 + H2O) system, particularly for high reactivity carbonates, such as calcite, at reservoir conditions. For these systems, both pH and the activity of CO2(aq) influence the dissolution rate. Based on the experimental results, kinetic models have been developed and parameterised to describe the dissolution of different carbonate minerals. The results of this study should facilitate more rigorous modelling of mineral dissolution in deep saline aquifers used for CO2 storage. We gratefully acknowledge the funding of QCCSRC provided jointly by Qatar Petroleum, Shell, and the Qatar Science & Technology Park. Keywords: Carbon Dioxide, Carbonate, High Pressure, High Temperature, Reaction Kinetics.

Atmospheric weathering and silica-coated feldspar: analogy with zeolite molecular sieves, granite weathering, soil formation, ornamental slabs, and ceramics.

Science.gov (United States)

Smith, J V

1998-03-31

Feldspar surfaces respond to chemical, biological, and mechanical weathering. The simplest termination is hydroxyl (OH), which interacts with any adsorption layer. Acid leaching of alkalis and aluminum generated a silica-rich, nanometers-thick skin on certain feldspars. Natural K, Na-feldspars develop fragile surfaces as etch pits expand into micrometer honeycombs, possibly colonized by lichens. Most crystals have various irregular coats. Based on surface-catalytic processes in molecular sieve zeolites, I proposed that some natural feldspars lose weakly bonded Al-OH (aluminol) to yield surfaces terminated by strongly bonded Si-OH (silanol). This might explain why some old feldspar-bearing rocks weather slower than predicted from brief laboratory dissolution. Lack of an Al-OH infrared frequency from a feldspar surface is consistent with such a silanol-dominated surface. Raman spectra of altered patches on acid-leached albite correspond with amorphous silica rather than hydroxylated silica-feldspar, but natural feldspar may respond differently. The crystal structure of H-exchanged feldspar provides atomic positions for computer modeling of complex ideas for silica-terminated feldspar surfaces. Natural weathering also depends on swings of temperature and hydration, plus transport of particles, molecules, and ionic complexes by rain and wind. Soil formation might be enhanced by crushing granitic outcrops to generate new Al-rich surfaces favorable for chemical and biological weathering. Ornamental slabs used by architects and monumental masons might last longer by minimizing mechanical abrasion during sawing and polishing and by silicifying the surface. Silica-terminated feldspar might be a promising ceramic surface.

Microfluidic Leaching of Soil Minerals: Release of K+ from K Feldspar

Science.gov (United States)

Ciceri, Davide; Allanore, Antoine

2015-01-01

The rate of K+ leaching from soil minerals such as K-feldspar is believed to be too slow to provide agronomic benefit. Currently, theories and methods available to interpret kinetics of mineral processes in soil fail to consider its microfluidic nature. In this study, we measure the leaching rate of K+ ions from a K-feldspar-bearing rock (syenite) in a microfluidic environment, and demonstrate that at the spatial and temporal scales experienced by crop roots, K+ is available at a faster rate than that measured with conventional apparatuses. We present a device to investigate kinetics of mineral leaching at an unprecedented simultaneous resolution of space (~101-102 μm), time (~101-102 min) and fluid volume (~100-101 mL). Results obtained from such a device challenge the notion that silicate minerals cannot be used as alternative fertilizers for tropical soils. PMID:26485160

8 Dissolution Kinetics

African Journals Online (AJOL)

user

Experiments measuring the dissolution rates of stilbite (NaCa [Al Si O ].14H O) in pH-buffered ... The rate law was established as R = k (a ) , where k is ... crystalline hydrated aluminosilicate minerals ..... from the crushing process, thin edges or.

Effects of natural organic matter properties on the dissolution kinetics of zinc oxide nanoparticles

Science.gov (United States)

Jiang, Chuanjia; Aiken, George R.; Hsu-Kim, Heileen

2015-01-01

The dissolution of zinc oxide (ZnO) nanoparticles (NPs) is a key step of controlling their environmental fate, bioavailability, and toxicity. Rates of dissolution often depend upon factors such as interactions of NPs with natural organic matter (NOM). We examined the effects of 16 different NOM isolates on the dissolution kinetics of ZnO NPs in buffered potassium chloride solution using anodic stripping voltammetry to directly measure dissolved zinc concentrations. The observed dissolution rate constants (kobs) and dissolved zinc concentrations at equilibrium increased linearly with NOM concentration (from 0 to 40 mg C L–1) for Suwannee River humic and fulvic acids and Pony Lake fulvic acid. When dissolution rates were compared for the 16 NOM isolates, kobs was positively correlated with certain properties of NOM, including specific ultraviolet absorbance (SUVA), aromatic and carbonyl carbon contents, and molecular weight. Dissolution rate constants were negatively correlated to hydrogen/carbon ratio and aliphatic carbon content. The observed correlations indicate that aromatic carbon content is a key factor in determining the rate of NOM-promoted dissolution of ZnO NPs. The findings of this study facilitate a better understanding of the fate of ZnO NPs in organic-rich aquatic environments and highlight SUVA as a facile and useful indicator of NOM interactions with metal-based nanoparticles.

Dissolution study of tremolite and anthophyllite: pH effect on the reaction kinetics

International Nuclear Information System (INIS)

Rozalen, M.; Ramos, M.E.; Gervilla, F.; Kerestedjian, T.; Fiore, S.; Huertas, F.J.

2014-01-01

Highlights: • Dissolution rates strongly depend on pH and it is different for each mineral. • Anthophyllite dissolves up to 8 times faster than tremolite in similar conditions. • SEM images show different particle breakage and carbonation effects at basic pHs. • Our results are a good background to develop remediation processes of contaminated sites. - Abstract: The effect of pH on the kinetics of tremolite and anthophyllite dissolution was investigated at 25 °C in batch reactors over the pH range of 1–13.5, in inorganic buffered solutions. Dissolution rates were obtained based on the release of Si and Mg. Results obtained in this study show different behaviors for both minerals. For tremolite, dissolution rates show a noticeable dependence on pH between 1 and 8, decreasing as pH increases and reaching a minimum around neutral conditions. At basic pH this dependence becomes even stronger, but dissolution takes place together with collateral effects of saturation and carbonation. A preferential release of Ca and Mg is observed in acid media, lowering the Mg/Si ratio to the extent that Mg solubility decreases with pH. For anthophyllite, dissolution rates also show a strong dependence on pH, between 1 and 9.5. At the same pH, anthophyllite dissolves up to 8 times faster than tremolite. For pH > 9.5 this dependence is smooth, and it is probably associated with effects of saturation and carbonation. Dissolution is also non-stoichiometric with a faster release of Mg with respect to Si in acid media. SEM observations show differences in the breakage mechanism of the fibers. The anthophyllite particle breakage during dissolution consists of the splitting of bundle fibers parallel to the fiber longitudinal direction. However, for tremolite, other than fiber splitting, particles shorten induced by coalescence of etch pits developed perpendicular to c axe

The kinetics of Dissolution of Biologically Formed Calcific Deposits.

Science.gov (United States)

Rokidi, Stamatia; Koutsoukos, Petros

2015-04-01

The calcification of aortic valves results in the formation of non stoichiometric apatitic deposits which may have serious health implications because of the fact that these minerals adhere tenaciously on tissues like heart valves and arteries causing permanent damage which is partly due to their low solubility. In the present work, calcium phosphate biominerals were extracted from clinically removed tissues and were characterized with respect to their mineralogical constituents and other properties including morphology, specific surface area analyses and thermogravimetric analysis. In all cases, the biominerals may be described as non stoichiometric apatitic materials, although traces of the precursor phase of octacalcium phosphate (Ca8H2(PO4)6•5H2O, OCP) were identified on the basis of their morphological examination. The kinetics of dissolution of the biomineral deposits was investigated in solutions undersaturated with respect to hydroxyapatite (Ca5(PO4)3OH, HAP) at conditions of constant undersaturation at pH 7.40, 37°C, 0.15M NaCl. Synthetic stoichiometric HAP was used as the control mineral. The experiments in the present work used solutions prepared from calcium chloride and sodium hydrogen phosphate and the relative undersaturation, σ, was in the range 0.38-0.74 with respect to HAP and 0.49-0.85 with respect to OCP (σ=1 in water). The dissolution process started immediately upon the introduction of an accurately weighted amount of powdered biomineral in the undersaturated solutions homogenized by magnetic stirring. Inert atmosphere was ensured with the bubbling of water vapor saturated nitrogen through the demineralizing solutions. A glass/Ag/AgCl combination electrode was used as a probe to monitor the process and to control the addition of diluent solutions with the stoichiometry of the dissolving mineral. The measurements of the rates of crystal dissolution, showed a parabolic dependence on the relative solution undersaturation for HAP and higher

Kinetics and thermodynamics of aluminium dissolution in 1.0M sulphuric acid containing chloride ions

Energy Technology Data Exchange (ETDEWEB)

Abdel-Gaber, A.M. [Department of Chemistry, Faculty of Science, Alexandria University, P.O. Box 426, Ibrahimia, Alexandria 21321 (Egypt)]. E-mail: ashrafmoustafa@yahoo.com; Abd-El-Nabey, B.A. [Department of Chemistry, Faculty of Science, Alexandria University, P.O. Box 426, Ibrahimia, Alexandria 21321 (Egypt); Sidahmed, I.M. [Department of Chemistry, Faculty of Science, Alexandria University, P.O. Box 426, Ibrahimia, Alexandria 21321 (Egypt); El-Zayady, A.M. [Department of Chemistry, Faculty of Science, Alexandria University, P.O. Box 426, Ibrahimia, Alexandria 21321 (Egypt); Saadawy, M. [Department of Chemistry, Faculty of Science, Alexandria University, P.O. Box 426, Ibrahimia, Alexandria 21321 (Egypt)

2006-08-01

The dissolution of aluminium in 1M sulphuric acid solutions containing different chloride ion concentrations (0.01-0.06M) were studied at 25, 30, 35 and 40deg. C using electrochemical impedance spectroscopy (EIS) technique and polarization curves measurements. The kinetic rate equation, under the experimental condition described, was derived and found to verify the following relationship:V=k{sub obs}K{sub 2}C{sub Cl{sup -}}{sup n}1+K{sub 2}C{sub Cl{sup -}}{sup n}where V is the corrosion rate, k{sub obs} and K{sub 2} are the dissolution rate constant of aluminium oxide-chloride complex and the equilibrium constant of chloride ions adsorbed at aluminium oxide surface, respectively. The kinetic and thermodynamic energy parameters were calculated and their values indicate that chloride ions are chemisorbed onto the aluminium oxide surface and the formation of oxide-chloride complex is the rate-determining step.

Feldspar, Infrared Stimulated Luminescence

DEFF Research Database (Denmark)

Jain, Mayank

2014-01-01

This entry primarily concerns the characteristics and the origins of infrared-stimulated luminescence in feldspars.......This entry primarily concerns the characteristics and the origins of infrared-stimulated luminescence in feldspars....

Dissolution kinetics of volatile organic compound vapors in water : An integrated experimental and computational study

NARCIS (Netherlands)

G. Mahmoodlu, Mojtaba; Pontedeiro, Elizabeth M.; Pérez Guerrero, Jesús S.; Raoof, Amir; Hassanizadeh, S. Majid; van Genuchten, Martinus Th

In this study we performed batch experiments to investigate the dissolution kinetics of trichloroethylene (TCE) and toluene vapors in water at room temperature and atmospheric pressure. The batch systems consisted of a water reservoir and a connected headspace, the latter containing a small glass

The release of iron-bearing minerals and dissolution of feldspars by heterotrophic bacteria of Bacillus species

Czech Academy of Sciences Publication Activity Database

Štyriaková, I.; Štyriak, I.; Galko, I.; Hradil, David; Bezdička, Petr

2003-01-01

Roč. 47, č. 1 (2003), s. 20-26 ISSN 0862-5468 Grant - others:AV SR(SK) 2/2107/22; GA SR(SK) 73/2000 Institutional research plan: CEZ:AV0Z4032918 Keywords : bioleaching * feldspars * Bacillus Subject RIV: CA - Inorganic Chemistry Impact factor: 0.449, year: 2003

Kinetic model for quartz and spinel dissolution during melting of high-level-waste glass batch

International Nuclear Information System (INIS)

Pokorny, Richard; Rice, Jarrett A.; Crum, Jarrod V.; Schweiger, Michael J.; Hrma, Pavel

2013-01-01

The dissolution of quartz particles and the growth and dissolution of crystalline phases during the conversion of batch to glass potentially affects both the glass melting process and product quality. Crystals of spinel exiting the cold cap to molten glass below can be troublesome during the vitrification of iron-containing high-level wastes. To estimate the distribution of quartz and spinel fractions within the cold cap, we used kinetic models that relate fractions of these phases to temperature and heating rate. Fitting the model equations to data showed that the heating rate, apart from affecting quartz and spinel behavior directly, also affects them indirectly via concurrent processes, such as the formation and motion of bubbles. Because of these indirect effects, it was necessary to allow one kinetic parameter (the pre-exponential factor) to vary with the heating rate. The resulting kinetic equations are sufficiently simple for the detailed modeling of batch-to-glass conversion as it occurs in glass melters. The estimated fractions and sizes of quartz and spinel particles as they leave the cold cap, determined in this study, will provide the source terms needed for modeling the behavior of these solid particles within the flow of molten glass in the melter

Kinetic of the COLUMBO-TANTALITE dissolution in aqueous solutions of hydrofluoric acid

International Nuclear Information System (INIS)

Rodriguez, Mario; Quiroga, Oscar; Ruiz, Maria del Carmen

2003-01-01

The dissolution rate of a columbo-tantalite of the San Luis Province in aqueous solutions of hydrofluoric acid has been studied.Experiments at different temperatures were carried out in a pressure reactor.The experimental results show that the mineral dissolution increases with the reaction time.This effect is greater when the temperature increases from 348 up to 396 K, but it is little 493 K. The experimental data were treated with different models, which have been deduced for the kinetic study of solid-fluid non-catalytic heterogeneous reactions. As a result, the better model that fit the experimental data is a model based on the nucleation and growth theory.This model is physically according to the attack observed by means of scanning electron microscopy (SEM) and energy-dispersive X-ray spectrometry (EDXS) on the mineral residues.These residues show an irregular located-type attack

The Thermal Expansion Of Feldspars

Science.gov (United States)

Hovis, G. L.; Medford, A.; Conlon, M.

2009-12-01

Hovis and others (1) investigated the thermal expansion of natural and synthetic AlSi3 feldspars and demonstrated that the coefficient of thermal expansion (α) decreases significantly, and linearly, with increasing room-temperature volume (VRT). In all such feldspars, therefore, chemical expansion limits thermal expansion. The scope of this work now has been broadened to include plagioclase and Ba-K feldspar crystalline solutions. X-ray powder diffraction data have been collected between room temperature and 925 °C on six plagioclase specimens ranging in composition from anorthite to oligoclase. When combined with thermal expansion data for albite (2,3,4) a steep linear trend of α as a function of VRT emerges, reflecting how small changes in composition dramatically affect expansion behavior. The thermal expansion data for five synthetic Ba-K feldspars ranging in composition from 20 to 100 mole percent celsian, combined with data for pure K-feldspar (3,4), show α-VRT relationships similar in nature to the plagioclase series, but with a slope and intercept different from the latter. Taken as a group all Al2Si2 feldspars, including anorthite and celsian from the present study along with Sr- (5) and Pb-feldspar (6) from other workers, show very limited thermal expansion that, unlike AlSi3 feldspars, has little dependence on the divalent-ion (or M-) site occupant. This apparently is due to the necessitated alternation of Al and Si in the tetrahedral sites of these minerals (7), which in turn locks the tetrahedral framework and makes the M-site occupant nearly irrelevant to expansion behavior. Indeed, in feldspar series with coupled chemical substitution it is the change away from a 1:1 Al:Si ratio that gives feldspars greater freedom to expand. Overall, the relationships among α, chemical composition, and room-temperature volume provide useful predictive tools for estimating feldspar thermal expansion and give insight into the controls of expansion behavior in

Kinetics of ikaite precipitation and dissolution in seawater-derived brines at sub-zero temperatures to 265 K

Science.gov (United States)

Papadimitriou, Stathys; Kennedy, Hilary; Kennedy, Paul; Thomas, David N.

2014-09-01

The kinetics of calcium carbonate hexahydrate (ikaite) precipitation and dissolution were investigated in seawater and seawater-derived brines at sub-zero temperatures using the constant addition experimental technique. The steady state rate of these two processes was found to be a function of the deviation of the solution from equilibrium with respect to ikaite and conformed to the same empirical rate law as the anhydrous CaCO3 polymorphs, calcite and aragonite. In addition to the saturation state of the brine with respect to ikaite, the salinity of the brine and the temperature of the reaction evidently exerted some control on the ikaite precipitation kinetics, while the dissolution kinetics of the polymorph were not noticeably influenced by these two parameters. The experimental salinity and temperature conditions were equivalent to those at thermal equilibrium between brine and ice in the sea ice cover of polar seas. Simple modelling of the CO2 system by extrapolation of the oceanic equivalent to sea ice brines showed that the physical concentration of seawater ions and the changes in ikaite solubility as a function of salinity and temperature, both inherent in the sea ice system, would be insufficient to drive the emergent brines to ikaite supersaturation and precipitation in sea ice down to -8 °C. The loss of dissolved inorganic carbon to the gas phase of sea ice and to sympagic autotrophs are two independent mechanisms which, in nature, could prompt the brine CO2 system towards ikaite supersaturation and precipitation. Under these conditions, the steady state precipitation rate of ikaite was found to be fast enough for rapid formation within short time scales (days to weeks) in sea ice. The observed ikaite dissolution kinetics were also found conducive to short turn-over time scales of a few hours to a few days in corrosive solutions, such as surface seawater.

Feldspar 40Ar/39Ar dating of ICDP PALEOVAN cores

Science.gov (United States)

Engelhardt, Jonathan Franz; Sudo, Masafumi; Stockhecke, Mona; Oberhänsli, Roland

2017-11-01

Volcaniclastic fall deposits in ICDP drilling cores from Lake Van, Turkey, contain sodium-rich sanidine and calcium-rich anorthoclase, which both comprise a variety of textural zoning and inclusions. An age model records the lake's history and is based on climate-stratigraphic correlations, tephrostratigraphy, paleomagnetics, and earlier 40Ar/39Ar analyses (Stockhecke et al., 2014b). Results from total fusion and stepwise heating 40Ar/39Ar analyses presented in this study allow for the comparison of radiometric constraints from texturally diversified feldspar and the multi-proxy lacustrine age model and vice versa. This study has investigated several grain-size fractions of feldspar from 13 volcaniclastic units. The feldspars show textural features that are visible in cathodoluminescence (CL) or back-scattered electron (BSE) images and can be subdivided into three dominant zoning-types: (1) compositional zoning, (2) round pseudo-oscillatory zoning and (3) resorbed and patchy zoning (Ginibre et al., 2004). Round pseudo-oscillatory zoning records a sensitive alternation of Fe and Ca that also reflects resorption processes. This is only visible in CL images. Compositional zoning reflects anticorrelated anorthite and orthoclase contents and is visible in BSE. Eleven inverse isochron ages from total fusion and three from stepwise heating analyses fit the age model. Four experiments resulted in older inverse isochron ages that do not concur with the model within 2σ uncertainties and that deviate from 1 ka to 17 ka minimum. C- and R-type zoning are interpreted as representing growth in magma chamber cupolas, as wall mushes, or in narrow conduits. Persistent compositions of PO-type crystals and abundant surfaces recording dissolution features correspond to formation within a magma chamber. C-type zoning and R-type zoning have revealed an irregular incorporation of melt and fluid inclusions. These two types of zoning in feldspar are interpreted as preferentially

Quantitative analysis of time-resolved infrared stimulated luminescence in feldspars

Energy Technology Data Exchange (ETDEWEB)

Pagonis, Vasilis, E-mail: vpagonis@mcdaniel.edu [McDaniel College, Physics Department, Westminster, MD 21157 (United States); Ankjærgaard, Christina [Soil Geography and Landscape Group & Netherlands Centre for Luminescence dating, Wageningen University, PO Box 47, 6700 AA Wageningen (Netherlands); Jain, Mayank [Center for Nuclear Technologies, Technical University of Denmark, DTU Risø Campus, Roskilde (Denmark); Chithambo, Makaiko L. [Department of Physics and Electronics, Rhodes University, PO BOX 94, Grahamstown 6140 (South Africa)

2016-09-15

Time-resolved infrared-stimulated luminescence (TR-IRSL) from feldspar samples is of importance in the field of luminescence dating, since it provides information on the luminescence mechanism in these materials. In this paper we present new analytical equations which can be used to analyze TR-IRSL signals, both during and after short infrared stimulation pulses. The equations are developed using a recently proposed kinetic model, which describes localized electronic recombination via tunneling between trapped electrons and recombination centers in luminescent materials. Recombination is assumed to take place from the excited state of the trapped electron to the nearest-neighbor center within a random distribution of luminescence recombination centers. Different possibilities are examined within the model, depending on the relative importance of electron de-excitation and recombination. The equations are applied to experimental TR-IRSL data of natural feldspars, and good agreement is found between experimental and modeling results.

DEVELOPMENT OF A KINETIC MODEL OF BOEHMITE DISSOLUTION IN CAUSTIC SOLUTIONS APPLIED TO OPTIMIZE HANFORD WASTE PROCESSING

International Nuclear Information System (INIS)

Disselkamp, R.S.

2011-01-01

Boehmite (e.g., aluminum oxyhydroxide) is a major non-radioactive component in Hanford and Savannah River nuclear tank waste sludge. Boehmite dissolution from sludge using caustic at elevated temperatures is being planned at Hanford to minimize the mass of material disposed of as high-level waste (HLW) during operation of the Waste Treatment Plant (WTP). To more thoroughly understand the chemistry of this dissolution process, we have developed an empirical kinetic model for aluminate production due to boehmite dissolution. Application of this model to Hanford tank wastes would allow predictability and optimization of the caustic leaching of aluminum solids, potentially yielding significant improvements to overall processing time, disposal cost, and schedule. This report presents an empirical kinetic model that can be used to estimate the aluminate production from the leaching of boehmite in Hanford waste as a function of the following parameters: (1) hydroxide concentration; (2) temperature; (3) specific surface area of boehmite; (4) initial soluble aluminate plus gibbsite present in waste; (5) concentration of boehmite in the waste; and (6) (pre-fit) Arrhenius kinetic parameters. The model was fit to laboratory, non-radioactive (e.g. 'simulant boehmite') leaching results, providing best-fit values of the Arrhenius A-factor, A, and apparent activation energy, E A , of A = 5.0 x 10 12 hour -1 and E A = 90 kJ/mole. These parameters were then used to predict boehmite leaching behavior observed in previously reported actual waste leaching studies. Acceptable aluminate versus leaching time profiles were predicted for waste leaching data from both Hanford and Savannah River site studies.

Hydrothermal alteration of the glass R7T7. Glass dissolution kinetics at 150 and 2500, role of neo-formed phases

International Nuclear Information System (INIS)

Caurel, J.

1990-01-01

The glass R7T7 is chosen in France for vitrification of solution from reprocessing. Safety requires the knowledge of R7T7 long term behavior in deep geologic formations. Temperature dependence of leaching between 50 and 300 0 C is studied by static tests for 7 days. An activation energy of 30kJ/Mole is calculated between 50; 75 or 100 0 C and 250 0 C. Results suggest similar corrosion mechanisms between 90-100 and 250 0 C by a complete change between 250 and 275 0 C. Glass corrosion kinetics at 150 0 C and 250 0 C between 1 day and 1 year evidence the precipitation of aluminosilicates and formation of thick amorphous gels progressively enriched with silica. Glass dissolution at 150 0 C and 250 0 C is simulated with the geochemical DISSOL code. Results suggest that dissolution kinetics are controlled by activity of H 4 SiO 4 in solution only. Silica contained into the gel controls corrosion kinetics different from 0. Even if the nature of dissolution mechanisms does not seem modified between 150 and 250 0 C, sample cracking at 250 0 C induces an increase of dissolved glass that does not allow a direct comparison of corrosion kinetics between 150 and 250 0 C [fr

Development of a kinetic model for the dissolution of the UO2 spent nuclear fuel. Application of the model to the minor radionuclides

International Nuclear Information System (INIS)

Bruno, J.; Cera, E.; Duro, L.; Pon, J.; Pablo, J. de; Eriksen, Trygve

1998-05-01

A kinetic model has been developed in order to explain the evolution of the spent fuel matrix/groundwater system. Mass balance equations have been used to follow the evolution of the system with time. The model has been calibrated by using experimental dissolution data from spent fuel leaching tests from Studsvik and KTH and from synthetic unirradiated UO 2 dissolution tests from VTT. The results of the testing exercise indicate that the combination of mass balance equations together with the kinetic rate laws constitute a useful tool to model and explain experimental dissolution data available in the literature for UO 2 solid phases, including uraninites, unirradiated UO 2 and spent fuel. Although the key processes are well identified and understood, there are still some remaining uncertainties concerning some of the critical parameters of the model. This is particularly true for the density of UO 2 sites prone to oxidation and the rates and mechanisms of the hydrogen peroxide and the combined oxygen and bicarbonate promoted dissolution of UO 2 for oxidant concentration ranges relevant to the spent fuel disposal system. The mass balance kinetic model developed has been extended to minor radionuclides contained in the matrix, i.e. Pu, Tc and Sr. In the case of Pu, the model presented reproduces the behaviour of this critical radionuclide even at early contact times. As it would be expected, Tc seems to follow a different mechanism for its release with respect to the UO 2 matrix dissolution, which is probably linked to the rate of oxidation of Tc metallic inclusions in the fuel. A co- dissolution process of Sr with the UO 2 matrix reproduces the long term dissolution behaviour of this radionuclide, better than the initial Sr release rates

Studies on the kinetics of UO2 dissolution in carbonate-bicarbonate medium using sodium hypochlorite as oxidant

International Nuclear Information System (INIS)

Sharma, J.N.; Bhattacharya, K.; Swami, R.G.; Tangri, S.K.; Mukherjee, T.K.

1996-01-01

The dissolution of UO 2 in carbonate-bicarbonate solutions containing sodium hypochlorite as an oxidant has been investigated. The effect of temperature, sodium hypochlorite concentration and stirring speed was examined. In the temperature range of 303 to 318 K, the leaching reaction displayed linear kinetics. Apparent activation energy obtained from the differential approach was found to be 57 kJ mol -1 . This relatively high activation energy value indicates a chemically controlled behavior of UO 2 dissolution. The order of reaction with respect to sodium hypochlorite concentration was found to be unity. (author). 18 refs., 6 figs

Principles of Thermal Expansion in Feldspars

Science.gov (United States)

Hovis, Guy; Medford, Aaron; Conlon, Maricate; Tether, Allison; Romanoski, Anthony

2010-05-01

Following the recent thermal expansion work of Hovis et al. (1) on AlSi3 feldspars, we have investigated the thermal expansion of plagioclase, Ba-K, and Ca-K feldspar crystalline solutions. X-ray powder diffraction data were collected between room temperature and 925 °C on six natural plagioclase specimens ranging in composition from anorthite to oligoclase, the K-exchanged equivalents of these plagioclase specimens, and five synthetic Ba-K feldspars with compositions ranging from 25 to 99 mol % BaAl2Si2O8. The resulting thermal expansion coefficients (α) for volume have been combined with earlier results for end-member Na- and K-feldspars (2,3). Unlike AlSi3 feldspars, Al2Si2 feldspars, including anorthite and celsian from the present study plus Sr- and Pb-feldspar from other workers (4,5), show essentially constant and very limited thermal expansion, regardless of divalent cation size. In the context of structures where the Lowenstein rule (6) requires Al and Si to alternate among tetrahedra, the proximity of bridging Al-O-Si oxygen ions to divalent neighbors (ranging from 0 to 2) produces short Ca-O (or Ba-O) bonds (7,8) that apparently are the result of local charge-balance requirements (9). Gibbs et al. (10) suggest that short bonds such as these have a partially covalent character. This in turn stiffens the structure. Thus, for feldspar series with coupled substitution the change away from a purely divalent M-site occupant gives the substituting (less strongly bonded) monovalent cations increasingly greater influence on thermal expansion. Overall, then, thermal expansion in the feldspar system is well represented on a plot of α against room-temperature volume, where one sees a quadrilateral bounded by data for (A) AlSi3 feldspars whose expansion behavior is controlled largely by the size of the monovalent alkali-site occupant, (B) Al2Si2 feldspars whose expansion is uniformly limited by partially-covalent bonds between divalent M-site occupants and

Development of a kinetic model for the dissolution of the UO{sub 2} spent nuclear fuel. Application of the model to the minor radionuclides

Energy Technology Data Exchange (ETDEWEB)

Bruno, J.; Cera, E.; Duro, L.; Pon, J. [QuantiSci SL, Barcelona (Spain); Pablo, J. de [UPC, Barcelona (Spain). Dept. Enginyeria Quimica; Eriksen, Trygve [Royal Inst. of Tech., Stockholm (Sweden). Dept. of Nuclear Chemistry

1998-05-01

A kinetic model has been developed in order to explain the evolution of the spent fuel matrix/groundwater system. Mass balance equations have been used to follow the evolution of the system with time. The model has been calibrated by using experimental dissolution data from spent fuel leaching tests from Studsvik and KTH and from synthetic unirradiated UO{sub 2} dissolution tests from VTT. The results of the testing exercise indicate that the combination of mass balance equations together with the kinetic rate laws constitute a useful tool to model and explain experimental dissolution data available in the literature for UO{sub 2} solid phases, including uraninites, unirradiated UO{sub 2} and spent fuel. Although the key processes are well identified and understood, there are still some remaining uncertainties concerning some of the critical parameters of the model. This is particularly true for the density of UO{sub 2} sites prone to oxidation and the rates and mechanisms of the hydrogen peroxide and the combined oxygen and bicarbonate promoted dissolution of UO{sub 2} for oxidant concentration ranges relevant to the spent fuel disposal system. The mass balance kinetic model developed has been extended to minor radionuclides contained in the matrix, i.e. Pu, Tc and Sr. In the case of Pu, the model presented reproduces the behaviour of this critical radionuclide even at early contact times. As it would be expected, Tc seems to follow a different mechanism for its release with respect to the UO{sub 2} matrix dissolution, which is probably linked to the rate of oxidation of Tc metallic inclusions in the fuel. A co- dissolution process of Sr with the UO{sub 2} matrix reproduces the long term dissolution behaviour of this radionuclide, better than the initial Sr release rates 49 refs, 22 figs, 2 tables

A kinetic study of plutonium dioxide dissolution in hydrochloric acid using iron (II) as an electron transfer catalyst

International Nuclear Information System (INIS)

Fife, K.W.

1996-09-01

Effective dissolution of plutonium dioxide has traditionally been accomplished by contact with strong nitric acid containing a small amount of fluoride at temperatures of ∼ 100 C. In spite of these aggressive conditions, PuO 2 dissolution is sometimes incomplete requiring additional contact with the solvent. This work focused on an alternative to conventional dissolution in nitric acid where an electron transfer catalyst, Fe(II), was used in hydrochloric acid. Cyclic voltammetry was employed as an in-situ analytical technique for monitoring the dissolution reaction rate. The plutonium oxide selected for this study was decomposed plutonium oxalate with > 95% of the material having a particle diameter (< 70 microm) as determined by a scanning laser microscopy technique. Attempts to dry sieve the oxide into narrow size fractions prior to dissolution in the HCl-Fe(II) solvent system failed, apparently due to significant interparticle attractive forces. Although sieve splits were obtained, subsequent scanning laser microscopy analysis of the sieve fractions indicated that particle segregation was not accomplished and the individual sieve fractions retained a particle size distribution very similar to the original powder assemblage. This phenomena was confirmed through subsequent dissolution experiments on the various screen fractions which illustrated no difference in kinetic behavior between the original oxide assemblage and the sieve fractions

SON68 nuclear glass dissolution kinetics: Current state of knowledge and basis of the new GRAAL model

Energy Technology Data Exchange (ETDEWEB)

Frugier, P. [CEA Marcoule, DTCD/SECM/LCLT, BP 17171, 30207 Bagnols-sur-Ceze cedex (France)], E-mail: pierre.frugier@cea.fr; Gin, S.; Minet, Y.; Chave, T. [CEA Marcoule, DTCD/SECM/LCLT, BP 17171, 30207 Bagnols-sur-Ceze cedex (France); Bonin, B. [CEA Saclay, DEN/DIR/DS, 91191 Gif-sur-Yvette cedex (France); Godon, N.; Lartigue, J.-E.; Jollivet, P. [CEA Marcoule, DTCD/SECM/LCLT, BP 17171, 30207 Bagnols-sur-Ceze cedex (France); Ayral, A. [IEM/CNRS-ENSCM Universite Montpellier 2, CC 047, Place Eugene Bataillon, 34095 Montpellier cedex 5 (France); De Windt, L. [ENSMP, CG, 35 rue St Honore, 77305 Fontainebleau cedex (France); Santarini, G. [CEA Saclay HC/CAB, 91191 Gif-sur-Yvette cedex (France)

2008-10-15

This article summarizes the present state of knowledge concerning aqueous alteration of R7T7-type nuclear containment glasses, represented mainly by the inactive reference glass designated SON68. Based on this review, we propose to describe the glass alteration kinetics up to and including the final residual rate regime by means of a new mechanistic model known as GRAAL (glassreactivitywithallowanceforthealterationlayer). Phenomenological analysis findings are reviewed for the various glass alteration regimes: interdiffusion, initial rate, rate drop, residual rate and, under very particular circumstances, resumption of alteration. These alteration regimes are associated with predominant mechanisms. Published work interpreting and modeling these mechanisms was examined in detail. There is a broad consensus on the general mechanisms of the initial rate and even the interdiffusion regime, whereas the mechanisms controlling the rate drop remain a subject of dispute not only with regard to nuclear glasses but also for the dissolution of silicate minerals. The reaction affinity responsible for the rate drop is expressed differently by different authors and depending on the underlying theories. The disagreement concerns the nature of the phase (glass or gel) or the activated complex controlling the rate drop, which in turn determines the elements that must be taken into account in the overall affinity term. Progress in recent years, especially in identifying the mechanisms responsible for the residual rate, has shed new light on these issues, allowing us to propose new theoretical foundations for modeling the different kinetic regimes of SON68 nuclear glass dissolution. The GRAAL model considers that water diffusion in the passivating reaction zone (the gel formed under saturation conditions) is a rate-limiting step in the overall glass dissolution kinetics. Moreover, this passivation zone is a soluble phase whose stability is directly dependent on the nature of the

Advances in heterogeneous autocatalytic reactions applied to uranium dissolution - 5317

International Nuclear Information System (INIS)

Marc, P.; Magnaldo, A.; Godard, J.; Schaer, E.

2015-01-01

Dissolution and the solubilization of the chemical elements is a milestone of the head-end of hydrometallurgical processes. When dissolving spent nuclear fuels, additional constraints are added due to the permanent need to strictly control and limit the hold-up. Thus the need for kinetic modeling concerning the dissolution of spent nuclear fuels in nitric acid. This study aims at better understanding the chemical and physical-chemical phenomena of uranium dioxide dissolution reactions in nitric medium. It has been documented that the nitric acid attack of sintering-manufactured uranium dioxide solids occurs through preferential attack sites. This non uniform attack leads to the development of cracks in the solids. Optical microscopy observations show that in some cases, the development of these cracks can lead to the solid cleavage. In this case, we show that the dissolution of the detached fragments is much slower than the time required for the complete cleavage of the solid. These points motivated the measurements of dissolution kinetics using optical microscopy and image processing. A comparison of the measured kinetics with the diffusion kinetics by the mean of the external resistance fraction allows discriminating between measured kinetics corresponding to the chemical reaction or mass-transport limitation. This capability to measure, for the very first time, the 'true' chemical kinetics of the reaction has enabled the confirmation of the highly autocatalytic nature of the reaction, and first evaluation of the constants of the chemical reactions kinetic laws. These data are fundamental to set the kinetic parameters of the chemical reactions in a future model of the dissolution of uranium dioxide sintered pellets. (authors)

Dissolution of covalent adaptable network polymers in organic solvent

Science.gov (United States)

Yu, Kai; Yang, Hua; Dao, Binh H.; Shi, Qian; Yakacki, Christopher M.

2017-12-01

It was recently reported that thermosetting polymers can be fully dissolved in a proper organic solvent utilizing a bond-exchange reaction (BER), where small molecules diffuse into the polymer, break the long polymer chains into short segments, and eventually dissolve the network when sufficient solvent is provided. The solvent-assisted dissolution approach was applied to fully recycle thermosets and their fiber composites. This paper presents the first multi-scale modeling framework to predict the dissolution kinetics and mechanics of thermosets in organic solvent. The model connects the micro-scale network dynamics with macro-scale material properties: in the micro-scale, a model is developed based on the kinetics of BERs to describe the cleavage rate of polymer chains and evolution of chain segment length during the dissolution. The micro-scale model is then fed into a continuum-level model with considerations of the transportation of solvent molecules and chain segments in the system. The model shows good prediction on conversion rate of functional groups, degradation of network mechanical properties, and dissolution rate of thermosets during the dissolution. It identifies the underlying kinetic factors governing the dissolution process, and reveals the influence of different material and processing variables on the dissolution process, such as time, temperature, catalyst concentration, and chain length between cross-links.

Na-rich feldspar as a luminescence dosimeter in infrared stimulated luminescence (IRSL) dating

DEFF Research Database (Denmark)

Sohbati, Reza; Murray, Andrew; Jain, Mayank

2013-01-01

on geological origin and erosion history, but the dosimetry of K-rich feldspar grains extracted from rocks is complicated because the internal dose rate is very dependent on the original feldspar grain size. The in situ grain size information is lost during the crushing process used to separate the grains...... settings for which independent age control is available. The blue and yellow luminescence emissions are measured for IR stimulation at 50 °C (IR50), and post-IR IR stimulation at 290 °C (pIRIR290). Thermal stability experiments imply that the corresponding signals in both emissions have comparable thermal...... stabilities and that all signals have similar recombination kinetics and are thermally stable over geological timescales. The IR50 doses measured using blue and yellow emissions are similar to or lower than quartz doses while pIRIR290 blue doses are higher than those from yellow emission and quartz doses...

Uranium carbide dissolution in nitric solution: Sonication vs. silent conditions

International Nuclear Information System (INIS)

Virot, Matthieu; Szenknect, Stéphanie; Chave, Tony; Dacheux, Nicolas; Moisy, Philippe; Nikitenko, Sergey I.

2013-01-01

The dissolution of uranium carbide (UC) in nitric acid media is considered by means of power ultrasound (sonication) or magnetic stirring. The induction period required to initiate UC dissolution was found to be dramatically shortened when sonicating a 3 M nitric solution (Ar, 20 kHz, 18 W cm −2 , 20 °C). At higher acidity, magnetic stirring offers faster dissolution kinetics compared to sonication. Ultrasound-assisted UC dissolution is found to be passivated after ∼60% dissolution and remains incomplete whatever the acidity which is confirmed by ICP–AES, LECO and SEM–EDX analyses. In general, the kinetics of UC dissolution is linked to the in situ generation of nitrous acid in agreement with the general mechanism of UC dissolution; the nitrous acid formation is reported to be faster under ultrasound at low acidity due to the nitric acid sonolysis. The carbon balance shared between the gaseous, liquid, and solid phases is strongly influenced by the applied dissolution procedure and HNO 3 concentration

Uranium carbide dissolution in nitric solution: Sonication vs. silent conditions

Science.gov (United States)

Virot, Matthieu; Szenknect, Stéphanie; Chave, Tony; Dacheux, Nicolas; Moisy, Philippe; Nikitenko, Sergey I.

2013-10-01

The dissolution of uranium carbide (UC) in nitric acid media is considered by means of power ultrasound (sonication) or magnetic stirring. The induction period required to initiate UC dissolution was found to be dramatically shortened when sonicating a 3 M nitric solution (Ar, 20 kHz, 18 W cm-2, 20 °C). At higher acidity, magnetic stirring offers faster dissolution kinetics compared to sonication. Ultrasound-assisted UC dissolution is found to be passivated after ∼60% dissolution and remains incomplete whatever the acidity which is confirmed by ICP-AES, LECO and SEM-EDX analyses. In general, the kinetics of UC dissolution is linked to the in situ generation of nitrous acid in agreement with the general mechanism of UC dissolution; the nitrous acid formation is reported to be faster under ultrasound at low acidity due to the nitric acid sonolysis. The carbon balance shared between the gaseous, liquid, and solid phases is strongly influenced by the applied dissolution procedure and HNO3 concentration.

CALCIUM CARBONATE DISSOLUTION RATE IN LIMESTONE CONTACTORS

Science.gov (United States)

The rate of carbonate mineral dissolution from limestone was studied using a rotating disk apparatus and samples of limestone of varied composition. The purpose of this study was to determine the effect of limestone composition on the kinetics of carbonate mineral dissolution. Th...

Organic ligand-induced dissolution kinetics of antimony trioxide

Institute of Scientific and Technical Information of China (English)

Xingyun Hu; Mengchang He

2017-01-01

The influence of low-molecular-weight dissolved organic matter (LMWDOM) on the dissolution rate of Sb2O3 was investigated.Some representative LMWDOMs with carboxyl,hydroxyl,hydrosulfuryl and amidogen groups occurring naturally in the solution were chosen,namely oxalic acid,citric acid,tartaric acid,EDTA,salicylic acid,phthalandione,glycine,thiolactic acid,xylitol,glucose and catechol.These LMWDOMs were dissolved in inert buffers at pH =3.7,6.6 and 8.6 and added to powdered Sb2O3 in a stirred,thermostatted reactor (25℃).The addition of EDTA,tartaric acid,thiolactic acid,citric acid and oxalic acid solutions at pH 3.7 and catechol at pH 8.6 increased the rate of release of antimony.In the 10 mmol/L thiolactic acid solution,up to 97％ by mass of the antimony was released after 120 min reaction.There was no effect on the dissolution of Sb2O3 for the other ligands.A weak correlation between dissolution rate with the dissociation constant of ligands and the stability of the dissolved complex was also found.All the results showed that the extent of the promoting effect of ligands on the dissolution of Sb2O3 was not determined by the stability of the dissolved complex,but by the dissociation constant of ligands and detachment rate of surface chelates from the mineral surface.This study can not only help in further understanding the effect of individual low-molecular-weight organic ligands,but also provides a reference to deduce the effect of natural organic matters with oxygen-bearing functional groups on the dissolution of antimony oxide minerals.

Kinetics of the isothermal decomposition of zirconium hydride: terminal solid solubility for precipitation and dissolution

Science.gov (United States)

Denisov, E. A.; Kompaniets, T. N.; Voyt, A. P.

2018-05-01

The hydrogen permeation technique in the surface-limited regime (SLR) was first used to study the isothermal decomposition of zirconium hydride. It is shown that under isothermal conditions, the hydrogen terminal solid solubility in the α-phase for hydride precipitation (TSSp) and dissolution (TSSd) differ only by 6%, in contrast to the 20-30% indicated in the available literature. It is demonstrated that even the minimum heating/cooling rate (1 C/min) used in the traditional methods of studying TSSp and TSSd is too high to exclude the effect of kinetics on the results obtained.

Long-term flow/chemistry feedback in a porous medium with heterogenous permeability: Kinetic control of dissolution and precipitation

International Nuclear Information System (INIS)

Bolton, E.W.; Lasaga, A.C.; Rye, D.M.

1999-01-01

The kinetics of dissolution and precipitation is of central importance to understanding the long-term evolution of fluid flows in crustal environments, with implications for problems as diverse as nuclear waste disposal and crustal evolution. The authors examine the dynamics of such evolution for several geologically relevant permeability distributions (models for en-echelon cracks, an isolated sloping fractured zone, and two sloping high-permeability zones that are close enough together to interact). Although the focus is on a simple quartz matrix system, generic features emerge from this study that can aid in the broader goal of understanding the long-term feedback between flow and chemistry, where dissolution and precipitation is under kinetic control. Examples of thermal convection in a porous medium with spatially variable permeability reveal features of central importance to water-rock interaction. After a transient phase, an accelerated rate of change of porosity may be used with care to decrease computational time, as an alternative to the quasi-stationary state approximation (Lichtner, 1988). Kinetic effects produce features not expected by traditional assumptions made on the basis of equilibrium, for example, that cooling fluids are oversaturated and heating fluids are undersaturated with respect to silicic acid equilibrium. Indeed, the authors observe regions of downwelling oversaturated fluid experiencing heating and regions of upwelling, yet cooling, undersaturated fluid. When oscillatory convection is present, the amplitudes of oscillation generally increase with time in near-surface environments, whereas amplitudes tend to decrease over long times near the heated lower boundary. The authors examine the scaling behavior of characteristic length scales, of terms in the solute equation, and of the typical deviation from equilibrium, each as a function of the kinetic rate parameters

Can cathodoluminescence of feldspar be used as provenance indicator?

Science.gov (United States)

Scholonek, Christiane; Augustsson, Carita

2016-05-01

We have studied feldspar from crystalline rocks for its textural and spectral cathodoluminescence (CL) characteristics with the aim to reveal their provenance potential. We analyzed ca. 60 rock samples of plutonic, volcanic, metamorphic, and pegmatitic origin from different continents and of 16 Ma to 2 Ga age for their feldspar CL textures and ca. 1200 feldspar crystals from these rocks for their CL color spectra. Among the analyzed rocks, igneous feldspar is most commonly zoned, whereby oscillatory zoning can be confirmed to be typical for volcanic plagioclase. The volcanic plagioclase also less commonly contains twin lamellae that are visible in CL light than crystals from other rock types. Alkali feldspar, particularly from igneous and pegmatitic rocks, was noted to be most affected by alteration features, visible as dark spots, lines and irregular areas. The size of all textural features of up to ca. 150 μm, in combination with possible alteration in both the source area and the sedimentary system, makes the CL textures of feldspar possible to use for qualitative provenance research only. We observed alkali feldspar mostly to luminesce in a bluish color and sometimes in red, and plagioclase in green to yellow. The corresponding CL spectra are dominated by three apparent intensity peaks at 440-520 nm (mainly blue), 540-620 nm (mainly green) and 680-740 nm (red to infrared). A dominance of the peak in the green wavelength interval over the blue one for plagioclase makes CL particularly useful for the differentiation of plagioclase from alkali feldspar. An apparent peak position in red to infrared at < 710 nm for plagioclase mainly is present in mafic rocks. Present-day coastal sand from Peru containing feldspar with the red to infrared peak position mainly exceeding 725 nm for northern Peruvian sand and a larger variety for sand from southern Peru illustrates a discriminative effect of different source areas. We conclude that the provenance application

Organic ligand-induced dissolution kinetics of antimony trioxide.

Science.gov (United States)

Hu, Xingyun; He, Mengchang

2017-06-01

The influence of low-molecular-weight dissolved organic matter (LMWDOM) on the dissolution rate of Sb 2 O 3 was investigated. Some representative LMWDOMs with carboxyl, hydroxyl, hydrosulfuryl and amidogen groups occurring naturally in the solution were chosen, namely oxalic acid, citric acid, tartaric acid, EDTA, salicylic acid, phthalandione, glycine, thiolactic acid, xylitol, glucose and catechol. These LMWDOMs were dissolved in inert buffers at pH=3.7, 6.6 and 8.6 and added to powdered Sb 2 O 3 in a stirred, thermostatted reactor (25°C). The addition of EDTA, tartaric acid, thiolactic acid, citric acid and oxalic acid solutions at pH3.7 and catechol at pH8.6 increased the rate of release of antimony. In the 10mmol/L thiolactic acid solution, up to 97% by mass of the antimony was released after 120min reaction. There was no effect on the dissolution of Sb 2 O 3 for the other ligands. A weak correlation between dissolution rate with the dissociation constant of ligands and the stability of the dissolved complex was also found. All the results showed that the extent of the promoting effect of ligands on the dissolution of Sb 2 O 3 was not determined by the stability of the dissolved complex, but by the dissociation constant of ligands and detachment rate of surface chelates from the mineral surface. This study can not only help in further understanding the effect of individual low-molecular-weight organic ligands, but also provides a reference to deduce the effect of natural organic matters with oxygen-bearing functional groups on the dissolution of antimony oxide minerals. Copyright © 2016. Published by Elsevier B.V.

Study of the kinetics and mechanism of the dissolution of PUO2 by Cr(II) ion in acidic medium

International Nuclear Information System (INIS)

Machuron-Mandard, X.

1991-11-01

The study of the dissolution of actinides oxides is a topic of particular importance in nuclear energy production. The present study deals with the understanding of the reductive dissolution of PuO 2 in sulfuric acid media under the action of Cr 2+ aq ion. In the first chapter of the document, crystallographic and electronic properties of PuO 2 are described, followed by informations related to its dissolution in acidic media. The second chapter concerns the presentation of the different theories usable to interpret the kinetics of heterogeneous reaction and those for the understanding of electronic transfer applied to semi-conductors. With the help of the above mathematical tools an empirical law rate is established and a reactional model proposed. It appears that the electronic transfer is purely of the heterogenous nature and that the limiting step of the overall process corresponds certainly to the rupture of plutonium oxygen bond [fr

Kinetics of hydrogen release from dissolutions of ammonia borane in different ionic liquids

International Nuclear Information System (INIS)

Valero-Pedraza, María José; Martín-Cortés, Alexandra; Navarrete, Alexander; Bermejo, María Dolores; Martín, Ángel

2015-01-01

Ammonia borane is a promising hydrogen storage material that liberates hydrogen by thermolysis at moderate temperatures, but it also presents major limitations for practical applications including a long induction time before the initiation of hydrogen release and a difficult regeneration. Previous works have demonstrated that by dissolution of ammonia borane into several ionic liquids, and particularly in 1-butyl-3-methylimidazolium chloride bmimCl, the induction period at the beginning of the thermolysis is eliminated, but some problems persist, including foaming and the formation of a residue after thermolysis that is insoluble in the ionic liquid. In this work, the release of hydrogen from ammonia borane dissolved in different ionic liquids has been analyzed, measuring the kinetics of hydrogen release, visually following the evolution of the sample during the process using pressure glass tube reactors, and analyzing the residue by spectroscopic techniques. While dissolutions of ammonia borane in most ionic liquids analyzed show similar properties as dissolutions in bmimCl, using ionic liquids with bis(trifluoromethylsulfanyl)imide Tf_2N anion the foaming problem is reduced, and in some cases the residue remains dissolved in the ionic liquid, while with ionic liquids with choline anion higher hydrogen yields are achieved that indicate that the decomposition of ammonia borane proceeds through a different path. - Highlights: • Hydrogen release from ammonia borane dissolved in 13 ionic liquids has been studied. • Induction time is shortened and hydrogen release rate is accelerated in all cases. • The best results are obtained using ionic liquids with Tf_2N anion. • Ch cation ionic liquids enable higher H_2 yield, but cyclotriborazane is produced.

Lead-isotope inhomogeneity in Precambrian igneous K-feldspars

International Nuclear Information System (INIS)

Ludwig, K.R.; Silver, L.T.

1977-01-01

Stepwise PB-removal experiments, using both vacuum volatilization and HF-leaching techniques, on acid-washed K-feldspar concentrates from Precambrian igneous rocks show that all contain some unsupported radiogenic Pb. Two types of radiogenic Pb were recognised. One has a 'normal' isotopic composition, with relative abundances of 206 Pb, 207 Pb and 208 Pb consistent with the age and U-Th contents of the rocks. The other type of unsupported radiogenic lead in the feldspars is apparently pure 206 Pb, derived from long-term migration and accumulation of radioactive daughter(s) of 238 U. This 'pure' 206 Pb lead occupies different sites from the 'normal' radiogenic lead, and tends to show a release maximum during vacuum volatilization at about 1150 0 C. The usefulness of stepwise vacuum volatilization may be limited by the tendency of a small amount of radiogenic lead to concentrate in the least volatile fraction. Stepwise partial HF attacks appear to give at least as good separation of radiogenic from original feldspar lead, and are recommended as a routine procedure for isotopic analyses of Precambrian feldspars. The fact that most of the five K-feldspars examined contained unsupported radiogenic lead implies that caution must be used in applying total-sample lead analyses of Precambrian feldspars to problems of lead-isotope evolution in crustal rocks. (author)

UO2 dissolution rates: A review

International Nuclear Information System (INIS)

McKenzie, W.F.

1992-09-01

This report reviews literature data on UO 2 dissolution kinetics and provides a framework for guiding future experimental studies as well as theoretical modeling studies. Under oxidizing conditions, UO 2 dissolution involves formation of an oxidized surface layer which is then dissolved by formation of aqueous complexes. Higher oxygen pressures or other oxidants are required at higher temperatures to have dissolution rates independent of oxygen pressure. At high oxygen pressures (1-5 atm, 25-70 C), the dissolution rate has a one-half order dependence on oxygen pressure, whereas at oxygen pressures below 0.2 atm, Grandstaff (1976), but nobody else, observed a first-order dependence on dissolution rate. Most people found a first-order dependence on carbonate concentration; Posey-Dowty (1987) found independence of carbonate at pH 7 to 8.2. Dissolution rates increase with temperature except in experiments involving granitic groundwater. Dissolution rates were generally greater under acid or basic conditions than near neutral pH

Kinetics of Ni3S2 sulfide dissolution in solutions of sulfuric and hydrochloric acids

Science.gov (United States)

Palant, A. A.; Bryukvin, V. A.; Vinetskaya, T. N.; Makarenkova, T. A.

2008-02-01

The kinetics of Ni3S2 sulfide (heazlewoodite) dissolution in solutions of hydrochloric and sulfuric acids is studied. The process under study in the temperature range of 30 90°C is found to occur in a kinetic regime and is controlled by the corresponding chemical reactions of the Ni3S2 decomposition by solutions of inorganic acids ( E a = 67 92 kJ/mol, or 16 22 kcal/mol). The only exception is the Ni3S2-HCl system at elevated temperatures (60 90°C). In this case, the apparent activation energy decreases sharply to 8.8 kJ/mol (2.1 kcal/mol), which is explained by the catalytic effect of gaseous chlorine formed under these conditions. The studies performed are related to the physicochemical substantiation of the hydrometallurgical processing of the copper-nickel converter mattes produced in the industrial cycle of the Norilsk Mining Company.

The dissolution of chalcopyrite in chloride media

International Nuclear Information System (INIS)

Ibanez, T.; Velasquez, L.

2013-01-01

The aim of this investigation is to determinate the effects of parameters and additives on the kinetics of dissolution of chalcopyrite on moderated conditions by means of dissolutions test with chalcopyrite concentrate and pure chalcopyrite in shake flasks and instrumented stirred reactors. A study of the dissolution of chalcopyrite in chloride solutions has demonstrated that the rate of dissolution of chalcopyrite is strongly dependent on the potential of the solution within a range of 540 to 630 mV (versus SHE). Leaching at pH around 2.5 results in increased rates of copper dissolution suggesting the possibility to keep the solution potential within the range. Both pyrite and silver ions enhance the dissolution of chalcopyrite and this effect increases when both species are present. The MnO 2 has a negative effect on the dissolution increasing the solution potential to values where the rate decreases considerably. (Author)

Modelling of the UO2 dissolution mechanisms in synthetic groundwater solutions. Dissolution experiments carried out under oxic conditions

International Nuclear Information System (INIS)

Cera, E.; Grive, M.; Bruno, J.; Ollila, K.

2001-02-01

The analytical data generated during the last three years within the 4th framework program of the European Community at VTT Chemical Technology concerning UO 2 dissolution under oxidising conditions have been modelled in the present work. The modelling work has been addressed to perform a kinetic study of the dissolution data generated by Ollila (1999) under oxidising conditions by using unirradiated uranium dioxide as solid sample. The average of the normalised UO 2 dissolution rates determined by using the initial dissolution data generated in all the experimental tests is (6.06 ± 3.64)* 10 -7 mol m -2 d -1 . This dissolution rate agrees with most of the dissolution rates reported in the literature under similar experimental conditions. The results obtained in this modelling exercise show that the same bicarbonate promoted oxidative dissolution processes operate for uranium dioxide, as a chemical analogue of the spent fuel matrix, independently of the composition of the aqueous solution used. (orig.)

Hydrothermal alteration of deep fractured granite: Effects of dissolution and precipitation

Science.gov (United States)

Nishimoto, Shoji; Yoshida, Hidekazu

2010-03-01

This paper investigates the mineralogical effects of hydrothermal alteration at depth in fractures in granite. A fracture accompanied by an alteration halo and filled with clay was found at a depth of 200 m in a drill core through Toki granite, Gifu, central Japan. Microscopic observation, XRD, XRF, EPMA and SXAM investigations revealed that the microcrystalline clays consist of illite, quartz and pyrite and that the halo round the fracture can be subdivided into a phyllic zone adjacent to the fracture, surrounded by a propylitic zone in which Fe-phyllosilicates are present, and a distinctive outer alteration front characterized by plagioclase breakdown. The processes that result in these changes took place in three successive stages: 1) partial dissolution of plagioclase with partial chloritization of biotite; 2) biotite dissolution and precipitation of Fe-phyllosilicate in the dissolution pores; 3) dissolution of K-feldspar and Fe-phyllosilicate, and illite precipitation associated with development of microcracks. These hydrothermal alterations of the granite proceed mainly by a dissolution-precipitation process resulting from the infiltration of hydrothermal fluid along microcracks. Such infiltration causes locally high mobility of Al and increases the ratio of fluid to rock in the alteration halo. These results contribute to an understanding of how granitic rock becomes altered in orogenic fields such as the Japanese island arc.

Surface properties, solubility and dissolution kinetics of bamboo phytoliths

Science.gov (United States)

Fraysse, Fabrice; Pokrovsky, Oleg S.; Schott, Jacques; Meunier, Jean-Dominique

2006-04-01

Although phytoliths, constituted mainly by micrometric opal, exhibit an important control on silicon cycle in superficial continental environments, their thermodynamic properties and reactivity in aqueous solution are still poorly known. In this work, we determined the solubility and dissolution rates of bamboo phytoliths collected in the Réunion Island and characterized their surface properties via electrophoretic measurements and potentiometric titrations in a wide range of pH. The solubility product of "soil" phytoliths ( pKsp0=2.74 at 25 °C) is equal to that of vitreous silica and is 17 times higher than that of quartz. Similarly, the enthalpy of phytoliths dissolution reaction (ΔHr25-80°C=10.85kJ/mol) is close to that of amorphous silica but is significantly lower than the enthalpy of quartz dissolution. Electrophoretic measurements yield isoelectric point pH IEP = 1.2 ± 0.1 and 2.5 ± 0.2 for "soil" (native) and "heated" (450 °C heating to remove organic matter) phytoliths, respectively. Surface acid-base titrations allowed generation of a 2-p K surface complexation model. Phytoliths dissolution rates, measured in mixed-flow reactors at far from equilibrium conditions at 2 ⩽ pH ⩽ 12, were found to be intermediate between those of quartz and vitreous silica. The dissolution rate dependence on pH was modeled within the concept of surface coordination theory using the equation: R=k1·{>SiOH2+}n+k2·{>SiOH0}+k3·{>SiO-}m, where {> i} stands for the concentration of the surface species present at the SiO 2-H 2O interface, ki are the rate constants of the three parallel reactions and n and m represent the order of the proton- and hydroxy-promoted reactions, respectively. It follows from the results of this study that phytoliths dissolution rates exhibit a minimum at pH ˜ 3. This can explain their good preservation in the acidic soil horizons of Réunion Island. In terms of silicon biogeochemical cycle, phytoliths represent a large buffering reservoir

Kiglapait Feldspar States 5 to Review

Science.gov (United States)

Morse, S. A.

2017-12-01

The 1305 Ga Kiglapait Intrusion of coastal Labrador records the crystallization of troctolite through olivine gabbro to magnetite- and apatite-bearing rocks to monoclinic sanidine- mesoperthite-ferrosyenite below an inverted stratigraphy of a thin Upper Border Zone. The crystallization history was about 1 Ma. ¶The evolutionary history of Kiglapait feldspars in an 8.4 km thick magma chamber runs from plagioclase An70 at 5 kbar and 1250°C, cooling through to ferrosyenite with mesoperthite and two feldspars at 3 kbar and 1,000°C. The residual magma encountered the binodal solvus and finished crystallizing as an azeotrope with plagioclase (Or 21, An 15) and sanidine (Or 52, An 8) in liquid (Xor = 1/3; An 11). Cooling in the subsolidus brought the feldspars to compositions An15-Or 3, An0-Or 80-85 at 800-730°C. Metastable mesoperthite on the coherent solvus in various stages of late equilibration persists in the local assemblages. Arrested to complete feldspar symplectites suggest the local presence of a vapor phase. ¶Splits of the final Or-rich feldspar were found by mass spectrometry to have a dominant quantity of Rb and 87Sr/86Sr along with % amounts of Ba; in contrast, the plag fraction has very low Rb and 87Sr/86Sr. The estimated timing of the isotopic segregation was plausibly continuous with major-element fractionation or perhaps at the moment(s) of exsolution. ¶The cooling record of the solidified intrusion at 3 kbar is shown by 40Ar/39Ar data to have been rapid, reaching an ambient temperature near 240°C within the first 20 Ma, compared to the ambient country-rock temperature before intrusion of 350°C. The difference suggests a late uplift of the region after the Kiglapait magmatism. ¶Contributions from Y. Yu, T. Krogh, M. Hamilton, D. Lindsley, D. DePaolo, M. Jercinovic and S.R. Hart are especially acknowledged.

Thermo-optical properties of optically stimulated luminescence in feldspars

DEFF Research Database (Denmark)

Poolton, N.R.J.; Bøtter-Jensen, L.; Johnsen, O.

1995-01-01

Optically stimulated luminescence processes in feldspars are subject to competing thermal enhancement and quenching processes: this article describes the thermal enhancement effects for orthoclase, albite and plagioclase feldspars. It is demonstrated that certain lattice vibrational modes can be ...

Application of Cathodoluminescence to The Study of Feldspars: Imaging and Spectrometry

Science.gov (United States)

Fonseca, Rute; Couto, Helena

2017-12-01

Cathodoluminescence (CL) studies were carried out on polished thin sections of different feldspar samples (from migmatites, granites, aplite-pegmatites and granitic aggregates) using a hot cathode CL equipment HC3-LM coupled to an optical microscope and to a spectrometer (SpectraPro 2300i and a CCD Pixis 400B detector and the software Winspec32) from the Faculty of Sciences of University of Porto. The system was operated at 14kV and a filament current of 0.18 mA. The samples were coated with a thin gold film using a Cressington 108 Auto device. Luminescence images were acquired during the CL analysis with an adapted digital video-camera (KAPPA PS 40C-285 (DX) with dual stage Peltier cooling) and an acquisition time between 351ms and 3,52s. The CL study, including imaging and spectrometry, proved to be an important tool to complement the feldspar petrography as it contributes to the identification of features not observed under optical microscope. The application of the Cathodoluminescence to feldspar allows distinguishing between potassic feldspar and plagioclase, differentiating generations of feldspar and displaying internal zoning and growth areas, among other. The spectrometry complements the CL imaging. It allows obtaining a qualitative level of emission intensity, which permits the interpretation of the nature of this luminescence in each feldspar. Bands shown in the spectra are related to the existing activator elements. In the present study, it was found an association of each feldspar to different spectra and respective colour. The plagioclases exhibit yellow or green luminescence. The activator element is Mn2+, showing a broad emission band between 550 - 570 nm specially detected on this type of feldspars, due to the replacement of K+ for Mn2+. The potassium feldspars have more or less intense blue colour associated with various activators elements: the activator element is Cu2+ showing a broad emission band between 420±5 nm. This emission band can be

[Study on the fine structure of K-feldspar of Qichun granite].

Science.gov (United States)

Du, Deng-Wen; Hong, Han-Lie; Fan, Kan; Wang, Chao-Wen; Yin, Ke

2013-03-01

Fine structure of K-feldspar from the Qichun granite was investigated using X-ray diffraction (XRD), Fourier infrared absorption spectroscopy (FTIR), and inductively coupled plasma mass spectrometry methods to understand the evolution of the granitic magmatism and its correlation to molybdenite mineralization. The XRD results showed that K-feldspar of the potassic alteration veins has higher ordering index and triclinicity and is namely microcline with triclinic symmetry. K-feldspar of the early cretaceous granite has relatively lower ordering index and has widening [131] peak and is locally triclinic ordering. K-feldspar of the late cretaceous granite has lowest ordering index and sharp [131] peak and is honiogeneously monoclinic. The FTIR results showed that the IR spectra of the Qichun K-feldspar are similar to that of orthoclase reported by Farmer (1974). The 640 cm-1 absorption band increases while the 540 cm-' absorption band decreases with increase in K-feldspar ordering index, also, the 1,010 cm-1 absorption band separates into 1,010 and 1,046 cm-1 absorption bands, with a change in the band shape from widening to sharp outline. The ICP-MS results suggested that K-feldspar of the early cretaceous granite has relatively higher metal elements and rare earth elements, and the granite exhibits better mineralization background, K-feldspar of the potassic alteration veins has markedly lower Sr and Ba, indicating that the alteration fluid originated from the granitic magmatism, and hence, potassic alteration is a good indicator for molybdenite exploration.

Thermodynamic and Kinetic Aspects of the Dissolution of Quartz-Kaolinite Mixtures by Alkalis Aspects thermodynamiques et cinétiques de la dissolution des mélanges quartz-kaolinite par les alcalis

Directory of Open Access Journals (Sweden)

Labrid J.

2006-11-01

Full Text Available Mineral-alkali interactions have received considerable attention in the recent literature dealing with enhanced oil recovery techniques and clay stabilization treatments. One of the critical factors to be considered is alkali consumption. Alkalinity decrease occurs through several mechanisms, which are ion exchange, precipitation, reaction with crude oil components, and dissolution of minerals. This paper describes the dissolution process. An original kinetic model is proposed to describe the alkaline dissolution of a clayey sandstone. This model is based first on results concerning quartz dissolution/condensation processes. It is also based on new experimental data, which demonstrate the inhibiting effect of aluminum and, as the reaction proceeds, the precipitation of an aluminosilicate whose the chemical composition has been determined. From these data, a kinetic scheme has been conceived in which adsorption of different chemical species is assumed to occur onto solid surfaces. These species play a more or less important role according to the extent of the reaction. In the mechanisms considered, the argillaceous fraction of the rock provides silicon and aluminum which inhibit the dissolution of the matrix while silicon coming from quartz interferes with clay attack. The kinetic model depicts the coupling of elementary dissolution processes and calculates dissolved silicon and aluminum. It has been tested for various operating conditions, providing initial reaction rates for quartz and clay. Results emphasize the definitive advantage of carbonate compared to other alkaline chemicals owing to the relative low pH of solutions, which is particularly favorable for promoting inhibition by aluminum and, as a general rule, for reducing mineral dissolution. Ce résumé contient des formules (*** qui ne peuvent s'afficher à l'écran L'emploi des agents alcalins pour améliorer la récupération du pétrole a été préconisé à l'origine dans le but

investigation of dissolution kinetics of a nigerian columbite

African Journals Online (AJOL)

user

1,2 DEPARTMENT OF CHEMICAL ENGINEERING, OBAFEMI AWOLOWO UNIVERSITY, ILE-IFE, OSUN STATE NIGERIA. E-mail addresses: ... Experimental results indicate that the dissolution rate is chemical reaction ..... Nuclear Instruments.

Simulation study of effects of initial particle size distribution on dissolution

International Nuclear Information System (INIS)

Wang, G.; Xu, D.S.; Ma, N.; Zhou, N.; Payton, E.J.; Yang, R.; Mills, M.J.; Wang, Y.

2009-01-01

Dissolution kinetics of γ' particles in binary Ni-Al alloys with different initial particle size distributions (PSD) is studied using a three-dimensional (3D) quantitative phase field model. By linking model inputs directly to thermodynamic and atomic mobility databases, microstructural evolution during dissolution is simulated in real time and length scales. The model is first validated against analytical solution for dissolution of a single γ' particle in 1D and numerical solution in 3D before it is applied to investigate the effects of initial PSD on dissolution kinetics. Four different types of PSD, uniform, normal, log-normal and bimodal, are considered. The simulation results show that the volume fraction of γ' particles decreases exponentially with time, while the temporal evolution of average particle size depends strongly on the initial PSD

Influence of a microwave radiation on dissolution kinetics of UO2, CeO2, and Co3O4 in nitric environment

International Nuclear Information System (INIS)

Joret, Laurent

1995-01-01

This research thesis addresses the issue of dissolution oxides present in spent nuclear fuels. As previous studies outlined important increases of oxide dissolution rate when submitted to microwaves, the issue is then to apply such a technique to PuO 2 which is the most difficult oxide to dissolve. As plutonium may be handled only in certified laboratories and under strict safety conditions, the author studied the influence of a microwave radiation on the dissolution kinetics of other and various metallic oxides in a nitric environment. The choice of this nitric environment is imposed by conditions met in the nuclear industry. Oxides are chosen according to two criteria: dissolution times ranging from few minutes to few days, various responses to electromagnetic radiation (different values for the real and imaginary parts of their dielectric permittivity). Three oxides are retained: UO 2 and CeO 2 (to model PuO 2 ) and Co 3 O 4 . After a recall of some theoretical aspects of the response of a dielectric material to an electromagnetic field, a comparison between conventional and microwave heating, the author presents the main results obtained by using microwaves in chemistry (organic synthesis, ceramic sintering, acid dissolution). He reports the experimental study of nitric dissolution of oxides by conventional heating, and the dielectric characterisation of the studied oxides. He presents the experimental microwave set-up, and reports and discusses experimental results obtained for the dissolution of UO 2 , CeO 2 and Co 3 O 4 in HNO 3 [fr

Reductive reactivity of iron(III) oxides in the east china sea sediments: characterization by selective extraction and kinetic dissolution.

Science.gov (United States)

Chen, Liang-Jin; Zhu, Mao-Xu; Yang, Gui-Peng; Huang, Xiang-Li

2013-01-01

Reactive Fe(III) oxides in gravity-core sediments collected from the East China Sea inner shelf were quantified by using three selective extractions (acidic hydroxylamine, acidic oxalate, bicarbonate-citrate buffered sodium dithionite). Also the reactivity of Fe(III) oxides in the sediments was characterized by kinetic dissolution using ascorbic acid as reductant at pH 3.0 and 7.5 in combination with the reactive continuum model. Three parameters derived from the kinetic method: m 0 (theoretical initial amount of ascorbate-reducible Fe(III) oxides), k' (rate constant) and γ (heterogeneity of reactivity), enable a quantitative characterization of Fe(III) oxide reactivity in a standardized way. Amorphous Fe(III) oxides quantified by acidic hydroxylamine extraction were quickly consumed in the uppermost layer during early diagenesis but were not depleted over the upper 100 cm depth. The total amounts of amorphous and poorly crystalline Fe(III) oxides are highly available for efficient buffering of dissolved sulfide. As indicated by the m 0, k' and γ, the surface sediments always have the maximum content, reactivity and heterogeneity of reactive Fe(III) oxides, while the three parameters simultaneously downcore decrease, much more quickly in the upper layer than at depth. Albeit being within a small range (within one order of magnitude) of the initial rates among sediments at different depths, incongruent dissolution could result in huge discrepancies of the later dissolution rates due to differentiating heterogeneity, which cannot be revealed by selective extraction. A strong linear correlation of the m 0 at pH 3.0 with the dithionite-extractable Fe(III) suggests that the m 0 may represent Fe(III) oxide assemblages spanning amorphous and crystalline Fe(III) oxides. Maximum microbially available Fe(III) predicted by the m 0 at pH 7.5 may include both amorphous and a fraction of other less reactive Fe(III) phases.

Dissolution kinetics of B clusters in crystalline Si

International Nuclear Information System (INIS)

De Salvador, D.; Napolitani, E.; Bisognin, G.; Carnera, A.; Bruno, E.; Mirabella, S.; Impellizzeri, G.; Priolo, F.

2005-01-01

Boron (B) clustering in crystalline Si induced by interaction with Si self-interstitials is a widely studied phenomenon of fundamental importance for Si micro- and nano-electronic technology. The requested B activation increase brings the B concentration to a very high level and a detailed understanding of B clustering at high concentration is demanded. In the present work we present some recent results regarding the B clustering process starting from B concentration both below and above the B solubility limit. We show that B clusters, produced by self-interstitial interaction with substitutional B in crystalline Si, dissolve under annealing according to two distinct paths with very different characteristic times. The two regimes generally coexist, but while the faster dissolution path is predominant for clusters formed at low B concentration (1 x 10 19 B/cm 3 ), the slower one is characteristic of clusters formed above the solubility limit and dominates the dissolution process at high B concentration (2 x 10 2 B/cm 3 ). The activation energies of both processes are characterized and discussed. It is shown that the faster path can be connected to a direct emission of mobile B from small clusters, while the slower path is demonstrated not to be self-interstitial limited and it is probably related to a more complex cluster dissolution process

Dissolution of UO2 in redox conditions

International Nuclear Information System (INIS)

Casas, I.; Pablo de, J.; Rovira, M.

1998-01-01

The performance assessment of the final disposal of the spent nuclear fuel in geological formations is strongly dependent on the spent fuel matrix dissolution. Unirradiated uranium (IV) dioxide has shown to be very useful for such purposes. The stability of UO 2 is very dependent on vault redox conditions. At reducing conditions, which are expected in deep groundwaters, the dissolution of the UO 2 -matrix can be explained in terms of solubility, while under oxidizing conditions, the UO 2 is thermodynamically unstable and the dissolution is kinetically controlled. In this report the parameters which affect the uranium solubility under reducing conditions, basically pH and redox potential are discussed. Under oxidizing conditions, UO 2 dissolution rate equations as a function of pH, carbonate concentration and oxidant concentration are reported. Dissolution experiments performed with spent fuel are also reviewed. The experimental equations presented in this work, have been used to model independent dissolution experiments performed with both unirradiated and irradiated UO 2 . (Author)

Dissolution kinetics of smectite in geological repository system of TRU waste

International Nuclear Information System (INIS)

Sato, Tsutomu

2005-02-01

Extensive use of cement for encapsulation, mine timbering, and grouting purposes is envisaged in geological repositories of TRU waste. Degradation of cement materials in the repositories can produce a high pH pore fluid initially ranging from pH 13.0 to 13.5. The high pH pore fluids can migrate and react chemically with the host rock and bentonites which were employed to enhance repository's integrity. These chemical reactions can effect the capacity of the rocks and bentonites in retarding the migration of radionuclides. Smectite, main component of bentonite, can lose some of their desirable properties at the early stages of bentonite-cement fluid interaction. This has been a key research issue in performance assessment of TRU waste disposal. In this study, firstly, the factors affected on dissolution rate of smectite and equations describing dissolution rate were reviewed. Secondly, the effect of dissolved silica on the dissolution behavior of Na-montmorillonite was investigated. Bulk sample flow-through dissolution experiments at alkaline condition (pH 13.3) with different dissolved silica concentrations at different temperatures were performed. Titration experiments were also carried out at similar conditions. Atomic Force Microscopy (AFM) ex situ observations (i.e. on samples from flow-through experiments) was also performed to obtain the dissolution rate. Current results from bulk sample surface titration experiments indicate that dissolved silica has no pronounced effect on the surface titration behavior of Na-montmorillonite at any temperature. However, the trends for the surface titration behavior represent the averaged behavior of all particle sizes (i.e. including colloids) such that within an order of magnitude change cannot be quantified appreciably. Bulk flow-through dissolution experiments coupled with ex situ AFM observations indicate that there is also no effect of dissolved silica with comparatively low concentration of the reacting solution on

Measurement of the dose in quartz in the presence of feldspar contamination

DEFF Research Database (Denmark)

Wallinga, J.; Murray, A.S.; Bøtter-Jensen, L.

2002-01-01

To allow the determination of the dose in quartz in the presence of feldspar contamination. the quartz-to-feldspar optically stimulated luminescence (OSL) ratio needs to be maximised. Experiments were carried Out to find the optimum procedure to bleach the feldspar by exposure to infrared light...

Experimental investigation of the effects of aqueous species on the dissolution kinetics of R7T7 glass; Etude experimentale de l`influence d`especes aqueuses sur la cinetique de dissolution du verre nucleaire R7T7

Energy Technology Data Exchange (ETDEWEB)

Gin, S

1994-10-01

This contribution to the study of aqueous corrosion of the French ``R7T7`` reference nuclear containment glass includes a bibliographic survey of prior investigations, highlighting the problems encountered in interpreting the interactions in systems containing clay materials in contact with the glass. An experimental methodology is proposed to investigate the effects of inorganic aqueous species separately from those of a few organic acids on the dissolution mechanisms and kinetics of R7T7 glass at 90 deg. C. The experimental results discussed support the idea that several glass network forming elements may have a kinetically limiting role. The most likely hypothesis to account for the absence of saturation conditions with respect to the glass in certain clay media involves the formation of complexes with kinetically limiting metallic elements such as aluminum released by glass corrosion. This work contributes to a better understanding of the basic mechanisms of nuclear glass dissolution in a geological repository environment. It facilitates the interpretation of glass alteration studies in realistic or actual solutions and may contribute to specifying near field chemical barriers in the form of additives (amorphous silica, aluminum hydroxides or phosphates) around the glass disposal package to enhance the stability of the glass matrix. (author). 148 refs., 40 figs., 32 tabs., 1 append.

Developing Effective Separation of Feldspar and Quartz While Recycling Tailwater by HF Pretreatment

Directory of Open Access Journals (Sweden)

Weiqing Wang

2018-04-01

Full Text Available The effect of hydrofluoric acid (HF pretreatment on flotation of feldspar and quartz using dodecylamine (DDA as collector was investigated by micro-flotation, zeta potential, pyrene fluorescence spectroscopy, attenuated total reflection flourier transformed infrared spectroscopy (ATR-FTIR, scanning electron microscope (SEM, X-ray photoelectron spectroscopy (XPS and bench scale flotation. The micro-flotation tests revealed that there was little difference in the flotation of feldspar and quartz at pH 2, using H2SO4 as pH regulator. After HF pretreatment, the floatability of feldspar significantly increased while the floatability of quartz showed no change. HF pretreatment resulted in leaching of SiO2 and enrichment of Na, K and Al on the feldspar surface. Consequently, the negative surface charge of feldspar increased at pH 2, which allowed for the flotation separation of the feasible minerals. This took place via an increased electrostatic adsorption between DDA and Na, K, Al on the feldspar surface, which effectively increased its hydrophobicity and as a result, improved the floatability of feldspar. An alternative process which exhibited effective separation of quartz and feldspar while recycling the tailwater from the flotation was proposed.

Formation of halloysite from feldspar: Low temperature, artificial weathering versus natural weathering

Science.gov (United States)

Parham, Walter E.

1969-01-01

Weathering products formed on surfaces of both potassium and plagioclase feldspar (An70), which were continuously leached in a Soxhlet extraction apparatus for 140 days with 7.21 of distilled water per day at a temperature of approximately 78°C, are morphologically identical to natural products developed on potassium feldspars weathered under conditions of good drainage in the humid tropics. The new products, which first appear as tiny bumps on the feldspar surface, start to develop mainly at exposed edges but also at apparently random sites on flat cleavage surfaces. As weathering continues, the bumps grow outward from the feldspar surface to form tapered projections, which then develop into wide-based thin films or sheets. The thin sheets of many projections merge laterally to form one continuous flame-shaped sheet. The sheets formed on potassium feldspars may then roll to form tubes that are inclined at a high angle to the feldspar surface. Etch pits of triangular outline on the artificially weathered potassium feldspars serve as sites for development of continuous, non-rolled, hollow tubes. It is inferred from its morphology that this weathering product is halloysite or its primitive form. The product of naturally weathered potassium feldspars is halloysite . 4H2O.The flame-shaped films or sheets formed on artificially weathered plagioclase feldspar do not develop into hollow tubes, but instead give rise to a platy mineral that is most probably boehmite. These plates form within the flame-shaped films, and with continued weathering are released as the film deteriorates. There is no indication from this experiment that platy pseudohexagonal kaolinite forms from any of these minerals under the initial stage of weathering.

Comparative evaluation of methods to quantify dissolution of nanomaterials

DEFF Research Database (Denmark)

Hartmann, Nanna B.; Kruse, Susanne; Baun, Anders

2015-01-01

Effects and behaviour of nanomaterials in the environment depends on the materials' specific physical and chemical properties and for certain nanomaterials (e.g., Ag, ZnO and CuO) aqueous solubility is of outmost importance. The solubility of metals salts is normally described as a maximum...... dissolved concentration or by the solubility constant (Ksp). For nanomaterials it is essential to also assess solubility kinetics as nanomaterials will often not dissolve instantaneously upon contact with artificial aqueous media or natural waters. Dissolution kinetics will thereby influence their short...... and long-term environmental fate as well as laboratory test results. This highlights the need to evaluate and improve the reliability of methods applied to assess the solubility kinetics of nanomaterials. Based on existing OECD guidelines and guidance documents on aqueous dissolution of metals and metal...

Assessment of bleaching of K-feldspar grains

International Nuclear Information System (INIS)

Zhang Jiafu; Li Shenghua; Tso, M-Y.W.

2001-01-01

Based on the difference in the bleaching rate between IRSL and TL signals, a new method of assessing the bleaching of sedimentary feldspar is proposed. All measurements for De and the bleaching factor (normalized ratio of IRSL to TL) are carried out on the same grain. K-feldspar grains from two sediments, a marine and an alluvium, from Hong Kong were tested. Their bleaching factors indicate that bleaching of the marine sediment was not uniform, whereas the latter was relatively homogeneous. Furthermore, the relatively well-bleached grains in each sample were identified

Acid-catalyzed kinetics of indium tin oxide etching

Energy Technology Data Exchange (ETDEWEB)

Choi, Jae-Hyeok; Kim, Seong-Oh; Hilton, Diana L. [School of Materials Science and Engineering, Nanyang Technological University, 50 Nanyang Avenue, 639798 (Singapore); Centre for Biomimetic Sensor Science, Nanyang Technological University, 50 Nanyang Drive, 637553 (Singapore); Cho, Nam-Joon, E-mail: njcho@ntu.edu.sg [School of Materials Science and Engineering, Nanyang Technological University, 50 Nanyang Avenue, 639798 (Singapore); Centre for Biomimetic Sensor Science, Nanyang Technological University, 50 Nanyang Drive, 637553 (Singapore); School of Chemical and Biomedical Engineering, Nanyang Technological University, 62 Nanyang Drive, 637459 (Singapore)

2014-08-28

We report the kinetic characterization of indium tin oxide (ITO) film etching by chemical treatment in acidic and basic electrolytes. It was observed that film etching increased under more acidic conditions, whereas basic conditions led to minimal etching on the time scale of the experiments. Quartz crystal microbalance was employed in order to track the reaction kinetics as a function of the concentration of hydrochloric acid and accordingly solution pH. Contact angle measurements and atomic force microscopy experiments determined that acid treatment increases surface hydrophilicity and porosity. X-ray photoelectron spectroscopy experiments identified that film etching is primarily caused by dissolution of indium species. A kinetic model was developed to explain the acid-catalyzed dissolution of ITO surfaces, and showed a logarithmic relationship between the rate of dissolution and the concentration of undisassociated hydrochloric acid molecules. Taken together, the findings presented in this work verify the acid-catalyzed kinetics of ITO film dissolution by chemical treatment, and support that the corresponding chemical reactions should be accounted for in ITO film processing applications. - Highlights: • Acidic conditions promoted indium tin oxide (ITO) film etching via dissolution. • Logarithm of the dissolution rate depended linearly on the solution pH. • Acid treatment increased ITO surface hydrophilicity and porosity. • ITO film etching led to preferential dissolution of indium species over tin species.

Simfuel dissolution studies in granitic groundwater

International Nuclear Information System (INIS)

Casas, I.; Caceci, M.S.; Bruno, J.; Sandino, A.; Ollila, K.

1991-09-01

The dissolution behavior of an unirradiated chemical analogue of spent nuclear fuel (SIMFUEL) has been studied in the presence of two different synthetic groundwater at 25 deg C and under both oxic and anoxic conditions. The release of U, Mo, Ba, Y and Sr was monitored during static (batch) leaching experiments of long duration (about 250 days). Preliminary results from continuous flow-through reactor experiments are also reported. The results obtained indicate the usefulness and limitations of SIMFUEL in the study of the kinetics and mechanism of dissolution of the minor components of spent nuclear fuel. Molybdenum, barium and strontium have shown a trend to congruent dissolution with the SIMFUEL matrix after a higher initial fractional release. Yttrium release has been found to be solubility controlled under the experimental conditions. A clear dependence on the partial pressure of O 2 of the rates of dissolution of uranium has been observed

SIMFUEL dissolution studies in granitic groundwater

International Nuclear Information System (INIS)

Casas, I.; Caceci, M.S.; Bruno, J; Sandino, A.

1991-09-01

The dissolution behavior of an unirradiated chemical analogue of spent nuclear fuel (SIMFUEL) has been studied in the presence of two different synthetic groundwaters at 25 degrees C and under both oxic and anoxic conditions. The release of U, Mo, Ba, Y and Sr was monitored during static (batch) leaching experiments of long duration (about 250 days). Preliminary results from continuous flow-through reactor experiments are also reported. The results obtained indicate the usefulness and limitations of SIMFUEL in the study of the kinetics and mechanism of dissolution of the minor components of spent nuclear fuel. Molybdenum, barium and strontium have shown a trend of congruent dissolution with the SIMFUEL matrix after a higher initial fractional release has been found to be solubility controlled under the experimental conditions. A clear dependence on the partial pressure of O 2 of the rate of dissolution of uranium has been observed. (au)

Effects of alteration product precipitation on glass dissolution

Energy Technology Data Exchange (ETDEWEB)

Strachan, Denis M.; Neeway, James J.

2014-06-01

Understanding the mechanisms that control the durability of nuclear waste glass is paramount if reliable models are to be constructed so that the glass dissolution rate in a given geological repository can be calculated. Presently, it is agreed that (boro)silicate glasses dissolve in water at a rate dependent on the solution concentration of orthosilicic acid (H₄SiO₄) with higher [H₄SiO₄] leading to lower dissolution rates. Once the reaction has slowed as a result of the buildup of H₄SiO₄, another increase in the rate has been observed that corresponds to the precipitation of certain silica-bearing alteration products. However, it has also been observed that the concentration of silica-bearing solution species does not significantly decrease, indicating saturation, while other glass tracer elements concentrations continue to increase, indicating that the glass is still dissolving. In this study, we have used the Geochemist’s Workbench code to investigate the relationship between glass dissolution rates and the precipitation rate of a representative zeolitic silica-bearing alteration product, analcime [Na(AlSi₂O₆)∙H₂O]. To simplify the calculations, we suppressed all alteration products except analcime, gibbsite (Al(OH)₃), and amorphous silica. The pseudo-equilibrium-constant matrix for amorphous silica was substituted for the glass pseudo-equilibrium-constant matrix because it has been shown that silicate glasses act as a silica-only solid with respect to kinetic considerations. In this article, we present the results of our calculations of the glass dissolution rate at different values for the analcime precipitation rate constant and the effects of varying the glass dissolution rate constant at a constant analcime precipitation rate constant. From the simulations we conclude, firstly, that the rate of glass dissolution is dependent on the kinetics of

The Relationship Between the Evolution of an Internal Structure and Drug Dissolution from Controlled-Release Matrix Tablets.

Science.gov (United States)

Kulinowski, Piotr; Hudy, Wiktor; Mendyk, Aleksander; Juszczyk, Ewelina; Węglarz, Władysław P; Jachowicz, Renata; Dorożyński, Przemysław

2016-06-01

In the last decade, imaging has been introduced as a supplementary method to the dissolution tests, but a direct relationship of dissolution and imaging data has been almost completely overlooked. The purpose of this study was to assess the feasibility of relating magnetic resonance imaging (MRI) and dissolution data to elucidate dissolution profile features (i.e., kinetics, kinetics changes, and variability). Commercial, hydroxypropylmethyl cellulose-based quetiapine fumarate controlled-release matrix tablets were studied using the following two methods: (i) MRI inside the USP4 apparatus with subsequent machine learning-based image segmentation and (ii) dissolution testing with piecewise dissolution modeling. Obtained data were analyzed together using statistical data processing methods, including multiple linear regression. As a result, in this case, zeroth order release was found to be a consequence of internal structure evolution (interplay between region's areas-e.g., linear relationship between interface and core), which eventually resulted in core disappearance. Dry core disappearance had an impact on (i) changes in dissolution kinetics (from zeroth order to nonlinear) and (ii) an increase in variability of drug dissolution results. It can be concluded that it is feasible to parameterize changes in micro/meso morphology of hydrated, controlled release, swellable matrices using MRI to establish a causal relationship between the changes in morphology and drug dissolution. Presented results open new perspectives in practical application of combined MRI/dissolution to controlled-release drug products.

On-line monitoring of lithium carbonate dissolution

Energy Technology Data Exchange (ETDEWEB)

Sun, Yuzhu; Song, Xingfu; Wang, Jin; Luo, Yan; Yu, Jianguo [National Engineering Research Center for Integrated Utilization Salt Lake Resources, East China University of Science and Technology, Shanghai (China)

2009-11-15

Dissolution of lithium carbonate (Li{sub 2}CO{sub 3}) in aqueous solution was investigated using three on-line apparatuses: the concentration of Li{sub 2}CO{sub 3} was measured by electrical conductivity equipment; CLD (Chord Length Distribution) was monitored by FBRM (Focused Beam Reflectance Measurement); crystal image was observed by PVM (Particle Video Microscope). Results show dissolution rate goes up with a decrease of particle size, and with an increase in temperature; stirring speed causes little impact on dissolution; ultrasound facilitates dissolution obviously. The CLD evolution and crystal images of Li{sub 2}CO{sub 3}powders in stirred fluid were observed detailedly by FBRM and PVM during dissolution. Experimental data were fitted to Avrami model, through which the activation energy was found to be 34.35 kJ/mol. PBE (Population Balance Equation) and moment transform were introduced to calculate dissolution kinetics, obtaining correlation equations of particle size decreasing rate as a function of temperature and undersaturation. (copyright 2009 WILEY-VCH Verlag GmbH and Co. KGaA, Weinheim) (orig.)

A kinetic model of the oxidative dissolution of brannerite, UTi2O6

International Nuclear Information System (INIS)

Thomas, B.S.; Zhang, Y.

2003-01-01

The aqueous dissolution of synthetic brannerite (UTi 2 O 6 ) in an open atmosphere has been investigated. Previous data in the literature have been combined with new experimental work, dealing with the release of uranium from brannerite as a function of solution pH and aqueous carbonate species, in oxygenated solutions. From these data we have developed a conceptual model for uranium release from brannerite consisting of two reaction steps: oxidation of surface uranium(IV) atoms, and subsequent detachment of U(VI) atoms into solution, which is catalysed by surface coordination with protons (acidic media) or carbonate species (alkaline media in equilibrium with the atmosphere). A kinetic rate law is derived for this simple reaction mechanism and fitted to experimental data. The resulting predictive equation for uranium release qualitatively describes the pH-dependent behaviour observed in experiment, and quantitatively gives an upper limit for uranium release from brannerite over a range of conditions and experiment types. (orig.)

Kinetics of dissolution of magnetite in PDCA based formulations

Energy Technology Data Exchange (ETDEWEB)

Ranganathan, S.; Prince, A.A.M.; Raghavan, P.S.; Gopalan, R. [Madras Christian Coll., Tambaram (India); Srinivasan, M.P.; Narasimhan, S.V.

1997-08-01

Magnetite is one of the important corrosion products of pressurized heavy water reactors (PHWRs) where carbon steel is the dominant surface in the primary heat transport system. Designing of formulations capable of dissolving magnetite is important for effective decontamination of such surfaces. The rate of dissolution of synthetically prepared magnetite was studied in low concentrations of PDCA containing acidic formulations. The effect of addition of ascorbic acid, citric acid, Fe{sup 2+}-PDCA complex on the rate was also studied. The effects of pH and the temperature on the dissolution rate were determined. The PDCA as a complexant has some positive factors like low protonation constant and enhanced stability to radiation. (author)

Kinetics of dissolution of magnetite in PDCA based formulations

International Nuclear Information System (INIS)

Ranganathan, S.; Prince, A.A.M.; Raghavan, P.S.; Gopalan, R.; Srinivasan, M.P.; Narasimhan, S.V.

1997-01-01

Magnetite is one of the important corrosion products of pressurized heavy water reactors (PHWRs) where carbon steel is the dominant surface in the primary heat transport system. Designing of formulations capable of dissolving magnetite is important for effective decontamination of such surfaces. The rate of dissolution of synthetically prepared magnetite was studied in low concentrations of PDCA containing acidic formulations. The effect of addition of ascorbic acid, citric acid, Fe 2+ -PDCA complex on the rate was also studied. The effects of pH and the temperature on the dissolution rate were determined. The PDCA as a complexant has some positive factors like low protonation constant and enhanced stability to radiation. (author)

Kinetics of reductive bulk dissolution of lepidocrocite, ferrihydrite, and geothite

DEFF Research Database (Denmark)

Larsen, O.; Postma, Diederik Jan

2001-01-01

of the reduction experiments, lepidocrocite crystals were subsampled and the change in crystal habit and size distribution was studied by transmission electron microscopy. The rate of complete dissolution was described by the function J/m0 5 k9(m/m0)g where J is the overall rate of dissolution (mol/s), m0...... for lepidocrocite showed strong etch-pitting of the crystals parallel to the c-axis resulting ultimately in disintegration of the crystals. For the different iron oxides, the initial rate was independent of the specific surface area, emphasizing the importance of the crystal structure for the dissolution rate....... However, among the lepidocrocites the initial rate was proportional to the specific surface area. The exponent, g was found to vary from a value near 1.0 for one of the 2-line ferrihydrites, two of the lepidocrocites and the goethite, to values close to 2.3 for the other 2-line ferrihydrite and the 6-line...

Synthesis, characterization, kinetic and thermodynamic studies of the dissolution of ThO2 and of solid solutions Th1-xMxO2 (M = U, Pu)

International Nuclear Information System (INIS)

Heisbourg, G.

2003-12-01

The aim of this work was to understand the mechanisms of dissolution of ThO 2 and of thorium mixed oxides such as Th 1-x U x O 2 and Th 1-x Pu x O 2 in aqueous, oxygenated or inert media. Several solids have been synthesized by precipitation in oxalic medium: Th 1-x U x O 2 (x= 0.11; 0.24; 0.37; 0.53; 0.67; 0.81 and 0.91) and Th 1-x Pu x O 2 (x= 0.13; 0.32 and 0.66). They have been characterized by XRD, SEM, TEM, XPS, XAS, PIXE and EPMA. The sintering conditions of these materials have been studied and optimized in order to obtain sintered samples with a measured density very near the theoretical densities. A kinetic study of the dissolution of ThO 2 and of solid solutions Th 1-x U x O 2 has been carried out in several aqueous media (HNO 3 , HCl, H 2 SO 4 ) in terms of several parameters: protons concentration, temperature, pH, ionic strength, nature of the electrolyte solution and uranium molar ratio for the solid solutions Th 1-x U x O 2 in order to determine the kinetic laws of dissolution of the solid solutions having different compositions comparatively to ThO 2 . The leaching tests carried out in natural waters of compositions near those of the deep geologic sites considered for the storage of nuclear wastes have shown that the dissolution of the solids was bound to the complexing effect of the constitutional ions of the water considered. The leaching tests carried out on sintered samples of the same composition have led to the same normalized dissolution velocities. The thermodynamic aspect of the dissolution of the solid solutions Th 1-x U x O 2 in nitric medium has been studied at last. (O.M.)

The effect of Ti and Nb on nitrogen dissolution reaction in stainless steel melt

International Nuclear Information System (INIS)

Jang, Min Whan; Hong, In Kook; Pak, Jong Jin; Song, Hyo Seok; Lee, Yong Deuk

2002-01-01

A kinetic study of nitrogen dissolution in STS304 stainless steel melt containing Ti and Nb has been carried out at 1500 degree C using an induction furnace and a levitation melting furnace. At low O and S levels, the nitrogen dissolution rate showed the first-order kinetics being controlled by the mass transfer of nitrogen in the melt. Ti addition to STS304 stainless melt significantly retarded the nitrogen dissolution rate by the formation of solid Ti oxide layer adhered on the melt surface. Nb did not affect the rate of nitrogen dissolution. In the levitation melting experiment where the oxide layer was removed from the melt surface, Ti did not retard the nitrogen dissolution rate. Simultaneous addition of Ti and Al increased the dissolution rate by the formation of non-wetting Al 2 O 3 on the melt surface. A small addition of CaO-Al 2 O 3 synthetic flux to Ti containing melt was very effective to remove the oxide layer, hence to increase the nitrogen dissolution rate

The effect of Ti and Nb on nitrogen dissolution reaction in stainless steel melt

Energy Technology Data Exchange (ETDEWEB)

Jang, Min Whan; Hong, In Kook; Pak, Jong Jin [Hanyang Univ., Ansan (Korea, Republic of); Song, Hyo Seok; Lee, Yong Deuk [POSCO, Pohang (Korea, Republic of)

2002-03-01

A kinetic study of nitrogen dissolution in STS304 stainless steel melt containing Ti and Nb has been carried out at 1500 degree C using an induction furnace and a levitation melting furnace. At low O and S levels, the nitrogen dissolution rate showed the first-order kinetics being controlled by the mass transfer of nitrogen in the melt. Ti addition to STS304 stainless melt significantly retarded the nitrogen dissolution rate by the formation of solid Ti oxide layer adhered on the melt surface. Nb did not affect the rate of nitrogen dissolution. In the levitation melting experiment where the oxide layer was removed from the melt surface, Ti did not retard the nitrogen dissolution rate. Simultaneous addition of Ti and Al increased the dissolution rate by the formation of non-wetting Al{sub 2}O{sub 3} on the melt surface. A small addition of CaO-Al{sub 2}O{sub 3} synthetic flux to Ti containing melt was very effective to remove the oxide layer, hence to increase the nitrogen dissolution rate.

Mechanistic analysis of solute transport in an in vitro physiological two-phase dissolution apparatus.

Science.gov (United States)

Mudie, Deanna M; Shi, Yi; Ping, Haili; Gao, Ping; Amidon, Gordon L; Amidon, Gregory E

2012-10-01

In vitro dissolution methodologies that adequately capture the oral bioperformance of solid dosage forms are critical tools needed to aid formulation development. Such methodologies must encompass important physiological parameters and be designed with drug properties in mind. Two-phase dissolution apparatuses, which contain an aqueous phase in which the drug dissolves (representing the dissolution/solubility component) and an organic phase into which the drug partitions (representing the absorption component), have the potential to provide meaningful predictions of in vivo oral bioperformance for some BCS II, and possibly some BCS IV drug products. Before such an apparatus can be evaluated properly, it is important to understand the kinetics of drug substance partitioning from the aqueous to the organic medium. A mass transport analysis was performed of the kinetics of partitioning of drug substance solutions from the aqueous to the organic phase of a two-phase dissolution apparatus. Major assumptions include pseudo-steady-state conditions, a dilute aqueous solution and diffusion-controlled transport. Input parameters can be measured or estimated a priori. This paper presents the theory and derivation of our analysis, compares it with a recent kinetic approach, and demonstrates its effectiveness in predicting in vitro partitioning profiles of three BCS II weak acids in four different in vitro two-phase dissolution apparatuses. Very importantly, the paper discusses how a two-phase apparatus can be scaled to reflect in vivo absorption kinetics and for which drug substances the two-phase dissolution systems may be appropriate tools for measuring oral bioperformance. Copyright © 2012 John Wiley & Sons, Ltd.

Quantifying Silica Reactivity in Subsurface Environments: Reaction Affinity and Solute Matrix Controls on Quartz and SiO2 Glass Dissolution Kinetics

International Nuclear Information System (INIS)

Dove, Patricia M.

1999-01-01

Our goal is to develop a quantitative and mechanistic understanding of amorphous silica, SiO2(am), dissolution kinetics in aqueous solutions. A knowledge of fundamental controls on the reactivity of simple Si-O bonded phases is the baseline of behavior for understanding highly complex silica phases. In the Earth, silicate minerals comprise >70% of the crust and dominate virtually every subsurface system. More importantly for the objectives of this EMSP project, the silicates are important because compositionally complex glasses will become the front line of defense in containing radioactive wastes in the nation's long term and interim storage strategies. To date, the behavior of SiO2(am) is largely inferred from studies of the better known crystalline polymorphs (e.g. alpha-quartz). In the first step towards constructing a general model for amorphous silica reactivity in the complex fluid compositions of natural waters, we are determining the dissolution behavior as a function of temperature, solution pH and cation concentration. With these data we are determining relationships between SiO2 glass structure and dissolution rates in aqueous solutions, as described below

Mathematical modeling of drug dissolution.

Science.gov (United States)

Siepmann, J; Siepmann, F

2013-08-30

The dissolution of a drug administered in the solid state is a pre-requisite for efficient subsequent transport within the human body. This is because only dissolved drug molecules/ions/atoms are able to diffuse, e.g. through living tissue. Thus, generally major barriers, including the mucosa of the gastro intestinal tract, can only be crossed after dissolution. Consequently, the process of dissolution is of fundamental importance for the bioavailability and, hence, therapeutic efficacy of various pharmaco-treatments. Poor aqueous solubility and/or very low dissolution rates potentially lead to insufficient availability at the site of action and, hence, failure of the treatment in vivo, despite a potentially ideal chemical structure of the drug to interact with its target site. Different physical phenomena are involved in the process of drug dissolution in an aqueous body fluid, namely the wetting of the particle's surface, breakdown of solid state bonds, solvation, diffusion through the liquid unstirred boundary layer surrounding the particle as well as convection in the surrounding bulk fluid. Appropriate mathematical equations can be used to quantify these mass transport steps, and more or less complex theories can be developed to describe the resulting drug dissolution kinetics. This article gives an overview on the current state of the art of modeling drug dissolution and points out the assumptions the different theories are based on. Various practical examples are given in order to illustrate the benefits of such models. This review is not restricted to mathematical theories considering drugs exhibiting poor aqueous solubility and/or low dissolution rates, but also addresses models quantifying drug release from controlled release dosage forms, in which the process of drug dissolution plays a major role. Copyright © 2013 Elsevier B.V. All rights reserved.

Bleaching of the thermoluminescence of feldspars by sunlight

International Nuclear Information System (INIS)

Robertson, G.B.; Prescott, J.R.; Hutton, J.T.

1991-01-01

Feldspars are an important component of materials used for thermoluminescence (TL) and photoluminescence (PL) dating of sediments; and successful dating implies a knowledge of the degree of re-setting by exposure to sunlight of the stored luminescence energy. We have studied the bleaching by full sunlight of the TL of six alkali feldspars of representative composition and of one oligoclase. The high potassium and high sodium feldspars are the brightest, and are also the least easily bleached, whereas those of intermediate (K-Na) composition bleach quickly. On a time scale of upwards of 16 h, all samples would have bleached enough for them to be useful for TL dating. A search was made for individual glow curve peaks that bleach particularly quickly (and are thus similar to the well-known 325 o C peak used in the TL dating of quartz). In the samples studied, there was only one glow curve peak that was selectively susceptible to bleaching: the 280 o C peak in oligoclase. (author)

Revisiting classical silicate dissolution rate laws under hydrothermal conditions

Science.gov (United States)

Pollet-Villard, Marion; Daval, Damien; Saldi, Giuseppe; Knauss, Kevin; Wild, Bastien; Fritz, Bertrand

2015-04-01

In the context of geothermal energy, the relative intensities of primary mineral leaching and secondary mineral precipitation can affect porosity and permeability of the reservoir, thereby influencing its hydraulic performance and the efficiency of the geothermal power station. That is why the prediction of reaction kinetics of fluid/rock interactions represents a critical issue in this context. Moreover, in several geothermal systems such as the one of Soultz-sous-Forêts (Alsace, France), the circulation of aqueous fluids induces only modest modifications of their chemical composition. Therefore, fluid-rock interactions take place at close-to-equilibrium conditions, where the rate-affinity relations are poorly known and intensively debated [1]. To describe more precisely the dissolution processes, our strategy consists in investigating the dissolution of the main cleavages of K-spar minerals (one of the prevalent primary minerals in the reservoir of Soultz-sous-Forêts geothermal system) over a wide range of Gibbs free energy (ΔG) conditions. The aims are to decipher the impact of crystallographic orientation and microstructural surface modifications on the dissolution kinetics and to propose a relation between K-spar dissolution rate and ΔG. Our experimental work relies on a coupled approach which combines classical experiments of K-spar dissolution monitored by aqueous chemical analyses (ICP-AES) and innovative techniques of nm- to μm-scale characterization of solid surface (SEM, AFM, VSI) [2]. Our results confirm that K-spar dissolution is an anisotropic process: we measure a tenfold factor between the slowest and the fastest-dissolving surfaces. Moreover, the formation of etch pits on surfaces during their alteration has been evidenced on all of the different faces that have been studied. This complex evolution of the surface topography casts doubt of the relevance of a surface model based on shrinking particles and represents a possible cause of an

Chrysotile dissolution rates: Implications for carbon sequestration

International Nuclear Information System (INIS)

Thom, James G.M.; Dipple, Gregory M.; Power, Ian M.; Harrison, Anna L.

2013-01-01

Highlights: • Uncertainties in serpentine dissolution kinetics hinder carbon sequestration models. • A pH dependent, far from equilibrium dissolution rate law for chrysotile. • F chrysotile (mol/m 2 /s) = 10 −0.21pH−10.57 at 22 °C over pH 2–10. • Laboratory dissolution rates consistent with mine waste weathering observations. • Potential for carbon sequestration in mine tailings and aquifers is assessed. - Abstract: Serpentine minerals (e.g., chrysotile) are a potentially important medium for sequestration of CO 2 via carbonation reactions. The goals of this study are to report a steady-state, far from equilibrium chrysotile dissolution rate law and to better define what role serpentine dissolution kinetics will have in constraining rates of carbon sequestration via serpentine carbonation. The steady-state dissolution rate of chrysotile in 0.1 m NaCl solutions was measured at 22 °C and pH ranging from 2 to 8. Dissolution experiments were performed in a continuously stirred flow-through reactor with the input solutions pre-equilibrated with atmospheric CO 2 . Both Mg and Si steady-state fluxes from the chrysotile surface, and the overall chrysotile flux were regressed and the following empirical relationships were obtained: F Mg =-0.22pH-10.02;F Si =-0.19pH-10.37;F chrysotile =-0.21pH-10.57 where F Mg , F Si , and F chrysotile are the log 10 Mg, Si, and molar chrysotile fluxes in mol/m 2 /s, respectively. Element fluxes were used in reaction-path calculations to constrain the rate of CO 2 sequestration in two geological environments that have been proposed as potential sinks for anthropogenic CO 2 . Carbon sequestration in chrysotile tailings at 10 °C is approximately an order of magnitude faster than carbon sequestration in a serpentinite-hosted aquifer at 60 °C on a per kilogram of water basis. A serpentinite-hosted aquifer, however, provides a larger sequestration capacity. The chrysotile dissolution rate law determined in this study has

Kinetics of dissolution of thorium and uranium doped britholite ceramics

Energy Technology Data Exchange (ETDEWEB)

Dacheux, N., E-mail: nicolas.dacheux@univ-montp2.f [Groupe de Radiochimie, Institut de Physique Nucleaire d' Orsay, Bat. 100, Universite Paris-Sud-11, 91406 Orsay (France); Institut de Chimie Separative de Marcoule, UMR 5257 (Universite Montpellier 2/CNRS/CEA/ENSCM), Bat. 426, Centre de Marcoule, BP 17171, 30207 Bagnols sur ceze cedex (France); Du Fou de Kerdaniel, E. [Groupe de Radiochimie, Institut de Physique Nucleaire d' Orsay, Bat. 100, Universite Paris-Sud-11, 91406 Orsay (France); Clavier, N. [Groupe de Radiochimie, Institut de Physique Nucleaire d' Orsay, Bat. 100, Universite Paris-Sud-11, 91406 Orsay (France); Institut de Chimie Separative de Marcoule, UMR 5257 (Universite Montpellier 2/CNRS/CEA/ENSCM), Bat. 426, Centre de Marcoule, BP 17171, 30207 Bagnols sur ceze cedex (France); Podor, R. [Institut de Chimie Separative de Marcoule, UMR 5257 (Universite Montpellier 2/CNRS/CEA/ENSCM), Bat. 426, Centre de Marcoule, BP 17171, 30207 Bagnols sur ceze cedex (France); Institut Jean Lamour - Departement CP2S - Equipe 206, Faculte des Sciences et Techniques - Nancy Universite, BP 70239, 54506 Vandoeuvre les Nancy cedex (France); Aupiais, J. [CEA DAM DIF, 91297 Arpajon (France); Szenknect, S. [Institut de Chimie Separative de Marcoule, UMR 5257 (Universite Montpellier 2/CNRS/CEA/ENSCM), Bat. 426, Centre de Marcoule, BP 17171, 30207 Bagnols sur ceze cedex (France)

2010-09-01

In the field of immobilization of actinides in phosphate-based ceramics, several thorium and uranium doped britholite samples were submitted to leaching tests. The normalized dissolution rates determined for several pH values, temperatures and acidic media from the calcium release range from 4.7 x 10{sup -2} g m{sup -2} d{sup -1} to 21.6 g m{sup -2} d{sup -1}. Their comparison with that determined for phosphorus, thorium and uranium revealed that the dissolution is clearly incongruent for all the conditions examined. Whatever the leaching solution considered, calcium and phosphorus elements were always released with higher R{sub L} values than the other elements (Nd, Th, U). Simultaneously, thorium was found to quickly precipitate as alteration product, leading to diffusion phenomena for uranium. For all the media considered, the uranium release is higher than that of thorium, probably due to its oxidation from tetravalent oxidation state to uranyl. Moreover, the evaluation of the partial order related to proton concentration and the apparent energy of activation suggest that the reaction of dissolution is probably controlled by surface chemical reactions occurring at the solid/liquid interface. Finally, comparative leaching tests performed in sulphuric acid solutions revealed a significant influence of such media on the chemical durability of the leached pellets, leading to higher normalized dissolution rates for all the elements considered. On the basis of the results of chemical speciation, this difference was mainly explained in the light of higher complexion constants by sulfate ions compared to nitrate, chloride and phosphate.

In vitro release of ketoprofen suppositories using the USP basket and the flow-through cell dissolution methods.

Science.gov (United States)

Medina, José Raúl; Padilla, Adrián Roberto; Hurtado, Marcela; Cortés, Alma Rosa; Domínguez-Ramírez, Adriana Miriam

2014-05-01

In order to study the release characteristics of ketoprofen suppositories under the hydrodynamic environment generated by USP Apparatus 1 and 4, the dissolution profiles of the Mexican reference product (100 mg) were determined. Phosphate buffer pH 8 and 1% sodium lauryl sulfate (SLS) aqueous solutions were proved as dissolution mediums. Baskets were rotated at 100 rpm with USP Apparatus 1 and different flow rates from 16-32 mL/min with USP Apparatus 4 were used. Drug samples were taken and quantified during 60 min by UV analysis at 260 nm. Mean dissolution time (MDT) and dissolution efficiency (DE) were calculated by model-independent methods. Data were also fitted to several kinetic models. Poor dissolution was found in both dissolution mediums when USP basket method was used ( 0.99). The results suggest the need to establish an adequate dissolution method to evaluate the release kinetics of ketoprofen from suppositories.

Rapid and gradual modes of aerosol trace metal dissolution in seawater

Directory of Open Access Journals (Sweden)

Katherine Rose Marie Mackey

2015-01-01

Full Text Available Atmospheric deposition is a major source of trace metals in marine surface waters and supplies vital micronutrients to phytoplankton, yet measured aerosol trace metal solubility values are operationally defined and there are relatively few multi-element studies on aerosol-metal solubility in seawater. Here we measure the solubility of aluminum (Al, cadmium (Cd, cobalt (Co, copper (Cu, iron (Fe, manganese (Mn, nickel (Ni, lead (Pb, and zinc (Zn from natural aerosol samples in seawater over a 7 day period to (1 evaluate the role of extraction time in trace metal dissolution behavior and (2 explore how the individual dissolution patterns could influence biota. Dissolution behavior occurs over a continuum ranging from rapid dissolution, in which the majority of soluble metal dissolved immediately upon seawater exposure (Cd and Co in our samples, to gradual dissolution, where metals dissolved slowly over time (Zn, Mn, Cu, and Al in our samples. Additionally, dissolution affected by interactions with particles was observed in which a decline in soluble metal concentration over time occurred (Fe and Pb in our samples. Natural variability in aerosol chemistry between samples can cause metals to display different dissolution kinetics in different samples, and this was particularly evident for Ni, for which samples showed a broad range of dissolution rates. The elemental molar ratio of metals in the bulk aerosols was 23,189Fe: 22,651Al: 445Mn: 348Zn: 71Cu: 48Ni: 23Pb: 9Co: 1Cd, whereas the seawater soluble molar ratio after 7 days of leaching was 11Fe: 620Al: 205Mn: 240Zn: 20Cu: 14Ni: 9Pb: 2Co: 1Cd. The different kinetics and ratios of aerosol metal dissolution have implications for phytoplankton nutrition, and highlight the need for unified extraction protocols that simulate aerosol metal dissolution in the surface ocean.

Kinetic Controls on the Desorption/Dissolution of Sorbed U(VI) and their Influence on Reactive Transport

International Nuclear Information System (INIS)

Zachara, John M.; Chongxuan Liu; Qafoku, Nikolla P.; McKinley, James P.; Catalano, Jeffrey G.; Brown, Gordon E. Jr.; Davis, James A.

2006-01-01

A number of published studies have sought to understand geochemical kinetic process of uranium (U) that are relevant to nuclear waste sites and repositories by studying the weathering of U ore bodies and downgradient transport of weathering products. Such studies have provided important insights on processes operative over many thousand to millions of years. This project also seeks knowledge on the geochemical kinetics of U, but for shorter in-ground time periods (e.g., 20-50 years) relevant to DOE legacy waste sites. Several representative field sites were selected for intense study at Hanford as part of EMSP research to provide: (1) fundamental insights on intermediate duration geochemical events of U controlling fate and transport, and (2) key scientific information needed for remedial action assessment and informed decision making. The site discussed in this poster is the 300 A uranium plume. This plume is located at the south end of Hanford and discharges directly to the Columbia River. The plume resulted from the discharge of fuels fabrication wastes (nitric acid solutions containing U and Cu) and cladding dissolution wastes (basic sodium aluminate) to the North and South Process Ponds between 1943 and 1975 near the Columbia River. A Kd-based remedial action assessment fifteen years ago predicted that the plume would dissipate to concentrations below the DWS within 10 y. As a result of this assessment, an interim, MNA remedial decision was agreed to by DOE and state/federal regulators. It has been 15 y since the above assessment, and groundwater concentrations have not decreased (attenuated) as projected. Stakeholders are now demanding remedial intervention, and DOE seeks science-based conceptual and numeric models for more accurate future projections. The objectives are: (1) Identify the chemical speciation (e.g., adsorption complexes precipitates), mineral residence, and physical location of contaminant U in a depth sequence of sediments from the disposal

Kinetic Controls on the Desorption/Dissolution of Sorbed U(VI) and Their Influence on Reactive Transport

International Nuclear Information System (INIS)

J. M. Zachara; C. Liu; N. Qafoku; J. P. McKinley; J. A. Davis; D. Stoliker; Y. Arai; J. G. Catalano; G. E. Brown, Jr.

2007-01-01

A number of published studies have sought to understand geochemical kinetic process of uranium (U) that are relevant to nuclear waste sites and repositories by studying the weathering of U ore bodies and downgradient transport of weathering products. Such studies have provided important insights on processes operative over many thousand to millions of years. This project also seeks knowledge on the geochemical kinetics of U, but for shorter in-ground time periods (e.g., 20-50 years) relevant to DOE legacy waste sites. Several representative field sites were selected for intense study at Hanford as part of EMSP research to provide: (1) fundamental insights on intermediate duration geochemical events of U controlling fate and transport, and (2) key scientific information needed for remedial action assessment and informed decision making. The site discussed in this poster is the 300 A uranium plume. This plume is located at the south end of Hanford and discharges directly to the Columbia River. The plume resulted from the discharge of fuels fabrication wastes (nitric acid solutions containing U and Cu) and cladding dissolution wastes (basic sodium aluminate) to the North and South Process Ponds between 1943 and 1975 near the Columbia River. A Kd-based remedial action assessment fifteen years ago predicted that the plume would dissipate to concentrations below the DWS within 10 y. As a result of this assessment, an interim, MNA remedial decision was agreed to by DOE and state/federal regulators. It has been 15 y since the above assessment, and groundwater concentrations have not decreased (attenuated) as projected. Stakeholders are now demanding remedial intervention, and DOE seeks science-based conceptual and numeric models for more accurate future projections. The objectives are: (1) Identify the chemical speciation (e.g., adsorption complexes or precipitates), mineral residence, and physical location of contaminant U in a depth sequence of sediments from the

Use of rice straw ash as substitute of feldspar in triaxial porcelain

International Nuclear Information System (INIS)

Alvaro Guzman, A.; Silverio Delvasto, A.; Enrique Sanchez, V.; Vicente Amigo, B.

2013-01-01

The substitution of raw materials for processing high energy consumption materials by agricultural and agro-industrial wastes causes a positive impacts on the environment preservation. One of these residues is rice straw, which according to FAO estimation, its annual production is about 600 million tons. In this research was studied the use of rice straw ash as substitute of the use of feldspar in the white ware production. Clay-feldspar-quartz porcelains are referred to as triaxial white ware. Specimens of semidry triaxial mixtures, where feldspar was substituted for different percentages of CTA, were prepared by uniaxial pressing, followed by drying and sintering. Physical and mechanical properties of sintered bodies were evaluated. The porosity and the compressive strength of the fired pieces do increase with additions of up to 75% of CTA in substitution of feldspar. Their mineralogical phases were determined by DRX and SEM; grains of quartz, and needles of primary and secondary mullite were identified in a vitreous phase. It was concluded that feldspar can be substituted positively by CTA in white ware pastes. (Author) 22 refs.

Characterisation and dissolution of depleted uranium aerosols produced during impacts of kinetic energy penetrators against a tank

International Nuclear Information System (INIS)

Chazel, V.; Gerasimo, P.; Debouis, V.; Laroche, P.; Paquet, F.

2003-01-01

Aerosols produced during impacts of depleted uranium (DU) penetrators against the glacis (sloping armour) and the turret of a tank were sampled. The concentration and size distribution were determined. Activity median aerodynamic diameters were 1 μm (geometric standard deviation, s g = 3.7) and 2 μm (s g = 2.5), respectively, for glacis and turret. The mean air concentration was 120 Bq m -3 , i.e. 8.5 mg m -3 of DU. Filters analysed by scanning electron microscopy (SEM) and X ray diffraction showed two types of particles (fine particles and large molten particles) composed mainly of a mixture of uranium and aluminium. The uranium oxides were mostly U 3 O 8 , UO 2.25 and probably UO 3.01 and a mixed compound of U and Al. The kinetics of dissolution in three media (HCO 3 - , HCl and Gamble's solution) were determined using in-vitro tests. The slow dissolution rates were respectively slow, and intermediate between slow and moderate, and the rapid dissolution fractions were mostly intermediate between moderate and fast. According to the in-vitro results for Gamble's solution, and based on a hypothetical single acute inhalation of 90 Bq, effective doses integrated up to 1 y after incorporation were 0.54 and 0.56 mSv respectively, for aerosols from glacis and turret. In comparison, the ICRP limits are 20 mSv y -1 for workers and 1 mSv y -1 for members of public. A kidney concentration of approximately 0.1 μg U g -1 was predicted and should not, in this case, lead to kidney damage. (author)

Characterisation and dissolution of depleted uranium aerosols produced during impacts of kinetic energy penetrators against a tank.

Science.gov (United States)

Chazel, V; Gerasimo, P; Dabouis, V; Laroche, P; Paquet, F

2003-01-01

Aerosols produced during impacts of depleted uranium (DU) penetrators against the glacis (sloping armour) and the turret of a tank were sampled. The concentration and size distribution were determined. Activity median aerodynamic diameters were 1 microm (geometric standard deviation, sigma(g) = 3.7) and 2 microm (sigma(g) = 2.5), respectively, for glacis and turret. The mean air concentration was 120 Bq m(-3), i.e. 8.5 mg m(-3) of DU. Filters analysed by scanning electron microscopy (SEM) and X ray diffraction showed two types of particles (fine particles and large molten particles) composed mainly of a mixture of uranium and aluminium. The uranium oxides were mostly U3O8, UO2.25 and probably UO3.01 and a mixed compound of U and Al. The kinetics of dissolution in three media (HCO3-, HCl and Gamble's solution) were determined using in-vitro tests. The slow dissolution rates were respectively slow, and intermediate between slow and moderate, and the rapid dissolution fractions were mostly intermediate between moderate and fast. According to the in-vitro results for Gamble's solution, and based on a hypothetical single acute inhalation of 90 Bq, effective doses integrated up to 1 y after incorporation were 0.54 and 0.56 mSv, respectively, for aerosols from glacis and turret. In comparison, the ICRP limits are 20 mSv y(-1) for workers and 1 mSv y(-1) for members of the public. A kidney concentration of approximately 0.1 microg U g(-1) was predicted and should not, in this case, lead to kidney damage.

The effect of antimony presence in anodic copper on kinetics and mechanism of anodic dissolution and cathodic deposition of copper

Directory of Open Access Journals (Sweden)

Stanković Z.D.

2008-01-01

Full Text Available The influence of the presence of Sb atoms, as foreign metal atoms in anode copper, on kinetics, and, on the mechanism of anodic dissolution and cathodic deposition of copper in acidic sulfate solution has been investigated. The galvanostatic single-pulse method has been used. Results indicate that presence of Sb atoms in anode copper increase the exchange current density as determined from the Tafel analysis of the electrode reaction. It is attributed to the increase of the crystal lattice parameter determined from XRD analysis of the electrode material.

Mechanisms and kinetics laws of inactive R7T7 reference glass dissolution in water at 90 deg C: initial dissolution rate measurements

International Nuclear Information System (INIS)

Advocat, T.; Ghaleb, D.; Vernaz, E.

1993-02-01

The initial dissolution rate of inactive R7T7 reference glass was measured at 90 deg C in dilute aqueous solutions first at unspecified pH, then with imposed pH values. In distilled water, R7T7 glass corrosion initially involved preferential extraction of boron and network modifier elements (Li, Na, Ca) as long as the solution pH remained acid. When the solution pH became alkaline, glass dissolution was stoichiometric. These two mechanisms were confirmed by dissolution tests in aqueous solutions at imposed pH values under acid and alkaline conditions. The initial dissolution rate r 0 in mole.cm -3 .s -1 also increased significantly in alkaline media when the pH of the aqueous phase increased: in slightly acid media, selective glass dissolution formed a residual, de-alkalinized, hydrated glass that was characterized by transmission electron microscopy and secondary ion mass spectrometry. Under steady-state dissolution conditions, the initial glass corrosion rate (in mole.cm -3 .s -1 ) was: in acid and alkaline media, amorphous and crystallized alteration products formed after complete dissolution of the silicated glass network. The first products formed consisted mainly of Zr, Rare Earths, Fe and Al. (author). 67 refs., 29 figs., 26 tabs., 21 plates

Bio-beneficiation of kaolin and feldspar and its effect on fired

Indian Academy of Sciences (India)

Presence of iron compounds as impurities in kaolin and feldspar, impart reddish colour to ceramic products manufactured using these minerals. The quality of kaolin and feldspar was enriched mainly through iron removal by biological methods. Bacteria isolated from kaolin of Indian origin were used for bioleaching.

K-Ar dating: incomplete extraction of radiogenic argon from alkali feldspar - a comment

International Nuclear Information System (INIS)

Baksi, A.K.

1984-01-01

In a recent paper, McDowell (1983) discussed the difficulties involved in obtaining accurate K-Ar ages on alkali feldspar samples. These difficulties primarily stem from the fact that the feldspars melt at high temperatures and lack structural volatiles which could flush out all of the 40 Ar* from the viscous melt at temperatures below 1600 0 C. Evidently, if feldspar samples could be satisfactorily melted at lower temperatures by the use of a suitable flux, complete release of 40 Ar* should occur. McDowell (1983) also commented on the lack of a suitable feldspar standard sample for argon dating work. This comment will briefly address these two problems. (Auth.)

Dissolution studies of synthetic soddyite and uranophane

International Nuclear Information System (INIS)

Casas, I.; Perez, I.; Torrero, E.; Bruno, J.; Cera, E.; Duro, L.

1997-09-01

The dissolution of synthetically obtained soddyite and uranophane has been studied in solutions of low ionic strength. These are the likely final phases of the oxidative alternation pathway of uranium dioxide. The thermodynamic and kinetic dissolution properties of these phases have been determined at different bicarbonate concentrations. The solubilities determined in the experiments with soddyite correspond fairly well to the theoretical model calculated with a log K 0 s0 =3.9±0.7. For uranophane, the best fitting was obtained for a log K 0 s0 =11.7±0.6. The dissolution rate in the presence of bicarbonate gave for soddyite an average value of 6.8(±4.4) 10 -10 mol m -2 s -1 . For uranophane, under the same experimental conditions, the following dissolution rate equation has been derived: r 0 (mol m -2 s -1 )=10 -9±2. [HCO 3 - ] 0.69±0.09 2

New insights into the oleate flotation response of feldspar particles of different sizes: Anisotropic adsorption model.

Science.gov (United States)

Xu, Longhua; Tian, Jia; Wu, Houqin; Deng, Wei; Yang, Yaohui; Sun, Wei; Gao, Zhiyong; Hu, Yuehua

2017-11-01

The anisotropic adsorption of sodium oleate (NaOL) on feldspar surfaces was investigated to elucidate the different flotation properties of feldspar particles of four different size ranges. Microflotation experiments showed that the feldspar flotation recovery of particles with sizes spanning different ranges decreased in the order 0-19>19-38>45-75>38-45μm. Zeta potential and FTIR measurements showed that NaOL was chemically adsorbed on the Al sites of the feldspar surface. The anisotropic surface energies and broken bond densities estimated by density functional theory calculations showed that, although feldspar mostly exposed (010) and (001) surfaces, only the (001) surfaces contained the Al sites needed for NaOL adsorption. The interaction energies calculated by molecular dynamics simulations confirmed the more favorable NaOL adsorption on (001) than (010) surfaces, which may represent the main cause for the anisotropic NaOL adsorption on feldspar particles of different sizes. SEM measurements showed that the main exposed surfaces on coarse and fine feldspar particles were the side (010) and basal (001) ones, respectively. A higher fraction of Al-rich (001) surfaces is exposed on fine feldspar particles, resulting in better floatability compared with coarse particles. XPS and adsorption measurements confirmed that the Al content on the feldspar surface varied with the particle size, explaining the different NaOL flotation of feldspar particles of different sizes. Therefore, the present results suggest that coarsely ground ore should be used for the separation of feldspar gangue minerals. Further improvements in the flotation separation of feldspar from associated valuable minerals can be achieved through selective comminution or grinding processes favoring the exposure of (010) surfaces. Copyright © 2017 Elsevier Inc. All rights reserved.

Impacts of seawater saturation state (ΩA = 0.4-4.6) and temperature (10, 25 °C) on the dissolution kinetics of whole-shell biogenic carbonates

Science.gov (United States)

Ries, Justin B.; Ghazaleh, Maite N.; Connolly, Brian; Westfield, Isaac; Castillo, Karl D.

2016-11-01

Anthropogenic increase of atmospheric pCO2 since the Industrial Revolution has caused seawater pH to decrease and seawater temperatures to increase-trends that are expected to continue into the foreseeable future. Myriad experimental studies have investigated the impacts of ocean acidification and warming on marine calcifiers' ability to build protective shells and skeletons. No studies, however, have investigated the combined impacts of ocean acidification and warming on the whole-shell dissolution kinetics of biogenic carbonates. Here, we present the results of experiments designed to investigate the effects of seawater saturation state (ΩA = 0.4-4.6) and temperature (10, 25 °C) on gross rates of whole-shell dissolution for ten species of benthic marine calcifiers: the oyster Crassostrea virginica, the ivory barnacle Balanus eburneus, the blue mussel Mytilus edulis, the conch Strombus alatus, the tropical coral Siderastrea siderea, the temperate coral Oculina arbuscula, the hard clam Mercenaria mercenaria, the soft clam Mya arenaria, the branching bryozoan Schizoporella errata, and the coralline red alga Neogoniolithon sp. These experiments confirm that dissolution rates of whole-shell biogenic carbonates decrease with calcium carbonate (CaCO3) saturation state, increase with temperature, and vary predictably with respect to the relative solubility of the calcifiers' polymorph mineralogy [high-Mg calcite (mol% Mg > 4) ≥ aragonite > low-Mg calcite (mol% Mg carbonates. Furthermore, the severity of the temperature effects on gross dissolution rates also varied with respect to carbonate polymorph solubility, with warming (10-25 °C) exerting the greatest effect on biogenic high-Mg calcite, an intermediate effect on biogenic aragonite, and the least effect on biogenic low-Mg calcite. These results indicate that both ocean acidification and warming will lead to increased dissolution of biogenic carbonates in future oceans, with shells/skeletons composed of the more

Dissolution, agglomerate morphology, and stability limits of protein-coated silver nanoparticles.

Science.gov (United States)

Martin, Matthew N; Allen, Andrew J; MacCuspie, Robert I; Hackley, Vincent A

2014-09-30

Little is understood regarding the impact that molecular coatings have on nanoparticle dissolution kinetics and agglomerate formation in a dilute nanoparticle dispersion. Dissolution and agglomeration processes compete in removing isolated nanoparticles from the dispersion, making quantitative time-dependent measurements of the mechanisms of nanoparticle loss particularly challenging. In this article, we present in situ ultra-small-angle X-ray scattering (USAXS) results, simultaneously quantifying dissolution, agglomeration, and stability limits of silver nanoparticles (AgNPs) coated with bovine serum albumin (BSA) protein. When the BSA corona is disrupted, we find that the loss of silver from the nanoparticle core is well matched by a second-order kinetic rate reaction, arising from the oxidative dissolution of silver. Dissolution and agglomeration are quantified, and morphological transitions throughout the process are qualified. By probing the BSA-AgNP suspension around its stability limits, we provide insight into the destabilization mechanism by which individual particles rapidly dissolve as a whole rather than undergo slow dissolution from the aqueous interface inward, once the BSA layer is breached. Because USAXS rapidly measures over the entire nanometer to micrometer size range during the dissolution process, many insights are also gained into the stabilization of NPs by protein and its ability to protect the labile metal core from the solution environment by prohibiting the diffusion of reactive species. This approach can be extended to a wide variety of coating molecules and reactive metal nanoparticle systems to carefully survey their stability limits, revealing the likely mechanisms of coating breakdown and ensuing reactions.

Paleodosimetrical properties of sodium alkali feldspars and problems of luminescence dating of sediments

International Nuclear Information System (INIS)

Huett, Galina; Jaek, Ivar

1996-01-01

Emission spectra of natural alkali feldspars extracted from sediments are studied using a CCD-camera based high sensitivity spectrometer. Applying a semiconductor laser (860± 1 nm), two dominant emission bands, blue (410 nm) and orange (570 nm), are revealed in infrared optically stimulated luminescence (IROSL) spectra for the most of the sediments from Scandinavian sections. Luminescence and dosimetric al properties of the hole traps, the induced orange emission band typical of sodium alkali feldspars are studied. As a result, high light bleach ability but low stability of the dosimetric al information lit sodium alkali feldspars are established. Problems of luminescence dating of sediments based on the mixture of potassium-sodium alkali feldspars are discussed. (author)

Optically stimulated luminescence characteristics of natural and doped quartz and alkali feldspars

Energy Technology Data Exchange (ETDEWEB)

Huett, G.; Jaek, I.; Brodski, L. [Institute of Geology at Tallinn Technical University, Tallinn (Estonia); Vasilchenko, V. [Institute of Experimental Physics and Technology of Tartu University, Tartu (Estonia)

1999-05-01

Natural alkali feldspars and quartz were doped by Tl and Cu by thermodiffusion and electrodiffusion technology. As a result of doping, intensive UV emission bands were created. The OSL stimulation spectra of irradiated natural and doped quartz and alkali feldspars were measured in the span of 400-1300 nm using UV emission of Tl at 280 nm and of Cu at 380 nm. One-trap centre conception was confirmed for high-temperature palaeodosimetrical TL peaks and OSL stimulation spectrum bands: for alkali feldspars at 880 and 420 nm and visible region of the spectrum for quartz. A thermooptical mechanism of the optical depopulation of the corresponding trap is confirmed in alkali feldspars, but there is no evidence for processes of this kind in quartz. An analogy between the physical background of OSL properties of both minerals is discussed.

Optically stimulated luminescence characteristics of natural and doped quartz and alkali feldspars

International Nuclear Information System (INIS)

Huett, G.; Jaek, I.; Brodski, L.; Vasilchenko, V.

1999-01-01

Natural alkali feldspars and quartz were doped by Tl and Cu by thermodiffusion and electrodiffusion technology. As a result of doping, intensive UV emission bands were created. The OSL stimulation spectra of irradiated natural and doped quartz and alkali feldspars were measured in the span of 400-1300 nm using UV emission of Tl at 280 nm and of Cu at 380 nm. One-trap centre conception was confirmed for high-temperature palaeodosimetrical TL peaks and OSL stimulation spectrum bands: for alkali feldspars at 880 and 420 nm and visible region of the spectrum for quartz. A thermooptical mechanism of the optical depopulation of the corresponding trap is confirmed in alkali feldspars, but there is no evidence for processes of this kind in quartz. An analogy between the physical background of OSL properties of both minerals is discussed

Laboratory fading rates of various luminescence signals from feldspar-rich sediment extracts

DEFF Research Database (Denmark)

Thomsen, Kristina Jørkov; Murray, A.S.; Jain, Mayank

2008-01-01

Feldspar as a retrospective dosimeter is receiving more and more attention because of its useful luminescence properties; in particular the dose response curve extends to significantly higher doses than quartz. However, feldspars have one major disadvantage; both the thermoluminescence (TL...

Isochron measurements of naturally irradiated K-feldspar grains

International Nuclear Information System (INIS)

Li Bo; Li Shenghua; Wintle, Ann G.; Zhao Hui

2007-01-01

The equivalent doses of K-feldspar grains in a range of grain sizes from 90 to 250μm diameter were measured using a single-aliquot regenerative-dose protocol for the infrared stimulated luminescence (IRSL) signals for two samples of desert sand. The equivalent doses for each sample were compared with that for the 125-150μm grains of quartz from the same samples. The results suggested that the K-feldspar equivalent doses were underestimated because of anomalous fading. Measurements of the decay of the IRSL signals following laboratory irradiation for these two samples, and an additional one from a previously published isochron study, showed anomalous fading during the period of laboratory storage. The decay rate was about 3% per decade for all samples and was independent of the grain size used. Using plots of equivalent doses for K-feldspars as a function of their calculated internal dose rate, and the quartz equivalent dose as a function of grain size, it was concluded that the IRSL signal derived from the internal dose rate had not faded over the 13,000 years that had elapsed since the grains were deposited

Quantitative analysis of time-resolved infrared stimulated luminescence in feldspars

DEFF Research Database (Denmark)

Pagonis, Vasilis; Ankjærgaard, Christina; Jain, Mayank

2016-01-01

Time-resolved infrared-stimulated luminescence (TR-IRSL) from feldspar samples is of importance in the field of luminescence dating, since it provides information on the luminescence mechanism in these materials. In this paper we present new analytical equations which can be used to analyze TR-IR....... The equations are applied to experimental TR-IRSL data of natural feldspars, and good agreement is found between experimental and modeling results....

Characterisation and dissolution of depleted uranium aerosols produced during impacts of kinetic energy penetrators against a tank

Energy Technology Data Exchange (ETDEWEB)

Chazel, V.; Gerasimo, P.; Debouis, V.; Laroche, P.; Paquet, F

2003-07-01

Aerosols produced during impacts of depleted uranium (DU) penetrators against the glacis (sloping armour) and the turret of a tank were sampled. The concentration and size distribution were determined. Activity median aerodynamic diameters were 1 {mu}m (geometric standard deviation, s{sub g} = 3.7) and 2 {mu}m (s{sub g} = 2.5), respectively, for glacis and turret. The mean air concentration was 120 Bq m{sup -3}, i.e. 8.5 mg m{sup -3} of DU. Filters analysed by scanning electron microscopy (SEM) and X ray diffraction showed two types of particles (fine particles and large molten particles) composed mainly of a mixture of uranium and aluminium. The uranium oxides were mostly U{sub 3}O{sub 8}, UO{sub 2.25} and probably UO{sub 3.01} and a mixed compound of U and Al. The kinetics of dissolution in three media (HCO{sub 3}{sup -}, HCl and Gamble's solution) were determined using in-vitro tests. The slow dissolution rates were respectively slow, and intermediate between slow and moderate, and the rapid dissolution fractions were mostly intermediate between moderate and fast. According to the in-vitro results for Gamble's solution, and based on a hypothetical single acute inhalation of 90 Bq, effective doses integrated up to 1 y after incorporation were 0.54 and 0.56 mSv respectively, for aerosols from glacis and turret. In comparison, the ICRP limits are 20 mSv y{sup -1} for workers and 1 mSv y{sup -1} for members of public. A kidney concentration of approximately 0.1 {mu}g U g{sup -1} was predicted and should not, in this case, lead to kidney damage. (author)

Long-term kinetic effects and colloid formations in dissolution of LWR spent fuels

Energy Technology Data Exchange (ETDEWEB)

Ahn, T.M.

1996-11-01

This report evaluates continuous dissolution and colloid formation during spent-fuel performance under repository conditions in high-level waste disposal. Various observations suggest that reprecipitated layers formed on spent-fuel surfaces may not be protective. This situation may lead to continuous dissolution of highly soluble radionuclides such as C-14, Cl-36, Tc-99, I-129, and Cs-135. However, the diffusion limits of various species involved may retard dissolution significantly. For low-solubility actinides such as Pu-(239+240) or Am-(241+243), various processes regarding colloid formation have been analyzed. The processes analyzed are condensation, dispersion, and sorption. Colloid formation may lead to significant releases of low-solubility actinides. However, because there are only limited data available on matrix dissolution, colloid formation, and solubility limits, many uncertainties still exist. These uncertainties must be addressed before the significance of radionuclide releases can be determined. 118 refs.

Long-term kinetic effects and colloid formations in dissolution of LWR spent fuels

International Nuclear Information System (INIS)

Ahn, T.M.

1996-11-01

This report evaluates continuous dissolution and colloid formation during spent-fuel performance under repository conditions in high-level waste disposal. Various observations suggest that reprecipitated layers formed on spent-fuel surfaces may not be protective. This situation may lead to continuous dissolution of highly soluble radionuclides such as C-14, Cl-36, Tc-99, I-129, and Cs-135. However, the diffusion limits of various species involved may retard dissolution significantly. For low-solubility actinides such as Pu-(239+240) or Am-(241+243), various processes regarding colloid formation have been analyzed. The processes analyzed are condensation, dispersion, and sorption. Colloid formation may lead to significant releases of low-solubility actinides. However, because there are only limited data available on matrix dissolution, colloid formation, and solubility limits, many uncertainties still exist. These uncertainties must be addressed before the significance of radionuclide releases can be determined. 118 refs

Study of the dissolution of (U,P)O2 mixed oxides with a high plutonium content

International Nuclear Information System (INIS)

Fournier, S.

2001-01-01

Plutonium from nuclear reactors is partially integrated in the fuel cycle as Mixed OXide (U,Pu)O 2 (MOX). Their dissolution in nitric acid is needed to reprocess them in present reprocessing plants. The main difficulty of this study is that dissolution is a phenomenon depending on solution characteristics as well as the structural properties of the pellets, which depend themselves on the material fabrication process. After showing kinetic and thermodynamic dissolution data of mixed oxides in nitric media, an inventory of the parameters which affect the dissolution process has been made. A separable variable concept was introduced in order to describe the process by studying separately the role of chemical parameters of the solution and geometric parameters of the material. The first part of the study estimates the effect of nitric solution chemical parameters (concentrations, acidity, temperature) on the dissolution and underlines the role of the oxide surface protonation step. The second part of this work deals with the study of surface area evolution for materials with controlled plutonium rich heterogeneities. Experimental results show that the pellet surface undergoes erosion and is progressively weakened by the formation of fault lines in the bulk of the material followed by the dispersion of sub-millimeter fragments in the solution. An heterogeneous kinetic model derived from study of solid-gas interface systems has been applied to fuel pellets dissolution, allowing a mechanism to be proposed, based on surface dissolution of the oxide as well as fault creation in the volume. The dissolution kinetics are therefore dependant on the microstructure and mechanical strength and cohesion of the pellets. (author)

Zirconium-nickel crystals—hydrogen accumulators: Dissolution and penetration of hydrogen atoms in alloys

Science.gov (United States)

Matysina, Z. A.; Zaginaichenko, S. Yu.; Shchur, D. V.; Gabdullin, M. T.; Kamenetskaya, E. A.

2016-07-01

The calculation of the free energy, thermodynamic equilibrium equations, and kinetic equations of the intermetallic compound Zr2NiH x has been carried out based on molecular-kinetic concepts. The equilibrium hydrogen concentration depending on the temperature, pressure, and energy parameters has been calculated. The absorption-desorption of hydrogen has been studied, and the possibility of the realization of the hysteresis effect has been revealed. The kinetics of the dissolution and permeability of hydrogen is considered, the time dependence of these values has been found, and conditions for the extremum character of their time dependence have been determined. Relaxation times of the dissolution and permeability of hydrogen into the alloy have been calculated. The calculation results are compared with the experimental data available in the literature.

OSL-thermochronometry of feldspar from the KTB borehole, Germany

DEFF Research Database (Denmark)

Guralnik, Benny; Jain, Mayank; Herman, Frédéric

2015-01-01

a new thermochronometer based on the infrared stimulated luminescence (IRSL) from feldspar, and validate the extrapolation of its response to artificial radiation and heat in the laboratory to natural environmental conditions. Specifically, we present a new detailed Na-feldspar IRSL thermochronology...... the current geothermal gradient, or (ii) inverted into a geothermal palaeogradient of 29±2 °C km−1, integrating natural thermal conditions over the last ∼65 ka. The demonstrated ability to invert a depth–luminescence dataset into a meaningful geothermal palaeogradient opens new venues for reconstructing...

Single-grain dating of young sediments using the pIRIR signal from feldspar

DEFF Research Database (Denmark)

Reimann, Tony; Thomsen, Kristina Jørkov; Jain, Mayank

2012-01-01

In this article we test for the first time the potential of single-grains of K-rich feldspar to date well-bleached and poorly bleached sediments using a post-IR IRSL (pIRIR) protocol. We measure natural dose distributions using K-rich feldspars from four coastal samples applying the pIRIR protocol.......5%.The analysis of the well-bleached samples shows that only the brightest 30% of the grains give pIRIR single-grain ages in agreement with the age control; this effect may arise from the suggested correlation between blue emission and potassium content of individual grains. Comparison of single......-grain quartz and feldspar dose distributions from the poorly bleached samples shows that quartz is relatively better bleached; nevertheless, selection of a reliable ‘minimum’ feldspar dose was achieved using two different statistical models....

Aluminum Target Dissolution in Support of the Pu-238 Program

Energy Technology Data Exchange (ETDEWEB)

McFarlane, Joanna [ORNL; Benker, Dennis [ORNL; DePaoli, David W [ORNL; Felker, Leslie Kevin [ORNL; Mattus, Catherine H [ORNL

2014-09-01

Selection of an aluminum alloy for target cladding affects post-irradiation target dissolution and separations. Recent tests with aluminum alloy 6061 yielded greater than expected precipitation in the caustic dissolution step, forming up to 10 wt.% solids of aluminum hydroxides and aluminosilicates. We present a study to maximize dissolution of aluminum metal alloy, along with silicon, magnesium, and copper impurities, through control of temperature, the rate of reagent addition, and incubation time. Aluminum phase transformations have been identified as a function of time and temperature, using X-ray diffraction. Solutions have been analyzed using wet chemical methods and X-ray fluorescence. These data have been compared with published calculations of aluminum phase diagrams. Temperature logging during the transients has been investigated as a means to generate kinetic and mass transport data on the dissolution process. Approaches are given to enhance the dissolution of aluminum and aluminosilicate phases in caustic solution.

Iron removal on feldspar by using Averrhoa bilimbii as bioleaching agent

Science.gov (United States)

Amin, Muhammad; Aji, Bramantyo B.; Supriyatna, Yayat Iman; Bahfie, Fathan

2017-01-01

Investigation of Averrhoa bilimbii as bioleaching agent was carried out. Parameters of leaching duration, acid concentration, and temperature were performed in iron removal process. Feldspar with sized 149 µm was diluted in 30 ml acid solution in order to reduce its iron content. The experimental results showed a good technical feasibility of the process which iron oxide content of feldspar was decreased from 2.24% to 0.29%. The lowest iron concentration remained was obtained after 5 hours of leaching treatment at 60 °C, and concentrated (100 vol%) Averrhoa bilimbii extract as bioleaching agent. SEM characterizations were carried out on the feldspar before and after the leaching treatment. The result shows that there were no significant effect of leaching process on the ore morphology.

Effect of alteration phase formation on the glass dissolution rate

International Nuclear Information System (INIS)

Ebert, W.L.

1997-01-01

The dissolution rates of many glasses have been observed to increase upon the formation of certain alteration phases. While simulations have predicted the accelerating effect of formation of certain phases, the phases predicted to form in computer simulations are usually different than those observed to form in experiments. This is because kinetically favored phases form first in experiments, while simulations predict the thermodynamically favored phases. Static dissolution tests with crushed glass have been used to measure the glass dissolution rate after alteration phases form. Because glass dissolution rates are calculated on a per area basis, an important effect in tests conducted with crushed glass is the decrease in the surface area of glass that is available for reaction as the glass dissolves. This loss of surface area must be taken into account when calculating the dissolution rate. The phases that form and their effect on the dissolution rate are probably related to the glass composition. The impact of phase formation on the glass dissolution rate also varies according to the solubility products of the alteration phases and how the orthocilicic acid activity is affected. Insight into the relationship between the glass dissolution rate, solution chemistry and alteration phase formation is provided by the results of accelerated dissolution tests

Effect of alteration phase formation on the glass dissolution rate

Energy Technology Data Exchange (ETDEWEB)

Ebert, W L [Argonne National Laboratory, Chemical Technology Div. (United States)

1997-07-01

The dissolution rates of many glasses have been observed to increase upon the formation of certain alteration phases. While simulations have predicted the accelerating effect of formation of certain phases, the phases predicted to form in computer simulations are usually different than those observed to form in experiments. This is because kinetically favored phases form first in experiments, while simulations predict the thermodynamically favored phases. Static dissolution tests with crushed glass have been used to measure the glass dissolution rate after alteration phases form. Because glass dissolution rates are calculated on a per area basis, an important effect in tests conducted with crushed glass is the decrease in the surface area of glass that is available for reaction as the glass dissolves. This loss of surface area must be taken into account when calculating the dissolution rate. The phases that form and their effect on the dissolution rate are probably related to the glass composition. The impact of phase formation on the glass dissolution rate also varies according to the solubility products of the alteration phases and how the orthocilicic acid activity is affected. Insight into the relationship between the glass dissolution rate, solution chemistry and alteration phase formation is provided by the results of accelerated dissolution tests.

Salinity-Dependent Adhesion Response Properties of Aluminosilicate (K-Feldspar) Surfaces

DEFF Research Database (Denmark)

Lorenz, Bärbel; Ceccato, Marcel; Andersson, Martin Peter

2017-01-01

is composed predominantly of quartz with some clay, but feldspar grains are often also present. While the wettability of quartz and clay surfaces has been thoroughly investigated, little is known about the adhesion properties of feldspar. We explored the interaction of model oil compounds, molecules...... in well sorted sandstone. Adhesion forces, measured with the chemical force mapping (CFM) mode of atomic force microscopy (AFM), showed a low salinity effect on the fresh feldspar surfaces. Adhesion force, measured with -COO(H)-functionalized tips, was 60% lower in artificial low salinity seawater (LS......, ∼1500 ppm total dissolved solids) than in the high salinity solution, artificial seawater (HS, ASW, ∼35 600 ppm). Adhesion with the -CH3 tips was as much as 30% lower in LS than in HS. Density functional theory calculations indicated that the low salinity response resulted from expansion of the electric...

Feldspar basalts in lunar soil and the nature of the lunar continents

Science.gov (United States)

Reid, A. M.; Ridley, W. I.; Harmon, R. S.; Warner, J.; Brett, R.; Jakes, P.; Brown, R. W.

1974-01-01

It is found that 25% on the Apollo-14 glasses have the same composition as the glasses in two samples taken from the Luna-16 column. The compositions are equivalent to feldspar basalt and anorthosite gabbro, and are similar to the feldspar basalts identified from Surveyor-7 analysis for lunar continents.

Dissolution kinetics of heulandite at pH 2--12 and 25 degrees C

International Nuclear Information System (INIS)

Ragnarsdottir, K.V.

1993-01-01

Because of their favourable cation exchange reactions, heulandite and clinoptilolite have been suggested as being capable of immobilizing radionuclides and therefore could possibly act as an important barrier for nuclear waste. Recent studies of laboratory-reacted minerals indicate, however, that hydrated surface layers tend to accumulate highly hydrolyzable heavy elements. These hydrated layers may therefore be the most important retardants for radionuclides. The dissolution rate of heulandite depends strongly on pH. Based on silica release, the logarithm of the steady-state dissolution rate at pH 2 is -13.1 mol cm -2 s -1 . The logarithm of the rate decreases to -15.8 mol cm -2 s -1 at pH 7.2 and increases again to -14.6 mol cm -2 s -1 at pH 12.2. At low pH, Al is released preferentially to silica; but at intermediate and high pH, the release of silica appears to be congruent relative to Al. The change in dissolution rate with pH indicates that at low pH, the dissolution mechanism is controlled by the detachment of a positively charged Al species, >Al-OH 2 + . Below pH 5, however, a silica-rich surface layer is formed requiring diffusion through the layer. At intermediate and high pH, it is likely that the dissolution rate is controlled by the detachment of a negatively charged silica species, >Si - O - . The reaction order of the hydrogen ion under low pH conditions is 0.7, and the reaction order of the OH - ion is 0.3 at high pH. The measured dissolution rates indicate that a 1 mm heulandite crystal would dissolve in 300,000 yrs if the solution composition is maintained undersaturated. 75 refs., 11 figs., 3 tabs

Study on the dissolution of uranium dibutyl phosphate deposits

International Nuclear Information System (INIS)

Rufus, A.L.; Sathyaseelan, V.S.; Velmurugan, S.; Narasimhan

2008-01-01

An insoluble sticky complex of uranium dibutyl phosphate (U-DBP) formed on the inner surfaces of a reprocessing facility can host radioactive nuclides resulting in radiation exposure hazard. Removal of this layer will greatly result in the reduction of radiation field. Hence, dissolution studies with synthetically prepared U-DBP were carried out. A two-step dissolution process consisting of an initial oxidation with acid permanganate followed by reduction with NAC (NTA, Ascorbic acid and Citric acid) was used. Oxidation kinetics of DBP by permanganate, dissolution of synthetic U-DBP complex as a powder and also as a film over SS surface was studied. XRF and SEM techniques were used to monitor the process of dissolution. Material compatibility of welded SS-304 specimens was also studied. It was found that the two-step process was more efficient when compared to either permanganate or NAC treatment alone. (author)

Study on the dissolution of uranium dibutyl phosphate deposits

Energy Technology Data Exchange (ETDEWEB)

Rufus, A.L.; Sathyaseelan, V.S.; Velmurugan, S.; Narasimhan [Bhabha Atomic Research Centre Facilities, Water and Steam Chemistry Div., Kalpakkam (India)], E-mail: svn@igcar.gov.in

2008-07-01

An insoluble sticky complex of uranium dibutyl phosphate (U-DBP) formed on the inner surfaces of a reprocessing facility can host radioactive nuclides resulting in radiation exposure hazard. Removal of this layer will greatly result in the reduction of radiation field. Hence, dissolution studies with synthetically prepared U-DBP were carried out. A two-step dissolution process consisting of an initial oxidation with acid permanganate followed by reduction with NAC (NTA, Ascorbic acid and Citric acid) was used. Oxidation kinetics of DBP by permanganate, dissolution of synthetic U-DBP complex as a powder and also as a film over SS surface was studied. XRF and SEM techniques were used to monitor the process of dissolution. Material compatibility of welded SS-304 specimens was also studied. It was found that the two-step process was more efficient when compared to either permanganate or NAC treatment alone. (author)

Stoneware tile manufacturing using rice straw ash as feldspar replacement

International Nuclear Information System (INIS)

Alvaro Guzman, A.; John Torres, L.; Martha Cedeno, V.; Silvio Delvasto, A.; Vicente Amigo, B.; Enrique Sanchez, V.

2013-01-01

In this research are presented the results of using rice straw ash (RSA) in low proportions as substitute of feldspar for manufacturing stoneware tiles. Specimens of semidry triaxial mixtures, where feldspar was substituted for different percentages (25 % and 50 %) of RSA, were prepared by uniaxial pressing, followed by drying and sintering. Physical and mechanical properties of sintered bodies were evaluated. Porcelain stoneware tile specimens C0 and CF25 reached bending strength and water absorption values were in accordance with standard ISO 13006 (Annex G, BIa) ( ≥ 35 MPa and ≤ 0.5 %, respectively). However, in porcelain stoneware tile specimens CF50 due to bloating phenomenon was not possible obtain commercial tiles in accordance with standard ISO 13006. By using Scanning Electron Microscopy (SEM) needles of primary and secondary mullite were identified in a vitreous phase; and by using X-Ray Diffraction (XRD) mullite and quartz phases were identified. It was concluded that feldspar can be substituted positively by RSA in stoneware tile pastes. (Author)

Probing luminescence centers in Na rich feldspar

DEFF Research Database (Denmark)

Prasad, Amit Kumar; Lapp, Torben; Kook, Myung Ho

2016-01-01

our understanding of the luminescence mechanisms and recombination sites, in a sample of Na rich plagioclase feldspar (oligoclase). Both the UV and violet–blue emissions show resonant excitations arising from a distribution of energy levels. We propose, contrary to the general understanding...

Determining the K-content of single-grains of feldspar for luminescence dating

International Nuclear Information System (INIS)

Smedley, R.K.; Duller, G.A.T.; Pearce, N.J.G.; Roberts, H.M.

2012-01-01

Feldspars form a solid-solution series whereby the K-content may range from 0 to 14%. LA-ICP-MS measurements for density-separated single-grains of feldspar yielded realistic concentrations of K within the range of those naturally occurring, and also highlighted the difficulty in isolating the pure end members during density-separation. No direct relationship was found between the thermal stability of the infrared-stimulated luminescence (IRSL) signal and measured K-content of individual grains. However, the brightest IRSL and post-IR IRSL signals originated from grains with ∼12% K-content. All grains giving a measurable signal had K-content between 6 and 13%, therefore it is suggested that an internal K-content of 10 ± 2% can be assumed for routine single-grain dating of density-separated K-feldspars. - Highlights: ► Measure range of K for single-grains of density separated feldspar using LA-ICP-MS. ► Single-grain thermal stability and brightness do not directly relate to K-content. ► Brightest 3 grains measured ∼12% K and provided the majority of the IRSL signals.

Dissolution of minerals with rough surfaces

Science.gov (United States)

de Assis, Thiago A.; Aarão Reis, Fábio D. A.

2018-05-01

We study dissolution of minerals with initial rough surfaces using kinetic Monte Carlo simulations and a scaling approach. We consider a simple cubic lattice structure, a thermally activated rate of detachment of a molecule (site), and rough surface configurations produced by fractional Brownian motion algorithm. First we revisit the problem of dissolution of initial flat surfaces, in which the dissolution rate rF reaches an approximately constant value at short times and is controlled by detachment of step edge sites. For initial rough surfaces, the dissolution rate r at short times is much larger than rF ; after dissolution of some hundreds of molecular layers, r decreases by some orders of magnitude across several time decades. Meanwhile, the surface evolves through configurations of decreasing energy, beginning with dissolution of isolated sites, then formation of terraces with disordered boundaries, their growth, and final smoothing. A crossover time to a smooth configuration is defined when r = 1.5rF ; the surface retreat at the crossover is approximately 3 times the initial roughness and is temperature-independent, while the crossover time is proportional to the initial roughness and is controlled by step-edge site detachment. The initial dissolution process is described by the so-called rough rates, which are measured for fixed ratios between the surface retreat and the initial roughness. The temperature dependence of the rough rates indicates control by kink site detachment; in general, it suggests that rough rates are controlled by the weakest microscopic bonds during the nucleation and formation of the lowest energy configurations of the crystalline surface. Our results are related to recent laboratory studies which show enhanced dissolution in polished calcite surfaces. In the application to calcite dissolution in alkaline environment, the minimal values of recently measured dissolution rate spectra give rF ∼10-9 mol/(m2 s), and the calculated rate

Use of micro-reactors to obtain new insights into the factors influencing tricalcium silicate dissolution

International Nuclear Information System (INIS)

Suraneni, Prannoy; Flatt, Robert J.

2015-01-01

A micro-reactor approach, developed previously, is used to study the early dissolution of tricalcium silicate. This approach uses micron-sized gaps mimicking particles in close contact to understand dissolution, nucleation, and growth processes. The main factors influencing the dissolution kinetics of tricalcium silicate are presented. We show that the presence of defects caused by polishing does not affect the extent of dissolution. A strong effect of aluminum in solution reducing the extent of dissolution is however identified. This effect is highly dependent on the pH, and is much lower above pH 13. We show also that superplasticizers reduce the extent of dissolution; however, the exact reason for this effect is not clear.

OSL, TL and IRSL emission spectra of sedimentary quartz and feldspar samples

International Nuclear Information System (INIS)

Lomax, Johanna; Mittelstraß, Dirk; Kreutzer, Sebastian; Fuchs, Markus

2015-01-01

This contribution presents a variety of different luminescence emission spectra from sedimentary feldspar and quartz samples under various stimulation modes. These are green stimulated quartz (OSL-) spectra, quartz TL spectra, feldspar IRSL and post-IR IRSL spectra. A focus was set at recording OSL and IRSL spectra at elevated stimulation temperatures such as routinely applied in luminescence dating. This was to test whether optical stimulation at elevated temperatures results in a shift of emission peaks. For OSL emissions of quartz, this has so far not been tested. In case of feldspar emissions, post-IR IRSL conditions, hence IRSL emissions at a low temperature, directly followed by high temperature post-IRSL emissions, are explicitly investigated. All spectra were recorded using a new system incorporated into a Lexsyg luminescence reader. Thus, this study, besides presenting new spectral data, also serves as a feasibility study for this new device. It is shown that (a) the new device is capable of automatically measuring different sorts of spectra, also at elevated temperatures, (b) known thermally and optically stimulated peak emissions of quartz and feldspar are confirmed, (c) obtained IRSL and OSL spectra indicate that there is no significant relation between peak emission and stimulation temperature. - Highlights: • We have measured OSL, IRSL and TL emission spectra of sedimentary quartz and feldspar samples. • Spectral analyses were performed at elevated stimulation temperatures. • Emission spectra show very little variation with stimulation temperatures.

Further investigations into pulsed optically stimulated luminescence from feldspars using blue and green light

DEFF Research Database (Denmark)

Ankjærgaard, Christina; Jain, Mayank; Kalchgruber, R.

2009-01-01

The purpose of this paper is to investigate characteristics of luminescence signals resulting from pulsed optical stimulation of feldspars and thereby to understand the underlying processes giving rise to the signal. Fourteen different feldspar specimens were investigated using time-resolved opti......The purpose of this paper is to investigate characteristics of luminescence signals resulting from pulsed optical stimulation of feldspars and thereby to understand the underlying processes giving rise to the signal. Fourteen different feldspar specimens were investigated using time...... suggests that the TR-OSL signal decay is governed by the recombination process and not by the excited state lifetime. Furthermore data from the TR-OSL signal dependence on stimulation time and preheat temperature suggest that the recombination process may not be a sum of exponentials, although the model...... cannot be rejected definitively....

Dissolution kinetics of UO2: Flow-through tests on UO2.00 pellets and polycrystalline schoepite samples in oxygenated, carbonate/bicarbonate buffer solutions at 25 degree C

International Nuclear Information System (INIS)

Nguyen, S.N.; Weed, H.C.; Leider, H.R.; Stout, R.B.

1991-10-01

The modelling of radionuclide release from waste forms is an important part of the performance assessment of a potential, high-level radioactive waste repository. Since spent fuel consists of UO 2 containing actinide elements and other fission products, it is necessary to determine the principal parameters affecting UO 2 dissolution and quantify their effects on the dissolution rate before any prediction of long term release rates of radionuclides from the spent fuel can be made. As part of a complex matrix to determine the dissolution kinetics of UO 2 as a function of time, pH, carbonate/bicarbonate concentration and oxygen activity, we have measured the dissolution rates at 25 degrees C of: (1) UO 2 pellets; (2) UO 2.00 powder and (3) synthetic dehydrated schoepite, UO 3 .H 2 O using a single-pass flow through system in an argon-atmosphere glove box. Carbonate, carbonate/bicarbonate, and bicarbonate buffers with concentrations ranging from 0.0002 M to 0.02 M and pH values form 8 to 11 have been used. Argon gas mixtures containing oxygen (from 0.002 to 0.2 atm) and carbon dioxide (from 0 to 0.011 atm) were bubbled through the buffers to stabilize their pH values. 12 refs., 2 tabs

Application of pulsed OSL to the separation of the luminescence components from a mixed quartz/feldspar sample

International Nuclear Information System (INIS)

Denby, P.M.; Botter-Jensen, L.; Murray, A.S.; Thomsen, K.J.; Moska, P.

2006-01-01

It is known that the pulsed optically stimulated luminescence (OSL) characteristics of quartz and feldspars are very different. These differences can be used to preferentially discriminate against the feldspar signal in mixed quartz-bar feldspar mineral assemblages, or in separated quartz contaminated with a feldspar signal. We have developed instrumentation for the study of high-speed pulse stimulated OSL. Our system uses the standard blue/IR LED stimulation unit of a Riso reader (allowing stimulation pulses down to 1-2μs duration) and can thus be applied to the routine analysis of samples. Using this stimulation source, and high-speed photon timing, the OSL yield can be monitored throughout the pulsing cycle and subsequent OSL decay. It is found that the total photon yield per unit stimulation power in pulsed mode is, for quartz, twice and, for feldspar, nearly four times, that in continuous wave mode. Observation of this OSL signal, between stimulation pulses, is seen to be characteristic of the mineral being examined, and has been used to preferentially discriminate against feldspar contamination in a mixed quartz/feldspar sample. Simple implementation of this technique by gating the counting period, so that counts are only accumulated during a windowed period, reduces the feldspar signal to 1.6% of its original value relative to that of the quartz

Natural radioactivity and Rare Earth elements in feldspar samples, Central Eastern desert, Egypt

International Nuclear Information System (INIS)

Walley El-Dine, Nadia; El-Shershaby, Amal; Afifi, Sofia; Sroor, Amany; Samir, Eman

2011-01-01

The pegmatite bodies of the Eastern Desert of Egypt are widely distributed especially along the Marsa-Alam-Idfu road. The Abu Dob area covers about 150 km 2 of the Arabian Nubian shield at the central part of the Eastern Desert of Egypt. Most of the pegmatite is zoned; the zonation starts with milky quartz at the core followed by alkali feldspar at the margins. The feldspars vary in color from rose to milky and in composition from K-feldspar to Na-feldspar, sometimes interactions of both types are encountered. Thirteen feldspar samples were collected from different locations in the Abu Dob area for measuring the natural radioactivity of 238 U, 232 Th and 40 K using an HPGe detector. The variation in concentration of radionuclides for the area under investigation can be classified into regions of high, medium and low natural radioactivity. The average concentration in BqKg -1 has been observed to be from 9.5 to 183675.7 BqKg -1 for 238 U, between 6.1 and 94,314.2 BqKg -1 for 232 Th and from 0 to 7894.6 BqKg -1 for 40 K. Radium equivalent activities (Ra eq ), dose rate (D R ) and external hazard (H ex ) have also been determined. In the present work, the concentration of rare earth elements are measured for two feldspar samples using two techniques, Environmental Scanning Electron microscope XIL 30 ESEM, Philips, and Inductively Coupled Plasma Mass Spectroscopy (ICP-MS). The existence of rare earth elements in this area are very high and can be used in different important industries.

Natural radioactivity and Rare Earth elements in feldspar samples, Central Eastern desert, Egypt

Energy Technology Data Exchange (ETDEWEB)

Walley El-Dine, Nadia, E-mail: nadia_walley5@hotmail.co [Department of physics, Faculty of girls for Art, Science and Education, Ain Shams University, Heliopolis, Cairo (Egypt); El-Shershaby, Amal [Department of physics, Faculty of girls for Art, Science and Education, Ain Shams University, Heliopolis, Cairo (Egypt); Afifi, Sofia [Nuclear Materials Authority (Egypt); Sroor, Amany; Samir, Eman [Department of physics, Faculty of girls for Art, Science and Education, Ain Shams University, Heliopolis, Cairo (Egypt)

2011-05-15

The pegmatite bodies of the Eastern Desert of Egypt are widely distributed especially along the Marsa-Alam-Idfu road. The Abu Dob area covers about 150 km{sup 2} of the Arabian Nubian shield at the central part of the Eastern Desert of Egypt. Most of the pegmatite is zoned; the zonation starts with milky quartz at the core followed by alkali feldspar at the margins. The feldspars vary in color from rose to milky and in composition from K-feldspar to Na-feldspar, sometimes interactions of both types are encountered. Thirteen feldspar samples were collected from different locations in the Abu Dob area for measuring the natural radioactivity of {sup 238}U, {sup 232}Th and {sup 40}K using an HPGe detector. The variation in concentration of radionuclides for the area under investigation can be classified into regions of high, medium and low natural radioactivity. The average concentration in BqKg{sup -1} has been observed to be from 9.5 to 183675.7 BqKg{sup -1} for {sup 238}U, between 6.1 and 94,314.2 BqKg{sup -1} for {sup 232}Th and from 0 to 7894.6 BqKg{sup -1} for {sup 40}K. Radium equivalent activities (Ra{sub eq}), dose rate (D{sub R}) and external hazard (H{sub ex}) have also been determined. In the present work, the concentration of rare earth elements are measured for two feldspar samples using two techniques, Environmental Scanning Electron microscope XIL 30 ESEM, Philips, and Inductively Coupled Plasma Mass Spectroscopy (ICP-MS). The existence of rare earth elements in this area are very high and can be used in different important industries.

The dissolution of chalcopyrite in chloride media; Lixiviacion de la calcopirita en medios clorurados

Energy Technology Data Exchange (ETDEWEB)

Ibanez, T.; Velasquez, L.

2013-06-01

The aim of this investigation is to determinate the effects of parameters and additives on the kinetics of dissolution of chalcopyrite on moderated conditions by means of dissolutions test with chalcopyrite concentrate and pure chalcopyrite in shake flasks and instrumented stirred reactors. A study of the dissolution of chalcopyrite in chloride solutions has demonstrated that the rate of dissolution of chalcopyrite is strongly dependent on the potential of the solution within a range of 540 to 630 mV (versus SHE). Leaching at pH around 2.5 results in increased rates of copper dissolution suggesting the possibility to keep the solution potential within the range. Both pyrite and silver ions enhance the dissolution of chalcopyrite and this effect increases when both species are present. The MnO{sub 2} has a negative effect on the dissolution increasing the solution potential to values where the rate decreases considerably. (Author)

IRSL dating of K-feldspars: Modelling natural dose response curves to deal with anomalous fading and trap competition

International Nuclear Information System (INIS)

Kars, Romee H.; Wallinga, Jakob

2009-01-01

We recently proposed a model that reconstructs the natural dose response curve for K-rich feldspars, using laboratory fading measurements and dose response as input parameters. The model is based on the relationship between recombination centre density and trap lifetime. In this study we test the working of the model by comparing modelled feldspar ages with known quartz OSL ages of the same samples and with anomalous fading-corrected feldspar ages. The modelled feldspar ages are in good agreement with quartz OSL ages and corrected feldspar ages, opening possibilities for future use of the model on samples without independent age constraints. Furthermore, we investigate the effects of trap competition on the build-up of IRSL signal using two new variations of the model. Results show that incorporating trap competition into the model reduces the agreement between feldspar IRSL ages and quartz OSL ages.

Radionuclide transport in fractured porous media -- Analytical solutions for a system of parallel fractures with a kinetic solubility-limited dissolution model

International Nuclear Information System (INIS)

Li, S.H.; Chen, C.T.

1997-01-01

Analytical solutions are developed for the problem of radionuclide transport in a system of parallel fractures situated in a porous rock matrix. A kinetic solubility-limited dissolution model is used as the inlet boundary condition. The solutions consider the following processes: (a) advective transport in the fractures, (b) mechanical dispersion and molecular diffusion along the fractures, (c) molecular diffusion from a fracture to the porous matrix, (d) molecular diffusion within the porous matrix in the direction perpendicular to the fracture axis, (e) adsorption onto the fracture wall, (f) adsorption within the porous matrix, and (g) radioactive decay. The solutions are based on the Laplace transform method. The general transient solution is in the form of a double integral that is evaluated using composite Gauss-Legendre quadrature. A simpler transient solution that is in the form of a single integral is also presented for the case that assumes negligible longitudinal dispersion along the fractures. The steady-state solutions are also provided. A number of examples are given to illustrate the effects of the following important parameters: (a) fracture spacings, (b) dissolution-rate constants, (c) fracture dispersion coefficient, (d) matrix retardation factor, and (e) fracture retardation factor

Optimising the separation of quartz and feldspar optically stimulated luminescence using pulsed excitation

International Nuclear Information System (INIS)

Ankjaergaard, C.; Jain, M.; Thomsen, K.J.; Murray, A.S.

2010-01-01

In luminescence dating, the two most commonly used natural minerals, quartz and feldspar, are exposed to different dose rates in the natural environment, and so record different doses. The luminescence signals also have different stabilities. For accurate dosimetry, the signals from these two minerals must be separated, either by physical separation of the mineral grains, or by instrumental separation of the luminescence signals. The luminescence signals from quartz and feldspar have different luminescence lifetimes under pulsed optical stimulation. This difference in lifetime can be used to discriminate between the two signals from a mixed quartz-feldspar sample. The purpose of this study is to identify optimum measurement conditions for the best separation of quartz OSL from that of feldspar in a mixed sample using pulsed stimulation and time-resolved OSL. We integrate the signal from 5 μs after the LEDs are switched off until just before the LEDs are switched on again, with the pulse on-time equal to the pulse off-time of 50 μs. By using only the initial interval of the pulsed OSL decay curve (equivalent to 0.2 s of CW-OSL using blue light at 50 mW cm -2 ) we find that the quartz to feldspar pulsed OSL intensity ratio is at a maximum. By using these parameters with an additional infrared (IR) stimulation at 175 o C before measurement (to further reduce the feldspar signal intensity), we obtain a factor of 25 enhancement in signal separation compared to that from a conventional prior-IR CW measurement. This ratio can be further improved if the counting window in the pulse off-time is restricted to detect between 20 and 50 μs instead of the entire off-period.

Mesoporous Silica Molecular Sieve based Nanocarriers: Transpiring Drug Dissolution Research.

Science.gov (United States)

Pattnaik, Satyanarayan; Pathak, Kamla

2017-01-01

Improvement of oral bioavailability through enhancement of dissolution for poorly soluble drugs has been a very promising approach. Recently, mesoporous silica based molecular sieves have demonstrated excellent properties to enhance the dissolution velocity of poorly water-soluble drugs. Current research in this area is focused on investigating the factors influencing the drug release from these carriers, the kinetics of drug release and manufacturing approaches to scale-up production for commercial manufacture. This comprehensive review provides an overview of different methods adopted for synthesis of mesoporous materials, influence of processing factors on properties of these materials and drug loading methods. The drug release kinetics from mesoporous silica systems, the manufacturability and stability of these formulations are reviewed. Finally, the safety and biocompatibility issues related to these silica based materials are discussed. Copyright© Bentham Science Publishers; For any queries, please email at epub@benthamscience.org.

The dissolution behavior of borosilicate glasses in far-from equilibrium conditions

Science.gov (United States)

Neeway, James J.; Rieke, Peter C.; Parruzot, Benjamin P.; Ryan, Joseph V.; Asmussen, R. Matthew

2018-04-01

An area of agreement in the waste glass corrosion community is that, at far-from-equilibrium conditions, the dissolution of borosilicate glasses used to immobilize nuclear waste is known to be a function of both temperature and pH. The aim of this work is to study the effects of temperature and pH on the dissolution rate of three model nuclear waste glasses (SON68, ISG, AFCI). The dissolution rate data are then used to parameterize a kinetic rate model based on Transition State Theory that has been developed to model glass corrosion behavior in dilute conditions. To do this, experiments were conducted at temperatures of 23, 40, 70, and 90 °C and pH (22 °C) values of 9, 10, 11, and 12 with the single-pass flow-through (SPFT) test method. Both the absolute dissolution rates and the rate model parameters are compared with previous results. Rate model parameters for the three glasses studied here are nearly equivalent within error and in relative agreement with previous studies though quantifiable differences exist. The glass dissolution rates were analyzed with a linear multivariate regression (LMR) and a nonlinear multivariate regression performed with the use of the Glass Corrosion Modeling Tool (GCMT), with which a robust uncertainty analysis is performed. This robust analysis highlights the high degree of correlation of various parameters in the kinetic rate model. As more data are obtained on borosilicate glasses with varying compositions, a mathematical description of the effect of glass composition on the rate parameter values should be possible. This would allow for the possibility of calculating the forward dissolution rate of glass based solely on composition. In addition, the method of determination of parameter uncertainty and correlation provides a framework for other rate models that describe the dissolution rates of other amorphous and crystalline materials in a wide range of chemical conditions. The higher level of uncertainty analysis would provide

Dissolution behavior of irradiated mixed oxide fuel with short stroke shearing for fast reactor reprocessing

International Nuclear Information System (INIS)

Ikeuchi, Hirotomo; Sano, Yuichi; Shibata, Atsuhiro; Koizumi, Tsutomu; Washiya, Tadahiro

2013-01-01

An efficient dissolution process was established for future reprocessing in which mixed-oxide (MOX) fuels with high plutonium contents and dissolver solution with high heavy-metal (HM) concentrations (more than 500 g dm -3 ) will be treated. This dissolution process involves short stroke shearing of fuels (∼10 mm in length). The dissolution kinetics of irradiated MOX fuels and the effects of the Pu content, HM concentration, and fuel form on the dissolution rate were investigated. Irradiated fuel was found to dissolve as 10 2 -10 3 times fast as non-irradiated fuel, but the rate decreased with increasing Pu content. Kinetic analysis based on the fragmentation model, which considers the penetration and diffusion of nitric acid through fuel matrices prior to chemical reaction, indicated that the dissolution rate of irradiated fuel was affected not only by the volume ratio of liquid to solid (L/S ratio) but also by the exposed surface area per unit mole of nitric acid (A/m ratio). The penetration rate of nitric acid is expected to be decreased at high HM concentrations by a reduction in the L/S ratio, but enhanced by shearing the fuel pieces with short strokes and thus enlarging the A/m ratio. (author)

Oxidative dissolution of ruthenium deposits onto stainless steel by permanganate ions in alkaline medium

Energy Technology Data Exchange (ETDEWEB)

Floquet, S.; Eysseric, C.; Maurel, D. [Commissariat a l' Energie Atomique (CEA/Valrho), Bagnols-sur-Ceze (France)

2008-07-01

During spent nuclear fuel reprocessing ruthenium is liable to form black ruthenium deposits on the stainless steel walls of process equipments. These deposits promote corrosion and can eventually obstruct the off-gas lines. The results of decontamination of 304L stainless steel test specimens covered with RuO(OH){sub 2} . xH{sub 2}O deposits by permanganate ions in alkaline medium are described. The ruthenium deposits were dissolved by oxidation of RuO(OH){sub 2} to RuO{sub 4}{sup 2-} ions, while the permanganate ions were reduced to MnO{sub 4}{sup 2-} ions and then to manganese dioxide MnO{sub 2}. The parameters affecting the kinetics of oxidative dissolution of these deposits were examined. The results indicate that the oxidative dissolution kinetics depends on the instantaneous surface area of the deposit, and that the dissolution rate increases with the concentrations of MnO{sub 4}{sup -} and OH{sup -} ions. (orig.)

Effect of ageing of K-feldspar on its ice nucleating efficiency in immersion, deposition and contact freezing modes

Science.gov (United States)

Peckhaus, Andreas; Bachmann, Felix; Hoffmann, Nadine; Koch, Michael; Kiselev, Alexei; Leisner, Thomas

2015-04-01

Recently K-feldspar was identified as one of the most active atmospheric ice nucleating particles (INP) of mineral origin [1]. Seeking the explanation to this phenomena we have conducted extensive experimental investigation of the ice nucleating efficiency of K-feldspar in three heterogeneous freezing modes. The immersion freezing of K-feldspar was investigated with the cold stage using arrays of nanoliter-size droplets containing aqueous suspension of polydisperse feldspar particles. For contact freezing, the charged droplets of supercooled water were suspended in the laminar flow of the DMA-selected feldspar-containing particles, allowing for determination of freezing probability on a single particle-droplet contact [2]. The nucleation and growth of ice via vapor deposition on the crystalline surfaces of macroscopic feldspar particles have been investigated in the Environmental Scanning Electron Microscope (ESEM) under humidified nitrogen atmosphere. The ice nucleation experiments were supplemented with measurements of effective surface area of feldspar particles and ion chromatography (IC) analysis of the leached framework cations (K+, Na+, Ca2+, Mg2+). In this contribution we focus on the role of surface chemistry influencing the IN efficiency of K-feldspar, in particular the connection between the degree of surface hydroxylation and its ability to induce local structural ordering in the interfacial layer in water molecules (as suggested by recent modeling efforts). We mimic the natural process of feldspar ageing by suspending it in water or weak aqueous solution of carbonic acid for different time periods, from minutes to months, and present its freezing efficiency as a function of time. Our immersion freezing experiments show that ageing have a nonlinear effect on the freezing behavior of feldspar within the investigated temperature range (-40°C to -10°C). On the other hand, deposition nucleation of ice observed in the ESEM reveals clear different pattern

Climatic aridity over India 11,000 years ago: Evidence from feldspar distribution in shelf sediments

Digital Repository Service at National Institute of Oceanography (India)

Hashimi, N.H.; Nair, R.R.

Feldspars and quartz contents of sand and silt fractions of forty three samples from the western continental shelf of India were determined by the X-ray diffraction method. The results indicate that the feldspar content in the relict (9000...

Use of rice straw ash as substitute of feldspar in triaxial porcelain

OpenAIRE

Guzmán, Álvaro; Delvasto, Silvio; Sánchez, Enrique; Amigó Borrás, Vicente

2013-01-01

[EN] The substitution of raw materials for processing high energy consumption materials by agricultural and agro-industrial wastes causes a positive impacts on the environment preservation. One of these residues is rice straw, which according to FAO estimation, its annual production is about 600 million tons. In this research was studied the use of rice straw ash (RSA) as substitute of the use of feldspar in the whiteware production. Clay-feldspar-quartz porcelains are referred to...

Developing a quality by design approach to model tablet dissolution testing: an industrial case study.

Science.gov (United States)

Yekpe, Ketsia; Abatzoglou, Nicolas; Bataille, Bernard; Gosselin, Ryan; Sharkawi, Tahmer; Simard, Jean-Sébastien; Cournoyer, Antoine

2017-11-02

This study applied the concept of Quality by Design (QbD) to tablet dissolution. Its goal was to propose a quality control strategy to model dissolution testing of solid oral dose products according to International Conference on Harmonization guidelines. The methodology involved the following three steps: (1) a risk analysis to identify the material- and process-related parameters impacting the critical quality attributes of dissolution testing, (2) an experimental design to evaluate the influence of design factors (attributes and parameters selected by risk analysis) on dissolution testing, and (3) an investigation of the relationship between design factors and dissolution profiles. Results show that (a) in the case studied, the two parameters impacting dissolution kinetics are active pharmaceutical ingredient particle size distributions and tablet hardness and (b) these two parameters could be monitored with PAT tools to predict dissolution profiles. Moreover, based on the results obtained, modeling dissolution is possible. The practicality and effectiveness of the QbD approach were demonstrated through this industrial case study. Implementing such an approach systematically in industrial pharmaceutical production would reduce the need for tablet dissolution testing.

Complex Diffusion Mechanisms for Li in Feldspar: Re-thinking Li-in-Plag Geospeedometry

Science.gov (United States)

Holycross, M.; Watson, E. B.

2017-12-01

In recent years, the lithium isotope system has been applied to model processes in a wide variety of terrestrial environments. In igneous settings, Li diffusion gradients have been frequently used to time heating episodes. Lithium partitioning behavior during decompression or cooling events drives Li transfer between phases, but the extent of Li exchange may be limited by its diffusion rate in geologic materials. Lithium is an exceptionally fast diffuser in silicate media, making it uniquely suited to record short-lived volcanic phenomena. The Li-in-plagioclase geospeedometer is often used to time explosive eruptions by applying laboratory-calibrated Li diffusion coefficients to model concentration profiles in magmatic feldspar samples. To quantify Li transport in natural scenarios, experimental measurements are needed that account for changing temperature and oxygen fugacity as well as different feldspar compositions and crystallographic orientation. Ambient pressure experiments were run at RPI to diffuse Li from a powdered spodumene source into polished sanidine, albite, oligoclase or anorthite crystals over the temperature range 500-950 ºC. The resulting 7Li concentration gradients developed in the mineral specimens were evaluated using laser ablation ICP-MS. The new data show that Li diffusion in all feldspar compositions simultaneously operates by both a "fast" and "slow" diffusion mechanism. Fast path diffusivities are similar to those found by Giletti and Shanahan [1997] for Li diffusion in plagioclase and are typically 10 to 20 times greater than slow path diffusivities. Lithium concentration gradients in the feldspar experiments plot in the shape of two superimposed error function curves with the slow diffusion regime in the near-surface of the crystal. Lithium diffusion is most sluggish in sanidine and is significantly faster in the plagioclase feldspars. It is still unclear what diffusion mechanism operates in nature, but the new measurements may impact

Dissolution rates of over-the-counter painkillers: a comparison among formulations.

Science.gov (United States)

Alemanni, Matteo; Gatoulis, Sergio C; Voelker, Michael

2016-06-01

We wanted to compare the dissolution profile of several over-the-counter analgesics to understand whether the different formulation techniques employed to enhance absorption were associated with variations in the dissolution rate, a parameter known to affect drug absorption. We considered 5 formulations currently marketed in Italy: aspirin tablets (Aspirina Dolore e Infiammazione®), ibuprofen tablets and liquid capsules (Moment®), ibuprofen lysine tablets (Nurofenimmedia®) and dexketoprofen trometamol tablets (Enantyum®). Dissolution tests were performed according to the current USP/NF monograph dissolution procedure. Drug dissolution was evaluated at 1, 3, 6, 15, and 30 minutes since the start of the test. Dissolution was evaluated at three different pH: 1.2, 4.5 and 6.8. Every test was repeated 12 times. The aspirin formulation was by far the most rapid dissolving formulation, among those tested, with more than 80% of the tablet dissolved at 6 minutes for every pH considered. At pH 1.2 and 4.5, only the dexketoprofen formulation was able to reach the dissolution level of aspirin at 30 minutes, but had lower levels of dissolution at the previous time points. Instead, at pH 6.8, most of the formulations approached aspirin dissolution level, but only after 15 minutes. Ibuprofen capsules had the slowest kinetics, with a lag phase the first 6 minutes. Different formulation strategies can lead to great differences in the dissolution rates even among drugs of the same class, suggesting that enhancements in the formulation of painkillers can lead to improvements in drug absorption, and thus in the onset of analgesia.

Sub-minute kinetics of human red cell fumarase: 1 H spin-echo NMR spectroscopy and 13 C rapid-dissolution dynamic nuclear polarization.

Science.gov (United States)

Shishmarev, Dmitry; Wright, Alan J; Rodrigues, Tiago B; Pileio, Giuseppe; Stevanato, Gabriele; Brindle, Kevin M; Kuchel, Philip W

2018-03-01

Fumarate is an important probe of metabolism in hyperpolarized magnetic resonance imaging and spectroscopy. It is used to detect the release of fumarase in cancer tissues, which is associated with necrosis and drug treatment. Nevertheless, there are limited reports describing the detailed kinetic studies of this enzyme in various cells and tissues. Thus, we aimed to evaluate the sub-minute kinetics of human red blood cell fumarase using nuclear magnetic resonance (NMR) spectroscopy, and to provide a quantitative description of the enzyme that is relevant to the use of fumarate as a probe of cell rupture. The fumarase reaction was studied using time courses of 1 H spin-echo and 13 C-NMR spectra. 1 H-NMR experiments showed that the fumarase reaction in hemolysates is sufficiently rapid to make its kinetics amenable to study in a period of approximately 3 min, a timescale characteristic of hyperpolarized 13 C-NMR spectroscopy. The rapid-dissolution dynamic nuclear polarization (RD-DNP) technique was used to hyperpolarize [1,4- 13 C]fumarate, which was injected into concentrated hemolysates. The kinetic data were analyzed using recently developed FmR α analysis and modeling of the enzymatic reaction using Michaelis-Menten equations. In RD-DNP experiments, the decline in the 13 C-NMR signal from fumarate, and the concurrent rise and fall of that from malate, were captured with high spectral resolution and signal-to-noise ratio, which allowed the robust quantification of fumarase kinetics. The kinetic parameters obtained indicate the potential contribution of hemolysis to the overall rate of the fumarase reaction when 13 C-NMR RD-DNP is used to detect necrosis in animal models of implanted tumors. The analytical procedures developed will be applicable to studies of other rapid enzymatic reactions using conventional and hyperpolarized substrate NMR spectroscopy. Copyright © 2018 John Wiley & Sons, Ltd.

Evaluation of The Use of Bentonite, Kaolin and Feldspar For Immobilizing The Uranium Radionuclide Slugdewaste

International Nuclear Information System (INIS)

Prayitno

2006-01-01

The experimental investigation on the mixture of bentonite, kaolin, feldspar, sludge waste and with the ratio of bentonite, kaolin, feldspar for evaluating its effectiveness has been done. Experimentally, this investigation is the preliminary study of the use of bentonite, kaolin, feldspar as a material for the immobilization of sludge waste containing material element especially uranium. This investigation was conducted by mixing waste (2,5; 5; 7.5; 10; 12.5 and 15 %) of total weight sludge waste and bentonite, kaolin, feldspar with of 800, 900 and 1000 o C temperature. The obtained the process condition in which the uranium fraction immobilized could be kept in the limit of safety standard for the sludge waste. Therefore, it could be concluded that the addition of hay ash as an additive in the formation of block monolith tend to minimize the leached sludge waste in the leaching media. (author)

Understanding optically stimulated charge movement in quartz and feldspar using time-resolved measurements

International Nuclear Information System (INIS)

Ankjaergaard, C.

2010-02-01

Thermoluminescence (TL) and optically stimulated luminescence (OSL) from quartz and feldspar are widely used in accident dosimetry and luminescence dating. In order to improve already existing methods or to develop new methods towards extending the current limits of the technique, it is important to understand the charge movement within these materials. Earlier studies have primarily focussed on examination of the trap behaviour; however, this only tells half of the story as OSL is a combination of charge stimulation and recombination. By using time-resolved OSL (TR-OSL), one can directly examine the recombination route(s), and thus obtain insight into the other half of the process involved in luminescence emission. This thesis studies the TR-OSL and optically stimulated phosphorescence signals from quartz and feldspars spanning several orders of magnitude in time (few ns to the seconds time scale) in order to identify various charge transport mechanisms in the different time regimes. The techniques employed are time-resolved OSL, continuous-wave OSL, TL, optically stimulated exo-electron (OSE) emission and time-resolved OSE. These different techniques are used in combination with variable thermal or optical stimulation energy. The thesis first delves into three main methodological developments, namely (i) research and development of the equipment for TR-OSL measurements, (ii) finding the best method for multiple-exponential analysis of a TR-OSL curve, and (iii) optimisation of the pulsing configuration for the best separation of quartz OSL from a mixed quarts-feldspar sample. It then proceeds to study the different charge transport mechanisms subsequent to an optical stimulation pulse in quartz and feldspars. The results obtained for quartz conclude that the main lifetime component in quartz represents an excited state lifetime of the recombination centre, and the more slowly decaying components on the millisecond to seconds time scale arise from charge recycling

Understanding optically stimulated charge movement in quartz and feldspar using time-resolved measurements

Energy Technology Data Exchange (ETDEWEB)

Ankjaergaard, C.

2010-02-15

Thermoluminescence (TL) and optically stimulated luminescence (OSL) from quartz and feldspar are widely used in accident dosimetry and luminescence dating. In order to improve already existing methods or to develop new methods towards extending the current limits of the technique, it is important to understand the charge movement within these materials. Earlier studies have primarily focussed on examination of the trap behaviour; however, this only tells half of the story as OSL is a combination of charge stimulation and recombination. By using time-resolved OSL (TR-OSL), one can directly examine the recombination route(s), and thus obtain insight into the other half of the process involved in luminescence emission. This thesis studies the TR-OSL and optically stimulated phosphorescence signals from quartz and feldspars spanning several orders of magnitude in time (few ns to the seconds time scale) in order to identify various charge transport mechanisms in the different time regimes. The techniques employed are time-resolved OSL, continuous-wave OSL, TL, optically stimulated exo-electron (OSE) emission and time-resolved OSE. These different techniques are used in combination with variable thermal or optical stimulation energy. The thesis first delves into three main methodological developments, namely (i) research and development of the equipment for TR-OSL measurements, (ii) finding the best method for multiple-exponential analysis of a TR-OSL curve, and (iii) optimisation of the pulsing configuration for the best separation of quartz OSL from a mixed quarts-feldspar sample. It then proceeds to study the different charge transport mechanisms subsequent to an optical stimulation pulse in quartz and feldspars. The results obtained for quartz conclude that the main lifetime component in quartz represents an excited state lifetime of the recombination centre, and the more slowly decaying components on the millisecond to seconds time scale arise from charge recycling

Transient refractory material dissolution by a volumetrically-heated melt

Energy Technology Data Exchange (ETDEWEB)

Seiler, Jean Marie, E-mail: jean-marie.seiler@cea.fr [CEA, DEN, DTN, 17 Rue des Martyrs, 38054 Grenoble Cedex 9 (France); Ratel, Gilles [CEA, DEN, DTN, 17 Rue des Martyrs, 38054 Grenoble Cedex 9 (France); Combeau, Hervé [Institut Jean Lamour, UMR 7198, Lorraine University, Ecole des Mines de Nancy, Parc de Saurupt, 54042 Nancy Cedex (France); Gaus-Liu, Xiaoyang; Kretzschmar, Frank; Miassoedov, Alexei [Karlsruhe Institut of Technology, Hermann-von-Helmholtz-Platz 1, 76344 Eggenstein-Leopoldshafen (Germany)

2014-12-15

Highlights: • We describe a test investigating ceramic dissolution by a molten non-eutectic melt. • The evolution of the interface temperature between melt and refractory is measured. • A theoretical model describing dissolution kinetics is proposed. • When dissolution stops, interface temperature is the liquidus temperature of the melt. - Abstract: The present work addresses the question of corium–ceramic interaction in a core catcher during a core-melt accident in a nuclear power plant. It provides an original insight into transient aspects concerning dissolution of refractory material by a volumetrically heated pool. An experiment with simulant material (LIVECERAM) is presented. Test results clearly show that dissolution of solid refractory material can occur in a non-eutectic melt at a temperature which is lower than the melting temperature of the refractory material. During the dissolution transient, the interface temperature rises above the liquidus temperature, corresponding to the instantaneous average composition of the melt pool. With constant power dissipation in the melt and external cooling of the core-catcher, a final steady-state situation is reached. Dissolution stops when the heat flux (delivered by the melt to the refractory) can be removed by conduction through the residual thickness of the ceramic, with T{sub interface} = T{sub liquidus} (calculated for the average composition of the final liquid pool). The final steady state corresponds to a uniform pool composition and uniform interface temperature distribution. Convection in the pool is governed by natural thermal convection and the heat flux distribution is therefore similar to what would be obtained for a single component pool. An interpretation of the experiment with two model-based approaches (0D and 1D) is presented. The mass transfer kinetics between the interface and the bulk is controlled by a diffusion sublayer within the boundary layer. During the dissolution transient

A kinetic model for the stability of spent fuel matrix under oxic conditions

International Nuclear Information System (INIS)

Bruno, J.; Cera, E.; Duro, L.; Eriksen, T.E.

1996-01-01

A kinetic model for the UO 2 -spent fuel dissolution has been developed by integrating all the fundamental and experimental evidence about the redox buffer capacity of the UO 2 matrix itself within the methodological framework of heterogeneous redox reactions and dissolution kinetics. The purpose of the model is to define the geochemical stability of the spent fuel matrix and its resistance to internal and external disturbances. The model has been built in basis the reductive capacity (RDC) of the spent fuel/water system. A sensitivity analysis has been performed in order to identify the main parameters that affect the RDC of the system, the oxidant consumption and the radionuclide release. The number of surface co-ordination sites, the surface area to volume ratio, the kinetics of oxidants generation by radiolysis and the kinetics of oxidative dissolution of UO 2 , have been found to be the main parameters that can affect the reductive capacity of the spent fuel matrix. The model has been checked against some selected UO 2 and spent fuel dissolution data, performed under oxidizing conditions. The results are quite encouraging. (orig.)

Metasomatic alkali-feldspar syenites (episyenites) of the Proterozoic Suomenniemi rapakivi granite complex, southeastern Finland

Science.gov (United States)

Suikkanen, E.; Rämö, O. T.

2017-12-01

Peralkaline to marginally metaluminous alkali-feldspar syenites and quartz alkali-feldspar syenites are hosted by subalkaline, ferroan rapakivi granites in the 1644 Ma Suomenniemi complex of southeastern Finland. These alkali syenites form NW-oriented dikes and small (fingerprints are, within error, identical to those of the subalkaline granites of the complex. We propose that the Suomenniemi alkali-feldspar syenites are episyenites, formed as the result of pervasive local metasomatism of the subalkaline granites caused by high-temperature oxidizing peralkaline fluids. The process led to major geochemical changes, e.g., addition of Na, Al and Fe3 +, depletion of Si and Fe2 +, and partial to complete recrystallization of the granites along fluid pathways.

Development of a Unified Dissolution and Precipitation Model and Its Use for the Prediction of Oral Drug Absorption.

Science.gov (United States)

Jakubiak, Paulina; Wagner, Björn; Grimm, Hans Peter; Petrig-Schaffland, Jeannine; Schuler, Franz; Alvarez-Sánchez, Rubén

2016-02-01

Drug absorption is a complex process involving dissolution and precipitation, along with other kinetic processes. The purpose of this work was to (1) establish an in vitro methodology to study dissolution and precipitation in early stages of drug development where low compound consumption and high throughput are necessary, (2) develop a mathematical model for a mechanistic explanation of generated in vitro dissolution and precipitation data, and (3) extrapolate in vitro data to in vivo situations using physiologically based models to predict oral drug absorption. Small-scale pH-shift studies were performed in biorelevant media to monitor the precipitation of a set of poorly soluble weak bases. After developing a dissolution-precipitation model from this data, it was integrated into a simplified, physiologically based absorption model to predict clinical pharmacokinetic profiles. The model helped explain the consequences of supersaturation behavior of compounds. The predicted human pharmacokinetic profiles closely aligned with the observed clinical data. In summary, we describe a novel approach combining experimental dissolution/precipitation methodology with a mechanistic model for the prediction of human drug absorption kinetics. The approach unifies the dissolution and precipitation theories and enables accurate predictions of in vivo oral absorption by means of physiologically based modeling.

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

Energy Technology Data Exchange (ETDEWEB)

Vu, T. H. Y., E-mail: thi-hai-yen.vu@polytechnique.edu; Ramjauny, Y.; Rizza, G.; Hayoun, M. [Laboratoire des Solides Irradiés, École Polytechnique, CNRS, CEA, Université Paris-Saclay, F-91128 Palaiseau (France)

2016-01-21

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

Controlled evaluation of silver nanoparticle dissolution using atomic force microscopy.

Science.gov (United States)

Kent, Ronald D; Vikesland, Peter J

2012-07-03

Incorporation of silver nanoparticles (AgNPs) into an increasing number of consumer products has led to concern over the potential ecological impacts of their unintended release to the environment. Dissolution is an important environmental transformation that affects the form and concentration of AgNPs in natural waters; however, studies on AgNP dissolution kinetics are complicated by nanoparticle aggregation. Herein, nanosphere lithography (NSL) was used to fabricate uniform arrays of AgNPs immobilized on glass substrates. Nanoparticle immobilization enabled controlled evaluation of AgNP dissolution in an air-saturated phosphate buffer (pH 7.0, 25 °C) under variable NaCl concentrations in the absence of aggregation. Atomic force microscopy (AFM) was used to monitor changes in particle morphology and dissolution. Over the first day of exposure to ≥10 mM NaCl, the in-plane AgNP shape changed from triangular to circular, the sidewalls steepened, the in-plane radius decreased by 5-11 nm, and the height increased by 6-12 nm. Subsequently, particle height and in-plane radius decreased at a constant rate over a 2-week period. Dissolution rates varied linearly from 0.4 to 2.2 nm/d over the 10-550 mM NaCl concentration range tested. NaCl-catalyzed dissolution of AgNPs may play an important role in AgNP fate in saline waters and biological media. This study demonstrates the utility of NSL and AFM for the direct investigation of unaggregated AgNP dissolution.

Full analysis of feldspar texture and crystal structure by combining X-ray and electron techniques

DEFF Research Database (Denmark)

Balic Zunic, Tonci; Piazolo, Sandra; Katerinopoulou, Anna

2013-01-01

identification plus crystal structure refinement of all components in a feldspar intergrowth. This procedure was applied to perthitic intergrowths in feldspars from two different pegmatites in the Larvik plutonic complex in the southern part of the Oslo region, Norway. It revealed that the two starting high...

Dissolution kinetics for alumina in cryolite melts. Distribution of alumina in the electrolyte of industrial aluminium cells

Energy Technology Data Exchange (ETDEWEB)

Kobbeltvedt, Ove

1997-12-31

This thesis contributes to the understanding of which factors determine the rate of dissolution of alumina added to the bath in alumina reduction cells. Knowing this may help reduce the occurrences of operation interruptions and thus make it possible to produce aluminium using less energy. When alumina powder was added to a stirred cryolite melt, the alumina dissolved in two distinct main stages. In the first stage, the dissolution rate was very high, which reflects dissolution of single alumina grains that are being dispersed in the bath upon addition. In the second stage, lumps of alumina infiltrated with bath dissolved at a rate considerably slower than that of the first stage. The formation of these alumina agglomerates is the most important contributor to slow dissolution. The parameters varied in the experiments were convection, batch size, and temperature of the bath and of the added alumina. Increased gas stirring of the bath speeded up dissolution in both stages but the size of the batch was of little significance. Increasing the bath temperature had no effect in the first stage but speeded up dissolution considerably in the second stage. Compared to adding alumina at room temperature, preheating it to a high temperature (600 {sup o}C) increased the dissolution rate in the first stage while preheating to lower temperatures (100-300 {sup o}C) decreased the dissolution rate. In the second stage, preheating slowed the dissolution. The two latter phenomena of reduced dissolution rates are ascribed to the removal of moisture from the alumina upon preheating. The bath flow and the distribution of alumina in the bath were measured in four different types of cells. It was found that if a certain asymmetry of the magnetic field traverse to the cell was present, due to the presence of risers, then loops of high velocity bath flow occurred near the short ends of the cell. Thus, alumina added near the short ends is effectively transferred away from the feeding

Dissolution performance of plutonium nitride based fuel materials

Energy Technology Data Exchange (ETDEWEB)

Aneheim, E.; Hedberg, M. [Nuclear Chemistry, Chemistry and Chemical Engineering, Chalmers University of Technology, Kemivaegen 4, Gothenburg, SE41296 (Sweden)

2016-07-01

Nitride fuels have been regarded as one viable fuel option for Generation IV reactors due to their positive features compared to oxides. To be able to close the fuel cycle and follow the Generation IV concept, nitrides must, however, demonstrate their ability to be reprocessed. This means that the dissolution performance of actinide based nitrides has to be thoroughly investigated and assessed. As the zirconium stabilized nitrides show even better potential as fuel material than does the pure actinide containing nitrides, investigations on the dissolution behavior of both PuN and (Pu,Zr)N has been undertaken. If possible it is desirable to perform the fuel dissolutions using nitric acid. This, as most reprocessing strategies using solvent-solvent extraction are based on a nitride containing aqueous matrix. (Pu,Zr)N/C microspheres were produced using internal gelation. The spheres dissolution performance was investigated using nitric acid with and without additions of HF and Ag(II). In addition PuN fuel pellets were produced from powder and their dissolution performance were also assessed in a nitric acid based setting. It appears that both PuN and (Pu,Zr)N/C fuel material can be completely dissolved in nitric acid of high concentration with the use of catalytic amounts of HF. The amount of HF added strongly affects dissolution kinetics of (Pu, Zr)N and the presence of HF affects the 2 solutes differently, possibly due to inhomogeneity o the initial material. Large additions of Ag(II) can also be used to facilitate the dissolution of (Pu,Zr)N in nitric acid. PuN can be dissolved by pure nitric acid of high concentration at room temperature while (Pu, Zr)N is unaffected under similar conditions. At elevated temperature (reflux), (Pu,Zr)N can, however, also be dissolved by concentrated pure nitric acid.

Time-resolved infrared stimulated luminescence signals in feldspars: Analysis based on exponential and stretched exponential functions

International Nuclear Information System (INIS)

Pagonis, V.; Morthekai, P.; Singhvi, A.K.; Thomas, J.; Balaram, V.; Kitis, G.; Chen, R.

2012-01-01

Time-resolved infrared-stimulated luminescence (TR-IRSL) signals from feldspar samples have been the subject of several recent experimental studies. These signals are of importance in the field of luminescence dating, since they exhibit smaller fading effects than the commonly employed continuous-wave infrared signals (CW-IRSL). This paper presents a semi-empirical analysis of TR-IRSL data from feldspar samples, by using a linear combination of exponential and stretched exponential (SE) functions. The best possible estimates of the five parameters in this semi-empirical approach are obtained using five popular commercially available software packages, and by employing a variety of global optimization techniques. The results from all types of software and from the different fitting algorithms were found to be in close agreement with each other, indicating that a global optimum solution has likely been reached during the fitting process. Four complete sets of TR-IRSL data on well-characterized natural feldspars were fitted by using such a linear combination of exponential and SE functions. The dependence of the extracted fitting parameters on the stimulation temperature is discussed within the context of a recently proposed model of luminescence processes in feldspar. Three of the four feldspar samples studied in this paper are K-rich, and these exhibited different behavior at higher stimulation temperatures, than the fourth sample which was a Na-rich feldspar. The new method of analysis proposed in this paper can help isolate mathematically the more thermally stable components, and hence could lead to better dating applications in these materials. - Highlights: ► TR-IRSL from four feldspars were analyzed using exponential and stretched exponential functions. ► A variety of global optimization techniques give good agreement. ► Na-rich sample behavior is different from the three K-rich samples. ► Experimental data are fitted for stimulation temperatures

Understanding optically stimulated charge movement in quartz and feldspar using time-resolved measurements

DEFF Research Database (Denmark)

Ankjærgaard, Christina

. Although, results are only presented for some quartz and feldspar samples, they were found to be very similar within the each group during the course of this work.Thermoluminescence (TL) and optically stimulated luminescence (OSL) from quartz and feldspar are widely used in accident dosimetry...... stimulation energy. The thesis first delves into three main methodological developments, namely (i) research and development of the equipment for TR-OSL measurements, (ii) finding the best method for multiple-exponential analysis of a TR-OSL curve, and (iii) optimisation of the pulsing configuration...... of the equipment for TR-OSL measurements, (ii) finding the best method for multiple-exponential analysis of a TR-OSL curve, and (iii) optimisation of the pulsing configuration for the best separation of quartz OSL from a mixed quarts-feldspar sample. It then proceeds to study the different charge transport...

Dissolution of uranium and plutonium particles: simulations using the Mercer equation

International Nuclear Information System (INIS)

Cowan, C.E.; Jenne, E.A.

1983-10-01

There is a need to be able to predict the amount of plutonium that will be in solution at a given time from dissolution of particles in order to better predict the environmental behavior and possible adverse effects of plutonium spills. The equation developed by Mercer (1967) to simulate the dissolution of particles in lungs was parameterized and used to simulate the dissolution of a population of plutonium or uranium particles in the soil. Parameter values for the size distribution of particles in soil, and the density of the particles were found; however, values for the shape factors, and the dissolution rate were virtually non-existent. The calculated mass dissolved was most sensitive to the median diameter of the population of particles and least sensitive to the geometric standard deviation. A given percent change in the shape parameter and the dissolution rate resulted in approximately an equal percent change in the mass dissolved. Provided that the population of particles follows a log-normal distribution, the particles are homogeneous in composition and the dissolution can be represented by first-order kinetics, this equation can probably be applied with slight modification to estimate the mass dissolved at a given time. 66 references, 7 figures, 4 tables

Radioluminescence dating: the IR emission of feldspar

International Nuclear Information System (INIS)

Schilles, Thomas.; Habermann, Jan

2000-01-01

A new luminescence reader for radioluminescence (RL) measurements is presented. The system allows detection of RL emissions in the near infrared region (IR). Basic bleaching properties of the IR-RL emission of feldspars are investigated. Sunlight-bleaching experiments as a test for sensitivity changes are presented. IR-bleaching experiments were carried out to obtain information about the underlying physical processes of the IR-RL emission

The Dissolution Behavior of Borosilicate Glasses in Far-From Equilibrium Conditions

Energy Technology Data Exchange (ETDEWEB)

Neeway, James J.; Rieke, Peter C.; Parruzot, Benjamin PG; Ryan, Joseph V.; Asmussen, Robert M.

2018-02-10

In far-from-equilibrium conditions, the dissolution of borosilicate glasses used to immobilize nuclear waste is known to be a function of both temperature and pH. The aim of this paper is to study effects of these variables on three model waste glasses (SON68, ISG, AFCI). To do this, experiments were conducted at temperatures of 23, 40, 70, and 90 °C and pH(RT) values of 9, 10, 11, and 12 with the single-pass flow-through (SPFT) test method. The results from these tests were then used to parameterize a kinetic rate model based on transition state theory. Both the absolute dissolution rates and the rate model parameters are compared with previous results. Discrepancies in the absolute dissolution rates as compared to those obtained using other test methods are discussed. Rate model parameters for the three glasses studied here are nearly equivalent within error and in relative agreement with previous studies. The results were analyzed with a linear multivariate regression (LMR) and a nonlinear multivariate regression performed with the use of the Glass Corrosion Modeling Tool (GCMT), which is capable of providing a robust uncertainty analysis. This robust analysis highlights the high degree of correlation of various parameters in the kinetic rate model. As more data are obtained on borosilicate glasses with varying compositions, the effect of glass composition on the rate parameter values could possibly be obtained. This would allow for the possibility of predicting the forward dissolution rate of glass based solely on composition

Etude cinetique et thermodynamique de la dissolution de la fluorapatite dans l'acide phosphorique

International Nuclear Information System (INIS)

Brahim, K.; Khattech, I.; Dubes, J.P.; Jemal, M.

2005-01-01

A modification on the reversal cells of a C-80 SETARAM calorimeter allows a Joule effect in the reaction cells to determine a transfer function in experimental conditions close to those of dissolution of a solid in a liquid. The calorimeter was then used to determine in isothermal conditions both thermodynamic and kinetic parameters associated with dissolution of synthetic fluorapatite in phosphoric acid solutions. Due to the rapidity of reaction, the heat flow recordings were deconvoluted and the resulting curves were analyzed iteratively to obtain the rates of digestion and the enthalpy of dissolution at 298 K of fluorapatite in phosphoric acid solution containing 10, 18 or 30 wt% P 2 O 5 . The results agree with a two-step dissolution mechanism. The first step is the dissolution of the solid in phosphoric acid, and the second is the formation of the complex Ca(H 2 PO 4 ) +

Optimization of dissolution process parameters for uranium ore concentrate powders

Energy Technology Data Exchange (ETDEWEB)

Misra, M.; Reddy, D.M.; Reddy, A.L.V.; Tiwari, S.K.; Venkataswamy, J.; Setty, D.S.; Sheela, S.; Saibaba, N. [Nuclear Fuel Complex, Hyderabad (India)

2013-07-01

Nuclear fuel complex processes Uranium Ore Concentrate (UOC) for producing uranium dioxide powder required for the fabrication of fuel assemblies for Pressurized Heavy Water Reactor (PHWR)s in India. UOC is dissolved in nitric acid and further purified by solvent extraction process for producing nuclear grade UO{sub 2} powder. Dissolution of UOC in nitric acid involves complex nitric oxide based reactions, since it is in the form of Uranium octa oxide (U{sub 3}O{sub 8}) or Uranium Dioxide (UO{sub 2}). The process kinetics of UOC dissolution is largely influenced by parameters like concentration and flow rate of nitric acid, temperature and air flow rate and found to have effect on recovery of nitric oxide as nitric acid. The plant scale dissolution of 2 MT batch in a single reactor is studied and observed excellent recovery of oxides of nitrogen (NO{sub x}) as nitric acid. The dissolution process is automated by PLC based Supervisory Control and Data Acquisition (SCADA) system for accurate control of process parameters and successfully dissolved around 200 Metric Tons of UOC. The paper covers complex chemistry involved in UOC dissolution process and also SCADA system. The solid and liquid reactions were studied along with multiple stoichiometry of nitrous oxide generated. (author)

Aqueous dissolution of sodium aluminosilicate geopolymers derived from metakaolin

Energy Technology Data Exchange (ETDEWEB)

Aly, Z., E-mail: zaynab.aly@ansto.gov.au [Institute of Materials Engineering, Australian Nuclear Science and Technology Organisation, Locked Bag 2001, Kirrawee DC, NSW 2232 (Australia); Vance, E.R. [Institute of Materials Engineering, Australian Nuclear Science and Technology Organisation, Locked Bag 2001, Kirrawee DC, NSW 2232 (Australia); Perera, D.S. [School of Materials Science, University of NSW, Kensington, NSW 2052 (Australia)

2012-05-15

Highlights: Black-Right-Pointing-Pointer In dilute solutions, Na, Al and Si releases were not sensitive to pH in range 4-10. Black-Right-Pointing-Pointer On heating from 18 to 90 Degree-Sign C in DIW, Na dissolution rate increased by a factor of {approx}4. Black-Right-Pointing-Pointer Elemental extractions in DIW at 18 Degree-Sign C increased linearly with time over 1-7 days. Black-Right-Pointing-Pointer Na release kinetics in DIW followed a pseudo-second-order kinetic model. Black-Right-Pointing-Pointer Contact with KCl, KHCO{sub 3} and phthalate buffers (pH6 and 10) resulted in Na{sup +} {r_reversible} K{sup +} exchange. - Abstract: In dilute aqueous solutions, the elemental releases of Na, Al and Si from a metakaolin-based sodium aluminosilicate geopolymer were not very sensitive to pH in the range of 4-10 but increased outside this range, particularly on the acidic side. To minimise pH drifts, experiments were carried out using small amounts of graded powders in relatively large volumes of water. In deionised water, the Na dissolution rate in 7 days was dominant and increased by at least a factor of {approx}4 on heating from 18 to 90 Degree-Sign C, with greater increases in the extractions of Al and Si. At 18 Degree-Sign C the elemental extractions in deionised water increased approximately linearly with time over the 1-7 days period. Further exposure led to a slower extraction into solution for Na and Si, with a decrease in extraction of Al. It was deduced that framework dissolution was important in significantly acidic or alkaline solutions, but that contributions from water transfer from pores to elemental extractions were present, even at low temperatures in neutral solutions. It was also deduced from the Na release data that the Na leaching kinetics of geopolymer in deionised water (dilute solutions) followed the pseudo-second-order kinetic model and the pseudo-second-order rate constant evaluated. Contact with KCl, KHCO{sub 3}, and pH {approx}6 and 10

Impact of dissolution and carbonate precipitation on carbon storage in basalt

Science.gov (United States)

Wells, R. K.; Xiong, W.; Tadeoye, J.; Menefee, A.; Ellis, B. R.; Skemer, P. A.; Giammar, D.

2016-12-01

The spatial evolution of silicate mineral dissolution, carbonate precipitation, and the transport of fluids influence the viability of carbon storage in basalt reservoirs. Dissolution of natural basalt and subsequent carbonate precipitation in systems with different transport processes operating were characterized using static and flow-through (5 mL/hr) experiments at 50, 100, and 150 °C, and 100 bar CO2. Intact samples and cores with milled pathways that simulate fractures were tested. Spatial and mineralogical patterns in dissolution and precipitation were analyzed using optical and electron microscopy, microCT scanning, and surface roughness data. Precipitates and fluid chemistry were analyzed using Raman spectroscopy, SEM-EDS, and ICP-MS. Analysis of the bulk solution and surface topography suggests dissolution of olivine and pyroxene grains begins within hours of the start of the experiments. In flow-through experiments, total effluent cation concentrations reach a peak concentration within a few hours then drop towards a steady state within a few days. In static experiments, the initial rate of cation release is faster than it is after several weeks. In both cases Ca2+, Mg2+, and Fe2+ are the dominant cations in solution in the initial stages of reaction. Lower concentrations of Na2+, K+, and Al3+, and the preservation of feldspar and matrix grains after several weeks of reaction indicate the slow reactivity of these minerals. As the reaction progresses, the surface roughness increases steadily with cavities developing at the sites of olivine and pyroxene grains. Post-reaction analysis of basalt samples reacted at static conditions with milled pathways reveals that both siderite and amorphous silica precipitated within diffusion-limited zones as early as 4-6 weeks. Siderite abundance varies with distance along the pathway with the highest concentration of carbonates 1-2 cm below the fracture opening. Siderite precipitates are large enough to fill fracture

Mathematical characterization of continuous wave infrared stimulated luminescence signals (CW-IRSL) from feldspars

International Nuclear Information System (INIS)

Pagonis, V.; Phan, Huy; Goodnow, Rebecca; Rosenfeld, Sara; Morthekai, P.

2014-01-01

Continuous-wave infrared stimulated luminescence signals (CW-IRSL) from feldspars have been the subject of many experimental studies, due to their importance in luminescence dating and dosimetry. Accurate mathematical characterization of the shape of these CW-IRSL signals in feldspars is of practical and theoretical importance, especially in connection with “anomalous fading” of luminescence signals in dating studies. These signals are known to decay in a non-exponential manner and their exact mathematical shape as a function of stimulation time is an open research question. At long stimulation times the IRSL decay has been shown experimentally to follow a power law of decay, and previous researchers have attempted to fit the overall shape of these signals empirically using the well known Becquerel function (or compressed hyperbola decay law). This paper investigates the possibility of fitting CW-IRSL curves using either the Becquerel decay law, or a recently developed analytical equation based on localized electronic recombination of donor–acceptor pairs in luminescent materials. It is shown that both mathematical approaches can give excellent fits to experimental CW-IRSL curves, and the precision of the fitting process is studied by analyzing a series of curves measured using a single aliquot of a feldspar sample. Both fitting equations are solutions of differential equations involving numerically similar time dependent recombination probabilities k(t). It is concluded that both fitting equations provide approximately equivalent mathematical descriptions of the CW-IRSL curves in feldspars, and can be used as mathematical representations of the shape of CW-IRSL signals. - Highlights: • Feldspar CW-IRSL curves fitted using Becquerel decay law and new analytical equation. • Both mathematical approaches give excellent fits to experimental CW-IRSL curves. • Series of experimental CW-IRSL curves analyzed using both fitting expressions. • The time

On the effect of optical and isothermal treatments on luminescence signals from feldspars

International Nuclear Information System (INIS)

Pagonis, Vasilis; Polymeris, George; Kitis, George

2015-01-01

During luminescence dosimetry and luminescence dating applications it is often necessary to precondition the geological samples by applying a thermal or optical treatment before measuring the luminescence signal. In luminescence applications using apatites or feldspars, measurement of continuous-wave infrared or optically stimulated signals (CW-IRSL and CW-OSL) are customarily preceded by either an isothermal heating of the samples at a fixed temperature for a short time interval, or alternatively by optically bleaching the samples using light from LEDs with the appropriate wavelength. This paper presents new analytical equations which can be used to describe these commonly employed double experimental procedures. The equations are based on a recently published model which assumes that tunneling processes are taking place in random distributions of donor–acceptor pairs. The concentration of charge carriers during the CW-IRSL or CW-OSL experiment is expressed in terms of the parameters of the preceding thermal or optical bleaching procedure, and depends also on the distribution of distances between electron and hole pairs. The analytical equations in this paper are compared with experimental data from a feldspar sample which undergoes an isothermal procedure followed by measurement of the CW-IRSL signal. Additional comparisons with experiment are provided using a feldspar sample which undergoes an infrared bleaching process, followed by measurement of the CW-OSL signal. These results and conditions under which the equations can be used are discussed within the framework of the model. - Highlights: • CW-IRSL and CW-OSL measurements are preceded by heating or optical bleaching. • New analytical equations are derived to describe these double experimental procedures. • Equations are compared with data from a feldspar sample following isothermal procedure. • Equations are compared with data from a feldspar sample following optical bleaching.

Investigation of the dissolution of uranium dioxide in nitric media: a new approach aiming at understanding interface mechanisms

International Nuclear Information System (INIS)

Delwaulle, Celine

2011-01-01

This research thesis deals with the back-end cycle of the nuclear fuel by improving, modernizing and optimizing the processes used for all types of fuels which are to be re-processed. After a presentation of the industrial context and of the state of the art concerning dissolution kinetic data for uranium dioxide and mixed oxide, the author proposes a model which couples dissolution kinetics and hydrodynamics of a solid in presence of auto-catalytic species, in order to better understand phenomena occurring at the solid-liquid-gas interface. The next part reports dissolution experiments on a non-radioactive material (copper) and out of a nuclear environment. Then, the author identifies steps which are required to transpose this experiment within a nuclear environment. The first results obtained on uranium dioxide are discussed. Recommendations for further studies conclude the report

Colloid-facilitated effects on migration of radionuclides in fractured rock with a kinetic solubility-limited dissolution model

International Nuclear Information System (INIS)

Jen Chunping; Tien Nengchuan

2010-01-01

Nuclides can move with groundwater either as solutes or colloids, where the latter mechanism generally results in much shorter traveling time as the nuclides interact strongly with solid phases, such as actinides. In the performance assessment, it is therefore essential to assess the relative importance of these two transport mechanisms for different nuclides. The relative importance of colloids depends on the nature and concentration of the colloids in groundwater. Plutonium (Pu), neptunium (Np), uranium (U) and americium (Am) are four nuclides of concern for the long-term emplacement of nuclear wastes at potential repository sites. These four actinides have a high potential for migrating if attached to iron oxide, clay or silica colloids in the groundwater.Strong sorption of the actinides by colloids in the groundwater may facilitate the transport of these nuclides along potential flow paths. The solubility-limited dissolution model can be used to assess the safety of the release of nuclear waste in geological disposal sites. Usually, it has been assumed that the solubility of the waste form is constant. If a nuclide reaches its solubility limit at an inner location near the waste form, it is unlikely that the same nuclide will reach its solubility limit at an outer location unless this nuclide has a parent nuclide. It is unlikely that the daughter nuclides will exceed their solubility limit due to decay of their parent nuclide. The present study investigates the effect of colloids on the transport of solubility-limited nuclides under the kinetic solubility-limited dissolution (KSLD) boundary condition in fractured media. The release rate of the nuclides is proportional to the difference between the saturation concentration and the inlet aqueous concentration of the nuclides. The presence of colloids decreases the aqueous concentration of nuclides and, thus, increases the release flux of nuclides from the waste form. (authors)

Faster dissolution of PuO2 in nitrous media by means of electrolytic oxidation

International Nuclear Information System (INIS)

Baumgaertner, F.; Kim, J.I.; Luckner, N.; Brueckl, N.; Lieberer, E.

1984-03-01

The contribution shows that the dissolution of PuO 2 in HNO 3 can be accelerated considerably by means of electrolytic oxidation. A glass apparatus has been developed which uses platinum electrodes providing for sufficient contact between electrodes and solids. Increase of temperature, acid concentration, and electrode current density, and a good contact between electrode and metal oxide will improve the dissolution kinetics. The reaction could be made even faster by addition of Ce 4+ . (orig.) [de

Mechanical behavior of alumina and alumina-feldspar based ceramics in an acetic acid (4%) environment

International Nuclear Information System (INIS)

Stumpf, Aisha S.G.; Bergmann, Carlos P.; Vicenzi, Juliane; Fetter, Rebecca; Mundstock, Karina S.

2009-01-01

This study investigates the mechanical properties of alumina-feldspar based ceramics when exposed to an aggressive environment (acetic acid 4%). Alumina ceramics containing different concentrations of feldspar (0%, 1%, 5%, 10%, or 40%) were sintered at either 1300, 1600, or 1700 o C. Flaws (of width 0%, 30%, or 50%) were introduced into the specimens using a saw. Half of these ceramic bodies were exposed to acetic acid. Their flexural strength, K IC , and porosity were measured and the fractured samples were evaluated using scanning electronic- and optical microscopy. It was found that in the ceramic bodies sintered at 1600 o C, feldspar content up to 10% improved flexural strength and K IC, and reduced porosities. Generally, it was found that acetic acid had a weakening effect on the flexural strength of samples sintered at 1700 o C but a beneficial effect on K IC of ceramics sintered at 1600 o C. It was concluded that alumina-based ceramics with feldspar content up to 10% and sintered at higher temperatures would perform better in an aggressive environment similar to oral cavity.

Dissolution process of atmospheric aerosol particles into cloud droplets; Processus de dissolution des aerosols atmospheriques au sein des gouttes d'eau nuageuses

Energy Technology Data Exchange (ETDEWEB)

Desboeufs, K

2001-01-15

Clouds affect both climate via the role they play in the Earth's radiation balance and tropospheric chemistry since they are efficient reaction media for chemical transformation of soluble species. Cloud droplets are formed in the atmosphere by condensation of water vapour onto aerosol particles, the cloud condensation nuclei (CCN). The water soluble fraction of these CCN governs the cloud micro-physics, which is the paramount factor playing on the radiative properties of clouds. Moreover, this soluble fraction is the source of species imply in the oxidation/reduction reactions in the aqueous phase. Thus, it is of particular importance to understand the process controlling the solubilization of aerosols in the cloud droplets. The main purpose of this work is to investigate experimentally and theoretically the dissolution of particles incorporated in the aqueous phase. From the studies conducted up to now, we have identify several factors playing on the dissolution reaction of aerosols. However, the quantification of the effects of these factors is difficult since the current means of study are not adapted to the complexity of cloud systems. First, this work consisted to perform a experimental system, compound by an open flow reactor, enabling to follow the kinetic of dissolution in conditions representative of cloud. This experimental device is used to a systematic characterisation of the known factors playing on the dissolution, i.e. pH, aerosol nature, aerosol weathering... and also for the identification and the quantification of the effects of other factors: ionic strength, acid nature, clouds processes. These experiments gave quantitative results, which are used to elaborate a simple model of aerosol dissolution in the aqueous phase. This model considers the main factors playing on the dissolution and results in a general mechanism of aerosol dissolution extrapolated to the cloud droplets. (author)

Magnesite dissolution and precipitation rates at hydrothermal conditions

International Nuclear Information System (INIS)

Saldi, Giuseppe

2009-01-01

complexation model originally developed at 25 deg. C. The decrease of dissolution rates observed from 150 to 200 deg. C can be explained by the increasing carbonation and hydrolysis of the rate controlling >MgOH 2 + sites. As a result of the decreasing rates of dissolution, the achievement of alkaline conditions and temperatures higher than 100 deg. C by CO 2 -rich fluids represents a favorable condition for CO 2 sequestration as dissolved alkalinity in deep aquifers where carbonate minerals are major constituting phases. The use of a hydrogen electrode concentration cell (HECC) corroborates the kinetic data obtained at close to equilibrium conditions by the precise determination of magnesite solubility product as a function of temperature (50-200 deg. C). These measurements allowed generating the thermodynamic properties of this phase and comparing them with those obtained from calorimetric measurements and phase equilibria experiments. The results of this study significantly improve our understanding of the kinetic behaviour of carbonate minerals in hydrothermal systems and provide an essential database for the future study of dissolution/precipitation reactions of carbonate minerals in complex systems. This work also provides important kinetic constraints for the geochemical modeling of CO 2 sequestration processes and will help the evaluation of impact and risks connected to a long-term storage. (author) [fr

Anodic dissolution and corrosion of alloy Cu30Ni in chloride solutions

International Nuclear Information System (INIS)

Zolotarev, E.I.

1989-01-01

The anodic and corrosion behavior of alloy Cu30Ni is studied in a solution of 3 N NaCl + 0.01 N HCl by a radiometric method using gamma isotopes of 58 Co (as a marker for Ni) and 64 Cu in combination with electrochemical measurements. It was established that under stationary conditions there was uniform dissolution of the alloy both during free corrosion and anodic polarization. The authors obtained partial anodic dissolution curves for the components of the alloy. It was shown that the dissolution kinetics differed from the mechanisms controlling dissolution of the corresponding pure metals. During corrosion of the alloy in an oxygen atmosphere a back precipitation of copper on the surface of the alloy was not observed. The characteristics observed in the corrosion-electrochemical behavior of the alloy in concentrated chloride solutions can be explained by the presence of Ni on the surface of the dissolving alloy

Time-resolved luminescence from feldspars: New insight into fading

DEFF Research Database (Denmark)

Tsukamoto, S.; Denby, P.M.; Murray, A.S.

2006-01-01

Time-resolved infrared optically stimulated luminescence (IR-OSL) signals of K- and Na-feldspar samples extracted from sediments were measured in UV, blue and red detection windows, using a fast photon counter and pulsed IR stimulation (lambda = 875 nm). We observe that the relative contribution ...

Role of nitrous acid during the dissolution of UO2 in nitric acid

International Nuclear Information System (INIS)

Deigan, N.; Pandey, N.K.; Kamachi Mudali, U.; Joshi, J.B.

2016-01-01

Understanding the dissolution behaviour of sintered UO 2 pellet in nitric acid is very important in designing an industrial scale dissolution system for the plutonium rich fast reactor MOX fuel. In the current article we have established the role of nitrous acid on the dissolution kinetics of UO 2 pellets in nitric acid. Under the chemical conditions that prevail in a typical Purex process, NO and NO 2 gases gets generated in the process streams. These gases produce nitrous acid in nitric acid medium. In addition, during the dissolution of UO 2 in nitric acid medium, nitrous acid is further produced in-situ at the pellet solution interface. As uranium dissolves oxidatively in nitric acid medium wherein it goes from U(IV) in solid to U(VI) in liquid, presence of nitrous acid (a good oxidizing agent) accelerates the reaction rate. Hence for determining the reaction mechanism of UO 2 dissolution in nitric acid medium, knowing the nitrous acid concentration profile during the course of dissolution is important. The current work involves the measurement of nitrous acid concentration during the course of dissolution of sintered UO 2 pellets in 8M starting nitric acid concentration as a function of mixing intensity from unstirred condition to 1500 RPM

Strontium and argon isotopes in naturally weathered biotites, muscovites and feldspars

International Nuclear Information System (INIS)

Clauer, N.

1981-01-01

A Rb-Sr and K-Ar isotopical study on progressively weathered biotites, muscovites and feldspars from plutonic and eruptive rocks shows that their continental weathering is a complex phenomenon controlled by environmental conditions. During weathering of biotites, the K-Ar couple often mimics the Rb-Sr couple. The radiogenic Sr and Ar isotopes are systematically leached out, but the behaviour of the elemental Rb, K, Sr and Ar depends upon the environment. In contrast, the Sr and Ar balances of muscovites are maintained, even during very intensive weathering. In mixtures of feldspars, the common Sr seems to be leached out preferentially to the radiogenic isotope, while the K-Ar balance is maintained. (Auth.)

Mesoporous silica formulation strategies for drug dissolution enhancement: a review.

Science.gov (United States)

McCarthy, Carol A; Ahern, Robert J; Dontireddy, Rakesh; Ryan, Katie B; Crean, Abina M

2016-01-01

Silica materials, in particular mesoporous silicas, have demonstrated excellent properties to enhance the oral bioavailability of poorly water-soluble drugs. Current research in this area is focused on investigating the kinetic profile of drug release from these carriers and manufacturing approaches to scale-up production for commercial manufacture. This review provides an overview of different methods utilized to load drugs onto mesoporous silica carriers. The influence of silica properties and silica pore architecture on drug loading and release are discussed. The kinetics of drug release from mesoporous silica systems is examined and the manufacturability and stability of these formulations are reviewed. Finally, the future prospects of mesoporous silica drug delivery systems are considered. Substantial progress has been made in the characterization and development of mesoporous drug delivery systems for drug dissolution enhancement. However, more research is required to fully understand the drug release kinetic profile from mesoporous silica materials. Incomplete drug release from the carrier and the possibility of drug re-adsorption onto the silica surface need to be investigated. Issues to be addressed include the manufacturability and regulation status of formulation approaches employing mesoporous silica to enhance drug dissolution. While more research is needed to support the move of this technology from the bench to a commercial medicinal product, it is a realistic prospect for the near future.

Solubility and dissolution kinetics study of uranium phosphates and vanadates: implications for the front end of the electronuclear cycle

International Nuclear Information System (INIS)

Cretaz, F.

2013-01-01

In the current context of restart of the nuclear energy, the needs in uranium are expected to increase significantly. Moreover, in a perspective of sustainable development, the exploitation, the treatment and the purification of uranium ores need to be optimized. It is thus necessary to determine reliable thermodynamic data (and especially solubility constants) for the systems of interest, especially uranium(VI) phosphates and vanadates. In this aim, a multi parametric study of the dissolution of meta-torbernite Cu 0.8 (H 3 O) 0.2 (UO 2 ) 2 (PO 4 ) 2.8 H 2 O, meta-autunite Ca(UO 2 ) 2 (PO 4 ) 2.6 H 2 O, meta-ankoleite K 2 (UO 2 ) 2 (PO 4 ) 2.6 H 2 O and carnotite K 2 (UO 2 ) 2 (VO 4 ) 2.3 H 2 O was undertaken. First, analogues of these four minerals were synthesized, based only on dry chemistry process for carnotite or on wet chemistry methods for the phosphate phases. They were then extensively characterized (in terms of structure, microstructure and chemical composition). It particularly highlighted the similar structures of such compounds. The anionic groups (PO 4 3- or V 2 O 8 6- ) and uranyl form parallel layers between which counter cations (Cu 2+ , Ca 2+ or K + ) and water molecules are inserted. However, the counter cations present in the interlayer space of the three phosphate phases present different lability. The synthetic phases were also compared to their natural analogues, except for meta-ankoleite, which allowed us to point out significant differences in the composition (presence of impurities in natural samples) and the morphology (grain size). The dissolution of these phases was then studied from a kinetic and thermodynamic point of view, through leaching tests in static and dynamic conditions, in various acid media (sulfuric, nitric and hydrochloric) and at different temperatures. In these conditions, the dissolution of meta-autunite was found to be un-congruent due to the precipitation of uranyl phosphate then avoiding the determination of

Dissolution behaviour of 238U, 234U and 230Th deposited on filters from personal dosemeters

International Nuclear Information System (INIS)

Beckova, V.; Malatova, I.

2008-01-01

Kinetics of dissolution of 238 U, 234 U and 230 Th dust deposited on filters from personal alpha dosemeters was studied by means of a 26-d in vitro dissolution test with a serum ultra-filtrate simulant. Dosemeters had been used by miners at the uranium mine 'Dolni Rozinka' at Rozna, Czech Republic. The sampling flow-rate as declared by the producer is 4 l h -1 and the sampling period is typically 1 month. Studied filters contained 125 ± 6 mBq 238 U in equilibrium with 234 U and 230 Th; no 232 Th series nuclides were found. Half-time of rapid dissolution of 1.4 d for 238 U and 234 U and slow dissolution half-times of 173 and 116 d were found for 238 U and 234 U, respectively. No detectable dissolution of 230 Th was found. (authors)

Dissolution processes

International Nuclear Information System (INIS)

Silver, G.L.

1976-01-01

This review contains more than 100 observations and 224 references on the dissolution phenomenon. The dissolution processes are grouped into three categories: methods of aqueous attack, fusion methods, and miscellaneous observations on phenomena related to dissolution problems

Attenuation of glass dissolution in the presence of natural additives

Energy Technology Data Exchange (ETDEWEB)

Sang, Jing C.; Barkatt, Aaron [Department of Chemistry, The Catholic University of America, Washington, DC (United States); O`Keefe, John A. [National Aeronautics and Space Administration, Goddard Space Flight Center, Greenbelt, MD (United States)

1996-11-01

The dissolution kinetics of silicate glasses in aqueous environments in systems which included a variety of natural crystalline solids in addition to the glass itself and the aqueous phase are reported. The results demonstrate the possibility of a dramatic decrease in the rate of dissolution of silicate glass in the presence of certain varieties of olivine-based materials. This decrease in dissolution rate was shown to be due to the fact that these additives consist mostly of Mg-based material but also contain minor amounts of Al and Ca. The combined presence of Mg with these minor species affected the corrosion rate of the glass as a whole, including its most soluble components such as boron. This study has potentially important implications to the durability of glasses exposed to natural environments. The results may be relevant to the use of active backfill materials in burial sites for nuclear waste glasses, as well as to better understanding of the environmental degradation of natural and ancient glasses.

water alteration processes and kinetics of basaltic glasses, natural analogue of nuclear glasses

International Nuclear Information System (INIS)

Techer, I.; Advocat, Th.; Vernaz, E.; Lancelot, J.R.; Liotard, J.M.

1997-01-01

Dissolution experiments of a basaltic glass were carried out at 90 deg C for different reaction progresses. The initial dissolution rate was compared with values obtained for rhyolitic glass and the R7T7 nuclear glass. The activation energy was also determined by computing literature data. The results provide similar reactional mechanism for basaltic and nuclear glasses. Dissolution rates measured under saturation conditions were compared to theoretical dissolution rates. These ones were calculated using two kinetic models: the first rate equation is the Grambow's law which only takes into account ortho-silica acid activity; the second rate equation was proposed by Daux et al., where silica and aluminum are combined to formulate the affinity. The comparison between experimental and theoretical results point out that these two models are not appropriate to describe the alteration kinetic of basaltic glasses. (authors)

Dissolution process of atmospheric aerosol particles into cloud droplets; Processus de dissolution des aerosols atmospheriques au sein des gouttes d'eau nuageuses

Energy Technology Data Exchange (ETDEWEB)

Desboeufs, K.

2001-01-15

Clouds affect both climate via the role they play in the Earth's radiation balance and tropospheric chemistry since they are efficient reaction media for chemical transformation of soluble species. Cloud droplets are formed in the atmosphere by condensation of water vapour onto aerosol particles, the cloud condensation nuclei (CCN). The water soluble fraction of these CCN governs the cloud micro-physics, which is the paramount factor playing on the radiative properties of clouds. Moreover, this soluble fraction is the source of species imply in the oxidation/reduction reactions in the aqueous phase. Thus, it is of particular importance to understand the process controlling the solubilization of aerosols in the cloud droplets. The main purpose of this work is to investigate experimentally and theoretically the dissolution of particles incorporated in the aqueous phase. From the studies conducted up to now, we have identify several factors playing on the dissolution reaction of aerosols. However, the quantification of the effects of these factors is difficult since the current means of study are not adapted to the complexity of cloud systems. First, this work consisted to perform a experimental system, compound by an open flow reactor, enabling to follow the kinetic of dissolution in conditions representative of cloud. This experimental device is used to a systematic characterisation of the known factors playing on the dissolution, i.e. pH, aerosol nature, aerosol weathering... and also for the identification and the quantification of the effects of other factors: ionic strength, acid nature, clouds processes. These experiments gave quantitative results, which are used to elaborate a simple model of aerosol dissolution in the aqueous phase. This model considers the main factors playing on the dissolution and results in a general mechanism of aerosol dissolution extrapolated to the cloud droplets. (author)

Sorption of Eu(III) at feldspar/water interface. Effects of pH, organic matter, counter ions, and temperature

Energy Technology Data Exchange (ETDEWEB)

Li, Ping; Liang, Jianjun; Fan, Qiaohui [Chinese Academy of Sciences, Lanzhou (China). Key Lab. of Petroleum Resources Research; Wu, Hanyu [Chinese Academy of Sciences, Lanzhou (China). Key Lab. of Petroleum Resources Research; Lanzhou Univ. (China). Radiochemistry Lab.; Yin, Zhuoxin; Pan, Duoqiang; Wu, Wangsuo [Lanzhou Univ. (China). Radiochemistry Lab.; Xu, Di [Chinese Academy of Sciences, Nanjing (China). State Key Lab. of Lake Science and Environment

2017-07-01

The sorption of Eu(III) on potassium feldspar (K-feldspar) was studied under various physicochemical conditions such as pH, temperature, counter ions and organic matter. The results showed that the sorption of Eu(III) on K-feldspar significantly increased with the increase of pH, and high Eu(III) concentration can inhibit such immobility to some extent. The presence of humic acid (HA) can increase the sorption of Eu(III) on K-feldspar in low pH range; while inhibit to a large extent under alkaline conditions. It is very interesting that at pH ∝6.5, high ionic strength can promote the sorption of Eu(III) on K-feldspar in the presence of HA. In contrast, Eu(III) sorption was restricted obviously by NaCl in the absence of HA. The sorption procedure was involved with ion exchange and/or outer-sphere complexation as well as inner-sphere complexation. The presence of F{sup -} and PO{sub 4}{sup 3-} dramatically enhanced Eu(III) sorption on K-feldspar, whereas both SO{sub 4}{sup 2-} and CO{sub 3}{sup 2-} had negative effects on Eu(III) sorption. X-ray photoelectron spectroscopy analysis indicated that Eu(III) tended to form hydrolysates at high initial concentration (3 x 10{sup -4} mol/L) and high temperature (338 K).

Synthesis, characterization, kinetic and thermodynamic studies of the dissolution of ThO{sub 2} and of solid solutions Th{sub 1-x}M{sub x}O{sub 2} (M = U, Pu); Synthese, caracterisation et etudes cinetique et thermodynamique de la dissolution de ThO{sub 2} et des solutions solides Th{sub 1-x}M{sub x}O{sub 2} (M = U, Pu)

Energy Technology Data Exchange (ETDEWEB)

Heisbourg, G

2003-12-01

The aim of this work was to understand the mechanisms of dissolution of ThO{sub 2} and of thorium mixed oxides such as Th{sub 1-x}U{sub x}O{sub 2} and Th{sub 1-x}Pu{sub x}O{sub 2} in aqueous, oxygenated or inert media. Several solids have been synthesized by precipitation in oxalic medium: Th{sub 1-x}U{sub x}O{sub 2} (x= 0.11; 0.24; 0.37; 0.53; 0.67; 0.81 and 0.91) and Th{sub 1-x}Pu{sub x}O{sub 2} (x= 0.13; 0.32 and 0.66). They have been characterized by XRD, SEM, TEM, XPS, XAS, PIXE and EPMA. The sintering conditions of these materials have been studied and optimized in order to obtain sintered samples with a measured density very near the theoretical densities. A kinetic study of the dissolution of ThO{sub 2} and of solid solutions Th{sub 1-x}U{sub x}O{sub 2} has been carried out in several aqueous media (HNO{sub 3}, HCl, H{sub 2}SO{sub 4}) in terms of several parameters: protons concentration, temperature, pH, ionic strength, nature of the electrolyte solution and uranium molar ratio for the solid solutions Th{sub 1-x}U{sub x}O{sub 2} in order to determine the kinetic laws of dissolution of the solid solutions having different compositions comparatively to ThO{sub 2}. The leaching tests carried out in natural waters of compositions near those of the deep geologic sites considered for the storage of nuclear wastes have shown that the dissolution of the solids was bound to the complexing effect of the constitutional ions of the water considered. The leaching tests carried out on sintered samples of the same composition have led to the same normalized dissolution velocities. The thermodynamic aspect of the dissolution of the solid solutions Th{sub 1-x}U{sub x}O{sub 2} in nitric medium has been studied at last. (O.M.)

A comparative study of the luminescence characteristics of polymineral fine grains and coarse-grained K-, and Na-rich feldspars

DEFF Research Database (Denmark)

Tsukamoto, Sumiko; Jain, Mayank; Murray, Andrew S.

2012-01-01

for K-feldspar samples, when a preheat temperature of 250 °C for 60 s is used. After preheating to a higher temperature (320 °C for 60 s) all samples show a TL reduction around 410 °C in the blue detection window. Pulse annealing experiments for IRSL and pIRIR signals for preheats between 320 °C and 500...... °C indicate that the signal stabilities are similar among the different feldspar types, when a higher preheat temperature (>320 °C) is used. Thermal activation energies for IRSL and pIRIR signals are largest in K-feldspar and smallest in polymineral fine grains, in both blue and UV detection windows...... for both fast time-resolved (TR) and continuous wave (CW) signals. These results suggest that IRSL and pIRIR signals in polymineral fine grains originate mainly from Na-feldspar grains; these signals are less thermally stable than those from K-feldspar, but a more stable signal (presumably from K...

Alkali feldspar syenites with shoshonitic affinities from Chhotaudepur area: Implication for mantle metasomatism in the Deccan large igneous province

Directory of Open Access Journals (Sweden)

K.R. Hari

2014-03-01

Full Text Available Two petrologically distinct alkali feldspar syenite bodies (AFS-1 and AFS-2 from Chhotaudepur area, Deccan Large Igneous Province are reported in the present work. AFS-1 is characterized by hypidiomorphic texture and consists of feldspar (Or55Ab43 to Or25Ab71, ferro-pargasite/ferro-pargasite hornblende, hastingsite, pyroxene (Wo47, En5, Fs46, magnetite and biotite. AFS-2 exhibits panidiomorphic texture with euhedral pyroxene (Wo47-50, En22-39, Fs12–31 set in a groundmass matrix of alkali feldspar (Or99Ab0.77 to Or1.33Ab98, titanite and magnetite. In comparison to AFS-1, higher elemental concentrations of Ba, Sr and ∑REE are observed in AFS-2. The average peralkaline index of the alkali feldspar syenites is ∼1 indicating their alkaline nature. Variation discrimination diagrams involving major and trace elements and their ratios demonstrate that these alkali feldspar syenites have a shoshonite affinity but emplaced in a within-plate and rifting environment. No evidence of crustal contamination is perceptible in the multi-element primitive mantle normalized diagram as well as in terms of trace elemental ratios. The enrichment of incompatible elements in the alkali feldspar syenites suggests the involvement of mantle metasomatism in their genesis.

Peculiar Feldspar And Quartz Inclusions Within Zircons From Anorthosites, North Eastern Desert, Egypt

Science.gov (United States)

Eliwa, H. A.; Dawoud, M. I.; Khalaf, I. M.; Negendank, J. F.; Itaya, T.

2004-12-01

Zircons from three anorthosite outcrops along Wadi Dib area, north Eastern Desert of Egypt contain abundant and conspicuous inclusions of quartz, feldspar, amphibole and apatite. These anorthosites, as (50-100m thick) layers, represent the top of mafic-ultramafic intrusions exhibiting rhythmic layering visible by reputation of melanocratic and leucocratic layers. Field and microscopic studies exhibit that these anorthosites were affected by the action of residual magmatic solutions associated with the late stage crystallization of the younger granites, which modified their mineralogical composition. They are composed totally of plagioclase with subordinate amount of clinoenstatite, augite, amphibole, biotite, K-feldspar, and quartz. Accessories are magnetite, ilmenite, apatite and zircon. The abundance and the mode of occurrence of K-feldspar, quartz, and biotite with apatite and zircon among the megacrysts suggest their formation is ascribed to the interaction with the residual solutions. The microprobe data exhibit difference between feldspar and amphiboles contained herein zircons and those as anorthosite mineral constituents. The genetic relationship between zircons and their inclusions suggests later growth of zircons than inclusions and most probably at the final stage of rock modification. Zircons are magmatic and found in the interstitial feldspar and quartz among plagioclase megacrysts in aggregates or as individual grains. The microscopic and SEM images investigation exhibit that most zircons are subhedral to euhedral equant and prismatic crystals. Most zircons have same range of crystal morphologies and internal growth structures with predominance of prism /{100/} and pyramid /{101/} and occasionally prism /{110/} and pyramid /{111/}. No evidences for poly-faceted grains, inherited cores or later overgrowths were detected. CL images distinguished zircons with visible core-rim structures and others with regular and continuous growth zones contained herein

Effect of particle size on solubility, dissolution rate, and oral bioavailability: evaluation using coenzyme Q10 as naked nanocrystals

Directory of Open Access Journals (Sweden)

Sun J

2012-11-01

Full Text Available Jiao Sun,1 Fan Wang,1,2 Yue Sui,1 Zhennan She,1 Wenjun Zhai,1 Chunling Wang,1 Yihui Deng11College of Pharmacy, Shenyang Pharmaceutical University, Shenyang, China; 2Beijing Zhijianjinrui Applied Pharmaceutical Science Inc, Beijing, ChinaAbstract: In this paper work, four naked nanocrystals (size range 80–700 nm were prepared without any surfactant or polymer using the solvent/nonsolvent method. The effects of particle size on their solubility, dissolution, and oral bioavailability were investigated. Solubility and dissolution testing were performed in three types of dissolution medium, and the studies demonstrated that the equilibrium solubilities of coenzyme Q10 nanocrystals and bulk drugs were not affected by the dissolution media but the kinetic solubilities were. Kinetic solubility curves and changes in particle size distribution were determined and well explained by the proposed solubilization model for the nanocrystals and bulk drugs. The particle size effect on dissolution was clearly influenced by the diffusion coefficients of the various dissolution media, and the dissolution velocity of coenzyme Q10 increased as particle size decreased. The bioavailability of coenzyme Q10 after oral administration in beagle dogs was improved by reducing the particle size. For 700 nm nanocrystals, the AUC0–48 was 4.4-fold greater than that for the coarse suspensions, but a further decrease in particle size from 700 nm to 120 nm did not contribute to improvement in bioavailability until the particle size was reduced to 80 nm, when bioavailability was increased by 7.3-fold.Keywords: particle size, solubility, dissolution, nanocrystal, bioavailability, coenzyme Q10

Dissolution behaviour of 238U, 234U and 230Th deposited on filters from personal dosemeters.

Science.gov (United States)

Becková, Vera; Malátová, Irena

2008-01-01

Kinetics of dissolution of (238)U, (234)U and (230)Th dust deposited on filters from personal alpha dosemeters was studied by means of a 26-d in vitro dissolution test with a serum ultrafiltrate simulant. Dosemeters had been used by miners at the uranium mine 'Dolní Rozínka' at Rozná, Czech Republic. The sampling flow-rate as declared by the producer is 4 l h(-1) and the sampling period is typically 1 month. Studied filters contained 125 +/- 6 mBq (238)U in equilibrium with (234)U and (230)Th; no (232)Th series nuclides were found. Half-time of rapid dissolution of 1.4 d for (238)U and (234)U and slow dissolution half-times of 173 and 116 d were found for (238)U and (234)U, respectively. No detectable dissolution of (230)Th was found.

From laboratory experiments to a geological disposal vault: calculation of used nuclear fuel dissolution rates

International Nuclear Information System (INIS)

Sunder, S.; Shoesmith, D.W.; Kolar, M.; Leneveu, D.M.

1998-01-01

Calculation of used nuclear fuel dissolution rates in a geological disposal vault requires a knowledge of the redox conditions in the vault. For redox conditions less oxidizing than those causing UO 2 oxidation to the U 3 O 7 , stage, a thermodynamically-based model is appropriate. For more oxidizing redox conditions a kinetic or an electrochemical model is needed to calculate these rates. The redox conditions in a disposal vault will be affected by the radiolysis of groundwater by the ionizing radiation associated with the fuel. Therefore, we have calculated the alpha-, beta- and gamma-dose rates in water in contact with the reference used fuel in the Canadian Nuclear Fuel Waste Management Program (CNFWMP) as a function of cooling time. Also, we have determined dissolution rates of UO 2 fuel as a function of alpha and gamma dose rates from our electrochemical measurements. These room-temperature rates are used to calculate the dissolution rates of used fuel at 100 o C, the highest temperature expected in a container in the CNFWMP, as a function of time since emplacement. It is shown that beta radiolysis of water will be the main cause of oxidation of used CANDU fuel in a failed container. The use of a kinetic or an electrochemical corrosion model, to calculate fuel dissolution rates, is required for a period of ∼1000 a following emplacement of copper containers in the geologic disposal vault envisaged in the CNFWMP. Beyond this time period a thermodynamically-based model adequately predicts the fuel dissolution rates. The results presented in this paper can be adopted to calculate used fuel dissolution rates for other used UO 2 fuels in other waste management programs. (author)

Correlation of basic TL, OSL and IRSL properties of ten K-feldspar samples of various origins

Energy Technology Data Exchange (ETDEWEB)

Sfampa, I.K. [Aristotle University of Thessaloniki, Nuclear Physics Laboratory, 54124 Thessaloniki (Greece); Polymeris, G.S. [Institute of Nuclear Sciences, Ankara University, 06100 Besevler, Ankara (Turkey); Pagonis, V. [McDaniel College, Physics Department, Westminster, MD 21157 (United States); Theodosoglou, E. [Department of Mineralogy-Petrology-Economic Geology, School of Geology, Aristotle University of Thessaloniki, 54124 Thessaloniki (Greece); Tsirliganis, N.C. [Laboratory of Radiation Applications and Archaeological Dating, Department of Archaeometry and Physicochemical Measurements, ‘Athena’ R.& I.C., Kimmeria University Campus, GR67100 Xanthi (Greece); Kitis, G., E-mail: gkitis@auth.gr [Aristotle University of Thessaloniki, Nuclear Physics Laboratory, 54124 Thessaloniki (Greece)

2015-09-15

Highlights: • OSL and IRSL bleaching behavior of ten K-feldspar samples is presented. • OSL and IRSL decay curves were component resolved using tunneling model. • The growth of integrated OSL and IRSL signals versus time was described by new expression based on tunneling model. • Correlation between TL, OSL and IRSL signals and of all properties with K-feldspar structure was discussed. - Abstract: Feldspars stand among the most widely used minerals in dosimetric methods of dating using thermoluminescence (TL), optically stimulated luminescence (OSL) and infrared stimulated luminescence (IRSL). Having very good dosimetric properties, they can in principle contribute to the dating of every site of archaeological and geological interest. The present work studies basic properties of ten naturally occurring K-feldspar samples belonging to three feldspar species, namely sanidine, orthoclase and microcline. The basic properties studied are (a) the influence of blue light and infrared stimulation on the thermoluminescence glow-curves, (b) the growth of OSL, IRSL, residual TL and TL-loss as a function of OSL and IRSL bleaching time and (c) the correlation between the OSL and IRSL signals and the energy levels responsible for the TL glow-curve. All experimental data were fitted using analytical expressions derived from a recently developed tunneling recombination model. The results show that the analytical expressions provide excellent fits to all experimental results, thus verifying the tunneling recombination mechanism in these materials and providing valuable information about the concentrations of luminescence centers.

Dissolution of aluminium

International Nuclear Information System (INIS)

Uriarte Hueda, A.; Berberana Eizmendi, M.; Pereira Sanchez, G.

1968-01-01

The dissolution of aluminum with acid solutions ( nitric acid-mercuric nitrate) and alkaline solutions (sodium hydroxide-sodium nitrate) has been studied. The instantaneous dissolution rate (IDR) has been studied in function of the concentration of the used reagents and the dissolution temperature. The complete dissolution has been included in the second part of this report, to know the total dissolution time, the consume of reagents and the stability of the resultant solutions. (Author)

Determination of potassium in feldspars by beta counting using a GM multicounter system

Energy Technology Data Exchange (ETDEWEB)

Boetter-Jensen, L; Mejdahl, V

1985-01-01

A gas flow multicounter system developed at Risoe National laboratory for low-level beta counting applications was adopted for measuring potassium in feldspars extracted from archaeological and geological materials, in connection with TL dating work. A guard counter reduces the background by using an anticoincidence technique. Calibration was accomplished by measuring KCl and a feldspar standard. A potassium content of 1% yields a net beta count rate (background subtracted) of about 40 c.p.h.; the background is around 15 c.p.h. The precision in repeated measurements is better than 2% and the estimated accuracy is about 3%.

Identifying well-bleached quartz using the different bleaching rates of quartz and feldspar luminescence signals

DEFF Research Database (Denmark)

Murray, A.S.; Thomsen, Kristina Jørkov; Masuda, N.

2012-01-01

When dating older sedimentary deposits using quartz, there are no unambiguous methods for identifying the presence of incomplete bleaching. Current statistical analysis of dose distributions depends entirely on the assumption that incomplete bleaching and mixing are the main causes of any excess...... dispersion in the distribution; the only existing way to test this assumption is using independent age control. Here we suggest a new approach to this question, based on the differential bleaching rates of quartz and feldspar luminescence signals. We first present data that confirm the differences...... in relative bleaching rates of quartz optically stimulated luminescence (OSL) and feldspar luminescence stimulated at 50 °C by infrared light (IR50) and feldspar luminescence stimulated at 290 °C by infrared light after a stimulation at 50 °C (pIRIR290), and use recently deposited samples to determine...

Solvents effects on crystallinity and dissolution of β-artemether.

Science.gov (United States)

Xu, Jianghui; Singh, Vikramjeet; Yin, Xianzhen; Singh, Parbeen; Wu, Li; Xu, Xiaonan; Guo, Tao; Sun, Lixin; Gui, Shuangying; Zhang, Jiwen

2017-03-01

β-artemether (ARM) is a widely used anti-malarial drug isolated from the Chinese antimalarial plant, Artemisia annua. The solvent effects on crystal habits and dissolution of ARM were thoroughly investigated and discussed herein. The ARM was recrystallized in nine different solvents of varied polarity, namely, methanol, ethanol, isopropanol, tetrahydrofuran, dichloromethane, trichloromethane, ethyl acetate, acetone and hexane by solvent evaporation method. The obtained crystals were morphologically characterized using scanning electron microscope (SEM). The average sizes of crystals were 1.80-2.64 μm calculated from microscopic images using Image-Pro software. No significant change in chemical structure was noticed after recrystallization and the specific band at 875 cm -1 wavenumber (C-O-O-C) confirmed the presence of most sensitive functional group in the ARM chemical structure. The existence and production of two polymorphic forms, polymorph A and polymorph B, was confirmed by differential scanning calorimetry (DSC) and powder X-ray diffraction (PXRD). The data suggested that the fabrication of polymorph B can be simply obtained from the recrystallization of ARM in a specific solvent. Significant effects of solvent polarity, crystals shapes and sizes on drug dissolution were noticed during in vitro dissolution test. The release kinetics were calculated and well fitted by the Higuchi and Hixon-Crowell models. The ARM-methanol and ARM-hexane showed highest and slowest dissolution, respectively, due to the effects of solvent polarity and crystal morphologies. Overall, proper selection of the solvents for the final crystallization of ARM helps to optimize dissolution and bioavailability for a better delivery of anti-malarial drug.

Beneficiation of feldspar ore for application in the ceramic industry: Influence of composition on the physical characteristics

Directory of Open Access Journals (Sweden)

M.E. Gaied

2015-03-01

Experimental studies indicate that an acceptable concentrate for industrial application can be obtained from these rocks. The feldspar yield was used to evaluate the process efficiency. Besides, the cone shrinkage, water absorption, degree of vitrification, mechanical properties (flexural strength and dielectric behaviour were used to monitor the quality of the recovered feldspars.

Thermal quenching of luminescence processes in feldspars

DEFF Research Database (Denmark)

Poolton, N.R.J.; Bøtter-Jensen, L.; Duller, G.A.T.

1995-01-01

, which display very different behaviour. The first involves the internal transitions of common transition metal ions. The second is typical of centres not displaying excited states within the band gap that are likely to arise from direct recombination between the conduction band and the ground state......The technique of optically stimulated luminescence has important uses in the dose evaluation of irradiated feldspars. The luminescence process involves the eviction of electrons from donor traps, charge transfer through the conduction band, and recombination at acceptor sites; each...

Dissolution of various metal oxides in different forms in dilute organic complexants

Energy Technology Data Exchange (ETDEWEB)

Srinivasan, M.P.; Chandramohan, P.; Velmurugan, S.; Narasimhan, S.V. [Water and Steam Chemistry Lab., BARC Facilities, Tamilnadu (India); Ranganathan, S. [Madras Univ. (India). Research Scholar

2002-07-01

The dissolution of iron containing metal oxides is of importance in various power plant industries from the point of crud and scale removal for efficient operation and better performance of plant. The removal of these oxides has to be accomplished with minimum corrosion to the structural material, with minimum cost and removal duration and also with minimum waste generation for easy disposal. Activity build-up due to pick up of {sup 60}Co and fission products occurs on PHT system surfaces of nuclear power plants. The dissolution kinetics of these oxides are influenced by pH, redox potential, chelating strength, concentration and temperature of the solution, constitution of oxides, and the physical form of existence of oxides. In this paper the influence of the existence of different forms of iron oxides on the ability of the dissolution characteristics of the different formulations have been brought out. How the change in dissolution characteristics can be ingenuously used to characterize both qualitatively and quantitatively the mixtures of oxides have been brought out. How the magnetite dissolution behaviour varies for base metal unaided condition in different formulation in static condition, in regenerative mode is also brought out. The OCP values and iron release behaviour for magnetite coated CS surface and magnetite pellet were also described. (authors)

Dissolution of various metal oxides in different forms in dilute organic complexants

International Nuclear Information System (INIS)

Srinivasan, M.P.; Chandramohan, P.; Velmurugan, S.; Narasimhan, S.V.; Ranganathan, S.

2002-01-01

The dissolution of iron containing metal oxides is of importance in various power plant industries from the point of crud and scale removal for efficient operation and better performance of plant. The removal of these oxides has to be accomplished with minimum corrosion to the structural material, with minimum cost and removal duration and also with minimum waste generation for easy disposal. Activity build-up due to pick up of 60 Co and fission products occurs on PHT system surfaces of nuclear power plants. The dissolution kinetics of these oxides are influenced by pH, redox potential, chelating strength, concentration and temperature of the solution, constitution of oxides, and the physical form of existence of oxides. In this paper the influence of the existence of different forms of iron oxides on the ability of the dissolution characteristics of the different formulations have been brought out. How the change in dissolution characteristics can be ingenuously used to characterize both qualitatively and quantitatively the mixtures of oxides have been brought out. How the magnetite dissolution behaviour varies for base metal unaided condition in different formulation in static condition, in regenerative mode is also brought out. The OCP values and iron release behaviour for magnetite coated CS surface and magnetite pellet were also described. (authors)

Quantitative analysis of time-resolved infrared stimulated luminescence in feldspars

DEFF Research Database (Denmark)

Pagonis, Vasilis; Ankjærgaard, Christina; Jain, Mayank

2016-01-01

Time-resolved infrared-stimulated luminescence (TR-IRSL) from feldspar samples is of importance in the field of luminescence dating, since it provides information on the luminescence mechanism in these materials. In this paper we present new analytical equations which can be used to analyze TR-IR...

Mechanism of the transpassive dissolution and secondary passivation of chromium in sulphuric acid solutions

International Nuclear Information System (INIS)

Bojinov, M.; Betova, I.; Raicheff, R.; Fabricius, G.; Laitinen, T.; Saario, T.

1998-01-01

The transpassive dissolution and secondary passivation of Cr in 1..10 M H 2 SO 4 solutions were studied by a combination of different electrochemical methods. The steady-state polarization curves for transpassive dissolution exhibited a Tafel behaviour with a slope being independent on the acid concentration. Lower dissolution rates were measured for higher acid concentrations. Ring-disk measurements showed a release of both soluble Cr(VI) and Cr(III) during transpassivity. Impedance spectra were qualititatively similar in all acid concentrations, comprising one capacitive and two inductive semicircles. A kinetic model comprising two parallel transpassive dissolution paths was consistent with the experimental results. Typical passivation diagrams were observed for Cr in 10 M H 2 SO 4 , and a secondary passive state was established at higher potentials. The formation of the secondary passive film was confirmed by contact electric resistance (CER) measurements. A renewed version of the surface charge approach was consistent with the experimental results in the region of the secondary passivation. (orig.)

Detrital K-feldspar thermochronology of the Nanaimo Group: Characterization of Basement and Extraregional Basin Contributions

Science.gov (United States)

Isava, V.; Grove, M.; Mahoney, J. B.; Kimbrough, D. L.

2016-12-01

The Late Cretaceous-Early Paleogene Nanaimo Group covers the contact between Triassic basement Wrangellia terrane and the Jurassic-Cretaceous Coast Plutonic Complex (CPC) in southern British Columbia. Prior detrital zircon U-Pb and Hf studies indicate a change in sediment source for the Nanaimo basin, from the primitive CPC in Santonian-Early Campanian time to an isotopically evolved continental extraregional source during the late Campanian/Maastrictian. Two notably different areas have been proposed as potential source regions: (1) the Idaho/Boulder batholith and Belt Supergroup, and (2) the Mojave/Salinia segment of structurally disrupted late Cretaceous southern California margin. Single crystal 40Ar/39Ar laser fusion of ca. 100-200 grains apiece from seven detrital K-feldspar samples from Santonian-Maastrichtian strata of the northern Nanaimo Group constrain the history of the sediments' source regions. The two oldest samples, from the K-feldspar poor Comox and Extension Fms., display a monotonic increasing distribution of cooling ages 80-125 Ma that reflects shallow erosion of the CPC. In contrast, Late Campanian strata of the Cedar District and De Courcy Fms. exhibit a more pronounced cluster of cooling ages 80-95 Ma as well as a greater proportion of Jurassic ages that represent progressively deeper erosion of the CPC. Evidence for an extraregional sediment source appears abruptly in the Geoffrey Fm. by 72 Ma, matching the time of local-to-extraregional shift indicated in detrital zircon U-Pb studies. Over 90% of the detrital K-feldspars from these arkosic sandstones yield cooling ages of 70-80 Ma, with sparse older ages associated with the CPC. Samples from the successively younger Spray and Gabriola Fms. also yield >90% K-feldspar ages younger than 80 Ma and exhibit age maxima of 68 Ma and 65 Ma, respectively. These results are distinct from detrital zircon U-Pb and K-feldspar 40Ar/39Ar ages of the southern Sierra Nevada, Mojave/Salina, and northern

Electrons in feldspar I: On the wavefunction of electrons trapped at simple lattice defects

DEFF Research Database (Denmark)

Poolton, H.R.J.; Wallinga, J.; Murray, A.S.

2002-01-01

The purpose of this article is to make an initial consideration of the physical properties of electrons trapped at classic hydrogenic lattice defects in feldspar. We are particularly interested to determine the radial extent of the electron wavefunctions in the ground and excited states. It is sh......The purpose of this article is to make an initial consideration of the physical properties of electrons trapped at classic hydrogenic lattice defects in feldspar. We are particularly interested to determine the radial extent of the electron wavefunctions in the ground and excited states...

Luminescence at the end of the tunnelling - Investigating charge transfer mechanisms and luminescence dating methods for feldspar minerals

NARCIS (Netherlands)

Kars, R.H.

2014-01-01

This thesis comprises analyses of mineral physics with an application in geology and archeology. The thesis contributes to the development of feldspar luminescence dating methods in order to extend the applicable age range of feldspar luminescence dating in the Quaternary (last 2.6 Ma). The research

Potassium self-diffusion in a K-rich single-crystal alkali feldspar

CERN Document Server

Hergemöller, Fabian; Deicher, Manfred; Wolf, Herbert; Brenner, Florian; Hutter, Herbert; Abart, Rainer; Stolwijk, Nicolaas A.

The paper reports potassium diffusion measurements performed on gem-quality single-crystal alkali feldspar in the temperature range from 1169 to 1021 K. Natural sanidine from Volkesfeld, Germany was implanted with {}^{43}K at the ISOLDE/CERN radioactive ion-beam facility normal to the (001) crystallographic plane. Diffusion coefficients are well described by the Arrhenius equation with an activation energy of 2.4 eV and a pre-exponential factor of 5×10^{-6}m^{2}/s, which is more than three orders of magnitude lower than the {}^{22}Na diffusivity in the same feldspar and the same crystallographic direction. State-of-the-art considerations including ionic conductivity data on the same crystal and Monte Carlo simulations of diffusion in random binary alloy structures point to a correlated motion of K and Na through the interstitialcy mechanism.

Study of anodic dissolution of Fe-Ru alloy with the aid of mossbauer spectroscopy

International Nuclear Information System (INIS)

Khlystov, A.S.; Fasman, A.B.; Kil'dibekova, G.A.

1986-01-01

This paper uses Fe 57 Mossbauer spectroscopy, whereby iron compounds may be identified quantitatively and their composition and structure can be determined, for the study of the relationships of slime formation from Fe-Ru binary alloys. Both the products of dissolution and the composition and state of intermediate phases formed at various stages of anodic dissolution were studied simultaneously. It was found that the slimes formed both during chemical and during electrochemical destruction of ruthenium-iron alloys are finely dispersed systems of complex composition, analogous to those formed in the course of electrochemical dissolution of Ni-Ru alloys, which were found to contain oxide phases of ruthenium (by x-ray spectroscopy and ESCA) and of nickel (by x-ray phase analysis). The difference between the slime compositions is determined mainly by kinetic factors

Kinetic study of the annealing reactions in Cu-Ni-Fe alloys

International Nuclear Information System (INIS)

Donoso, E.

2014-01-01

The thermal aging of a Cu-45Ni-4Fe, Cu-34Ni-11Fe and Cu-33Ni-22Fe alloys tempered from 1173 K have been studied from Differential Scanning Calorimetry (DSC) and microhardness measurements. The analysis of DSC curves, from room temperature to 950 K, shows the presence of one exothermic reaction associated to the formation of FeNi 3 phase nucleating from a modulate structure, and one endothermic peak attributed to dissolution of this phase. Kinetic parameters were obtained using the usual Avrami-Erofeev equation, modified Kissinger method and integrated kinetic functions. Microhardness measurements confirmed the formation and dissolution of the FeNi 3 phase. (Author)

Bleaching of the thermoluminescence of feldspars by selected wavelengths present in sunlight

International Nuclear Information System (INIS)

Robertson, G.B.; Prescott, J.R.; Hutton, J.T.

1993-01-01

Feldspars occur in many sediments, and dating them by thermoluminescence (TL) requires a knowledge of how efficiently sunlight bleaches these minerals. The relative bleaching efficiencies of various wavelengths have been investigated for four alkali feldspars and an oligoclase, using the natural TL of the samples and the artificial TL induced by laboratory irradiation, bleached by wavelengths in the range 322-550 nm. Ultraviolet wavelengths are more efficient than the longer wavelengths at bleaching all the glow-curve peaks and are responsible for most of the phototransfer from high-temperature peaks to low-temperature peaks. Some feldspars show an initial increase in TL intensity with bleaching. Two sanidines of similar bulk composition but different TL glow curves show different dependences on bleaching wavelength. In a sodic sanidine with a dominant 240 o C peak the energy required to bleach to 50% was a thousand times greater at 550 nm than at 322 nm. In contrast, another sanidine with a complex glow curve between 150 and 450 o C showed a much slower change in the 330 o C peak with wavelength - a factor of 10 between 322 and 550 nm - with a region between 400 and 500 nm which was almost independent of wavelength. This behaviour is explained by competing mechanisms of phototransfer and bleaching which depend on wavelength in different ways. (author)

pH-metric solubility. 3. Dissolution titration template method for solubility determination.

Science.gov (United States)

Avdeef, A; Berger, C M

2001-12-01

The main objective of this study was to develop an effective potentiometric saturation titration protocol for determining the aqueous intrinsic solubility and the solubility-pH profile of ionizable molecules, with the specific aim of overcoming incomplete dissolution conditions, while attempting to shorten the data collection time. A modern theory of dissolution kinetics (an extension of the Noyes-Whitney approach) was applied to acid-base titration experiments. A thermodynamic method was developed, based on a three-component model, to calculate interfacial, diffusion-layer, and bulk-water reactant concentrations in saturated solutions of ionizable compounds perturbed by additions of acid/base titrant, leading to partial dissolution of the solid material. Ten commercial drugs (cimetidine, diltiazem hydrochloride, enalapril maleate, metoprolol tartrate, nadolol, propoxyphene hydrochloride, quinine hydrochloride, terfenadine, trovafloxacin mesylate, and benzoic acid) were chosen to illustrate the new titration methodology. It was shown that the new method is about 10 times faster in determining equilibrium solubility constants, compared to the traditional saturation shake-flask methods.

Enhancement of the glass corrosion in the presence of clay minerals: testing experimental results with an integrated glass dissolution model

International Nuclear Information System (INIS)

Godon, N.; Vernaz, E.Y.

1992-01-01

Recent glass dissolution experiments, conducted at 90 deg C in the presence of potential backfill materials, indicate remarkably faster glass corrosion in the presence of clay, compared to tests where the glass is leached either alone or with alternative backfill materials. This effect correlates with the clay content in the backfill, and may be attributed to the removal of silica from solution. Scorpion, or dissolution with reprecipitation of a silica-rich clay, have been proposed as possible mechanisms for the silica consumption. The results of some experiments have been tested against a glass dissolution model, in which a widely used kinetic equation for glass corrosion is coupled with diffusive silica transport through a single porosity, linearly sorbing medium, which represents the backfilling. Because the glass corrosion rates imposed by the kinetic equation are inversely proportional to the silicic acid concentration of the leachant contacting the glass, the model predicts enhanced glass dissolution if silica is sorbed by the porous medium. The experimental data proved to be consistent with the predicted enhancement of the glass dissolution. Moreover, the model-estimated distribution coefficients for silica sorption (K d ) fall within the range of values extracted from available literature data, thus supporting the hypothesis that the observed high corrosion rates are due to sorption of silica on the clay mineral surfaces. (author)

Kinetics of dissolution of sapphire in melts in the CaO-Al2O3-SiO2 system

Science.gov (United States)

Shaw, Cliff S. J.; Klausen, Kim B.; Mao, Huahai

2018-05-01

The dissolution rate of sapphire in melts in the CAS system of varying silica activity, viscosity and degree of alumina saturation has been determined at 1600 °C and 1.5 GPa. After an initiation period of up to 1800 s, dissolution is controlled by diffusion of cations through the boundary layer adjacent to the dissolving sapphire. The dissolution rate decreases with increasing silica activity, viscosity and molar Al2O3/CaO. The calculated diffusion matrix for each solvent melt shows that CAS 1 and 9 which have molar Al2O3/CaO of 0.33 and 0.6 and dissolution rate constants of 0.65 × 10-6 and 0.59 × 10-6 m/s0.5 have similar directions and magnitudes of diffusive coupling: DCaO-Al2O3 and DAl2O3-CaO are both negative are approximately equal. The solvent with the fastest dissolution rate: CAS 4, which has a rate constant of 1.5 × 10-6 m/s0.5 and Al2O3/CaO of 0.31 has positive DCaO-Al2O3 and negative DAl2O3-CaO and the absolute values vary by a factor of 4. Although many studies show that aluminium is added to the melts via the reaction: Si4+ =Al3+ + 0.5Ca2+ the compositional profiles show that this reaction is not the only one involved in accommodating the aluminium added during sapphire dissolution. Rather, aluminium is incorporated as both tetrahedrally coordinated Al charge balanced by Ca and as aluminium not charge balanced by Ca (termed Alxs). This reaction: AlIV -Ca =Alxs +CaNBO where CaNBO is a non-bridging oxygen associated with calcium, may involve the formation of aluminium triclusters. The shape of the compositional profiles and oxide-oxide composition paths is controlled by the aluminium addition reaction. When Alxs exceeds 2%, CaO diffusion becomes increasingly anomalous and since the bond strength of Alxs correlates with CaO/CaO + Al2O3, the presence of more than 2% Alxs leads to significantly slower dissolution than when Alxs is absent or at low concentration. Thus, dissolution is controlled by diffusion of cations through the boundary layer, but this

CHARACTERIZATION AND ALUMINUM DISSOLUTION DEMONSTRATION WITH A 3 LITER TANK 51H SAMPLE

International Nuclear Information System (INIS)

Hay, M; John Pareizs, J; Cj Bannochie, C; Michael Stone, M; Damon Click, D; Daniel McCabe, D

2008-01-01

A 3-liter sludge slurry sample was sent to SRNL for demonstration of a low temperature aluminum dissolution process. The sludge was characterized before and after the aluminum dissolution. Post aluminum dissolution sludge settling and the stability of the decanted supernate were also observed. The characterization of the as-received 3-liter sample of Tank 51H sludge slurry shows a typical high aluminum HM sludge. The XRD analysis of the dried solids indicates Boehmite is the predominant crystalline form of aluminum in the sludge solids. However, amorphous phases of aluminum present in the sludge would not be identified using this analytical technique. The low temperature (55 C) aluminum dissolution process was effective at dissolving aluminum from the sludge. Over the three week test, ∼42% of the aluminum was dissolved out of the sludge solids. The process appears to be selective for aluminum with no other metals dissolving to any appreciable extent. At the termination of the three week test, the aluminum concentration in the supernate had not leveled off indicating more aluminum could be dissolved from the sludge with longer contact times or higher temperatures. The slow aluminum dissolution rate in the test may indicate the dissolution of the Boehmite form of aluminum however; insufficient kinetic data exists to confirm this hypothesis. The aluminum dissolution process appears to have minimal impact on the settling rate of the post aluminum dissolution sludge. However, limited settling data were generated during the test to quantify the effects. The sludge settling was complete after approximately twelve days. The supernate decanted from the settled sludge after aluminum dissolution appears stable and did not precipitate aluminum over the course of several months. A mixture of the decanted supernate with Tank 11 simulated supernate was also stable with respect to precipitation

Kinetic Modelling of Drug Release from Pentoxifylline Matrix Tablets based on Hydrophilic, Lipophilic and Inert Polymers

Directory of Open Access Journals (Sweden)

Mircia Eleonora

2015-12-01

Full Text Available Pentoxifylline is a xanthine derivative used in the treatment of peripheral vascular disease, which because of its pharmacokinetic and pharmacologic profile is an ideal candidate for the development of extended release formulations. The aim of this study is to present a kinetic analysis of the pentoxifylline release from different extended release tablets formulations, using mechanistic and empirical kinetic models. A number of 28 formulations were prepared and analysed; the analysed formulations differed in the nature of the matrix forming polymers (hydrophilic, lipophilic, inert and in their concentrations. Measurements were conducted in comparison with the reference product Trental 400 mg (Aventis Pharma. The conditions for the dissolution study were according to official regulations of USP 36: apparatus no. 2, dissolution medium water, volume of dissolution medium is 1,000 mL, rotation speed is 50 rpm, spectrophotometric assay at 274 nm. Six mathematical models, five mechanistic (0 orders, 1st-order release, Higuchi, Hopfenberg, Hixson-Crowell and one empirical (Peppas, were fitted to pentoxifylline dissolution profile from each pharmaceutical formulation. The representative model describing the kinetics of pentoxifylline release was the 1st-order release, and its characteristic parameters were calculated and analysed.

Theoretical study of thin metallic deposit layers: from electronic structure to kinetics

International Nuclear Information System (INIS)

Senhaji, Abdelali

1993-01-01

We have studied the relation between the equilibrium surface segregation in an alloy A c B 1-c and the kinetics of dissolution of a few metallic layers of A (or B) deposited on a B (or A) substrate. We used an energetic model derived from the electronic structure (T.B.I.M.) allowing us to study the surface segregation both in disordered and in ordered alloys. Moreover we have developed a kinetic model (K.T.B.I.M.) consistent with the TBIM energetic model to study the kinetics both of segregation and dissolution. This process has been applied to the Cu-Pt system for which Auger, LEED and photoemission experiments are in progress at L.U.R.E. Concerning the equilibrium surface segregation in the ordered state we have studied all the possible terminations for the (111) and (100) faces in the various ordered structures occurring on the F.C.C. lattice (L1 0 , L1 1 - L1 2 and L'). In particular we have determined the domain of (meta)stability of each termination, which is very useful to understand the competition between single and double steps in ordered alloys. Studying the kinetics of dissolution of a few layers of Cu (or Pt) deposited on the (111) or (100) face of a Pt (or Cu) substrate, we have shown the formation of surface compounds with a great variety of behaviours depending on the face or on the temperature. All these behaviours can be rationalized with the local equilibrium concept, which we have defined accurately within our model and which allows to connect the dissolution mode with the equilibrium segregation. (author) [fr

Thermoluminescence of annealed and shock-loaded feldspar

International Nuclear Information System (INIS)

Hartmetz, C.P.

1988-01-01

Samples of oligoclase and bytownite were shock-loaded to a variety of pressures, and annealed for a variety of temperatures and times. The effect of Mrad doses of gamma-rays on oligoclase TL were also studied. After these treatments, thermoluminescence (TL) and X-ray diffraction (XRD) measurements were made to: (1) determine the effects of shock on terrestrial feldspar and compare with variations in the TL emission of ordinary chondrites (OCs); (2) determine if disordering in feldspar was responsible for any related changes in TL properties of OCs; (3) determine if the combined effect of shock plus annealing causes the changes in TL properties; (4) see if radiation damage from cosmic ray exposure plays a role in the TL variations; (5) examine the implications of this work to the thermal and shock histories of OCs. The lightly shock-loaded and annealed oligoclase samples have a dominant peak temperature of 120-140 C, identical to type 3.3-3.5 OCs. The heavily shocked samples dominant peak is at 230C, similar to type > 3.5 OCs . While the heavily annealed/disordered oligoclase samples have a peak at 280C, this peak is rarely observed in OCs. Radiation damage from Mrad doses of gamma-rays produced no change in peak temperature, but facilitated the shift to higher peak temperatures. The TL sensitivity of the shocked samples decreased by a factor of 25. Samples annealed at low temperatures (438-533C) showed a factor of 2 decrease in TL, but at the highest temperatures, the TL was a factor of 8 higher

To the problem of paleodosimetrical information stability in alkali feldspars

International Nuclear Information System (INIS)

Huett, Galina; Jaek, Ivar

1997-01-01

The stability of holes of the centres of recombination in alkali feldspars, extracted from sediments, is studied. For the emission centres with 410 and 570 nm the energy of activation of thermal quenching is obtained (> 2 eV). Problems of fading and difference between thermoluminescence (TL) and optically stimulated luminescence (OSL), as well as bleach abilities, are discussed. Values of thermal activation energy (> 2 eV) obtained for two different emission bands (410 and 570 nm) in alkali feldspars prove the upper limit of dating (c 10 5 years). The absence of a permanent channel of fading is supported by experimental data. Differences in bleach ability, as well as in residuals of TL and OSL response dating signals, are explained within the frame of the proposed model of identity of defects responsible for those signals. It is supposed that better bleach ability of the OSL signal is connected with optical selection of more transparent grains (or more easily bleach able centres). The applicability of the orange band of emission (570 nm) for dating is recommended for future study

On the shape of continuous wave infrared stimulated luminescence signals from feldspars: A case study

DEFF Research Database (Denmark)

Pagonis, V.; Jain, Mayank; Thomsen, Kristina Jørkov

2014-01-01

The continuous-wave IRSL (CW-IRSL) signals from feldspars are known to decay in a non-exponential manner, and their exact mathematical description is of great importance in dosimetric and dating studies. This paper investigates the possibility of fitting experimental CW-IRSL curves from a variety...... to guide future modeling work on luminescence processes in feldspars. Small statistical differences were found between K-rich and Na-rich fractions of the same sample. However, the experimental data shows that the parameters depend on the irradiation dose, but do not depend on the time elapsed after...

Biochemical evolution. I. Polymerization on internal, organophilic silica surfaces of dealuminated zeolites and feldspars

Science.gov (United States)

Smith, Joseph V.

1998-01-01

Catalysis at mineral surfaces might generate replicating biopolymers from simple chemicals supplied by meteorites, volcanic gases, and photochemical gas reactions. Many ideas are implausible in detail because the proposed mineral surfaces strongly prefer water and other ionic species to organic ones. The molecular sieve silicalite (Union Carbide; = Al-free Mobil ZSM-5 zeolite) has a three-dimensional, 10-ring channel system whose electrically neutral Si-O surface strongly adsorbs organic species over water. Three -O-Si tetrahedral bonds lie in the surface, and the fourth Si-O points inwards. In contrast, the outward Si-OH of simple quartz and feldspar crystals generates their ionic organophobicity. The ZSM-5-type zeolite mutinaite occurs in Antarctica with boggsite and tschernichite (Al-analog of Mobil Beta). Archean mutinaite might have become de-aluminated toward silicalite during hot/cold/wet/dry cycles. Catalytic activity of silicalite increases linearly with Al-OH substitution for Si, and Al atoms tend to avoid each other. Adjacent organophilic and catalytic Al-OH regions in nanometer channels might have scavenged organic species for catalytic assembly into specific polymers protected from prompt photochemical destruction. Polymer migration along weathered silicic surfaces of micrometer-wide channels of feldspars might have led to assembly of replicating catalytic biomolecules and perhaps primitive cellular organisms. Silica-rich volcanic glasses should have been abundant on the early Earth, ready for crystallization into zeolites and feldspars, as in present continental basins. Abundant chert from weakly metamorphosed Archaean rocks might retain microscopic clues to the proposed mineral adsorbent/catalysts. Other framework silicas are possible, including ones with laevo/dextro one-dimensional channels. Organic molecules, transition-metal ions, and P occur inside modern feldspars. PMID:9520372

Dissolution profiles of perindopril and indapamide in their fixed-dose formulations by a new HPLC method and different mathematical approaches

Directory of Open Access Journals (Sweden)

Gumieniczek Anna

2015-09-01

Full Text Available A new HPLC method was introduced and validated for simultaneous determination of perindopril and indapamide. Validation procedure included specificity, sensitivity, robustness, stability, linearity, precision and accuracy. The method was used for the dissolution test of perindopril and indapamide in three fixed-dose formulations. The dissolution procedure was optimized using different media, different pH of the buffer, surfactants, paddle speed and temperature. Similarity of dissolution profiles was estimated using different model-independent and model-dependent methods and, additionally, by principal component analysis (PCA. Also, some kinetic models were checked for dissolved amounts of drugs as a function of time.

Influence of pH and temperature on alunite dissolution rates and products

Science.gov (United States)

Acero, Patricia; Hudson-Edwards, Karen

2015-04-01

, leading to dissolved Al/K ratios between 0.5 and 2.5. This depletion of Al in the solution is especially clear for the experiments at pH 4.5-4.8 and 8 and it is consistent with the results of elemental quantifications of the same proportions in the reacted alunite surfaces using X-ray Photoelectron Spectroscopy (XPS). REFERENCES Flaten, T.P. (2001): Aluminium as a risk factor in Alzheimzer's disease, with emphasis on drinking water. Brain Research Bulletin 55: 187-196. Nordstrom, D.K. (2011): Hydrogeochemical processes governing the origin, transport and fate of major and trace elements from mine wastes and mineralized rock to surface waters. Applied Geochemistry 26: 1777-1791. Prietzel, J., & Hirsch, C. (1998). Extractability and dissolution kinetics of pure and soil-added synthesized aluminium hydroxy sulphate minerals. European journal of soil science, 49(4), 669-681. Swayze, G.A., Ehlmann, B.L., Milliken, R.E., Poulet, F., Wray, J.J., Rye, R.O., Clark, R.N., Desborough, G.A., Crowley, J.K., Gondet, B., Mustard, J.F., Seelos, K.D. and Murchie, S.L., 2008. Discovery of the Acid-Sulfate Mineral Alunite in Terra Sirenum, Mars, Using MRO CRISM: Possible Evidence for Acid-Saline Lacustrine Deposits?, American Geophysical Union, Fall Meeting 2008, abstract #P44A-04. Welch, S. A., Kirste, D., Christy, A. G., Beavis, F. R., & Beavis, S. G. (2008): Jarosite dissolution II'Reaction kinetics, stoichiometry and acid flux. Chemical Geology, 254(1), 73-86.

Possible reasons for anomalous fading in alkali feldspars used for luminescence dating of Quaternary deposits

Directory of Open Access Journals (Sweden)

Jaek, Ivar

2007-09-01

Full Text Available According to many publications, alkali feldspars are characterized by specific athermal (anomalous fading of their thermoluminescence and optically-stimulated luminescence. This phenomenon is manifested as spontaneous decline in luminescence intensity over relatively long (months and years time after laboratory irradiation, possibly due to tunnelling of electrons from lattice defects and impurities acting as dosimetric traps. It can hamper reliable luminescent dating of Quaternary deposits on the basis of feldspar extractions due to possible unpredictable underestimation of the ages. In this paper we present some experimental results related to the manifestation of the phenomenon. It is found that, in general case, the assumed long-term anomalous fading cannot be connected to electron tunnelling from the deep dosimetric traps. At the same time, some decrease in the dosimetric luminescence signal observable in just irradiated feldspar samples can really be caused by tunnelling. However, the probability of this process quickly goes down, already within some days after irradiation. Interpretation of some other short- and long-term anomalous fading-like effects requires involvement of radiation- and thermo-induced ionic processes.

Luminescence characteristics of quartz and feldspar from tectonically uplifted terraces in Kashmir Basin, Jammu and Kashmir, India

International Nuclear Information System (INIS)

Jaiswal, Manoj K.; Bhat, M.I.; Bali, B.S.; Ahmad, Shabir; Chen, Y.G.

2009-01-01

The Kashmir Valley or the Jhelum basin is an intermontane-basin in NW Himalaya bounded by the Pir Panjal Range in the south and southwest and the Great Himalayan Range in the north and northeast. The valley is marked by active major thrust boundaries in its south and southwestern parts. Remote sensing studies and morphometric analysis suggest neo-tectonic activities and the formation of tectonic terraces due to uplift on the major thrust boundaries in NW Himalayas. The quartz from freshly eroded mountain belts is usually found to show very poor luminescence sensitivity and thus not suitable for optical dating. Similar problems occurred with the quartz from the Srinagar Basin. Due to this, feldspar was selected as a natural dose meter for dating tectonically uplifted terraces in an active and dynamic belt of the NW Himalayas. We report here for the first time the luminescence characteristics of quartz and feldspar minerals from the study area. However, feldspar also shows poor luminescence sensitivity, although enough to perform optical dating. Athermal fading was observed in all the feldspar samples, which was corrected using 'g' values; a large scatter was found in the g values, probably due to intermixing of feldspar grains from varying source rock types and also due to poor luminescence sensitivity. An average g value correction to the mean paleodose was found to agree if compared with the thermo-luminescence date of loess deposit dated earlier. The ages show that the terrace formation started taking place at ∼100 ka in the southwestern part of the Jhelum basin and continued with pulses at 50 ka and 11 ka towards the northwestern part.

Testing feldspar luminescence dating of young archaeological heated materials using potshards from Pella (Tell Tabqat Fahl) in the Jordan valley

DEFF Research Database (Denmark)

Khasswneh, Sahar Al; Murray, Andrew Sean; Bourke, Stephen

2017-01-01

Recent developments in the use of more stable feldspar signals in the luminescence dating of sediments offer the possibility of obtaining accurate feldspar luminescence ages for ceramic artefacts; this is especially interesting in locations which do not provide suitable quartz extracts. Here we e...

Structural and silver/vanadium ratio effects on silver vanadium phosphorous oxide solution formation kinetics: impact on battery electrochemistry.

Science.gov (United States)

Bock, David C; Takeuchi, Kenneth J; Marschilok, Amy C; Takeuchi, Esther S

2015-01-21

The detailed understanding of non-faradaic parasitic reactions which diminish battery calendar life is essential to the development of effective batteries for use in long life applications. The dissolution of cathode materials including manganese, cobalt and vanadium oxides in battery systems has been identified as a battery failure mechanism, yet detailed dissolution studies including kinetic analysis are absent from the literature. The results presented here provide a framework for the quantitative and kinetic analyses of the dissolution of cathode materials which will aid the broader community in more fully understanding this battery failure mechanism. In this study, the dissolution of silver vanadium oxide, representing the primary battery powering implantable cardioverter defibrillators (ICD), is compared with the dissolution of silver vanadium phosphorous oxide (Ag(w)VxPyOz) materials which were targeted as alternatives to minimize solubility. This study contains the first kinetic analyses of silver and vanadium solution formation from Ag0.48VOPO4·1.9H2O and Ag2VP2O8, in a non-aqueous battery electrolyte. The kinetic results are compared with those of Ag2VO2PO4 and Ag2V4O11 to probe the relationships among crystal structure, stoichiometry, and solubility. For vanadium, significant dissolution was observed for Ag2V4O11 as well as for the phosphate oxide Ag0.49VOPO4·1.9H2O, which may involve structural water or the existence of multiple vanadium oxidation states. Notably, the materials from the SVPO family with the lowest vanadium solubility are Ag2VO2PO4 and Ag2VP2O8. The low concentrations and solution rates coupled with their electrochemical performance make these materials interesting alternatives to Ag2V4O11 for the ICD application.

Exchange of Na+ and K+ between water vapor and feldspar phases at high temperature and low vapor pressure

Science.gov (United States)

Fournier, R.O.

1976-01-01

In order to determine whether gas (steam) containing a small amount of dissolved alkali chloride is effective in promoting base exchange of Na+ and K+ among alkali feldspars and coexisting brine or brine plus solid salt, experiments were carried out at 400-700??C and steam densities ranging down to less than 0.05. For bulk compositions rich in potassium, the low pressure results are close to previous high-pressure results in composition of the fluid and coexisting solid phase. However, when the bulk composition is more sodic, alkali feldspars are relatively richer in potassium at low pressure than at high pressure. This behaviour corresponds to enrichment of potassium in the gas phase relative to coexisting brine and precipitation of solid NaCl when the brine plus gas composition becomes moderately sodic. The gas phase is very effective in promoting base exchange between coexisting alkali feldspars at high temperature and low water pressure. This suggests that those igneous rocks which contain coexisting alkali feldspars out of chemical equilibrium either remained very dry during the high-temperature part of their cooling history or that the pore fluid was a gas containing very little potassium relative to sodium. ?? 1976.

Some evidence of uranium in volcanic feldspar rocks in the state of Sonora

Energy Technology Data Exchange (ETDEWEB)

Marquina M, O. E. [Uranio Mexicano, Mexico City

1983-05-15

Description is given of four projects of exploration and survey for uranium associated with tertiary volcanic feldspar rocks importantly dispersed in the State of Sonora and being carried out by Uranium Mexicano.

Experimental early crystallization of K-feldspar in granitic systems. Implications on the origin of magmatic fabrics in granitic rocks

Energy Technology Data Exchange (ETDEWEB)

Díaz-Alvarado, J.

2017-07-01

One of the most outstanding characteristics of some granodioritic to granitic rocks is the presence of K-feldspar megacrysts. For instance, granodiorites and monzogranites of the Spanish Central System batholith present variable amounts of large (up to 10cm in length) euhedral K-feldspar crystals. The porphyritic textures, the euhedral shape, the alignment of plagioclase and biotite inclusions and the magmatic fabrics point to a magmatic origin for these megacrysts. This work presents a phase equilibria study in a high-K2O granodioritic system. A series of experiments were conducted with a granodioritic composition (GEMbiot) to study the crystallization sequence at the emplacement conditions in the Gredos massif, i.e. 4 H2O wt.% and 0.4GPa. Experimental results show that orthopiroxene is the liquidus phase at 1010ºC, which reacts with the H2O-rich melt to stabilize biotite between 980 and 940ºC. Plagioclase crystallizes at around 910ºC, and K-feldspar crystallizes in the matrix between 750 and 700ºC when the crystal fraction is around 0.5. However, at 850 ºC, a pelite-doped experiment shows euhedral K-feldspar (≈5vol%) in both the reactive xenolith domain together with cordierite and the granodioritic domain, where the K2O wt.% rise from 4.5 in the normal experiment to 5.9 in the doped experiment. These results suggest that the bulk-assimilation process promotes the bulk and heterogeneous K2O enrichment in a huge granodioritic magma volume, which triggers an early crystallization of K-feldspar megacrysts. Because of this early crystallization of the megacrysts, the magmatic foliations defined by K-feldspar megacrysts are formed during and after the emplacement processes and are highly influenced by tectonic kinematics.

Quartz dissolution and silica deposition in hot-dry-rock geothermal systems

Energy Technology Data Exchange (ETDEWEB)

Robinson, B.A.

1982-07-01

The kinetics of quartz dissolution control the produced fluid dissolved silica concentration in geothermal systems in which the downhole residence time is finite. The produced fluid of the Phase I, Run Segment 5 experimental Hot Dry Rock (HDR) geothermal system at Fenton Hill, NM, was undersaturated with respect to quartz in one pass through the reservoir, suggesting that the rate of granite dissolution governed the outlet dissolved silica concentration in this system. The literature data for the rate of quartz dissolution in water from 65 to 625/sup 0/C is correlated using an empirical rate law which is first order in quartz surface area and degree of undersaturation of the fluid. The Arrhenius plot (ln k vs T/sup -1/) is linear over eight orders of magnitude of the rate constant, verifying the validity of the proposed rate expression. Carefully performed quartz dissolution experiments in the present study duplicated the literature data and completed the data base in the temperature range from 150 to 250/sup 0/C. Identical experiments using crushed granite indicate that the rate of quartz dissolution in the presence of granite could be as much as 1 to 2 orders of magnitude faster than the rates observed in the pure quartz experiments. A temperature dependent HDR reservoir model incorporates the quartz dissolution rate law to simulate the dissolved silica behavior during the Fenton Hill Run Segment 5 experiment. For this low-permeability, fracture-dominated reservoir, the assumptions of one-dimensional plug flow through a vertically-inclined rectangular fracture and one-dimensional rock heat conduction perpendicular to the direction of flow are employed. These simplifications lead to an analytical solution for the temperature field in the reservoir.

Radiation-induced growth and isothermal decay of infrared-stimulated luminescence from feldspar

DEFF Research Database (Denmark)

Guralnik, Benny; Li, Bo; Jain, Mayank

2015-01-01

the growth and decay of laboratory-regenerated luminescence signals. Here we review a selection of common models describing the response of infrared stimulated luminescence (IRSL) of feldspar to constant radiation and temperature as administered in the laboratory. We use this opportunity to introduce...

Beneficiation of feldspar ore for application in the ceramic industry: Influence of composition on the physical characteristics

OpenAIRE

Gaied, M.E.; Gallala, W.

2015-01-01

In this study, physical and physicochemical experiments were carried out to improve the quality of feldspar ore in Sidi Aïch massive, located in the Gafsa region of south-western Tunisia. After determination of the mineralogical and the chemical composition, flotation methods were applied. In this study, non-hydrofluoric acid flotation methods used in feldspar-quartz separation were compared with each other and with the conventional HF/amine method. The results showed that conventional HF/ami...

Solubility limits on radionuclide dissolution

Energy Technology Data Exchange (ETDEWEB)

Kerrisk, J.F.

1984-12-31

This paper examines the effects of solubility in limiting dissolution rates of a number of important radionuclides from spent fuel and high-level waste. Two simple dissolution models were used for calculations that would be characteristics of a Yucca Mountain repository. A saturation-limited dissolution model, in which the water flowing through the repository is assumed to be saturated with each waste element, is very conservative in that it overestimates dissolution rates. A diffusion-limited dissolution model, in which element-dissolution rates are limited by diffusion of waste elements into water flowing past the waste, is more realistic, but it is subject to some uncertainty at this time. Dissolution rates of some elements (Pu, Am, Sn, Th, Zr, Sm) are always limited by solubility. Dissolution rates of other elements (Cs, Tc, Np, Sr, C, I) are never solubility limited; their release would be limited by dissolution of the bulk waste form. Still other elements (U, Cm, Ni, Ra) show solubility-limited dissolution under some conditions. 9 references, 3 tables.

The dissolution kinetics of major elements in municipal solid waste incineration bottom ash particles

Science.gov (United States)

Bendz, David; Tüchsen, Peter L.; Christensen, Thomas H.

2007-12-01

Leaching and tracer experiments in batches at L/S 20 were performed with 3-month-old MSWI bottom ash separated into eight different particle sizes. The time-dependent leaching of major elements (Ca 2+, K +, Na +, Cl - and SO 4- 2 ) was monitored for up to 747 h. Physical properties of the particles, the specific surface (BET), pore volume and pore volume distribution over pore sizes (BJH) were determined for all particle classes by N 2 adsorption/desorption experiments. Some common features of physical pore structure for all particles were revealed. The specific surface and the particle pore volume were found to be negatively correlated with particle size, ranging from 3.2 m 2/g to 25.7 m 2/g for the surface area and from 0.0086 cm 3/g to 0.091 cm 3/g for the pore volume. Not surprisingly, the specific surface area was found to be the major material parameter that governed the leaching behavior for all elements (Ca 2+, K +, Na +, Cl - and SO 4- 2 ) and particle sizes. The diffusion resistance was determined independently by separate tracer (tritium) experiments. Diffusion gave a significant contribution to the apparent leaching kinetics for all elements during the first 10-40 h (depending on the particle size) of leaching and surface reaction was the overall rate controlling mechanism at late times for all particle sizes. For Ca 2+ and SO 4- 2 , the coupled effect of diffusion resistance and the degree of undersaturation in the intra particle pore volume was found to be a major rate limiting dissolution mechanism for both early and late times. The solubility control in the intra particulate porosity may undermine any attempt to treat bottom ash by washing out the sulfate. Even for high liquid/solid ratios, the solubility in the intra-particular porosity will limit the release rate.

In-vitro analysis of the dissolution kinetics and systemic availability of plutonium ingested in the form of 'hot' particles from the Semipalatinsk NTS.

Science.gov (United States)

Conway, M; León Vintró, L; Mitchell, P I; García-Tenorio, R; Jimenez-Ramos, M C; Burkitbayev, M; Priest, N D

2009-05-01

In-vitro leaching of radioactive 'hot' particles isolated from soils sampled at the Semipalatinsk Nuclear Test Site has been carried out in order to evaluate the fraction of plutonium activity released into simulated human stomach and small intestine fluids during digestion. Characterisation of the particles (10-100 Bq(239,240)Pu) and investigation of their dissolution kinetics in simulated fluids has been accomplished using a combination of high-resolution alpha-spectrometry, gamma-spectrometry and liquid scintillation counting. The results of these analyses indicate that plutonium transfer across the human gut following the ingestion of 'hot' particles can be up to two orders of magnitude lower than that expected for plutonium in a more soluble form, and show that for areas affected by local fallout, use of published ingestion dose coefficients, together with bulk radionuclide concentrations in soil, may lead to a considerable overestimation of systemic uptake via the ingestion pathway.

Fast dissolving cyclodextrin complex of piroxicam in solid dispersion part I: influence of β-CD and HPβ-CD on the dissolution rate of piroxicam.

Science.gov (United States)

Bouchal, F; Skiba, M; Chaffai, N; Hallouard, F; Fatmi, S; Lahiani-Skiba, M

2015-01-30

Sublingual drug delivery is an interesting route for drug having significant hepatic first-pass metabolism or requiring rapid pharmacological effect as for patients suffering from swallowing difficulties, nausea or vomiting. Sublingual absorption could however be limited by the kinetic of drug dissolution. This study evaluated influences of cyclodextrins (β-CD or HP-β-CD) and their different inclusion process (spray-drying or freeze-drying) on the drug dissolution kinetic of solid dispersions in poly(ethylene glycol) (PEG, Mw 6000Da) of piroxicam, used as poor hydrosoluble drug model. A secondary objective was to determine influences of drug dispersion process in PEG (evaporation or melting methods) on the drug dissolution kinetic of piroxicam. Piroxicam solid dispersions containing or not cyclodextrins were characterized by different scanning calorimetry (DSC), Thermogravometry analyser (TGA) and Fourier transform-infrared spectroscopy (FT-IR) spectroscopy. In vitro drug dissolution study of these solid dispersions was then performed. The results demonstrated the high potential and interest of solid dispersions of drug previously included in cyclodextrins for sublingual delivery of hydrophobic drugs. This study also showed the advantages of evaporation method on the melting ones during drug dispersion in PEG. Indeed, drug complexation with cyclodextrins as dispersion by melting prevented the presence in solid dispersions of drug in crystalline form which can represent up to 63%. Moreover, dispersion in PEG by evaporation method gave more porous drug delivery system than with melting methods. This allowed complete (limited at most at 80-90% with melting methods) and quick drug dissolution without rebound effect like with melting ones. Copyright © 2014 Elsevier B.V. All rights reserved.

Dissolution Dominating Calcification Process in Polar Pteropods Close to the Point of Aragonite Undersaturation

Science.gov (United States)

Bednaršek, Nina; Tarling, Geraint A.; Bakker, Dorothee C. E.; Fielding, Sophie; Feely, Richard A.

2014-01-01

Thecosome pteropods are abundant upper-ocean zooplankton that build aragonite shells. Ocean acidification results in the lowering of aragonite saturation levels in the surface layers, and several incubation studies have shown that rates of calcification in these organisms decrease as a result. This study provides a weight-specific net calcification rate function for thecosome pteropods that includes both rates of dissolution and calcification over a range of plausible future aragonite saturation states (Ωar). We measured gross dissolution in the pteropod Limacina helicina antarctica in the Scotia Sea (Southern Ocean) by incubating living specimens across a range of aragonite saturation states for a maximum of 14 days. Specimens started dissolving almost immediately upon exposure to undersaturated conditions (Ωar∼0.8), losing 1.4% of shell mass per day. The observed rate of gross dissolution was different from that predicted by rate law kinetics of aragonite dissolution, in being higher at Ωar levels slightly above 1 and lower at Ωar levels of between 1 and 0.8. This indicates that shell mass is affected by even transitional levels of saturation, but there is, nevertheless, some partial means of protection for shells when in undersaturated conditions. A function for gross dissolution against Ωar derived from the present observations was compared to a function for gross calcification derived by a different study, and showed that dissolution became the dominating process even at Ωar levels close to 1, with net shell growth ceasing at an Ωar of 1.03. Gross dissolution increasingly dominated net change in shell mass as saturation levels decreased below 1. As well as influencing their viability, such dissolution of pteropod shells in the surface layers will result in slower sinking velocities and decreased carbon and carbonate fluxes to the deep ocean. PMID:25285916

Aqueous corrosion mechanisms of the nuclear glass R7T7. Experimental approach. Kinetics and thermodynamic simulation

International Nuclear Information System (INIS)

Advocat, T.

1991-01-01

An inactive borosilicate glass made of about 30 oxides is studied. The composition was developed by the CEA for encapsulation of calcinated fission product solutions from reprocessing. Hydration energy of glass is first calculated for 8 glasses and results are compared to experimental data. Dissolution of R7T7 glass is examined at 90 0 C in a large range of pH and S/V ratios (glass surface/solution volume). In dilute media (S/V = 0.1 cm -1 ) dissolution is selective at acid pH and stoichiometric at basic pH. In alkaline media dissolution rate increases with pH. Corrosion products, generally amorphous or badly crystallized are observed on glass surface. For high S/V ratios (4, 20, 80 and 200 cm -1 ) the very low dissolution rate is explained by saturation. Orthosilic acid controls corrosion kinetics. A kinetic equation is proposed taking into account pH, S/V ratio and dissolved silica concentration. Geochemical consequences of R7T7 dissolution are modelled at 100 0 C and 90 0 C. Affinity of dissolution reaction depends upon many factors (pH, silica concentration, nature and crystallinity of secondary phases. Reaction affinity is not constant for the long-term [fr

Dynamics of the deep red Fe3+ photoluminescence emission in feldspar

DEFF Research Database (Denmark)

Prasad, Amit Kumar; Jain, Mayank

2018-01-01

be exploited for site discrimination within a complex feldspar sample. The radiative relaxation in Fe3+ (4T1 → 6A1) is shown to be a dynamic process depending on whether the ion is excited using resonant or non-resonant transition. We suggest that during resonant excitation, the excited state of Fe3+ undergoes...

A kinetics database and scripts for PHREEQC

Science.gov (United States)

Hu, B.; Zhang, Y.; Teng, Y.; Zhu, C.

2017-12-01

Kinetics of geochemical reactions has been increasingly used in numerical models to simulate coupled flow, mass transport, and chemical reactions. However, the kinetic data are scattered in the literature. To assemble a kinetic dataset for a modeling project is an intimidating task for most. In order to facilitate the application of kinetics in geochemical modeling, we assembled kinetics parameters into a database for the geochemical simulation program, PHREEQC (version 3.0). Kinetics data were collected from the literature. Our database includes kinetic data for over 70 minerals. The rate equations are also programmed into scripts with the Basic language. Using the new kinetic database, we simulated reaction path during the albite dissolution process using various rate equations in the literature. The simulation results with three different rate equations gave difference reaction paths at different time scale. Another application involves a coupled reactive transport model simulating the advancement of an acid plume in an acid mine drainage site associated with Bear Creek Uranium tailings pond. Geochemical reactions including calcite, gypsum, and illite were simulated with PHREEQC using the new kinetic database. The simulation results successfully demonstrated the utility of new kinetic database.

Laboratory batch experiments and geochemical modelling of water-rock-supercritical CO2 reactions in Southern San Joaquin Valley, California oil field sediments: Implications for future carbon capture and sequestration projects.

Science.gov (United States)

Mickler, P. J.; Rivas, C.; Freeman, S.; Tan, T. W.; Baron, D.; Horton, R. A.

2015-12-01

Storage of CO2 as supercritical liquid in oil reservoirs has been proposed for enhanced oil recovery and a way to lower atmospheric CO2 levels. The fate of CO2 after injection requires an understanding of mineral dissolution/precipitation reactions occurring between the formation minerals and the existing formation brines at formation temperatures and pressures in the presence of supercritical CO2. In this study, core samples from three potential storage formations, the Vedder Fm. (Rio Bravo oil field), Stevens Fm. (Elk Hills oil field) and Temblor Fm. (McKittrick oil field) were reacted with a synthetic brine and CO2(sc) at reservoir temperature (110°C) and pressure (245-250 bar). A combination of petrographic, SEM-EDS and XRD analyses, brine chemistry, and PHREEQ-C modelling were used to identify geochemical reactions altering aquifer mineralogy. XRD and petrographic analyses identified potentially reactive minerals including calcite and dolomite (~2%), pyrite (~1%), and feldspars (~25-60%). Despite the low abundance, calcite dissolution and pyrite oxidation were dominant geochemical reactions. Feldspar weathering produced release rates ~1-2 orders of magnitude slower than calcite dissolution. Calcite dissolution increased the aqueous concentrations of Ca, HCO3, Mg, Mn and Sr. Silicate weathering increased the aqueous concentrations of Si and K. Plagioclase weathering likely increased aqueous Ca concentrations. Pyrite oxidation, despite attempts to remove O2 from the experiment, increased the aqueous concentration of Fe and SO4. SEM-EDS analysis of post-reaction samples identified mixed-layered illite-smectites associated with feldspar grains suggesting clay mineral precipitation in addition to calcite, pyrite and feldspar dissolution. The Vedder Fm. sample underwent complete disaggregation during the reaction due to cement dissolution. This may adversely affect Vedder Formation CCS projects by impacting injection well integrity.

Theoretical study of the dissolution kinetics of galena and cerussite in an abandoned mining area (Zaida mine, Morocco)

Science.gov (United States)

El Alaoui, Lamiae; Dekayir, Abdelilah

2018-05-01

In the abandoned mine in Zaida, the pit lakes filled with water constitute significant water reserves. In these lakes, the waters are permanently in contact with ore deposit (cerussite and galena). The modelling of the interaction of waters with this mineralization shows that cerussite dissolves more rapidly than galena. This dissolution is controlled by the pH and dissolved oxygen concentration in solution. The lead concentrations recorded in these lakes come largely from the dissolution of cerussite.

Application of pulsed OSL to the separation of the luminescence components from a mixed quartz/feldspar sample

DEFF Research Database (Denmark)

Denby, Phil M.; Bøtter-Jensen, L.; Murray, A.S.

2006-01-01

with a feldspar signal. We have developed instrumentation for the study of high-speed pulse stimulated OSL. Our system uses the standard blue/IR LED stimulation unit of a Riso reader (allowing stimulation pulses down to 1-2 mu s duration) and can thus be applied to the routine analysis of samples. Using...... that counts are only accumulated during a windowed period, reduces the feldspar signal to 1.6% of its original value relative to that of the quartz. (c) 2006 Elsevier Ltd. All rights reserved....

Red-IR stimulated luminescence in K-feldspar: Single or multiple trap origin?

DEFF Research Database (Denmark)

Andersen, Martin Thalbitzer; Jain, Mayank; Tidemand-Lichtenberg, Peter

2012-01-01

We investigate on the origins of the infra-red stimulated luminescence (IRSL) signals in 3 potassium feldspars based on IR-red spectroscopy (700–1050 nm) using a fiber-coupled tunable Ti:Sapphire laser, in combination with different thermal and optical (pre)treatments of the samples. We also...

Geochemical thermodynamic and kinetic modeling that take into account the mass transfer phenomena in saturated porous medium

International Nuclear Information System (INIS)

Gerard, Frederic

1996-01-01

The mass transport mechanisms (advection. mechanical dispersion and molecular diffusion) have been introduced into the thermodynamic and kinetic geochemical code KINDIS. This innovative approach to couple chemical and transport mass transfers has allowed us to develop a reactive transport or hydrochemical code named KIRMAT, which naturally preserve the comprehensive geochemical functions of KINDIS. Mass transport phenomena through the total connected porosity of a water-saturated porous medium are solved over one spatial dimension (ID). The finite difference method is used. An explicit or forward time scheme is computed. The advective finite difference expression may be either centered or upstream weighted. Thus, ail of the hydrodynamic conditions may be modeled (from the pure advection to pure diffusion). The mass transport and geochemical flux are solved simultaneously (one-step algorithm). Moreover. the code KIRMAT is designed to quantify reactive mass transport through a double or dual porosity medium, in which the flow porosity (filled by free water) and the diffusion porosity (containing stagnant water) are viewed as two distinct sub mediums or Systems. Under some given conditions, the need to solve one or the other mass transport equation is a function of the water-rock System size. The accuracy of the kinetic constraint has been improved in KIRMAT. Two new kinetic rate laws have been introduced for the dissolution of the most abundant silicates (alkali feldspars, silica. etc.). These rate laws integrate the quantitatively important inhibitor and catalytic effects involved with some dissolved chemical elements that are ubiquitous in natural aqueous solutions. The basic step. the numerical verification of the code, has been tackled with two complementary approaches. The numerical results from KIRMAT have been compared to those calculated from an exact solution and a new method has been developed and used. We have compared the numerical results of KIRMAT in

Deformation-Induced Dissolution and Precipitation of Nitrides in Austenite and Ferrite of a High-Nitrogen Stainless Steel

Science.gov (United States)

Shabashov, V. A.; Makarov, A. V.; Kozlov, K. A.; Sagaradze, V. V.; Zamatovskii, A. E.; Volkova, E. G.; Luchko, S. N.

2018-02-01

Methods of Mössbauer spectroscopy and electron microscopy have been used to study the effect of the severe plastic deformation by high pressure torsion in Bridgman anvils on the dissolution and precipitation of chromium nitrides in the austenitic and ferritic structure of an Fe71.2Cr22.7Mn1.3N4.8 high-nitrogen steel. It has been found that an alternative process of dynamic aging with the formation of secondary nitrides affects the kinetics of the dissolution of chromium nitrides. The dynamic aging of ferrite is activated with an increase in the deformation temperature from 80 to 573 K.

Kinetic study of the thorium phosphate - diphosphate dissolution

International Nuclear Information System (INIS)

Dacheux, N.; Thomas, A.C.; Brandel, V.; Genet, M.

2000-01-01

The thorium phosphate-diphosphate Th 4 (PO 4 ) 4 P 2 O 7 (TPD) structure allows the replacement of large amounts of thorium by tetravalent actinides leading to the formation of solid solutions. This compound was obtained in powdered or sintered form after pressing at room temperature at 300-800 MPa then heating at 1250 deg. C for 10-30 hours. The resistance of this material to aqueous corrosion was determined by varying several parameters such as surface, leaching flow, acidity or temperature. It was thus possible to independently determine the influence of each parameter on the leaching rate provided that the saturation of the solution was not obtained. In acidic media, the partial order related to [H 3 O + ] was found to be in the 0.31-0.35 range while, in basic media, the partial order related to [OH - ] was almost the same (0.45). The activation energy (42 kJ/mol) was determined between 4 deg. C and 120 deg. C. Moreover, the addition of phosphate in the leachate slightly increased the TPD dissolution rate. When the saturation of the solution is reached, a gelatinous precipitate controls the thorium and phosphate concentrations. The complete characterization of this solid led to the proposed general formula Th 2 (PO 4 ) 2 (HPO 4 ). n H 2 O which conventional solubility product (at I = 0 M) is very low: K * S,0 10 -66.6±1.2 even in very acidic media. (authors)

Effect of drug loading method against the dissolution mechanism of encapsulated amoxicillin trihidrate drug in matrix of semi-IPN chitosan-poly (N-vinyl pyrrolidone) hydrogel with pore forming agent CaCO3

Science.gov (United States)

Nurjannah, Yanah; Budianto, Emil

2018-04-01

Heliobacter pylori (H.pylori) is a type of bacteria that causes inflammation in the lining of the stomach. The treatment of the bacterial infection by using conventional medicine which is amoxicillin trihidrate has a very short retention time in the stomach which is about 1-1,5 hours. Floating drug delivery system is expected to have a long retention time in the stomach so the efficiency of drug can be achieved. In this study, has been synthesized matrix of semi-IPN chitosan-Poly(N-vinil pyrrolidone) hydrogel with a pore-forming agent of CaCO3 under optimum conditions. Amoxicillin is encapsulated in a matrix hydrogel to be applied as a floating drug delivery system by in situ loading and post loading methods. The encapsulation efficiency and dissolution of in situ loading and post loading hydrogels are performed in vitro on gastric pH. In situ loading hydrogel shows higer percentage of encapsulation efficiency and dissolution compared to post loading hydrogel. The encapsulation efficiency of in situ and post loading hydrogels were 92,1% and 89,4%, respectively. The aim of drug dissolution by mathematical equation model is to know kinetics and the mecanism of dissolution. The kinetics release of in situ hydrogel tends to follow first order kinetics, while the post loading hydrogel follow the Higuchi model. The dissolution mecanism of hydrogels is erosion.

Dissolution Methods Database

Data.gov (United States)

U.S. Department of Health & Human Services — For a drug product that does not have a dissolution test method in the United States Pharmacopeia (USP), the FDA Dissolution Methods Database provides information on...

Rare earth element geochemistry of feldspars: examples from Fe-oxide Cu-Au systems in the Olympic Cu-Au Province, South Australia

Science.gov (United States)

Kontonikas-Charos, Alkis; Ciobanu, Cristiana L.; Cook, Nigel J.; Ehrig, Kathy; Krneta, Sasha; Kamenetsky, Vadim S.

2018-04-01

Rare earth element (REE) fractionation trends in feldspars are reported from Olympic Dam (including Wirrda Well and Phillip's Ridge) and Cape Donington (Port Lincoln), for comparison with two other igneous-hydrothermal terranes within the eastern Gawler Craton: Moonta-Wallaroo and Hillside. The case studies were selected as they represent 1590 Ma Hiltaba Suite and/or 1845 - 1810 Ma Donington Suite granites, and, aside from Cape Donington, are associated with Mesoproterozoic iron-oxide copper gold (IOCG)-type mineralization. Both plagioclase and alkali feldspar were analyzed within selected samples with the purpose of constraining and linking changes in REE concentrations and fractionation trends in feldspars to local and whole-rock textures and geochemistry. Two unique, reproducible fractionation trends were obtained for igneous plagioclase and alkali feldspars, distinguished from one another by light rare earth element enrichment, Eu-anomalies and degrees of fractionation (e.g. La/Lu slopes). Results for hydrothermal albite and K-feldspar indicate that REE concentrations and fractionation trends are generally inherited from igneous predecessors, however in some instances, significant amounts of REE appear to have been lost to the fluid. These results may have critical implications for the formation of world-class IOCG systems, in which widespread alkali metasomatism plays a key role by altering the physical and chemical properties of the host rocks during early stages of IOCG formation, as well as trapping trace elements (including REE).

Uranothorite solid solutions: From synthesis to dissolution

International Nuclear Information System (INIS)

Costin, Dan-Tiberiu

2012-01-01

USiO 4 coffinite appears as one of the potential phases formed in the back-end of the alteration of spent fuel, in reducing storage conditions. A study aiming to assess the thermodynamic data associated with coffinite through an approach based on the preparation of Th 1-x U x SiO 4 uranothorite solid solutions was then developed during this work. First, the preparation of uranothorite samples was successfully undertaken in hydrothermal conditions. However, the poly-phased samples systematically formed for x ≥ 0,2 underlined the kinetic hindering linked with the preparation of uranium-enriched samples, including coffinite end-member. Nevertheless, the characterization of the various samples led to confirm the formation of an ideal solid solution and allowed the constitution of a spectroscopic database. The purification of the samples was then performed by the means of different protocols based on physical (dispersion-centrifugation) or chemical (selective dissolution of secondary phases) methods. This latter led to a complete of the impurities (Th 1-y U y O 2 mixed oxide and amorphous silica) through successive washing steps in acid then basic media. Finally, dissolution experiments were undertaken on uranothorite samples (0 ≤ xexp. ≤ 0,5) and allowed pointing out the influence of composition, pH and temperature on the normalized dissolution rate of the compounds. Also, the associated thermodynamic data, such as activation energy, indicate that the reaction is controlled by surface reactions. Once the equilibrium is reached, the analogous solubility constants were determined for each composition studied, then allowing the extrapolation to coffinite value. It was then finally possible to conclude on the inversion of coffinitisation reaction with temperature. (author) [fr

Determination of Potassium in Feldspars by Beta Counting Using a GM Multicounter System

DEFF Research Database (Denmark)

Bøtter-Jensen, Lars; Mejdahl, V.

1985-01-01

A gas flow multicounter system developed at Riso National Laboratory for low-level beta counting applications was adopted for measuring potassium in feldspars extracted from archaeological and geological materials, in connection with TL dating work. A guard counter reduces the background by using...

Development and validation of a dissolution test for lodenafil carbonate based on in vivo data.

Science.gov (United States)

Codevilla, Cristiane Franco; Castilhos, Tamara dos Santos; Cirne, Carolina Araújo; Froehlich, Pedro Eduardo; Bergold, Ana Maria

2014-04-01

Lodenafil carbonate is a phosphodiesterase type 5 inhibitor used for the treatment of erectile dysfunction. Currently, there is no dissolution test reported for lodenafil carbonate and this drug is not listed in any pharmacopoeia. The present study focused on the development and validation of a dissolution test for lodenafil carbonate tablets, using a simulated absorption profile based on in vivo data. The appropriate conditions were determined after testing sink conditions. Different conditions as medium, surfactant concentration and rotation speed were evaluated. The percentage of dose absorbed was calculated by deconvolution, using the Wagner-Nelson method. According to the obtained results, the use of 0.1 M HCl + 1.5% SLS (900 mL, at 37 + 0.5 °C) as the dissolution medium, paddles at 25 rpm were considered adequate. The samples were quantified by UV spectroscopy at 295 nm and the validation was performed according to international guidelines. The method showed specificity, linearity, accuracy and precision, within the acceptable range. Kinetics of drug release was better described by the first-order model. The proposed dissolution test can be used for the routine quality control of lodenafil carbonate in tablets.

Radiolytic modelling of spent fuel oxidative dissolution mechanism. Calibration against UO2 dynamic leaching experiments

International Nuclear Information System (INIS)

Merino, J.; Cera, E.; Bruno, J.; Quinones, J.; Casas, I.; Clarens, F.; Gimenez, J.; Pablo, J. de; Rovira, M.; Martinez-Esparza, A.

2005-01-01

Calibration and testing are inherent aspects of any modelling exercise and consequently they are key issues in developing a model for the oxidative dissolution of spent fuel. In the present work we present the outcome of the calibration process for the kinetic constants of a UO 2 oxidative dissolution mechanism developed for using in a radiolytic model. Experimental data obtained in dynamic leaching experiments of unirradiated UO 2 has been used for this purpose. The iterative calibration process has provided some insight into the detailed mechanism taking place in the alteration of UO 2 , particularly the role of · OH radicals and their interaction with the carbonate system. The results show that, although more simulations are needed for testing in different experimental systems, the calibrated oxidative dissolution mechanism could be included in radiolytic models to gain confidence in the prediction of the long-term alteration rate of the spent fuel under repository conditions

Optimization of Dissolution Compartments in a Biorelevant Dissolution Apparatus Golem v2, Supported by Multivariate Analysis

Directory of Open Access Journals (Sweden)

Ivan Stupák

2017-11-01

Full Text Available Biorelevant dissolution instruments represent an important tool for pharmaceutical research and development. These instruments are designed to simulate the dissolution of drug formulations in conditions most closely mimicking the gastrointestinal tract. In this work, we focused on the optimization of dissolution compartments/vessels for an updated version of the biorelevant dissolution apparatus—Golem v2. We designed eight compartments of uniform size but different inner geometry. The dissolution performance of the compartments was tested using immediate release caffeine tablets and evaluated by standard statistical methods and principal component analysis. Based on two phases of dissolution testing (using 250 and 100 mL of dissolution medium, we selected two compartment types yielding the highest measurement reproducibility. We also confirmed a statistically ssignificant effect of agitation rate and dissolution volume on the extent of drug dissolved and measurement reproducibility.

Argonne National Laboratory HVEM Summer Institute lecture - kinetics II

International Nuclear Information System (INIS)

Westmacott, K.H.

1982-08-01

The purpose of this contribution is to outline some of the ways in which the High Voltage Electron Microscope can be used to study the kinetics of secondary defect shrinkage and precipitate particle growth and dissolution. In many cases, good agreement between the predictions of theory and the experimental observations are found and this provides not only insights into the mechanisms underlying the processes, but also quantitative measurement of parameters of metallurgical importance. To summarize, some of the advantages of the HVEM in kinetic studies include: (1) unlike bulk studies where only average behavior is measured, precise measurements on individual particles may be made; (2) in some systems it is useful for rapidly establishing phase boundaries, (3) anomolous behavior such as may occur by interactions with lattice defects and boundaries may be studied (4) growth and dissolution mechanisms may be established, (5) phase stability in an irradiation environment may be studied directly

Predicting dissolution patterns in variable aperture fractures: 1. Development and evaluation of an enhanced depth-averaged computational model

Energy Technology Data Exchange (ETDEWEB)

Detwiler, R L; Rajaram, H

2006-04-21

Water-rock interactions within variable-aperture fractures can lead to dissolution of fracture surfaces and local alteration of fracture apertures, potentially transforming the transport properties of the fracture over time. Because fractures often provide dominant pathways for subsurface flow and transport, developing models that effectively quantify the role of dissolution on changing transport properties over a range of scales is critical to understanding potential impacts of natural and anthropogenic processes. Dissolution of fracture surfaces is controlled by surface-reaction kinetics and transport of reactants and products to and from the fracture surfaces. We present development and evaluation of a depth-averaged model of fracture flow and reactive transport that explicitly calculates local dissolution-induced alterations in fracture apertures. The model incorporates an effective mass transfer relationship that implicitly represents the transition from reaction-limited dissolution to transport-limited dissolution. We evaluate the model through direct comparison to previously reported physical experiments in transparent analog fractures fabricated by mating an inert, transparent rough surface with a smooth single crystal of potassium dihydrogen phosphate (KDP), which allowed direct measurement of fracture aperture during dissolution experiments using well-established light transmission techniques [Detwiler, et al., 2003]. Comparison of experiments and simulations at different flow rates demonstrate the relative impact of the dimensionless Peclet and Damkohler numbers on fracture dissolution and the ability of the computational model to simulate dissolution. Despite some discrepancies in the small-scale details of dissolution patterns, the simulations predict the evolution of large-scale features quite well for the different experimental conditions. This suggests that our depth-averaged approach to simulating fracture dissolution provides a useful approach for

Reactivity of Primary Soil Minerals and Secondary Precipitates Beneath Leaking Hanford Waste Tanks

International Nuclear Information System (INIS)

Nagy, Kathryn L.; Sturchio, Neil C.

2003-01-01

This project, renewal of a previous EMSP project of the same title, is in its first year of funding at the University of Illinois at Chicago. The purpose is to continue investigating rates and mechanisms of reactions between primary sediment minerals found in the Hanford subsurface and leaked waste tank solutions. The goals are to understand processes that result in (1) changes in porosity and permeability of the sediment and resultant changes in flow paths of the contaminant plumes, (2) formation of secondary precipitates that can take up contaminants in their structures, and (3) release of mineral components that can drive redox reactions affecting dissolved contaminant mobility. A post-doctoral scientist, Dr. Sherry Samson, has been hired and two masters of science students are beginning to conduct experimental research. One research project that is underway is focused on measurement of the dissolution rates of plagioclase feldspar in high pH, high nitrate, high Al-bearing solutions characteristic of the BX tank farms. The first set of experiments is being conduced at room temperature. Subsequent experiments will examine the role of temperature because tank solutions in many cases were near boiling when leakage is thought to have occurred and temperature gradients have been observed beneath the SX and BX tank farms. The dissolution experiments are being conducted in stirred-flow kinetic reactors using powdered labradorite feldspar from Pueblo Park, New Mexico

Propagation of a hyperalkaline plume into the geological barrier surrounding a radioactive waste repository

International Nuclear Information System (INIS)

Lichtner, P.C.; Eikenberg, J.

1995-01-01

A coupled geochemical transport model (MPATH) which includes chemical reaction kinetics is used to evaluate the alteration of Swiss argillaceous sediments in a high-pH environment and to predict the spatial propagation of the hyperalkaline plume with time. The calculations predict dissolution of quartz, clay minerals and chlorite, and precipitation of zeolite minerals such as analcime and natrolite as well as he feldspars K-feldspar and albite. In addition, Portland cement-hydrates such as calcium silicate and aluminate hydrates, ettringite and friedel-salt are also predicted to form, depending on the composition of the inlet fluid and the host rock. The dissolution of clay minerals reduces the pH of the hyperalkaline plume to levels between approximately 8 and 10, depending on the composition of the inlet fluid and the host rock. For pure advective transport through porous medium, neglecting changes in porosity and permeability, the migration velocity of the high-pH front is calculated to be approximately one to two orders of magnitude less than that of the infiltrating groundwater. However, due to precipitation of secondary phases, in the present model concept a rapid decrease in porosity of the marl occurs several meters from the repository. At the interface between the marl host rock and cement the porosity increases as a consequence of the low silica concentration of the cement pore fluid. (author) 10 figs., 7 tabs., refs

Kinetic study of the thorium phosphate - diphosphate dissolution

Energy Technology Data Exchange (ETDEWEB)

Dacheux, N.; Thomas, A.C.; Brandel, V.; Genet, M. [Paris-11 Univ., 91 - Orsay (France). Inst. de Physique Nucleaire; Aupiais, J. [CEA/DAM-Ile de France, Dept. Analyse Surveillance Environnement, DASE, Service Radioanalyses Chimie Environnement, 91 - Bruyeres-Le-Chatel (France)

2000-07-01

The thorium phosphate-diphosphate Th{sub 4}(PO{sub 4}){sub 4}P{sub 2}O{sub 7} (TPD) structure allows the replacement of large amounts of thorium by tetravalent actinides leading to the formation of solid solutions. This compound was obtained in powdered or sintered form after pressing at room temperature at 300-800 MPa then heating at 1250 deg. C for 10-30 hours. The resistance of this material to aqueous corrosion was determined by varying several parameters such as surface, leaching flow, acidity or temperature. It was thus possible to independently determine the influence of each parameter on the leaching rate provided that the saturation of the solution was not obtained. In acidic media, the partial order related to [H{sub 3}O{sup +}] was found to be in the 0.31-0.35 range while, in basic media, the partial order related to [OH{sup -}] was almost the same (0.45). The activation energy (42 kJ/mol) was determined between 4 deg. C and 120 deg. C. Moreover, the addition of phosphate in the leachate slightly increased the TPD dissolution rate. When the saturation of the solution is reached, a gelatinous precipitate controls the thorium and phosphate concentrations. The complete characterization of this solid led to the proposed general formula Th{sub 2}(PO{sub 4}){sub 2}(HPO{sub 4}). n H{sub 2}O which conventional solubility product (at I = 0 M) is very low: K{sup *}{sub S,0} 10{sup -66.6{+-}}{sup 1.2} even in very acidic media. (authors)

OSL and IRSL characteristics of quartz and feldspar from southern California, USA

International Nuclear Information System (INIS)

Lawson, Michael J.; Roder, Belinda J.; Stang, Dallon M.; Rhodes, Edward J.

2012-01-01

Southern California comprises of a wide range of diverse landscapes and environments, from high mountains with glacial and periglacial sediments to deserts with large sand dunes, extensive alluvial fans and ephemeral playas. Highly active tectonic processes has exposed ancient (c. 2 Ga) plutonic and metamorphic basement from deep within the crust, while similar Palaeozoic, Mesozoic and Cenozoic rocks are also common. A rich array of volcanic lithologies extending into the late Quaternary complement many thick sedimentary sequences that formed in equally diverse ancient environments typical of an accreting active continental margin. In some locations, notably in the Coachella Valley close to Palm Springs and the Salton Sea, low OSL sensitivity and poor characteristics restrict the application of the quartz SAR protocol to date late Pleistocene and Holocene fluvial sediments. In other locations such as the Malibu coastline, high sensitivity of the quartz OSL signal is observed, despite local source rocks being dominated by volcanic lithologies. Problems of poor quartz characteristics, along with uncertainty in predicting quartz OSL behavior for future dating campaigns poses a significant problem for projects, in particular for neotectonic contexts. While K-feldspar has been used extensively to date eolian and fluvial sediments in southern California, little information regarding signal stability is available. We explore the characteristics of both quartz and feldspar sub-samples from eolian, fluvial, lacustrine environments, in order to help develop mineral selection criteria for optical dating applications and clarify these issues. The importance of radiation quenching in quartz grains recently eroded from bedrock and the role of fires in enhancing OSL sensitivity are considered. The relative bleachability of quartz and feldspar fractions, along with thermal stability considerations is discussed. A simple test for quartz OSL signal contamination based on thermal

Crystallization Kinetics of Barium and Strontium Aluminosilicate Glasses of Feldspar Composition

Science.gov (United States)

Hyatt, Mark J.; Bansal, Narottam P.

1994-01-01

Crystallization kinetics of BaO.Al2O3.2SiO2 (BAS) and SrO.Al2O3.2SiO2 (SAS) glasses in bulk and powder forms have been studied by non-isothermal differential scanning calorimetry (DSC). The crystal growth activation energies were evaluated to be 473 and 451 kJ/mol for bulk samples and 560 and 534 kJ/mol for powder specimens in BAS and SAS glasses, respectively. Development of crystalline phases on thermal treatments of glasses at various temperatures has been followed by powder x-ray diffraction. Powder samples crystallized at lower temperatures than the bulk and the crystallization temperature was lower for SAS glass than BAS. Crystallization in both glasses appeared to be surface nucleated. The high temperature phase hexacelsian, MAl2Si2O8 (M = Ba or Sr), crystallized first by nucleating preferentially on the glass surface. Also, monoclinic celsian does not nucleate directly in the glass, but is formed at higher temperatures from the transformation of the metastable hexagonal phase. In SAS the transformation to monoclinic celsian occurred rapidly after 1 h at 1100 C. In contrast, in BAS this transformation is sluggish and difficult and did not go to completion even after 10 h heat treatment at 1400 C. The crystal growth morphologies in the glasses have been observed by optical microscopy. Some of the physical properties of the two glasses are also reported.

Dissolution of nuclear fuels

International Nuclear Information System (INIS)

Uriarte Hueda, A.; Berberana Eizmendi, M.; Rainey, R.

1968-01-01

A laboratory study was made of the instantaneous dissolution rate (IDR) for unirradiated uranium metal rods and UO 2 , PuO 2 and PuO 2 -UO 2 pellets in boiling nitric acid alone and with additives. The uranium metal and UO 2 dissolved readily in nitric acid alone; PuO 2 dissolved slowly even with the addition of fluoride; PuO 2 -UO 2 pellets containing as much as 35% PuO 2 in UO 2 gave values of the instantaneous dissolution rate to indicate can be dissolved with nitric acid alone. An equation to calculate the time for complete dissolution has been determinate in function of the instantaneous dissolution rates. The calculated values agree with the experimental. Uranium dioxide pellets from various sources but all having a same density varied in instantaneous dissolution rate. All the pellets, however, have dissolved ved in the same time. The time for complete dissolution of PuO 2 -UO 2 pellets, having the same composition, and the concentration of the used reagents are function of the used reagents are function of the fabrication method. (Author) 8 refs

Further investigations into pulsed optically stimulated luminescence from feldspars using blue and green light

International Nuclear Information System (INIS)

Ankjaergaard, C.; Jain, M.; Kalchgruber, R.; Lapp, T.; Klein, D.; McKeever, S.W.S.; Murray, A.S.; Morthekai, P.

2009-01-01

The purpose of this paper is to investigate characteristics of luminescence signals resulting from pulsed optical stimulation of feldspars and thereby to understand the underlying processes giving rise to the signal. Fourteen different feldspar specimens were investigated using time-resolved optically stimulated luminescence (TR-OSL), and these signals can be mathematically described as a sum of 4 exponential components (a, b, c, d). The slowest component, d, increases with the duration of the light pulse as expected from the exponential model. The stimulation temperature dependence experiment suggests that the TR-OSL signal decay is governed by the recombination process and not by the excited state lifetime. Furthermore data from the TR-OSL signal dependence on stimulation time and preheat temperature suggest that the recombination process may not be a sum of exponentials, although the model cannot be rejected definitively.

Evaluation of a three compartment in vitro gastrointestinal simulator dissolution apparatus to predict in vivo dissolution.

Science.gov (United States)

Takeuchi, Susumu; Tsume, Yasuhiro; Amidon, Gregory E; Amidon, Gordon L

2014-11-01

In vitro dissolution tests are performed for new formulations to evaluate in vivo performance, which is affected by the change of gastrointestinal (GI) physiology, in the GI tract. Thus, those environmental changes should be introduced to an in vitro dissolution test. Many studies have successfully shown the improvement of in vitro-in vivo correlations (IVIVC) by introducing those physiological changes into dissolution tests. The gastrointestinal simulator (GIS), a multicompartment in vitro dissolution apparatus, was developed to evaluate in vivo drug dissolution. A gastric-emptying rate along with transit rate are key factors to evaluate in vivo drug dissolution and, hence, drug absorption. Dissolution tests with the GIS were performed with Biopharmaceutical Classification System class I drugs at five different gastric-emptying rates in the fasted state. Computational models were used to determine in vivo gastric-emptying time for propranolol and metoprolol based on the GIS dissolution results. Those were compared with published clinical data to determine the gastric half-emptying time. In conclusion, the GIS is a practical tool to assess dissolution properties and can improve IVIVC. © 2014 Wiley Periodicals, Inc. and the American Pharmacists Association.

Plutonium oxide dissolution

International Nuclear Information System (INIS)

Gray, J.H.

1992-01-01

Several processing options for dissolving plutonium oxide (PuO 2 ) from high-fired materials have been studied. The scoping studies performed on these options were focused on PuO 2 typically generated by burning plutonium metal and PuO 2 produced during incineration of alpha contaminated waste. At least two processing options remain applicable for dissolving high-fired PuO 2 in canyon dissolvers. The options involve solid solution formation of PuO 2 With uranium oxide (UO 2 ) and alloying incinerator ash with aluminum. An oxidative dissolution process involving nitric acid solutions containing a strong oxidizing agent, such as cerium (IV), was neither proven nor rejected. This uncertainty was due to difficulty in regenerating cerium (IV) ions during dissolution. However, recent work on silver-catalyzed dissolution of PuO 2 with persulfate has demonstrated that persulfate ions regenerate silver (II). Use of persulfate to regenerate cerium (IV) or bismuth (V) ions during dissolution of PuO 2 materials may warrant further study

Electrochemical and dissolution studies on coated film and magnetite pellet in PDCA and NTA based formulations

International Nuclear Information System (INIS)

Srinivasan, M.P.; Sumathi, S.; Rangarajan, S.; Narasimhan, S.V.

2000-01-01

In water cooled nuclear reactors magnetite often exists as both mobile particulate protective film on the inner surface of the PHT system. To determine the mechanism and kinetics of dissolution from a film coated on carbon steel (CS) and magnetite pellet electrochemical measurements were carried out in 2,6-pyridine dicarboxylic acid (PDCA) and nitrilo-triacetic acid (NTA) based formulations containing ascorbic acid (AA) and citric acid (CA) at 28 degC and 60 degC. The solution redox potential arises based on the release of relative amounts of Fe 2+ and Fe 3+ . Complexation, adsorption and reduction affect the concentration of these species in solutions. On coated specimen, the pore size and rate of formation via auto reduction contribute to the observed potential. In PDCA based formulation higher percentage of magnetite dissolution with lower base metal corrosion was observed as compared to that in NTA based formulation. The base metal aided dissolution due to the pores and microcracks in the film (Auto reduction) was observed for coated film. The dominant role of surface adsorption characteristics of PDCA, AA and CA were evident in magnetite pellet dissolution studies. (author)

FTIR measurements of OH in deformed quartz and feldspars of the South Tibetan Detachment, Greater Himalaya

Science.gov (United States)

Jezek, L.; Law, R. D.; Jessup, M. J.; Searle, M. P.; Kronenberg, A. K.

2017-12-01

OH absorption bands due to water in deformed quartz and feldspar grains of mylonites from the low-angle Lhotse Detachment (of the South Tibetan Detachment System, Rongbuk Valley north of Mount Everest) have been measured by Fourier Transform Infrared (FTIR) Spectroscopy. Previous microstructural studies have shown that these rocks deformed by dislocation creep at high temperature conditions in the middle crust (lower - middle amphibolite facies), and oxygen isotope studies suggest significant influx of meteoric water. OH absorption bands at 3400 cm-1 of quartz mylonites from the footwall of the Lhotse Detachment Fault are large, with the character of the molecular water band due to fluid inclusions in milky quartz. Mean water contents depend on structural position relative to the core of the Lhotse Detachment, from 1000 ppm (OH/106 Si) at 420 m below the fault to 11,350 (+/-1095) ppm near its center. The gradient in OH content shown by quartz grains implies influx of meteoric water along the Lhotse Detachment from the Tibetan Plateau ground surface to middle crustal depths, and significant fluid penetration into the extruding Himalayan slab by intergranular, permeable fluid flow processes. Feldspars of individual samples have comparable water contents to those of quartz and some are wetter. Large water contents of quartz and feldspar may have contributed to continued deformation and strain localization on the South Tibetan Detachment System. Dislocation creep in quartz is facilitated by water in laboratory experiments, and the water contents of the Lhotse fault rocks are similar to (and even larger than) water contents of quartz experimentally deformed during water weakening. Water contents of feldspars are comparable to those of plagioclase aggregates deformed experimentally by dislocation and diffusion creep under wet conditions.

Spent fuel dissolution mechanisms

International Nuclear Information System (INIS)

Ollila, K.

1993-11-01

This study is a literature survey on the dissolution mechanisms of spent fuel under disposal conditions. First, the effects of radiolysis products on the oxidative dissolution mechanisms and rates of UO 2 are discussed. These effects have mainly been investigated by using electrochemical methods. Then the release mechanisms of soluble radionuclides and the dissolution of the UO 2 matrix including the actinides, are treated. Experimental methods have been developed for measuring the grain-boundary inventories of radionuclides. The behaviour of cesium, strontium and technetium in leaching tests shows different trends. Comparison of spent fuel leaching data strongly suggests that the release of 90 Sr into the leachant can be used as a measure of the oxidation/dissolution of the fuel matrix. Approaches to the modelling UO 2 , dissolution are briefly discussed in the next chapter. Lastly, the use of natural material, uraninite, in the evaluation of the long-term performance of spent fuel is discussed. (orig.). (81 ref., 37 figs., 8 tabs.)

Preparation of chromous complexes and their effect on the dissolution of ferrites and chromites

International Nuclear Information System (INIS)

Sathyaseelan, V.S.; Rufus, A.L.; Velmurugan, S.; Pavithra, E.

2012-09-01

Decontamination of reactor coolant circuits is inevitable in minimising radiation exposure hazard especially during maintenance. Dilute chemical decontamination processes involving organic complexing agents viz., EDTA or NTA along with reducing agents such as ascorbic acid or oxalic acid are quite effective in dissolving magnetite, the predominant corrosion product oxide in carbon steel systems viz., PHWRs. However, dissolution of hematite, mixed ferrites and chromites found in stainless steel systems of BWRs and PWRs are not that easy to dissolve. A two-step process involving oxidation and reduction processes is required to dissolve these oxides. Studies were carried out to develop a single step process. Our earlier studies on high temperature decontamination at 160 deg. C have showed improved dissolution of magnetite, nickel ferrite and other oxides. In the present study, attempt has been made to carry out the oxide dissolution in formulations containing strong reducing agents such as chromous complexes. Dissolution of hematite is very effective under reducing conditions. Addition of ascorbic acid to the formulation containing EDTA and citric acid (EC) enhanced the kinetics 20 folds, while the addition of Cr (II)-EDTA to EC formulation increased the rate 100 folds. In the case of formulation containing NTA and citric acid (NC), the addition of chromous-NTA increased the rate 14 folds. NiFe 2 O 4 showed hardly any dissolution in EC formulation. However, in EAC (formulation containing EDTA, citric acid and ascorbic acid), the rate constant for the dissolution was 1.2x10 -3 min -1 , while it was 8.5x10 -3 min -1 in the case of ECCr (EDTA, citric acid containing chromous ions) formulation. In NTA based formulations also, dissolution rate was found to be enhanced in the presence of chromous ions. Further, there was no preferential dissolution of either Fe or Ni by both EDTA and NTA based formulations and also the rate of dissolution was found to depend linearly on the

Study of the Extraction Kinetics of Lithium by Leaching β-Spodumene with Hydrofluoric Acid

Directory of Open Access Journals (Sweden)

Gustavo D. Rosales

2016-09-01

Full Text Available Parameters affecting the kinetics of the dissolution of β-spodumene with hydrofluoric acid have been investigated. The experimental tests were carried out in a closed vessel. The influence of several parameters, such as stirring speed, temperature, and reaction time were studied in order to deduce the kinetics of the dissolution reaction. The other parameters, particle size −45 μm; HF concentration 4% v/v, and the solid–liquid ratio 0.95% w/v were kept constant. The results indicate that the stirring speed does not have an important effect on the dissolution of the mineral above 330 rpm. The extent of the leaching of β-spodumene increases with temperature and reaction time augmentations. Scanning electron microscope (SEM analyses of some residues in which the conversion was lower than 30% indicated a selective attack on certain zones of the particle. The treatment of the experimental data was carried out using the Modelado software. The model that best represents the dissolution of the mineral is the following: ln(1 − X = −b1 [ln(1 + b2t − b2t/(1 + b2t]. This model is based on “nucleation and growth of nuclei” theory, and describes the style of attack physically observed by SEM on the residues.

Pore Fluid Evolution Influenced by Volcanic Activities and Related Diagenetic Processes in a Rift Basin: Evidence from the Paleogene Medium-Deep Reservoirs of Huanghekou Sag, Bohai Bay Basin, China

Directory of Open Access Journals (Sweden)

Zhongheng Sun

2017-01-01

Full Text Available Volcanic activities exert a significant influence on pore fluid property and related diagenetic processes that substantially controlled reservoirs quality. Analysis of Paleogene medium-deep sandstones on the Huanghekou Sag provides insight into relating the diagenetic processes to pore fluid property evolution influenced by volcanic activities. Three distinct types of pore fluids were identified on the basis of an integrated and systematic analysis including core and thin section observation, XRD, SEM, CL, and trace element. Alkaline aqueous medium environment occurred in E2s1+2 where volcanic activities have insignificant influence on pore fluids, evidenced by typical alkaline diagenetic events such as K-feldspar albitization, quartz dissolution, feldspar dissolution, and carbonate cementation. During the deposition of E3d3, influx of terrestrial freshwater and alteration of ferromagnesian-rich pore water result in the formation of mixing aqueous medium environment through volcanic eruption dormancy causing zeolite dissolution, clay mineral transformation, and K-feldspar albitization. Ferromagnesian-rich aqueous medium environment developed resulting from the intensive hydrolysis of the unstable ferromagnesian minerals formed due to intense volcanic activities during E3d1+2 and corresponding predominant diagenetic processes were characterized by the precipitation and dissolution of low-silica zeolites. Therefore, the differential properties of pore fluids caused various diagenetic processes controlling reservoir quality.

Comparison of the properties of various optically stimulated luminescence signals from potassium feldspar

International Nuclear Information System (INIS)

Fu Xiao; Zhang Jiafu; Zhou Liping

2012-01-01

Various optically stimulated luminescence signals from K-feldspar have been used to determine the equivalent doses of sediment samples. Understanding the properties of these optical signals is critical to evaluate their applicability and limitations to optical dating. In this paper, some properties of IRSL, post-IR OSL and post-IR IRSL signals (detected in the UV region using U-340 filters) from a museum sample of K-feldspar were investigated by analyzing the relationships between optical and TL signals, and the effect of optical bleaching and heating on optical signals. The trap parameters of the different optical signals were calculated using the pulse annealing method. The results show that this sample exhibits two regenerated TL peaks at ∼140 and ∼330 °C. Corresponding to the low temperature TL peak, the OSL and post-IR OSL signals appear to be more associated with lower temperature TL than the IRSL signal measured at 50 °C. Corresponding to the high temperature TL peak, the post-IR IRSL signals mainly originate from the more thermally stable traps associated with the high temperature TL, compared with the IRSL and post-IR OSL signals. However, the post-IR IRSL 225°C signal is shown to be hard to be bleached by blue light and simulated sunlight, compared with the IRSL 50°C and low temperature post-IR IRSL signals. The implication for optical dating is that the elevated temperature post-IR IRSL signals can be preferentially applied over other signals from K-feldspar, but it is desirable that the effectiveness of the pre-depositional zeroing of these signals is assessed.

Dissolution testing of intermediary products in uranium dioxide production by the sol-gel method

International Nuclear Information System (INIS)

Melichar, F.; Landspersky, H.; Urbanek, V.

1979-01-01

A method was developed of dissolving polyuranates and uranium dioxides in sulphuric acid and in carbonate solutions for testing intermediate products in the sol-gel process preparation of uranium dioxide. A detailed granulometric analysis of spherical particle dispersion was included as part of the tests. Two different production methods were used for the two types of studied materials. The test results show that the test method is suitable for determining temperature sensitivity of the materials to dissolution reaction. The geometrical distribution of impurities in the spherical particles can be determined from the dissolution kinetics. The method allows the determination of the effect of carbon from impurities on the process of uranium dioxide leaching and is thus applicable for testing materials prepared by the sol-gel method. (Z.M.)

Research Article. Kinetics and Mechanism of Drug Release from Loratadine Orodispersible Tablets Developed without Lactose

Directory of Open Access Journals (Sweden)

Ciurba Adriana

2017-03-01

Full Text Available Objective: The aim of this study is to develop lactose-free orodispersible tablets with loratadine for patients with lactose intolerance. Materials and methods: Seven compositions (F1-F7 of 10 mg loratadine were prepared in form of orally disintegrating tablets, by direct compression, using croscarmellose sodium and pre-gelatinized starch in various concentrations as superdisintegrants, diluted with microcrystalline cellulose and combined with mannitol and maltodextrin as binder agents. The tablets had been studied in terms of their pharmacotechnical characteristics, by determining: the weight uniformity of the tablets, their friability, breaking strength and disintegration time, drug content and the dissolution profile of loratadine. The statistical analyses were performed with GraphPad Prism Software Inc. As dependent variables, both the hardness of the tablets and their disintegration ability differ between batches due to their compositional differences (as independent variables. DDSolver were used for modeling the kinetic of the dissolution processes by fitting the dissolution profiles with time-dependent equations (Zero-order, First-order, Higuchi, Korsmeyer-Peppas, Peppas-Sahlin. Results: All proposed formulas shows rapid disintegration, in less than 15 seconds, and the dissolution loratadine spans a period of about 10 minutes. Akaike index as well as R2 adjusted parameter have demonstrated that the studied dissolution profiles are the best fitted by Zero-order kinetic. Conclusion: In conclusion, association of croscarmellose sodium (7.5% with pre-gelatinized starch (6% as superdisintegrants and mannitol as the binder agent (35%, positively influences the dissolution properties of loratadine from orally fast dispersible tablets.

Comparative Studies on the Dissolution Profiles of Oral Ibuprofen Suspension and Commercial Tablets using Biopharmaceutical Classification System Criteria

Science.gov (United States)

Rivera-Leyva, J. C.; García-Flores, M.; Valladares-Méndez, A.; Orozco-Castellanos, L. M.; Martínez-Alfaro, M.

2012-01-01

In vitro dissolution studies for solid oral dosage forms have recently widened the scope to a variety of special dosage forms such as suspensions. For class II drugs, like Ibuprofen, it is very important to have discriminative methods for different formulations in physiological conditions of the gastrointestinal tract, which will identify different problems that compromise the drug bioavailability. In the present work, two agitation speeds have been performed in order to study ibuprofen suspension dissolution. The suspensions have been characterised relatively to particle size, density and solubility. The dissolution study was conducted using the following media: buffer pH 7.2, pH 6.8, 4.5 and 0.1 M HCl. For quantitative analysis, the UV/Vis spectrophotometry was used because this methodology had been adequately validated. The results show that 50 rpm was the adequate condition to discriminate the dissolution profile. The suspension kinetic release was found to be dependent on pH and was different compared to tablet release profile at the same experimental conditions. The ibuprofen release at pH 1.0 was the slowest. PMID:23626386

Solid dispersions, part II: new strategies in manufacturing methods for dissolution rate enhancement of poorly water-soluble drugs.

Science.gov (United States)

Bikiaris, Dimitrios N

2011-12-01

The absorption of poorly water-soluble drugs, when presented in the crystalline state to the gastrointestinal tract, is typically dissolution rate-limited, and according to BCS these drugs belong mainly to class II. Both dissolution kinetics and solubility are particle size dependent. Nowadays, various techniques are available to the pharmaceutical industry for dissolution rate enhancement of such drugs. Among such techniques, nanosuspensions and drug formulation in solid dispersions are those with the highest interest. This review discusses strategies undertaken over the last 10 years, which have been applied for the dissolution enhancement of poorly water-soluble drugs; such processes include melt mixing, electrospinning, microwave irradiation and the use of inorganic nanoparticles. Many problems in this field still need to be solved, mainly the use of toxic solvents, and for this reason the use of innovative new procedures and materials will increase over the coming years. Melt mixing remains extremely promising for the preparation of SDs and will probably become the most used method in the future for the preparation of solid drug dispersions.

Haw-glass dissolution and radionuclide release: mechanism - modelling - source term

Energy Technology Data Exchange (ETDEWEB)

Grambow, B [Forschungszentrum Karlsruhe, Institut fur Nukleare, Karlsruhe (Germany)

1997-07-01

Important release controlling processes are: 1) kinetics of glass matrix dissolution (leaching), 2) formation of secondary alteration products (controlling thermodynamic solubility), 3) sorption on surfaces in the engineered barrier system and 4) formation of mobile species. Quantification of these processes requires assessment of the energetics and dynamics of the various reversible and irreversible processes within an overall open non-equilibrium system. Corrosion/dissolution of the waste matrices is not necessarily associated with a proportional release of radionuclides. The formation of new secondary phases, such as silicates, molybdates, uranates, carbonates... establishes a new geochemical barrier for re-immobilization of radionuclides dissolved from the waste matrices. The presence of iron (corroding canisters during glass alteration) reduces the solution concentration of redox sensitive radionuclides. Consequently, the container, after being corroded, constitutes an important geochemical barrier for radionuclide re-immobilization. Geochemical modelling of the long-term behaviour of glasses must be performed in an integrated way, considering simultaneous reactions of the glass, of container corrosion, of repository rock and of backfill material. Until now, only few attempts were made for integral systems modelling. (A.C.)

Dissolution of aluminium; Disolucion de aluminio

Energy Technology Data Exchange (ETDEWEB)

Uriarte Hueda, A; Berberana Eizmendi, M; Pereira Sanchez, G

1968-07-01

The dissolution of aluminum with acid solutions ( nitric acid-mercuric nitrate) and alkaline solutions (sodium hydroxide-sodium nitrate) has been studied. The instantaneous dissolution rate (IDR) has been studied in function of the concentration of the used reagents and the dissolution temperature. The complete dissolution has been included in the second part of this report, to know the total dissolution time, the consume of reagents and the stability of the resultant solutions. (Author)

In Silico Modeling Approach for the Evaluation of Gastrointestinal Dissolution, Supersaturation, and Precipitation of Posaconazole.

Science.gov (United States)

Hens, Bart; Pathak, Shriram M; Mitra, Amitava; Patel, Nikunjkumar; Liu, Bo; Patel, Sanjaykumar; Jamei, Masoud; Brouwers, Joachim; Augustijns, Patrick; Turner, David B

2017-12-04

The aim of this study was to evaluate gastrointestinal (GI) dissolution, supersaturation, and precipitation of posaconazole, formulated as an acidified (pH 1.6) and neutral (pH 7.1) suspension. A physiologically based pharmacokinetic (PBPK) modeling and simulation tool was applied to simulate GI and systemic concentration-time profiles of posaconazole, which were directly compared with intraluminal and systemic data measured in humans. The Advanced Dissolution Absorption and Metabolism (ADAM) model of the Simcyp Simulator correctly simulated incomplete gastric dissolution and saturated duodenal concentrations of posaconazole in the duodenal fluids following administration of the neutral suspension. In contrast, gastric dissolution was approximately 2-fold higher after administration of the acidified suspension, which resulted in supersaturated concentrations of posaconazole upon transfer to the upper small intestine. The precipitation kinetics of posaconazole were described by two precipitation rate constants, extracted by semimechanistic modeling of a two-stage medium change in vitro dissolution test. The 2-fold difference in exposure in the duodenal compartment for the two formulations corresponded with a 2-fold difference in systemic exposure. This study demonstrated for the first time predictive in silico simulations of GI dissolution, supersaturation, and precipitation for a weakly basic compound in part informed by modeling of in vitro dissolution experiments and validated via clinical measurements in both GI fluids and plasma. Sensitivity analysis with the PBPK model indicated that the critical supersaturation ratio (CSR) and second precipitation rate constant (sPRC) are important parameters of the model. Due to the limitations of the two-stage medium change experiment the CSR was extracted directly from the clinical data. However, in vitro experiments with the BioGIT transfer system performed after completion of the in silico modeling provided an almost

The dissolution rate constant of magnetite in water at different temperatures and pH conditions

International Nuclear Information System (INIS)

Mohajery, Khatereh; Deydier de Pierrefeu, Laurent; Lister, Derek H.

2012-09-01

Under the nominal conditions of power system coolants, the corrosion of components made of carbon steel is limited by the magnetite films that develop on surfaces. In some situations, the magnetite film loses much of its protective ability and corrosion and loss of iron to the system are exacerbated. Common examples of such situations occur when the system is non-isothermal so that temperature gradients cause differences in magnetite solubility around the circuit; the resulting areas of under-saturation in iron give rise to dissolution of normally protective films. Condensing steam in two-phase systems may also promote oxide dissolution. When the turbulence in the system is high, oxide degradation is aggravated and flow-accelerated corrosion (FAC) results. The subsequent increased loading of systems with iron leads to fouling of flow passages and heat transfer surfaces and in reactor primary coolants to rising radiation fields, while FAC can have disastrous results in terms of pipe wall thinning and eventual rupture. Magnetite dissolution is clearly a key contributor to these processes. Thus, the conventional mechanistic description of FAC postulates magnetite dissolution in series with mass transfer of iron from the film to the bulk coolant. In the resulting equations, if the dissolution rate constant is considerably less than the mass transfer coefficient for a particular situation, dissolution will control and flow should have no effect. This is clearly untenable for FAC, so it is often assumed that mass transfer controls and the contribution from oxide dissolution is ignored - on occasion when data on dissolution kinetics are available and sometimes when those data show that dissolution should control. In most cases, however, dissolution rate constants for magnetite are not available. At UNB Nuclear we have a research program using a high-temperature loop to measure dissolution rates of magnetite in water under various conditions of flow, temperature and

Dissolution mechanism of austenitic stainless steels in lead-bismuth eutectic at 500 deg. C

International Nuclear Information System (INIS)

Roy, M.

2012-01-01

In the framework of the future nuclear power plants studies, lead-bismuth eutectic (LBE) is foreseen as a coolant in the primary or the secondary circuit in three nuclear systems. The use of this liquid alloy induces corrosion issues for structural steels. In liquid lead alloys, steels can undergo two corrosion phenomena: dissolution or oxidation depending on the temperature and the dissolved oxygen content in LBE. The goal of this study is to identify the dissolution mechanisms of austenitic steels in LBE at 500 deg. C. Four Fe-Cr-Ni model austenitic steels, the 316L steel and five other industrial steels were corroded in LBE up to, respectively, 3000, 6000 and 200 h. The dissolution mechanism is identical for all steels: it starts by a preferential dissolution of chromium and nickel. This dissolution leads to the formation of a ferritic corrosion layer penetrated by LBE and containing between 5 and 10 at% of chromium and almost no nickel. This study demonstrates that dissolutions of nickel and chromium are linked. Otherwise, the corrosion kinetics is linear whatever the tested austenitic steel. The controlling steps of the austenitic steels' corrosion rates have been identified. Natural convection in the LBE bath leads to the formation of a diffusion boundary layer at the steel surface. Chromium diffusion in this diffusion boundary layer seems to control the corrosion rates of the model and industrial austenitic steels except the 316L steel. Indeed, the corrosion rate of the 316L steel is controlled by an interfacial reaction which is either the simultaneous dissolution of nickel and chromium in Ni, Cr compounds or the nickel and chromium dissolution catalyzed by the dissolved oxygen in LBE. This study has permitted to highlight the major role of chromium on the corrosion mechanisms and the corrosion rates of austenitic steels: the corrosion rate increases when chromium activity increases. Finally, the impact of the dissolved oxygen and the minor alloying

Plagioclase-mantled K-feldspar in the Carboniferous porphyritic microgranite of Altenberg-Frauenstein, Eastern Erzgebirge/Krusné Hory

Directory of Open Access Journals (Sweden)

Axel Müller

2002-01-01

Full Text Available The Upper Carboniferous porphyritic microgranite of Altenberg-Frauenstein, formerly known as Granitporphyr (Dalmer 1896 and here abbreviated as GP, forms a 36 km long and up to 18 km wide complex of ring dykes related to the Teplice-Altenberg caldera in the German–Czech border region of the Eastern Erzgebirge/Krusné Hory. The microgranites are characterized by the occurrence of plagioclase-mantled K-feldspar phenocrysts. The microgranite varieties representtwo main stages of intrusion evolved from acid (GP I to intermediaterocks (GP II within the intrusion. The most acid rock (GP Icum occurs as enclaves in GP I and GP II and is interpreted as a cumulate of K-feldspar and quartz phenocrysts. The porphyritic microgranites show field, textural and geochemical evidence suggesting that some of them have formed as a result of interaction between felsic and mafic magmas. Mixing features are abundant in the porphyriticquartz-feldspar-hornblende microgranite (GP II interpreted as a hybrid rock. They are less discrete in the early phase (GP I and not obvious in the acid enclaves (GP Icum. This trend seems to reflect a continuous deflation of the magma chamber from the top to the bottom. According to the definition of rapakivi granites after Haapala and Rämö (1992, the porphyritic microgranite of Altenberg-Frauenstein may be considered as rapakivi granite although ovoid alkali feldspar megacrysts typical of classical rapakivi granites are not recorded.However, due to its Carboniferous age and being the only known granitewith rapakivi texture in the German–Czech part of the Variscan belt, the microgranite of Altenberg-Frauenstein is exceptional.

Comparative solubilisation of potassium carbonate, sodium bicarbonate and sodium carbonate in hot dimethylformamide: application of cylindrical particle surface-controlled dissolution theory.

Science.gov (United States)

Forryan, Claire L; Compton, Richard G; Klymenko, Oleksiy V; Brennan, Colin M; Taylor, Catherine L; Lennon, Martin

2006-02-07

A surface-controlled dissolution of cylindrical solid particles model is applied to potassium carbonate, sodium bicarbonate and sodium carbonate in dimethylformamide at elevated temperatures. Previously published data for the dissolution of potassium carbonate is interpreted assuming a cylindrical rather than a spherical shape of the particles, the former representing a closer approximation to the true shape of the particles as revealed by scanning electron microscopy. The dissolution kinetics of sodium carbonate and sodium bicarbonate in dimethylformamide at 100 degrees C were investigated via monitoring of the deprotonation of 2-cyanophenol with dissolved solid to form the 2-cyanophenolate anion that was detected with UV-visible spectroscopy. From fitting of experimental results to theory, the dissolution rate constant, k, for the dissolutions of potassium carbonate, sodium bicarbonate and sodium carbonate in dimethylformamide at 100 degrees C were found to have the values of (1.0 +/- 0.1) x 10(-7) mol cm(-2) s(-1), (5.5 +/- 0.3) x 10(-9) mol cm(-2) s(-1) and (9.7 +/- 0.8) x 10(-9) mol cm(-2) s(-1), respectively.

GLAMOR - Or How We Achieved A Common Understanding On The Decrease Of Glass Dissolution Kinetics Through International Cooperation

International Nuclear Information System (INIS)

Van Iseghem, Pierre; Aerstens, Marc; Gin, Stephane; Grambow, Bernd; Strachan, Denis M.; McGrail, B. Peter; Wicks, George G.; McMenamin, Thomas

2011-01-01

The objective of the EC funded GLAMOR project was to achieve a common understanding of the processes that control the decrease of the dissolution rate of high-level waste glass in water when silica becomes saturated. Is affinity control or a protective layer dominating? The following steps were taken: (1) review of the literature, (2) selection ofselect an experimental dataset, and selection of the models r(t) and GM2003, and (3) application apply by the GLAMOR partners of the models to the datasets. The main focus has beenwas on dissolution tests in pure water at different values of surface-to-volume and pH. Some of the main conclusions were: (1) both affinity and protective layer concepts must be considered in the interpretation of the rate decreasing stage, (2) the residual dissolution rate observed beyond the silica saturation stage is far more important in view of the long-term performance of the glass, and deserves more attention in future R and D. In the GLAMOR final report, we also discussed in detail the modeling parameters, such as the silica saturation concentration, the silica diffusion coefficient, the silica retention factor in the reaction layer, and the water diffusion coefficient.

Effect of sodium lauryl sulfate in dissolution media on dissolution of hard gelatin capsule shells.

Science.gov (United States)

Zhao, Fang; Malayev, Vyacheslav; Rao, Venkatramana; Hussain, Munir

2004-01-01

Sodium lauryl sulfate (SLS) is a commonly used surfactant in dissolution media for poorly water soluble drugs. However, it has occasionally been observed that SLS negatively impacts the dissolution of drug products formulated in gelatin capsules. This study investigated the effect of SLS on the dissolution of hard gelatin capsule shells. The USP paddle method was used with online UV monitoring at 214 nm (peptide bond). Empty size #0 capsule shells were held to the bottom of the dissolution vessel by magnetic three-prong sinkers. SLS significantly slowed down the dissolution of gelatin shells at pH < 5. Visually, the gelatin shells transformed into some less-soluble precipitate under these conditions. This precipitate was found to contain a higher sulfur content than the gelatin control sample by elemental analysis, indicating that SLS is part of the precipitate. Additionally, the slowdown of capsule shell dissolution was shown to be dependent on the SLS concentration and the ionic strength of the media. SLS interacts with gelatin to form a less-soluble precipitate at pH < 5. The use of SLS in dissolution media at acidic pH should be carefully evaluated for gelatin capsule products.

Quantifying Silica Reactivity in Subsurface Environments: Reaction Affinity and Solute Matrix Controls on Quartz and SiO2 Glass Dissolution Kinetics

International Nuclear Information System (INIS)

Dove, Patricia M.

2000-01-01

During the three years of this project, Professor Dove's laboratory made tremendous progress in understanding controls on amorphous silica dissolution kinetics in aqueous solutions. Our findings have already received considerable attention. In hydrothermal and low temperature studies, the work focused on determining quantitative and mechanistic controls on the most abundant silica polymorphs in Earth environments--quartz and amorphous silica. Our studies achieved goals set forth in the original proposal to establish a new quantitative understanding of amorphous silica dissolution. This support has resulted in 10 journal, 12 abstracts and 2 thesis publications. The PI and students were also recognized with 6 awards during this period. The 1998 EMSP conference in Chicago was an important meeting for our project. The symposium, enabled P.I. Dove to establish valuable contacts with ''users'' having specific needs for the findings of our EMSP project related to the urgency of problems in the Tanks Focus Area (TFA). Since that time, our working relations developed as Dove interacted with TFA scientists and engineers on the problems of waste glass properties. These interactions refined our experimental objectives to better meet their needs. Dove presented the results of EMSP research findings to a TFA subgroup at a Product Acceptance Workshop held in Salt Lake City during December 1998. The travel costs to attend this unanticipated opportunity were paid from EMSP project funds. In January 2000, Dove also attended a similar meeting in Atlanta with PNNL, SRL and BNF scientists/engineers to discuss new issues and make another level of decisions on the Product Acceptance goals. Our EMSP-funded research interfaced very well with the ongoing studies of Dr. Pete McGrail and colleagues in the Applied Geochemistry Group at PNNL. The value of our work to ''users'' was further demonstrated when Dove's EMSP-funded Postdoc, Dr. Jonathan Icenhower was hired by the same PNNL group. With

Solutal convection induced by dissolution. Influence on erosion dynamics and interface shaping.

Science.gov (United States)

Berhanu, Michael; Philippi, Julien; Cohen, Caroline; Derr, Julien; Courrech du Pont, Sylvain

2017-04-01

Rock fractures invaded by a water flow, are often subjected to dissolution, which let grow and evolve the initial fracture network, by evacuating the eroded minerals under a solute form. In the case of fast kinetic of dissolution, local erosion rate is set by the advection of the solute. The erosion velocity decreases indeed with the solute concentration at the interface and vanishes when this concentration reaches the saturation value. Even in absence of an imposed or external flow, advection can drive the dissolution, when buoyancy effects due to gravity induce a solutal convection flow, which controls the erosive dynamics and modifies the shape of the dissolving interface. Here, we investigate using model experiments with fast dissolving materials and numerical simulations in simplified situations, solutal convection induced by dissolution. Results are interpreted regarding a linear stability analysis of the corresponding solutal Rayleigh-Benard instability. A dissolving surface is suspended above a water height, initially at rest. In a first step, solute flux is transported through a growing diffusion layer. Then after an onset time, once the layer exceeds critical width, convection flow starts under the form of falling plumes. A dynamic equilibrium results in average from births and deaths of intermittent plumes, setting the size of the solute concentration boundary layer at the interface and thus the erosion velocity. Solutal convection can also induce a pattern on the dissolving interface. We show experimentally with suspended and inclined blocks of salt and sugar, that in a linear stage, the first wavelength of the dissolution pattern corresponds to the wavelength of the convection instability. Then pattern evolves to more complex shapes due to non-linear interactions between the flow and the eroded interface. More generally, we inquire what are the conditions to observe a such solutal convection instability in geological situations and if the properties of

Validating post IR-IRSL dating on K-feldspars through comparison with quartz OSL ages

NARCIS (Netherlands)

Kars, R.H.; Busschers, F.S.; Wallinga, J.

2012-01-01

Recent developments have opened up the possibilities of using potassium feldspar for dating Pleistocene sediments; a stable (less-fading) part of the infrared stimulated luminescence (IRSL) signal can be selected by largely depleting the unstable part of the IR signal, using a combination of thermal

Dependence of (anomalous) fading of infra-red stimulated luminescence on trap occupancy in feldspars

DEFF Research Database (Denmark)

Morthekai, P.; Jain, Mayank; Gach, Grzegorz

2013-01-01

Dose dependency of anomalous fading of infra-red stimulated luminescence (IRSL) from feldspars has been investigated using radiations of different ionisation qualities. The rate of fading of the IRSL signal after proton irradiation (9.4–30%/decade) is on an average almost twice compared...

Kinetics of piroxicam release from low-methylated pectin/zein hydrogel microspheres

Science.gov (United States)

The kinetics of a model drug (piroxicam) release from pectin/zein hydrogel microspheres was studied under conditions simulating the gastrointestinal tract. It is established that the rate-limiting step in the release mechanism is drug diffusion out of the microspheres rather than its dissolution. ...

Modeling of the Dissolution Kinetics of Arbutus Wild Berries-Based Tablets as Evaluated by Electric Conductivity

International Nuclear Information System (INIS)

Abbas-Aksil, T.; Benamara, S.

2015-01-01

Lyophilized powder (LP) from Algerian arbutus wild berries (Arbutus unedo L.) was obtained. This present paper reports about the dissolution (releasing) properties of LP-based tablets, evaluated through the electric conductivity (EC) of distilled water which is employed as surrounding medium, at three different temperatures (291, 298 and 309 K). In addition to this, secondary physicochemical characteristics such as elementary analysis, color and compressibility were evaluated. Regarding the modeling of ionic transfer, among the three tested models, namely Peleg, Singh et al. and Singh and Kulshestha, the latter seems to be the most appropriate (R2 = 0.99), particularly in the case of compacted tablets under 2000 Pa. The temperature dependence of the dissolution process was also studied applying Arrhenius equation (R2>0.8) which allowed to deduce the activation energy, ranging from 18.7 to 21.4 kJ.mol -1 according to the model and compression force employed. (author)

Structural changes in C–S–H gel during dissolution: Small-angle neutron scattering and Si-NMR characterization

Energy Technology Data Exchange (ETDEWEB)

Trapote-Barreira, Ana, E-mail: anatrapotebarreira@gmail.com [Institute of Environmental Assessment and Water Research (IDAEA), Barcelona 08034, Catalonia (Spain); Porcar, Lionel [National Institute of Standards and Technology (NIST), Gaithersburg, MD 20899 (United States); Large Scale Structure Group, Institut Laue Langevin, Grenoble (France); Cama, Jordi; Soler, Josep M. [Institute of Environmental Assessment and Water Research (IDAEA), Barcelona 08034, Catalonia (Spain); Allen, Andrew J. [National Institute of Standards and Technology (NIST), Gaithersburg, MD 20899 (United States)

2015-06-15

Flow-through experiments were conducted to study the calcium–silicate–hydrate (C–S–H) gel dissolution kinetics. During C–S–H gel dissolution the initial aqueous Ca/Si ratio decreases to reach the stoichiometric value of the Ca/Si ratio of a tobermorite-like phase (Ca/Si = 0.83). As the Ca/Si ratio decreases, the solid C–S–H dissolution rate increases from (4.5 × 10{sup −} {sup 14} to 6.7 × 10{sup −} {sup 12}) mol m{sup −} {sup 2} s{sup −} {sup 1}. The changes in the microstructure of the dissolving C–S–H gel were characterized by small-angle neutron scattering (SANS) and {sup 29}Si magic-angle-spinning nuclear magnetic resonance ({sup 29}Si-MAS NMR). The SANS data were fitted using a fractal model. The SANS specific surface area tends to increase with time and the obtained fit parameters reflect the changes in the nanostructure of the dissolving solid C–S–H within the gel. The {sup 29}Si MAS NMR analyses show that with dissolution the solid C–S–H structure tends to a more ordered tobermorite structure, in agreement with the Ca/Si ratio evolution.

Uranium dissolution in hyper-alkaline TMA-OH solutions: Preliminary results

Energy Technology Data Exchange (ETDEWEB)

Cachoir, C.; Salah, S.; Mennecart, T.; Lemmens, K. [Belgian Research Nuclear Centre - SCK-CEN, Boeretang 200, 2400 Mol (Belgium)

2016-07-01

Leaching experiments were performed with depleted UO{sub 2} powders in tetramethylammonium solutions (TMA-OH) at pH 13.5 and 12.5, and at different UO{sub 2} surface area to volume of solution (SA/V) ratio's to determine the solubility and the dissolution kinetics of UO{sub 2} at high pH in absence of cations dominating cementitious waters (Ca, Na, K). The solubility of UO{sub 2} increased from pH 12.5 to 13.5 and by increasing the SA/V ratio up to 100 m{sup -1}. However, no known U secondary-phases were predicted by geochemical calculations to control the measured U-concentrations. We interpreted the UO{sub 2} dissolution process as a 2-step process. For all experiments, we observe a fast initial rate, hydroxo promoted and likely surface controlled. Afterwards the rate is apparently negative at low SA/V over time while it is positive at higher SA/V ratio's. The former is interpreted to be related to a sorption process, while the latter reveals a continuous residual dissolution process. No solubility enhancing effect of U-colloids was observed in the TMA-OH media. However, there is much less uranium colloid formation in TMA-OH tests with low Ca (Na, K) concentration than in previous tests with higher Ca (Na, K) concentrations. This suggests that the colloid formation is promoted by alkali and/or alkali-earth elements.

In-vitro analysis of the dissolution kinetics and systemic availability of plutonium ingested in the form of 'hot' particles from the Semipalatinsk NTS

Energy Technology Data Exchange (ETDEWEB)

Conway, M. [School of Physics, University College Dublin, Belfield, Dublin 4 (Ireland); Leon Vintro, L. [School of Physics, University College Dublin, Belfield, Dublin 4 (Ireland)], E-mail: luis.leon@ucd.ie; Mitchell, P.I. [School of Physics, University College Dublin, Belfield, Dublin 4 (Ireland); Garcia-Tenorio, R.; Jimenez-Ramos, M.C. [Departamento de Fisica, Universidad de Sevilla, 41012 Sevilla (Spain); Burkitbayev, M. [Department of Inorganic Chemistry, Al-Farabi Kazakh National University, Almaty (Kazakhstan); Priest, N.D. [School of Health and Social Sciences, Middlesex University, Queensway, Enfield EN3 4SA (United Kingdom)

2009-05-15

In-vitro leaching of radioactive 'hot' particles isolated from soils sampled at the Semipalatinsk Nuclear Test Site has been carried out in order to evaluate the fraction of plutonium activity released into simulated human stomach and small intestine fluids during digestion. Characterisation of the particles (10-100 Bq {sup 239,240}Pu) and investigation of their dissolution kinetics in simulated fluids has been accomplished using a combination of high-resolution alpha-spectrometry, gamma-spectrometry and liquid scintillation counting. The results of these analyses indicate that plutonium transfer across the human gut following the ingestion of 'hot' particles can be up to two orders of magnitude lower than that expected for plutonium in a more soluble form, and show that for areas affected by local fallout, use of published ingestion dose coefficients, together with bulk radionuclide concentrations in soil, may lead to a considerable overestimation of systemic uptake via the ingestion pathway.

Predicting the oral pharmacokinetic profiles of multiple-unit (pellet) dosage forms using a modeling and simulation approach coupled with biorelevant dissolution testing: case example diclofenac sodium.

Science.gov (United States)

Kambayashi, Atsushi; Blume, Henning; Dressman, Jennifer B

2014-07-01

The objective of this research was to characterize the dissolution profile of a poorly soluble drug, diclofenac, from a commercially available multiple-unit enteric coated dosage form, Diclo-Puren® capsules, and to develop a predictive model for its oral pharmacokinetic profile. The paddle method was used to obtain the dissolution profiles of this dosage form in biorelevant media, with the exposure to simulated gastric conditions being varied in order to simulate the gastric emptying behavior of pellets. A modified Noyes-Whitney theory was subsequently fitted to the dissolution data. A physiologically-based pharmacokinetic (PBPK) model for multiple-unit dosage forms was designed using STELLA® software and coupled with the biorelevant dissolution profiles in order to simulate the plasma concentration profiles of diclofenac from Diclo-Puren® capsule in both the fasted and fed state in humans. Gastric emptying kinetics relevant to multiple-units pellets were incorporated into the PBPK model by setting up a virtual patient population to account for physiological variations in emptying kinetics. Using in vitro biorelevant dissolution coupled with in silico PBPK modeling and simulation it was possible to predict the plasma profile of this multiple-unit formulation of diclofenac after oral administration in both the fasted and fed state. This approach might be useful to predict variability in the plasma profiles for other drugs housed in multiple-unit dosage forms. Copyright © 2014 Elsevier B.V. All rights reserved.

Dissolution of two NWCF calcines: Extent of dissolution and characterization of undissolved solids

International Nuclear Information System (INIS)

Brewer, K.N.; Herbst, R.S.; Tranter, T.J.

1995-01-01

A study was undertaken to determine the dissolution characteristics of two NWCF calcine types. A two-way blended calcine made from 4 parts nonradioactive aluminum nitrate and one part WM-102 was studied to determine the extent of dissolution for aluminum-type calcines. A two-way blend of 3.5 parts fluorinel waste from WM-187 and 1 part sodium waste from WM-185 was used to determine the extent of dissolution for zirconium-type calcines. This study was necessary to develop suitable aqueous separation flowsheets for the partitioning of actinides and fission products from ICPP calcines and to determine the disposition of the resulting undissolved solids (UDS). The dissolution flowsheet developed by Herbst was used to dissolve these two NWCF calcine types. Results show that greater than 95 wt% of aluminum and zirconium calcine types were dissolved after a single batch contact with 5 M HNO 3 . A characterization of the UDS indicates that the weight percent of TRU elements in the UDS resulting from both calcine type dissolutions increases by approximately an order of magnitude from their concentrations prior to dissolution. Substantial activities of cesium and strontium are also present in the UDS resulting from the dissolution of both calcine types. Multiple TRU, Cs, and Sr analyses of both UDS types show that these solids are relatively homogeneous. From this study, it is estimated that between 63.5 and 635 cubic meters of UDS will be generated from the dissolution of 3800 M 3 of calcine. The significant actinide and fission product activities in these UDS will preclude their disposal as low-level waste. If the actinide and fission activity resulting from the UDS is the only considered source in the dissolved calcine solutions, an estimated 99.9 to 99.99 percent of the solids must be removed from this solution for it to meet non-TRU Class A low-level waste

Effects of Bacterial Siderophore and Biofilm Synthesis on Silicate Mineral Dissolution Kinetics: Results from Experiments with Targeted Mutants

Science.gov (United States)

Van Den Berghe, M. D.; West, A. J.; Nealson, K. H.

2018-05-01

This project aims to characterize and quantify the specific microbial mechanisms and metabolic pathways responsible for silicate mineral dissolution and micronutrient acquisition directly from mineral phases.

Luminescence from potassium feldspars stimulated by infrared and green light

DEFF Research Database (Denmark)

Duller, G.A.T.; Bøtter-Jensen, L.

1993-01-01

A series of experiments are reported which investigate stimulated luminescence from potassium feldspar. The aim is to provide a basic phenomenological description of the response of the material to stimulation by heat, infrared radiation (875 DELTA 80 nm) and a green light wavelength band from 5 15...... to 560 nm. Two conclusions are drawn: firstly it is suggested that the majority of the trapped charge responsible for the infrared stimulated luminescence signal does not give rise to a thermoluminescence signal, and secondly that a large traction of the two optically stimulated luminescence signals...

Wadi Ladid Al-JI,Dan Alkali Feldspar Granites and Associated Pegmatites, North Eastern Eser, Egypt:Geology,Mineralogy and Radioactivity

International Nuclear Information System (INIS)

Abu Steet, A.A.; Ayoub, R.R.; Bakhit, A.F.

2013-01-01

This article deals with the geology, structure, mineralogy and radioactivity of the alkali feldspar granites at wadi Ladid al-Ji,dan, north Eastern Desert of Egypt. Geologically, the area consists mainly of alkali feldspar granites. These granites are medium to coarse grained, pink to red in colour and form numbers of moderate to relatively high elevated outcrops. These rocks are altered in some parts due to secondary processes especially along the fault zones and contacts. The area displays primary and secondary structures. Primary structures comprise layering, volcanic flows, vesicular tops of lavas and volcanic bombs. The secondary structures are represented by exfoliation, joints and faults. The granites are dissected by several sets of joints predominating in the N-S direction, dipping 84°-88° mainly to west; E-W direction, dipping 70°-75° mainly to south and NW-SE direction, dipping 80°-82° to SW direction. The majority of joints are tension ones. These tension joints are commonly filled with quartz, feldspars, epidote, iron oxides, manganese oxides and aplite. The studied area is dissected by major regional faults. Along the fault zones; the granites are marked by fault breccia and alteration features, especially silicification, hematitization, kaolinitization and chloritization. The area is cutting by faults trending mainly in N-S, NE-SW and NNW-SSE directions. The average uranium and thorium contents of the alkali feldspar granites are 12 and 23 ppm and reaches up to 36 and 37 ppm in the normal pegmatites. In the anomalous pegmatites the maximum values recorded are 91 and 72 ppm. Generally, the averages of uranium and thorium contents in the studied pegmatites are higher than that of the world and Egyptian uraniferous pegmatites. The high uranium content in alkali feldspar granites is related to the presence of some accessory minerals such as zircon, fluorite and apatite but the high uranium content in the pegmatites is related to the presence of

Developing a numerical simulation for fading in feldspar

International Nuclear Information System (INIS)

Larsen, A.; Greilich, S.; Jain, M.; Murray, A.S.

2009-01-01

Most models describing anomalous fading in feldspars are based on analytical solutions. As an alternative approach we present an entirely numerical model based on statistical sampling that simulates stepwise the charge creation/trapping and recombination in a given phosphor. We assume the number density of electrons and holes at any time to be equal, although the model is not bound to that assumption. The model is flexible enough to be used on any combination of geological and laboratory timescales and for any defined configuration of defects. Using this approach we observed reorganization of nearest-neighbor distances with time. The best agreement with experimental data is achieved if we assume the crystal to consist of small subvolumes (nanocrystals) only within which charge carriers are allowed to recombine.

Effects of pore CaCO3 form agencies on dissolution mechanisms of amoxicillin drugs encapsulated in hydrogels full-IPN chitosan N-vinyl caprolactam

Science.gov (United States)

Budianto, Emil; Fauzia, Maghfira

2018-04-01

The administration of amoxicillin trihydrate in Helicobacter pylori infection is not effective enough because the conventional preparations used have a short retention time in the stomach. To overcome this problem, amoxicillin trihydrate was encapsulated into the floating drug delivery matrix-matrix. In this study, the full-ipn acetaldehyde crosslinked hydrogel (N-vinyl caprolactam) was synthesized with a 10% CaCO3 pore forming agent and then encapsulated on amoxicillin trihydrate and studied the mechanism of drug dissolution with its kinetic kinetics approach. The K-PNVCL Hydrogel produces optimal properties which are then loaded with amoxicillin trihydrate in situ and post loading. In this research, we have got the percentage of swelling, floating time, the efficiency of in situ and post loading 873%; 3.15 minutes; 99.8% and 99.4%. The dissolution test was performed on amoxicillin trihydrate which had been encapsulated K-PNVCL hydrogel in vitro at pH 1.2 resulting in 94.5% for in situ loading and 98.5% for post loading. Results of the kinetics of drug release for post loading and in situ loading methods tend to follow the Higuchi model kinetics. The drug release mechanism occurs by Fickian diffusion. Proof of drug release mechanism from K-PNVCL hydrogel matrix is further done by Scanning Electron Microscope (SEM) instrument.

Effects of pore forming agents of potassium bicarbonate and drug loading method against dissolution mechanisms of amoxicillin drugs encapsulated in hydrogel full-Ipn chitosan-poly(N-vinylcaprolactam) as a floating drug delivery system

Science.gov (United States)

Aini, Nurul; Rahayu, Dyah Utami Cahyaning; Budianto, Emil

2018-04-01

The limitation of amoxicillin trihydrate in the treatment of H. pylori bacteria is relatively short retention time in the stomach. The FDDS (Floating Drug Delivery System) amoxicillin trihydrate into a chitosan-poly(N-vinylcaprolactam) full-Ipn hydrogel matrix using a pore-forming agent KHCO3 is expected to overcome these limitations. The pore-forming agent to be used is 15% KHCO3 compound. Chemical kinetics approach is performed to determine the dissolution mechanism of amoxicillin trihydrate from K-PNVCL hydrogel in vitro on gastric pH and characterization using SEM performed to confirm the dissolution mechanism. Hydrogels with the addition of pore-forming agents will be loading in situ loading and post loading. Fourier Transform Infra Red (FTIR) spectroscopy was used to characterize K-PNVCL and UV-Vis hydrogels used to calculate the efficiency of encapsulation and drug dissolution rate in K-PNVCL hydrogel. Hydrogel K-PNVCL / KHCO3 that encapsulated by in situ loading method resulted in an encapsulation efficiency of 93.5% and dissolution of 93.4%. While the Hydrogel K-PNVCL / KHCO3 which is drug encapsulation resulted in an encapsulation efficiency of 87.2% with dissolution of 81.5%. Chemical kinetics approach to in situ encapsulation of loading and post loading shows the dissolution mechanism occurring in the K-PNVCL / KHCO3 hydrogel matrix occurs by diffusion. Observation using optical microscope and SEM showed the mechanism of drug dissolution in Hydrogel K-PNVCL occurred by diffusion.

Use of rice straw ash as substitute of feldspar in triaxial porcelain; Cenizas del tamo de arroz como substituto del feldespato en la fabricacion de ceramica blanca

Energy Technology Data Exchange (ETDEWEB)

Alvaro Guzman, A.; Silverio Delvasto, A.; Enrique Sanchez, V.; Vicente Amigo, B.

2013-02-01

The substitution of raw materials for processing high energy consumption materials by agricultural and agro-industrial wastes causes a positive impacts on the environment preservation. One of these residues is rice straw, which according to FAO estimation, its annual production is about 600 million tons. In this research was studied the use of rice straw ash as substitute of the use of feldspar in the white ware production. Clay-feldspar-quartz porcelains are referred to as triaxial white ware. Specimens of semidry triaxial mixtures, where feldspar was substituted for different percentages of CTA, were prepared by uniaxial pressing, followed by drying and sintering. Physical and mechanical properties of sintered bodies were evaluated. The porosity and the compressive strength of the fired pieces do increase with additions of up to 75% of CTA in substitution of feldspar. Their mineralogical phases were determined by DRX and SEM; grains of quartz, and needles of primary and secondary mullite were identified in a vitreous phase. It was concluded that feldspar can be substituted positively by CTA in white ware pastes. (Author) 22 refs.

Bleaching of the post-IR IRSL signal from individual grains of K-feldspar: Implications for single-grain dating

International Nuclear Information System (INIS)

Smedley, R.K.; Duller, G.A.T.; Roberts, H.M.

2015-01-01

Post-IR IRSL (pIRIR) signals from K-feldspar grains measured at elevated temperatures are increasingly being used for dating sediments. Unfortunately the pIRIR signal from K-feldspars bleaches more slowly than other signals (e.g. OSL from quartz) upon exposure to daylight, leading to concerns about residual signals remaining at deposition. However, earlier studies have not assessed whether the pIRIR signal bleaches at the same rate in all feldspar grains. In this study laboratory bleaching experiments have been conducted and for the first time the results show that the rate at which the pIRIR signal from individual K-feldspar grains bleach varies. To determine whether grain-to-grain variability in bleaching rate has a dominant control on equivalent dose (D e ) distributions determined using single grains, analysis was undertaken on three samples with independent age control from different depositional environments (two aeolian and one glaciofluvial). The D e value determined from each grain was compared with the rate at which the pIRIR 225 signal from the grain bleaches. The bleaching rate of each grain was assessed by giving a 52 Gy dose and measuring the residual D e after bleaching for an hour in a solar simulator. There is no clear relationship between the rate at which the pIRIR 225 signal of an individual grain bleaches and the magnitude of its D e . It is concluded that variability in the bleaching rate of the pIRIR 225 signal from one grain to another does not appear to be a dominant control on single grain D e distributions. - Highlights: • The bleaching rate of the pIRIR signal from single K-feldspar grains was assessed. • The pIRIR 225 signal bleaches more rapidly than the pIRIR 290 signal. • pIRIR 225 and pIRIR 290 signals reach the same level after 4–20 h of bleaching. • The bleaching rate of the pIRIR signal varies from one grain to another. • Variable pIRIR bleaching rates do not control single-grain D e distributions

High temperature dissolution of ferrites, chromites and bonaccordite in chelating media

Energy Technology Data Exchange (ETDEWEB)

Sathyaseelan, V.S.; Subramanian, H.; Anupkumar, B.; Rufus, A.L.; Velmurugan, S.; Narasimhan, S.V., E-mail: snv@igcar.gov.in [BARC Facilities, Water and Steam Chemistry Div., Tamilnadu (India)

2010-07-01

Different methods have been employed world wide for the decontamination of reactor coolant system surfaces. The success of a decontamination process mainly depends on the oxide dissolution efficiency of the decontamination formulation. Among the oxides, Fe{sub 3}O{sub 4} undergoes easy dissolution in organic acid media at normal temperatures. However, dissolution of chromites and mixed ferrites is not that easy in organic chelant media at normal temperatures even in the presence of redox reagents. Hence, a high temperature process was attempted for the dissolution of ferrites and chromites. A re-circulation system consisting of an autoclave, pump, heat exchanger etc. all lined with teflon was used for carrying out high temperature dissolution experiments. This study describes the high temperature dissolution kinetics of Fe{sub 3}O{sub 4}, NiFe{sub 2}O{sub 4}, and Cr{sub 2}O{sub 3}. Nitrilotriacetic acid (NTA), a well known solvent for metal oxides, was applied at temperatures ranging from 80 to 180{sup o}C. About six fold increase in dissolution rate was observed for Fe{sub 3}O{sub 4} in this temperature range. Effect of N{sub 2}H{sub 4} on oxide dissolution was studied. Lower dissolution rates were observed for Fe{sub 3}O{sub 4} and NiFe{sub 2}O{sub 4} in the presence of hydrazine. Oxide dissolution efficiency of other chelating agents like EDTA, PDCA etc. and the effect of reducing agents like oxalic acid and ascorbic acid on high temperature dissolution also has been studied. The effect of incorporation of boron and zinc in the iron and chromium oxides has also been studied. Bonaccordite (Ni{sub 2}FeBO{sub 5}) has been observed in the fuel deposits of pressurized Water Reactors especially in the AOA affected plants. Zinc ferrite/chromite are formed in reactors adopting zinc injection passivation technique to control radiation field. Bonaccordite and zinc ferrite/chromite formed over the reactor coolant system structural materials are also difficult to dissolve

Bioinspired co-crystals of Imatinib providing enhanced kinetic solubility.

Science.gov (United States)

Reggane, Maude; Wiest, Johannes; Saedtler, Marco; Harlacher, Cornelius; Gutmann, Marcus; Zottnick, Sven H; Piechon, Philippe; Dix, Ina; Müller-Buschbaum, Klaus; Holzgrabe, Ulrike; Meinel, Lorenz; Galli, Bruno

2018-05-04

Realizing the full potential of co-crystals enhanced kinetic solubility demands a comprehensive understanding of the mechanisms of dissolution, phase conversion, nucleation and crystal growth, and of the complex interplay between the active pharmaceutical ingredient (API), the coformer and co-existing forms in aqueous media. One blueprint provided by nature to keep poorly water-soluble bases in solution is the complexation with phenolic acids. Consequently, we followed a bioinspired strategy for the engineering of co-crystals of a poorly water-soluble molecule - Imatinib - with a phenolic acid, syringic acid (SYA). The dynamics of dissolution and solution-mediated phase transformations were monitored by Nuclear Magnetic Resonance (NMR) spectroscopy, providing mechanistic insights into the 60 fold-increased long lasting concentrations achieved by the syringate co-crystals as compared to Imatinib base and Imatinib mesylate. This lasting effect was linked to SYA's ability to delay the formation and nucleation of Imatinib hydrate - the thermodynamically stable form in aqueous media - through a metastable association of SYA with Imatinib in solution. Results from permeability studies evidenced that SYA did not impact Imatinib's permeability across membranes while suggesting improved bioavailability through higher kinetic solubility at the biological barriers. These results reflect that some degree of hydrophobicity of the coformer might be key to extend the kinetic solubility of co-crystals with hydrophobic APIs. Understanding how kinetic supersaturation can be shaped by the selection of an interactive coformer may help achieving the needed performance of new forms of poorly water-soluble, slowly dissolving APIs. Copyright © 2018. Published by Elsevier B.V.

Disintegration rate and properties of active pharmaceutical ingredient particles as determined from the dissolution time profile of a pharmaceutical formulation: an inverse problem.

Science.gov (United States)

Horkovics-Kovats, Stefan

2014-02-01

Dissolution profile of a finished dosage form (FDF) contains hidden information regarding the disintegration of the form and the particle properties of the active pharmaceutical ingredient. Here, an extraction of this information from the dissolution profile without limitation to sink conditions is provided. In the article, mathematical relationships between the continuously measured dissolution profile of an FDF containing uniform or heterogeneous particles and its disintegration rate are developed. Further, the determinability of the disintegration kinetics and particle properties released from an FDF using the derived recurrent procedure was analyzed. On the basis of the theoretical data sets, it was demonstrated that the introduced analysis of dissolution profiles correctly identifies the disintegration rate of FDF containing multiple particle types. Furthermore, for known disintegration rates, the intrinsic lifetime of particles (time needed for total particle dissolution in infinite volume) released from the FDF and their relative amount can be determined. The extractable information from FDF dissolution time profiles can be utilized in designing of the formulation process, resulting in improved understanding of FDF properties, contributing thus to the implementation of quality by design in the FDF development. © 2013 Wiley Periodicals, Inc. and the American Pharmacists Association.

Subdiffusion kinetics of nanoprecipitate growth and destruction in solid solutions

Science.gov (United States)

Sibatov, R. T.; Svetukhin, V. V.

2015-06-01

Based on fractional differential generalizations of the Ham and Aaron-Kotler precipitation models, we study the kinetics of subdiffusion-limited growth and dissolution of new-phase precipitates. We obtain the time dependence of the number of impurities and dimensions of new-phase precipitates. The solutions agree with the Monte Carlo simulation results.

Geoengineering impact of open ocean dissolution of olivine on atmospheric CO2, surface ocean pH and marine biology

International Nuclear Information System (INIS)

Köhler, Peter; Abrams, Jesse F; Völker, Christoph; Hauck, Judith; Wolf-Gladrow, Dieter A

2013-01-01

Ongoing global warming induced by anthropogenic emissions has opened the debate as to whether geoengineering is a ‘quick fix’ option. Here we analyse the intended and unintended effects of one specific geoengineering approach, which is enhanced weathering via the open ocean dissolution of the silicate-containing mineral olivine. This approach would not only reduce atmospheric CO 2 and oppose surface ocean acidification, but would also impact on marine biology. If dissolved in the surface ocean, olivine sequesters 0.28 g carbon per g of olivine dissolved, similar to land-based enhanced weathering. Silicic acid input, a byproduct of the olivine dissolution, alters marine biology because silicate is in certain areas the limiting nutrient for diatoms. As a consequence, our model predicts a shift in phytoplankton species composition towards diatoms, altering the biological carbon pumps. Enhanced olivine dissolution, both on land and in the ocean, therefore needs to be considered as ocean fertilization. From dissolution kinetics we calculate that only olivine particles with a grain size of the order of 1 μm sink slowly enough to enable a nearly complete dissolution. The energy consumption for grinding to this small size might reduce the carbon sequestration efficiency by ∼30%. (letter)

Luminescence and ESR properties of Brazilian feldspars

International Nuclear Information System (INIS)

Bitencourt, J.F.S.; Silva, D.M.; Silva, P.H.; Kinoshita, A.; Munita, C.S.; Tatumi, S.H.

2006-01-01

The IRSL and TL responses of three different feldspar crystals have been analysed. TL measurements were taken in the ultraviolet UV (290-370nm) and the visible VIS (340-610nm) regions of the spectrum. For the UV region and for a natural sample, peaks were observed at 283, 287 and 310 deg. C for grey, white and pink crystals, respectively. For samples irradiated after prior preheating, it was noted that TL peaks occurred at about 200 deg. C for all the samples; irradiation with high doses above 500Gy induced the formation of one additional peak at 170 deg. C. The VIS region results were similar to those for the UV. ESR experiments have been developed to verify the influence of radiation and heat treatments on the centres and preliminary results showed great variation in the intensities of [TiO 4 ] - , Al-O - -Al and Fe 3+ centres

The dissolution phenomenon of lysozyme crystals

Energy Technology Data Exchange (ETDEWEB)

Mueller, C.; Ulrich, J. [Martin Luther University Halle-Wittenberg, Department of Thermal Separation Processes, Centre of Engineering Science, Halle/Saale (Germany)

2012-02-15

Dissolution studies on lysozyme crystals were carried out since the observed dissolution pattern look different from non-protein dissolved crystals. The Tetragonal, High Temperature and Low Temperature Orthorhombic morphologies, crystallized using sodium chloride, were chosen and the influence of different pH, salt and protein concentration on their dissolution was investigated. An increase in pH and/or salt concentration can modify the dissolution behaviour. The pattern of the crystals during the dissolution process will, therefore, develop differently. Frequently a skeleton like crystal pattern followed by a falling apart of the crystals is observed. The multi-component character of the lysozyme crystal (protein, water, buffer, salt) as well as ''solvatomorphism'' gives first insights in the phenomena happening in the dissolution process. (copyright 2012 WILEY-VCH Verlag GmbH and Co. KGaA, Weinheim) (orig.)

Testing the application of quartz and feldspar luminescence dating to MIS 5 Japanese marine deposits

DEFF Research Database (Denmark)

Thiel, Christine; Tsukamoto, Sumiko; Tokuyasu, Kayoko

2015-01-01

The applicability of both quartz and feldspar luminescence dating was tested on twenty-five samples from a marine succession now forming a coastal cliff at Oga Peninsula, Honshu Island, Japan. The quartz optically stimulated luminescence (OSL) signal shows thermal instability and linear modulated...

To the problem on formation kinetics of absorption and polylayer films in anodic oxidation of cadmium in alkali hydroxides. Kinetics of irreversible absorption of oxide

International Nuclear Information System (INIS)

Grachev, D.K.

1978-01-01

An attempt is made to substantiate the formation of adsorption and polylayer films on cadmium electrode during its oxidation in KOH diluted solutions based on the interpretation of data from methods of the potential control. Using relaxation methods (voltammetry and chronoammetry) the conditions were determined at which irreversible abd sorption kinetics of the passivating oxide turns out to dominate the anodic dissolution process in the KOH 1-0.1 N solutions. Parts of monolayer and polylayer surface filling are shown. Kinetics of monolayer oxide growth is interpreted based on the Temkin-Zeldovich type equation for irreversible adsorption process. Ways of the kinetic equation precision are discussed for its full correspondence with the experiment obtained

Mesoporous carbon with spherical pores as a carrier for celecoxib with needle-like crystallinity: Improve dissolution rate and bioavailability

International Nuclear Information System (INIS)

Zhu, Wenquan; Zhao, Qinfu; Sun, Changshan; Zhang, Zhiwen; Jiang, Tongying; Sun, Jin; Li, Yaping; Wang, Siling

2014-01-01

The purposes of this investigation are to design mesoporous carbon (MC) with spherical pore channels and incorporate CEL to it for changing its needlelike crystal form and improving its dissolution and bioavailability. A series of solid-state characterization methods, such as SEM, TEM, DSC and XRD, were employed to systematically investigate the existing status of celecoxib (CEL) within the pore channels of MC. The pore size, pore volume and surface area of samples were characterized by nitrogen physical absorption. Gastric mucosa irritation test was carried out to evaluate the safety of mesoporous carbon as a drug carrier. Dissolution tests and in vivo pharmacokinetic studies were conducted to confirm the improvement in drug dissolution kinetics and oral bioavailability. Uptake experiments were conducted to investigate the mechanism of the improved oral bioavailability. The results of solid state characterization showed that MC was prepared successfully and CEL was incorporated into the mesoporous channels of the MC. The crystallinity of CEL in MC was affected by different loading methods, which involve evaporation method and melting method. The dissolution rate of CEL from MC was found to be significantly higher than that of pure CEL, which attributed to reduced crystallinity of CEL. The gastric mucosa irritation test indicated that the MC caused no harm to the stomach and produced a protective effect on the gastric mucosa. Uptake experiments indicated that MC enhanced the amount of CEL absorbed by Caco-2 cells. Moreover, oral bioavailability of CEL loaded within the MC was approximately 1.59-fold greater than that of commercial CEL. In conclusion, MC was a safe carrier to load water insoluble drug by controlling the crystallinity or crystal form with improvement in drug dissolution kinetics and oral bioavailability. - Highlights: • Mesoporous carbon with spherical pore structure was prepared according to the needlelike crystalline of celecoxib. • The

Mesoporous carbon with spherical pores as a carrier for celecoxib with needle-like crystallinity: Improve dissolution rate and bioavailability

Energy Technology Data Exchange (ETDEWEB)

Zhu, Wenquan; Zhao, Qinfu; Sun, Changshan [Department of Pharmaceutics, Shenyang Pharmaceutical University, Shenyang (China); Zhang, Zhiwen [Center of Pharmaceutics, Shanghai Institute of Materia Medica, Chinese Academy of Sciences, 501 Haike Road, Shanghai 201203 (China); Jiang, Tongying; Sun, Jin [Department of Pharmaceutics, Shenyang Pharmaceutical University, Shenyang (China); Li, Yaping [Center of Pharmaceutics, Shanghai Institute of Materia Medica, Chinese Academy of Sciences, 501 Haike Road, Shanghai 201203 (China); Wang, Siling, E-mail: silingwang@syphu.edu.cn [Department of Pharmaceutics, Shenyang Pharmaceutical University, Shenyang (China)

2014-06-01

The purposes of this investigation are to design mesoporous carbon (MC) with spherical pore channels and incorporate CEL to it for changing its needlelike crystal form and improving its dissolution and bioavailability. A series of solid-state characterization methods, such as SEM, TEM, DSC and XRD, were employed to systematically investigate the existing status of celecoxib (CEL) within the pore channels of MC. The pore size, pore volume and surface area of samples were characterized by nitrogen physical absorption. Gastric mucosa irritation test was carried out to evaluate the safety of mesoporous carbon as a drug carrier. Dissolution tests and in vivo pharmacokinetic studies were conducted to confirm the improvement in drug dissolution kinetics and oral bioavailability. Uptake experiments were conducted to investigate the mechanism of the improved oral bioavailability. The results of solid state characterization showed that MC was prepared successfully and CEL was incorporated into the mesoporous channels of the MC. The crystallinity of CEL in MC was affected by different loading methods, which involve evaporation method and melting method. The dissolution rate of CEL from MC was found to be significantly higher than that of pure CEL, which attributed to reduced crystallinity of CEL. The gastric mucosa irritation test indicated that the MC caused no harm to the stomach and produced a protective effect on the gastric mucosa. Uptake experiments indicated that MC enhanced the amount of CEL absorbed by Caco-2 cells. Moreover, oral bioavailability of CEL loaded within the MC was approximately 1.59-fold greater than that of commercial CEL. In conclusion, MC was a safe carrier to load water insoluble drug by controlling the crystallinity or crystal form with improvement in drug dissolution kinetics and oral bioavailability. - Highlights: • Mesoporous carbon with spherical pore structure was prepared according to the needlelike crystalline of celecoxib. • The

A New Experimental Design to Study the Kinetics of Solid Dissolution into Liquids at Elevated Temperature

Science.gov (United States)

Wang, Huijun; White, Jesse F.; Sichen, Du

2018-04-01

A new method was developed to study the dissolution of a solid cylinder in a liquid under forced convection at elevated temperature. In the new design, a rotating cylinder was placed concentrically in a crucible fabricated by boring four holes into a blank material for creating an internal volume with a quatrefoil profile. A strong flow in the radial direction in the liquid was created, which was evidently shown by computational fluid dynamic (CFD) calculations and experiments at both room temperature and elevated temperature. The new setup was able to freeze the sample as it was at experimental temperature, particularly the interface between the solid and the liquid. This freezing was necessary to obtain reliable information for understanding the reaction mechanism. This was exemplified by the study of dissolution of a refractory in liquid slag. The absence of flow in the radial direction in the traditional setup using a symmetrical cylinder was also discussed. The differences in the findings by past investigators using the symmetrical cylinder are most likely due to the extent of misalignment of the cylinder in the containment vessel.

Dissolution Coupled Biodegradation of Pce by Inducing In-Situ Biosurfactant Production Under Anaerobic Conditions

Science.gov (United States)

Dominic, J.; Nambi, I. M.

2013-12-01

Biosurfactants have proven to enhance the bioavailability and thereby elevate the rate of degradation of Light Non Aqueous Phase Liquids (LNAPLs) such as crude oil and petroleum derivatives. In spite of their superior characteristics, use of these biomolecules for remediation of Dense Non Aqueous Phase Liquids (DNAPLs) such as chlorinated solvents is still not clearly understood. In this present study, we have investigated the fate of tetrachloroethylene (PCE) by inducing in-situ biosurfactants production, a sustainable option which hypothesizes increase in bioavailability of LNAPLs. In order to understand the effect of biosurfactants on dissolution and biodegradation under the inducement of in-situ biosurfactant production, batch experiments were conducted in pure liquid media. The individual influence of each process such as biosurfactant production, dissolution of PCE and biodegradation of PCE were studied separately for getting insights on the synergistic effect of each process on the fate of PCE. Finally the dissolution coupled biodegradation of non aqueous phase PCE was studied in conditions where biosurfactant production was induced by nitrate limitation. The effect of biosurfactants was differentiated by repeating the same experiments were the biosurfactant production was retarded. The overall effect of in-situ biosurfactant production process was evaluated by use of a mathematical model. The process of microbial growth, biosurfactant production, dissolution and biodegradation of PCE were translated as ordinary differential equations. The modelling exercise was mainly performed to get insight on the combined effects of various processes that determine the concentration of PCE in its aqueous and non-aqueous phases. Model simulated profiles of PCE with the kinetic coefficients evaluated earlier from individual experiments were compared with parameters fitted for observations in experiments with dissolution coupled biodegradation process using optimization

Theoretical consideration on the application of the Aagaard-Helgeson rate law to the dissolution of silicate minerals and glasses

International Nuclear Information System (INIS)

Gin, S.; Jegou, C.; Frugier, P.; Minet, Y.

2008-01-01

The kinetic laws derived from the work of Aagaard and Helgeson are discussed, notably those applied to aluminosilicate or borosilicate glasses. Aagaard and Helgeson extended the kinetic formalism of an elementary reaction in a homogeneous medium to overall alteration processes in heterogeneous media by assuming they consist of a series of elementary steps. The dissolution rate of a mineral phase can thus be expressed as follows: r φ = k φ Π(i)a i -n ij (1-exp(-A/σRT)) (1) where k φ is the kinetic constant of hydrolysis of the mineral φ, a i the activity of the reactants i in the limiting elementary step j, n ij the stoichiometric coefficient for reactant i in the limiting reaction j, A the chemical affinity of the overall dissolution reaction, σ the average stoichiometric number of the overall reaction, R the ideal gas constant and T the temperature. We first illustrate the relation between transition state theory and a kinetic law such as Eq. (1) initially associated with an elementary reaction, using the simple example of hydriodic acid synthesis. We then discuss the extension of Eq. (1) to overall processes, showing that there is no obvious relation between the elementary limiting step and the contents of the affinity function and that this reflects a problem of scale in the Aagaard-Helgeson law between the kinetic constant (based on microscopic theories) and the affinity term (a macroscopic entity derived from classical thermodynamics). The discussion shows the difficulties encountered in attempting to determine the activity of the reactants in the elementary limiting step, particularly in the case of surface groups, and highlights the limited validity of extending a chemical affinity law of the type (1-exp(-ΔG/RT))- which is theoretically valid for an elementary reaction near equilibrium for an overall process. Our article then reviews Grambow's reasoning and the difficulties he encountered in applying the Aagaard-Helgeson law to the dissolution of

Thermodynamic stability and kinetic dissolution of perovskite in natural waters

International Nuclear Information System (INIS)

Nesbitt, H.W.; Bancroft, G.M.; Fyfe, W.S.; Karkhanis, S.; Melling, P.; Nishijima, A.

1981-01-01

Ringwood and coworkers have recently proposed using titanates and zirconates as hosts for nuclear waste in the Synroc B process. Three minerals are used as hosts: perovskite (CaTiO 3 ), Ba-hollandite (BaAl 2 Ti 6 O 16 ), and zirconolite (CaZrTi 2 O 7 ). The Synroc philosophy relies heavily on geological and geochemical observations in selecting stable host minerals. Although it has been recognized that the Synroc minerals are not thermodynamically compatible with siliceous rocks, the minerals are considered to be thermodynamically stable in the presence of water, and it has been reported that these minerals are kinetically stable under high-temperature (up to 900 0 C) hydrothermal conditions. Detailed thermodynamic calculations and leach tests have been performed which demonstrate: first, that perovskite is thermodynamically unstable in all known natural waters; and second, that pervoskite leaches at a significant rate even at 100 0 C. Hydrothermal leach tests have been made on natural and synthetic perovskite and perovskite analogues between 100 0 C and 300 0 C. Weight losses and solution concentrations were monitored. The results reported previously in the literature also show that perovskite is kinetically unstable in the presence of common silicates. Our results show that perovskite may be no more stable than siliceous glasses, such as rhyolite, which have been studied previously. Geologic evidence from common alkaline rocks also indicates that hollandite and zirconolite probably will not survive in common rock matrices

Microbially enhanced dissolution and reductive dechlorination of PCE by a mixed culture: Model validation and sensitivity analysis

Science.gov (United States)

Chen, Mingjie; Abriola, Linda M.; Amos, Benjamin K.; Suchomel, Eric J.; Pennell, Kurt D.; Löffler, Frank E.; Christ, John A.

2013-08-01

Reductive dechlorination catalyzed by organohalide-respiring bacteria is often considered for remediation of non-aqueous phase liquid (NAPL) source zones due to cost savings, ease of implementation, regulatory acceptance, and sustainability. Despite knowledge of the key dechlorinators, an understanding of the processes and factors that control NAPL dissolution rates and detoxification (i.e., ethene formation) is lacking. A recent column study demonstrated a 5-fold cumulative enhancement in tetrachloroethene (PCE) dissolution and ethene formation (Amos et al., 2009). Spatial and temporal monitoring of key geochemical and microbial (i.e., Geobacter lovleyi and Dehalococcoides mccartyi strains) parameters in the column generated a data set used herein as the basis for refinement and testing of a multiphase, compositional transport model. The refined model is capable of simulating the reactive transport of multiple chemical constituents produced and consumed by organohalide-respiring bacteria and accounts for substrate limitations and competitive inhibition. Parameter estimation techniques were used to optimize the values of sensitive microbial kinetic parameters, including maximum utilization rates, biomass yield coefficients, and endogenous decay rates. Comparison and calibration of model simulations with the experimental data demonstrate that the model is able to accurately reproduce measured effluent concentrations, while delineating trends in dechlorinator growth and reductive dechlorination kinetics along the column. Sensitivity analyses performed on the optimized model parameters indicate that the rates of PCE and cis-1,2-dichloroethene (cis-DCE) transformation and Dehalococcoides growth govern bioenhanced dissolution, as long as electron donor (i.e., hydrogen flux) is not limiting. Dissolution enhancements were shown to be independent of cis-DCE accumulation; however, accumulation of cis-DCE, as well as column length and flow rate (i.e., column residence time

Assessing the effect of dissolved organic ligands on mineral dissolution rates: An example from calcite dissolution

International Nuclear Information System (INIS)

DeMaio, T.; Grandstaff, D.E.

1997-01-01

Experiments suggest that dissolved organic ligands may primarily modify mineral dissolution rates by three mechanisms: (1) metal-ligand (M-L) complex formation in solution, which increases the degree of undersaturation, (2) formation of surface M-L complexes that attack the surface, and (3) formation of surface complexes which passivate or protect the surface. Mechanisms (1) and (2) increase the dissolution rate and the third decreases it compared with organic-free solutions. The types and importance of these mechanisms may be assessed from plots of dissolution rate versus degree of undersaturation. To illustrate this technique, calcite, a common repository cementing and vein-filling mineral, was dissolved at pH 7.8 and 22 C in Na-Ca-HCO 3 -Cl solutions with low concentrations of three organic ligands. Low citrate concentrations (50 microM) increased the dissolution rate consistent with mechanism (1). Oxalate decreased the rate, consistent with mechanism (3). Low phthalate concentration (<50 microM) decreased calcite dissolution rates; however, higher concentrations increased the dissolution rates, which became faster than in inorganic solutions. Thus, phthalate exhibits both mechanisms (2) and (3) at different concentrations. In such cases linear extrapolations of dissolution rates from high organic ligand concentrations may not be valid

Limits to depletion of blue-green light stimulated luminescence in feldspars: Implications for quartz dating

DEFF Research Database (Denmark)

Jain, M.; Singhvi, A.K.

2001-01-01

stimulation curve of otherwise pure quartz. In this study, the functional relationship between the infra-red stimulated luminescence (IRSL) and BGSL of feldspars, (1) at different preheats, and (2) with IR bleaching at different stimulation temperatures and durations, is examined. The results suggest two trap...

Development and validation of spectrophotometric method for assay determination and in vitro dissolution studies of sofosbuvir tablets

International Nuclear Information System (INIS)

Zaman, B.; Hassan, W.; Noreen, H.

2017-01-01

In vitro dissolution of sofosbuvir 400 mg tablets dosage form was performed, using USP dissolution apparatus type-II (paddle type), at 75rpm ± 4 %, and 900mL ± 1%, 0.05 M phosphate buffer pH 6.8 ± 0.05 equilibrated at 37.0 ± 0.5ºC as dissolution medium. Percentage of dissolved sofosbuvir as a function of time was determined using the straight line equation and linear regression using zero order and first order ANOVA based kinetics model. Comparative dissolution studies on two different generic brands A and B was performed comparing the drug release profile with innovator brand Sovaldi 400 mg tablets. The comparison of dissolution profiles was evaluated using model independent approach. The values of similarity factor f2 were (4 and 3) and the difference factor f1 were (64 and 50) for both generic products A and B respectively. A simple and precise spectrophotometric method was developed for estimation of sofosbuvir in dissolution medium based on spectrophotometric detection at wavelength 262 nm. The specific absorbance (A = 1%) of sofosbuvir was 178.5 ± 4% and Beer’s law was obeyed in the concentration ranges 4µg mL−1 to 48µg mL−1. The method was validated appropriately for accuracy, precision, linearity, and specificity, according the guidelines of United State Pharmacopoeia and International Conference on Harmonization. The calibration curve was linear with correlation coefficient (r > 0.9999) and there was no spectral interference from excipients present in the tablets dosage form. This method is precise, rapid and specific for determination of sofosbuvir in tablets dosage form and successfully applied for assay determination and in vitro dissolution studies. (author)

Studies of dissolution solutions of ruthenium metal, oxide and mixed compounds in nitric acid

International Nuclear Information System (INIS)

Mousset, F.; Eysseric, C.; Bedioui, F.

2004-01-01

Ruthenium is one of the fission products generated by irradiated nuclear fuel. It is present throughout all the steps of nuclear fuel reprocessing-particularly during extraction-and requires special attention due to its complex chemistry and high βγ activity. An innovative electro-volatilization process is now being developed to take advantage of the volatility of RuO 4 in order to eliminate it at the head end of the Purex process and thus reduce the number of extraction cycles. Although the process operates successfully with synthetic nitrato-RuNO 3+ solutions, difficulties have been encountered in extrapolating it to real-like dissolution solutions. In order to better approximate the chemical forms of ruthenium found in fuel dissolution solutions, kinetic and speciation studies on dissolved species were undertaken with RuO 2 ,xH 2 O and Ru 0 in nitric acid media. (authors)

Stability of IRSL signals from sedimentary K-feldspar samples

DEFF Research Database (Denmark)

Thomsen, Kristina Jørkov; Murray, A.S.; Jain, Mayank

2011-01-01

for potassium-rich sedimentary feldspars. We show that the natural post-IR IRSL (pIRIR) signal from a 3.6 Ma old sample is in apparent saturation on a laboratory generated dose response curve, i.e. it does not show detectable fading in nature although a low fading rate is observed on laboratory time scales. We...... be explained in terms of either a single- or multiple-trap model. We present evidence that may suggest that at least part of pIRIR signal is derived from a high temperature trap (∼550°C thermoluminescence (TL) peak), although again the data can also be explained in terms of a single-trap model. Finally, we...

Dissolution process for advanced-PWR-type fuels

International Nuclear Information System (INIS)

Black, D.E.; Decker, L.A.; Pearson, L.G.

1979-01-01

The new Fluorinel Dissolution Process and Fuel Storage (FAST) Facility at ICPP will provide underwater storage of spent PWR fuel and a new head-end process for fuel dissolution. The dissolution will be two-stage, using HF and HNO 3 , with an intermittent H 2 SO 4 dissolution for removing stainless steel components. Equipment operation is described

Affinity functions for modeling glass dissolution rates

Energy Technology Data Exchange (ETDEWEB)

Bourcier, W.L. [Lawrence Livermore National Lab., CA (United States)

1997-07-01

Glass dissolution rates decrease dramatically as glass approach ''saturation'' with respect to the leachate solution. Most repository sites are chosen where water fluxes are minimal, and therefore the waste glass is most likely to dissolve under conditions close to ''saturation''. The key term in the rate expression used to predict glass dissolution rates close to ''saturation'' is the affinity term, which accounts for saturation effects on dissolution rates. Interpretations of recent experimental data on the dissolution behaviour of silicate glasses and silicate minerals indicate the following: 1) simple affinity control does not explain the observed dissolution rate for silicate minerals or glasses; 2) dissolution rates can be significantly modified by dissolved cations even under conditions far from saturation where the affinity term is near unity; 3) the effects of dissolved species such as Al and Si on the dissolution rate vary with pH, temperature, and saturation state; and 4) as temperature is increased, the effect of both pH and temperature on glass and mineral dissolution rates decrease, which strongly suggests a switch in rate control from surface reaction-based to diffusion control. Borosilicate glass dissolution models need to be upgraded to account for these recent experimental observations. (A.C.)

Plant-Level Modeling and Simulation of Used Nuclear Fuel Dissolution

Energy Technology Data Exchange (ETDEWEB)

de Almeida, Valmor F. [Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States)

2012-09-07

for the dissolver device; this simulation is currently at reach for computational fluid mechanics given the existing CAD geometry. From chemical transport phenomena, a simulation of the particle-scale dissolution front is needed to derive an improved solid dissolution kinetics law by predicting the local surface area change; an example was provided in this report. In addition, the associated reaction mechanisms for dissolution are presently largely untested and simplified, hence even a parallel experimental program in reaction kinetics is needed to support modeling and simulation efforts. Last but not least, a simple account of finite rates of solid feed and transfer can be readily introduced via a coupled delayed model. These are some of the theoretical benefits of a rational plant-level modeling approach which guides the development of smaller length and time scale modeling. Practical, and other theoretical benefits have been presented on a previous report.

Dissolution glow curve in LLD

International Nuclear Information System (INIS)

Haverkamp, U.; Wiezorek, C.; Poetter, R.

1990-01-01

Lyoluminescence dosimetry is based upon light emission during dissolution of previously irradiated dosimetric materials. The lyoluminescence signal is expressed in the dissolution glow curve. These curves begin, depending on the dissolution system, with a high peak followed by an exponentially decreasing intensity. System parameters that influence the graph of the dissolution glow curve, are, for example, injection speed, temperature and pH value of the solution and the design of the dissolution cell. The initial peak does not significantly correlate with the absorbed dose, it is mainly an effect of the injection. The decay of the curve consists of two exponential components: one fast and one slow. The components depend on the absorbed dose and the dosimetric materials used. In particular, the slow component correlates with the absorbed dose. In contrast to the fast component the argument of the exponential function of the slow component is independent of the dosimetric materials investigated: trehalose, glucose and mannitol. The maximum value, following the peak of the curve, and the integral light output are a measure of the absorbed dose. The reason for the different light outputs of various dosimetric materials after irradiation with the same dose is the differing solubility. The character of the dissolution glow curves is the same following irradiation with photons, electrons or neutrons. (author)

Modeling of the shape of infrared stimulated luminescence signals in feldspars

DEFF Research Database (Denmark)

Pagonis, Vasilis; Jain, Mayank; Murray, Andrew S.

2012-01-01

This paper presents a new empirical model describing infrared (IR) stimulation phenomena in feldspars. In the model electrons from the ground state of an electron trap are raised by infrared optical stimulation to the excited state, and subsequently recombine with a nearest-neighbor hole via...... corresponds to a fast rate of recombination processes taking place along the infrared stimulated luminescence (IRSL) curves. The subsequent decay of the simulated IRSL signal is characterized by a much slower recombination rate, which can be described by a power-law type of equation.Several simulations...

Dissolution characteristics of chalcedony under alkaline condition. Study for changes in mineral composition of engineered barrier composed by bentonite

International Nuclear Information System (INIS)

Watanabe, Yasutaka; Yokoyama, Shingo

2016-01-01

In the engineered barrier of radioactive waste disposal facilities, it is expected that bentonite is exposed to alkaline groundwater which arise from leaching of cementations materials. Minerals contained in the bentonite will be dissolved by reactions of the alkaline groundwater. Some bentonite contains silica such as quartz and chalcedony. Chalcedony is categorized in intermediate silica which is microcrystalline. It is known that dissolution of silica influences to the dissolution of smectite by means of solubility. However, dissolution kinetics of chalcedony in the alkaline condition has not been investigated, which is an uncertainty in geochemical simulations to evaluate a long-term stability of the engineered barrier. Therefore, this study performed flow-through experiments in alkaline conditions using chalcedony in order to obtain the dissolution rate of the chalcedony. The flow-through experiments was performed using NaOH-NaCl solution adjusted to 0.3 mol/L of ionic strength. Initial pH of the solution was from 8.9 to 13.5. As a result, higher pH and higher temperature showed higher Si ion concentrations of reacted solutions. The dissolution rate of the samples was calculated using Si ion concentrations at steady state of the experiment. Note that, the dissolution rate of the chalcedony was almost same as that of quartz at same temperature. After the experiments, SEM observation showed that rough surface of the chalcedony partly changed to smooth surface like quartz. It is supposed that rough surface of chalcedony was rapidly dissolved because of low degree of crystallization. The dissolution rate obtained is supposedly applicable to highly crystalline SiO 2 of chalcedony. (author)

The study of photo-and thermally-induced diffusion and dissolution of Af in As30S70 amorphous films and its reastion products

Czech Academy of Sciences Publication Activity Database

Wágner, T.; Macková, Anna; Peřina, Vratislav; Rauhala, E.; Seppälä, A.; Kasap, S. O.; Frumar, M.; Vlček, M.

2002-01-01

Roč. 299, č. 1 (2002), s. 1028-1032 ISSN 0022-3093 R&D Projects: GA ČR GP102/01/D069 Keywords : state chemical-reaction * photoenhanced dissolution * kinetics * backscattering * layers * glass Subject RIV: BM - Solid Matter Physics ; Magnetism Impact factor: 1.435, year: 2002

The use of commercial microwave dissolution equipment for the fast and reliable dissolution of high-fired POX and MOX samples

International Nuclear Information System (INIS)

Tushingham, J.; McInnes, C.; Firkin, S.

1998-09-01

The use of commercially available microwave dissolution equipment for the fast and reliable dissolution of high-fired plutonium dioxide (POX) and mixed oxide (MOX) samples has been evaluated for application to Safeguards Analysis. Under the auspices of the UK R and D Support Programme to the IAEA, equipment has been purchased and tested for the high-pressure microwave dissolution of POX samples fired to 1250 deg. C and MOX samples fired to 1600 deg. C, in concentrated nitric acid and hydrofluoric acid mixture. Considerable problems were encountered during development of procedures for microwave dissolution, resulting largely from sudden changes in pressure within dissolution vessels, which resulted in actuation of safety interlocks designed to prevent overpressurisation. These difficulties were alleviated by controlling the microwave power to reduce the reaction temperature and pressure, and also by introducing additional safety valves into the digestion vessels. Using microwave digestion, dissolution times for high fired POX and MOX samples were substantially reduced. Samples which required ca. 10 hours to dissolve by conventional means could be dissolved in ca. 80 minutes by microwave digestion. Whilst a similar performance in terms of plutonium recovery was achieved for some materials by microwave and conventional dissolution, for other materials microwave dissolution gave higher plutonium recoveries but with poorer precision. This suggests the possible presence of some plutonium oxide within high-fired materials which is more difficult to dissolve than the bulk, and which is perhaps dissolved to an additional but variable degree by the current microwave dissolution procedure. Microwave dissolution has been demonstrated to increase the speed of dissolution of high-fired POX and MOX materials, compared with conventional dissolution. However, the technique has not yet proved satisfactory for the complete dissolution of all high-fired materials tested because of

Effect of hydrophobic inclusions on polymer swelling kinetics studied by magnetic resonance imaging.

Science.gov (United States)

Gajdošová, Michaela; Pěček, Daniel; Sarvašová, Nina; Grof, Zdeněk; Štěpánek, František

2016-03-16

The rate of drug release from polymer matrix-based sustained release formulations is often controlled by the thickness of a gel layer that forms upon contact with dissolution medium. The effect of formulation parameters on the kinetics of elementary rate processes that contribute to gel layer formation, such as water ingress, polymer swelling and erosion, is therefore of interest. In the present work, gel layer formation has been investigated by magnetic resonance imaging (MRI), which is a non-destructive method allowing direct visualization of effective water concentration inside the tablet and its surrounding. Using formulations with Levetiracetam as the active ingredient, HPMC as a hydrophilic matrix former and carnauba wax (CW) as a hydrophobic component in the matrix system, the effect of different ratios of these two ingredients on the kinetics of gel formation (MRI) and drug release (USP 4 like dissolution test) has been investigated and interpreted using a mathematical model. Copyright © 2016 Elsevier B.V. All rights reserved.

Self irradiation effects on the thorium phosphate diphosphate dissolution (TPD): simulation by external irradiations

International Nuclear Information System (INIS)

Tamain, C.; Ozgumus, A.; Dacheux, N.; Garrido, F.; Thome, L.; Corbel, C.; Genet, M.

2004-01-01

The Thorium Phosphate Diphosphate (TPD), proposed as a ceramic for the long term immobilization of actinides, was externally irradiated with several ions and energies (but also with gamma rays) in order to simulate the self-irradiation. The influence of the electronic energy loss was first investigated. Thus, the XRD measurements have shown a complete amorphization of the material under 10 13 ions of Kr.cm -2 , while no significant structural change occurred after 5.10 13 S.cm -2 , 2.10 16 He.cm -2 or 320 kGy of dose of gamma rays. The dissolution of the raw and irradiated pellets was studied versus several parameters such as amorphized fraction, energy loss of incident ions, radiolytic species produced in situ in the leachate during irradiation (such as H 2 O 2 ), temperature and acidity. The results reveal an important increase of the dissolution kinetics for amorphized pellets compared to raw ceramic. (authors)

Development of Dissolution Test Method for Drotaverine ...

African Journals Online (AJOL)

Development of Dissolution Test Method for Drotaverine ... Methods: Sink conditions, drug stability and specificity in different dissolution media were tested to optimize a dissolution test .... test by Prism 4.0 software, and differences between ...

Mechanistic Basis of Cocrystal Dissolution Advantage.

Science.gov (United States)

Cao, Fengjuan; Amidon, Gordon L; Rodríguez-Hornedo, Naír; Amidon, Gregory E

2018-01-01

Current interest in cocrystal development resides in the advantages that the cocrystal may have in solubility and dissolution compared with the parent drug. This work provides a mechanistic analysis and comparison of the dissolution behavior of carbamazepine (CBZ) and its 2 cocrystals, carbamazepine-saccharin (CBZ-SAC) and carbamazepine-salicylic acid (CBZ-SLC) under the influence of pH and micellar solubilization. A simple mathematical equation is derived based on the mass transport analyses to describe the dissolution advantage of cocrystals. The dissolution advantage is the ratio of the cocrystal flux to drug flux and is defined as the solubility advantage (cocrystal to drug solubility ratio) times the diffusivity advantage (cocrystal to drug diffusivity ratio). In this work, the effective diffusivity of CBZ in the presence of surfactant was determined to be different and less than those of the cocrystals. The higher effective diffusivity of drug from the dissolved cocrystals, the diffusivity advantage, can impart a dissolution advantage to cocrystals with lower solubility than the parent drug while still maintaining thermodynamic stability. Dissolution conditions where cocrystals can display both thermodynamic stability and a dissolution advantage can be obtained from the mass transport models, and this information is useful for both cocrystal selection and formulation development. Copyright © 2018 American Pharmacists Association®. Published by Elsevier Inc. All rights reserved.

Crystallization kinetics of the borax decahydrate

Science.gov (United States)

Ceyhan, A. A.; Sahin, Ö.; Bulutcu, A. N.

2007-03-01

The growth and dissolution rates of borax decahydrate have been measured as a function of supersaturation for various particle sizes at different temperature ranges of 13 and 50 °C in a laboratory-scale fluidized bed crystallizer. The values of mass transfer coefficient, K, reaction rate constant, kr and reaction rate order, r were determined. The relative importances of diffusion and integration resistance were described by new terms named integration and diffusion concentration fraction. It was found that the overall growth rate of borax decahydrate is mainly controlled by integration (reaction) steps. It was also estimated that the dissolution region of borax decahydrate, apart from other materials, is controlled by diffusion and surface reaction. Increasing the temperature and particle size cause an increase in the values of kinetic parameters ( Kg, kr and K). The activation energies of overall, reaction and mass transfer steps were determined as 18.07, 18.79 and 8.26 kJmol -1, respectively.

Kinetic and thermodynamic modelling of geochemical effects of a nuclear waste storage in granitic environment

International Nuclear Information System (INIS)

Made, B.; Fritz, B.

1993-01-01

In the world, various experimental sites are selected to study the behavior of different types of source rocks under nuclear waste storage influence. The surrounding rock tested to receive the waste storage must be a stable geological formation. In France, four geological formations are preselected for the feasibility study of repository for spent nuclear fuel at long term: shale, salt, clay and granite. At present time, numerous studies are carried out in Europe (Germany, Belgium, Sweden, Switzerland, United-Kingdom...), in North America (U.S.A. and Canada) and in Japan. Water-rock interactions control the most of rock transformations near the surface of the earth. The rock forming minerals react with the aqueous solutions, the primary minerals dissolution releases ionic species in solution and secondary minerals precipitate if equilibrium or oversaturation is reached. The weathering processes (hydrothermal or not) are always very complicated thus, geochemical codes has been developed to simulate the water-rock interactions. The first generation of codes is based on purely thermodynamic laws without reference to the time dependence of chemical reactions and then the dissolution path calculation refer to the irreversible dissolution of reactants and reversible precipitation of products ([1] to [4]). The system evolution is followed according to the reaction progress ξ which has been introduced in chemical system by Gibbs. Since few years, the experimental studies on the kinetics of minerals dissolution have allowed to take into account of dissolution rates data for the major minerals (silicates, carbonates...). More recently, a new geochemical codes generation appears based on thermodynamic potential and kinetic laws ([5] to [8]). The system evolution is followed according to the reaction time. (authors). 8 figs., 4 tabs., 24 refs

Hydroxylamine a potential reagent for dissolution off gas scrubbing in nuclear spent fuel reprocessing: kinetics of the iodine reduction

International Nuclear Information System (INIS)

Cau Dit Coumes, C.; Devisme, F.; Chopin, J.; Vargas, S.

1996-01-01

Iodine, which can be released inside the containment buildings when accident occurs, can be traced, in normal operating conditions, at the back end of the fuel cycle. Hydroxylamine has been selected as a regent of potential interest to trap iodine in the dissolution off gas treatment. The kinetics of the reaction between hydroxylamine and iodine has been studied in a narrow range of pH(1-2), with hydroxylamine in excess (ratios of hydroxylamine to iodine initial concentrations varying from 2 to 40), at constant temperature (30 deg. C) and ionic strength (0.1 mol/l). Spectrophotometry and voltametry have been coupled for analytical solved using a investigation. The problem of the rapid mixing of the reactants has been solved using a continuous reactor. Tri-iodine has been shown non reactive towards hydroxylamine. An initial rate law have been proposed, pointing out the first order of the reaction with respect to hydroxylamine and iodine, and the inhibitory effect and hydrogen ions. Nitrous acid has been identified as a transitory product. Nitrous oxide and nitrogen monoxide have been detected by gas chromatography, the ratio of the amounts of products formed depending on acidity. The complexity of the overall reaction has been ascribed to the competition of hour reactions (I 2 + I I 3 - NH 3 OH + + 2 I 2 + H 2 O ->HNO 2 + 4 I - + 5 H + ; NH 3 OH + + HNO 2 -> N 2 O + 2 H 2 O + H-+ 2HNO 2 + 2 I - + 2H-+ -> 2 NO + I 2 + H 2 O). (authors)

Estimate of long-term dissolution rate of basaltic glass. A case study on Mt. Fuji area

International Nuclear Information System (INIS)

Shikazono, Naotatsu; Takino, Akitsugu

2002-01-01

Bulk compositional, mineralogical and physical properties of weathered basaltic ash soil ('Andisol') derived mainly from Mt. Fuji were studied. Mineralogical studies revealed that the dominant primary material and weathering products are volcanic glass, allophane and halloysite and the sequence of weathering is volcanic glass → allophane → 10A halloysite → 7A halloysite. X-ray fluorescence analysis indicates that the relative elemental mobilities during the weathering is Na, Ca>K>Mg>P>Si>Ti, Fe>Al>Mn. The trends of soilwater chemistry (H 4 SiO 4 concentration) with depth were calculated based on dissolution - precipitation kinetics - fluid flow coupling model. In order to calculate the trends, the data on present-day annual rainfall, solubility of basalt glass, porosity and specific weight of soil, deposition rate of volcanic ash and grain size of volcanic glass were used. The calculated results were compared with analytical trends of soilwater chemistry. From this comparison the dissolution rate constant of basalt glass was estimated to be 10 -9.4 - 10 -9.2 (mole Si m -2 s -1 ). This value is consistent with previous experimental dissolution rate constant of basalt glass reported in the literature. (author)

Studies on dissolution enhancement and mathematical modeling of drug release of a poorly water-soluble drug using water-soluble carriers.

Science.gov (United States)

Ahuja, Naveen; Katare, Om Prakash; Singh, Bhupinder

2007-01-01

Role of various water-soluble carriers was studied for dissolution enhancement of a poorly soluble model drug, rofecoxib, using solid dispersion approach. Diverse carriers viz. polyethylene glycols (PEG 4000 and 6000), polyglycolized fatty acid ester (Gelucire 44/14), polyvinylpyrollidone K25 (PVP), poloxamers (Lutrol F127 and F68), polyols (mannitol, sorbitol), organic acid (citric acid) and hydrotropes (urea, nicotinamide) were investigated for the purpose. Phase-solubility studies revealed AL type of curves for each carrier, indicating linear increase in drug solubility with carrier concentration. The sign and magnitude of the thermodynamic parameter, Gibbs free energy of transfer, indicated spontaneity of solubilization process. All the solid dispersions showed dissolution improvement vis-à-vis pure drug to varying degrees, with citric acid, PVP and poloxamers as the most promising carriers. Mathematical modeling of in vitro dissolution data indicated the best fitting with Korsemeyer-Peppas model and the drug release kinetics primarily as Fickian diffusion. Solid state characterization of the drug-poloxamer binary system using XRD, FTIR, DSC and SEM techniques revealed distinct loss of drug crystallinity in the formulation, ostensibly accounting for enhancement in dissolution rate.

Infrared stimulated luminescence dating of an Eemian (MIS 5e) site in Denmark using K-feldspar

DEFF Research Database (Denmark)

Buylaert, Jan-Pieter; Huot, Sebastian; Murray, Andrew S.

2011-01-01

Infrared stimulated luminescence (IRSL) dating of K-feldspars may be an alternative to quartz optically stimulated luminescence (OSL) dating when the quartz OSL signal is too close to saturation or when the quartz luminescence characteristics are unsuitable. In this paper, Eemian (MIS 5e) coastal...

Accelerated dissolution of iron oxides in ice

Directory of Open Access Journals (Sweden)

D. Jeong

2012-11-01

Full Text Available Iron dissolution from mineral dusts and soil particles is vital as a source of bioavailable iron in various environmental media. In this work, the dissolution of iron oxide particles trapped in ice was investigated as a new pathway of iron supply. The dissolution experiments were carried out in the absence and presence of various organic complexing ligands under dark condition. In acidic pH conditions (pH 2, 3, and 4, the dissolution of iron oxides was greatly enhanced in the ice phase compared to that in water. The dissolved iron was mainly in the ferric form, which indicates that the dissolution is not a reductive process. The extent of dissolved iron was greatly affected by the kind of organic complexing ligands and the surface area of iron oxides. The iron dissolution was most pronounced with high surface area iron oxides and in the presence of strong iron binding ligands. The enhanced dissolution of iron oxides in ice is mainly ascribed to the "freeze concentration effect", which concentrates iron oxide particles, organic ligands, and protons in the liquid like ice grain boundary region and accelerates the dissolution of iron oxides. The ice-enhanced dissolution effect gradually decreased when decreasing the freezing temperature from −10 to −196 °C, which implies that the presence and formation of the liquid-like ice grain boundary region play a critical role. The proposed phenomenon of enhanced dissolution of iron oxides in ice may provide a new pathway of bioavailable iron production. The frozen atmospheric ice with iron-containing dust particles in the upper atmosphere thaws upon descending and may provide bioavailable iron upon deposition onto the ocean surface.

Kinetic Rate Law Parameter Measurements on a Borosilicate Waste Glass: Effect of Temperature, pH, and Solution Composition on Alkali Ion Exchange

International Nuclear Information System (INIS)

Pierce, Eric M.; McGrail, B PETER.; Icenhower, J P.; Rodriguez, Elsa A.; Steele, Jackie L.; Baum, Steven R.

2004-01-01

The reaction kinetics of glass is controlled by matrix dissolution and ion exchange (IEX). Dissolution of an alkali-rich simulated borosilicate waste glass was investigated using single-pass flow-through (SPFT) experiments. Experiments were conducted as a function of temperature, pH, and solution composition by varying the SiO 2 (aq) activity in the influent solution. Results showed that under dilute conditions matrix dissolution increased with increasing pH and temperature, and decreased with increasing SiO 2 (aq) activity. IEX rates decreased with increasing pH and temperature, and increased with increasing SiO 2 (aq) activity. Over the solution composition range interrogated in this study the dominant dissolution mechanism changed from matrix dissolution to IEX. These results suggest that ''secondary'' reactions may become dominant under certain environmental conditions and emphasize the need to incorporate these reactions into dissolution rate models

In vitro dissolution methodology, mini-Gastrointestinal Simulator (mGIS), predicts better in vivo dissolution of a weak base drug, dasatinib.

Science.gov (United States)

Tsume, Yasuhiro; Takeuchi, Susumu; Matsui, Kazuki; Amidon, Gregory E; Amidon, Gordon L

2015-08-30

USP apparatus I and II are gold standard methodologies for determining the in vitro dissolution profiles of test drugs. However, it is difficult to use in vitro dissolution results to predict in vivo dissolution, particularly the pH-dependent solubility of weak acid and base drugs, because the USP apparatus contains one vessel with a fixed pH for the test drug, limiting insight into in vivo drug dissolution of weak acid and weak base drugs. This discrepancy underscores the need to develop new in vitro dissolution methodology that better predicts in vivo response to assure the therapeutic efficacy and safety of oral drug products. Thus, the development of the in vivo predictive dissolution (IPD) methodology is necessitated. The major goals of in vitro dissolution are to ensure the performance of oral drug products and the support of drug formulation design, including bioequivalence (BE). Orally administered anticancer drugs, such as dasatinib and erlotinib (tyrosine kinase inhibitors), are used to treat various types of cancer. These drugs are weak bases that exhibit pH-dependent and high solubility in the acidic stomach and low solubility in the small intestine (>pH 6.0). Therefore, these drugs supersaturate and/or precipitate when they move from the stomach to the small intestine. Also of importance, gastric acidity for cancer patients may be altered with aging (reduction of gastric fluid secretion) and/or co-administration of acid-reducing agents. These may result in changes to the dissolution profiles of weak base and the reduction of drug absorption and efficacy. In vitro dissolution methodologies that assess the impact of these physiological changes in the GI condition are expected to better predict in vivo dissolution of oral medications for patients and, hence, better assess efficacy, toxicity and safety concerns. The objective of this present study is to determine the initial conditions for a mini-Gastrointestinal Simulator (mGIS) to assess in vivo

IR-RF dating of sand-sized K-feldspar extracts: A test of accuracy

DEFF Research Database (Denmark)

Buylaert, Jan-Pieter; Jain, Mayank; Murray, A.S.

2012-01-01

In this paper we use a recently developed radioluminescence (RL) attachment to the Risø TL/OSL reader to test the InfraRed-RadioFluorescence (IR-RF) dating method applied to K-feldspar rich extracts from our known-age archive samples. We present experiments to characterise the instrument performa......In this paper we use a recently developed radioluminescence (RL) attachment to the Risø TL/OSL reader to test the InfraRed-RadioFluorescence (IR-RF) dating method applied to K-feldspar rich extracts from our known-age archive samples. We present experiments to characterise the instrument...... performance and to test the reproducibility of IR-RF measurements. These experiments illustrate the high sensitivity and dose rate of our RL system, the negligible influence of the turntable movement on IR-RF signals and the effectiveness of the built in 395 nm LED at bleaching IR-RF signals. We measure IR......-RF ages on a set of samples with independent age control using a robust analytical method, which is able to detect any possible sensitivity change. Our IR-RF ages do not agree well with the independent age control; the ages of the younger samples (20–45 ka) are significantly over-estimated while the ages...

Dissolution characteristics of mixed UO2 powders in J-13 water under saturated conditions

International Nuclear Information System (INIS)

Veleckis, E.; Hoh, J.C.

1991-03-01

The Yucca Mountain Project/Spent Fuel program at Argonne National Laboratory is designed to determine radionuclide release rates by exposing high-level waste to repository-relevant groundwater. To gain experience for the tests with spent fuel, a scoping experiment was conducted at room temperature to determine the uranium release rate from an unirradiated UO 2 powder mixture (14.3 wt % enrichment in 235 U) to J-13 water under saturated conditions. Another goal set for the experiment was to develop a method for utilizing isotope dilution techniques to determine whether the dissolution rate of UO 2 matrix is in accordance with an existing kinetic model. Results of these analyses revealed unequal uranium dissolution rates from the enriched and depleted portions of the powder mixture because of undisclosed differences between them. Although the presence of this inhomogeneity has precluded the application of the kinetic model, it also provided an opportunity to elaborate on the utilization of isotope dilution data in recognizing and quantifying such conditions. Detailed listings of uranium release and solution chemistry data are presented. Other problems commonly associated with spent fuel, such as the effectiveness of filtering media, the existence of uranium concentration peaks during early stages of the leach tests, the need for concentration corrections due to water replenishments of sample volumes, and experience derived from isotope dilution data are discussed in the context of the present results. 10 refs., 5 figs., 7 tabs

Reactivity of Nanoscale Zero-Valent Iron in Unbuffered Systems: Effect of pH and Fe(II) Dissolution.

Science.gov (United States)

Bae, Sungjun; Hanna, Khalil

2015-09-01

While most published studies used buffers to maintain the pH, there is limited knowledge regarding the reactivity of nanoscale zerovalent iron (NZVI) in poorly buffered pH systems to date. In this work, the effect of pH and Fe(II) dissolution on the reactivity of NZVI was investigated during the reduction of 4-nitrophenol (4-NP) in unbuffered pH systems. The reduction rate increased exponentially with respect to the NZVI concentration, and the ratio of dissolved Fe(II)/initial NZVI was related proportionally to the initial pH values, suggesting that lower pH (6-7) with low NZVI loading may slow the 4-NP reduction through acceleration of the dissolution of NZVI particles. Additional experiments using buffered pH systems confirmed that high pH values (8-9) can preserve the NZVI particles against dissolution, thereby enhancing the reduction kinetics of 4-NP. Furthermore, reduction tests using ferrous ion in suspensions of magnetite and maghemite showed that surface-bound Fe(II) on oxide coatings can play an important role in enhancing 4-NP reduction by NZVI at pH 8. These unexpected results highlight the importance of pH and Fe(II) dissolution when NZVI technology is applied to poorly buffered systems, particularly at a low amount of NZVI (i.e., <0.075 g/L).

Development of cataclastic foliation in deformation bands in feldspar-rich conglomerates of the Rio do Peixe Basin, NE Brazil

Science.gov (United States)

Nicchio, Matheus A.; Nogueira, Francisco C. C.; Balsamo, Fabrizio; Souza, Jorge A. B.; Carvalho, Bruno R. B. M.; Bezerra, Francisco H. R.

2018-02-01

In this work we describe the deformation mechanisms and processes that occurred during the evolution of cataclastic deformation bands developed in the feldspar-rich conglomerates of the Rio do Peixe Basin, NE Brazil. We studied bands with different deformation intensities, ranging from single cm-thick tabular bands to more evolved clustering zones. The chemical identification of cataclastic material within deformation bands was performed using compositional mapping in SEM images, EDX and XRD analyses. Deformation processes were identified by microstructural analysis and by the quantification of comminution intensity, performed using digital image processing. The deformation bands are internally non homogeneous and developed during five evolutionary stages: (1) moderate grain size reduction, grain rotation and grain border comminution; (2) intense grain size reduction with preferential feldspar fragmentation; (3) formation of subparallel C-type slip zones; (4) formation of S-type structures, generating S-C-like fabric; and (5) formation of C‧-type slip zones, generating well-developed foliation that resembles S-C-C‧-type structures in a ductile environment. Such deformation fabric is mostly imparted by the preferential alignment of intensely comminuted feldspar fragments along thin slip zones developed within deformation bands. These processes were purely mechanical (i.e., grain crushing and reorientation). No clays or fluids were involved in such processes.

Post-IR IRSL₂₉₀ dating of K-rich feldspar sand grains in a wind-dominated system on Sardinia

DEFF Research Database (Denmark)

Andreucci, S.; Sechi, D.; Buylaert, Jan-Pieter

2017-01-01

The reliability of a post-IR elevated temperature IRSL (290 °C; pIRIR290) is tested on wind-blown, sand-sized (180–250 μm) K-rich feldspar grains. The pIRIR290 ages were compared with quartz SAR-OSL data, other independent age controls and historical information. Three study areas along the coast....... The pIRIR290 ages indicate an offset up to ∼1000 years. We can conclude that the pIRIR290 method on sand-sized K-feldspar grains shows great promise for samples at or beyond the quartz OSL age limit but should not be applied to Late Holocene or modern deposits....

Dissolution of metallic uranium and its alloys. Part 1. Review of analytical and process-scale metallic uranium dissolution

International Nuclear Information System (INIS)

Laue, C.A.; Gates-Anderson, D.; Fitch, T.E.

2004-01-01

This review focuses on dissolution/reaction systems capable of treating uranium metal waste to remove its pyrophoric properties. The primary emphasis is the review of literature describing analytical and production-scale dissolution methods applied to either uranium metal or uranium alloys. A brief summary of uranium's corrosion behavior is included since the corrosion resistance of metals and alloys affects their dissolution behavior. Based on this review, dissolution systems were recommended for subsequent screening studies designed to identify the best system to treat depleted uranium metal wastes at Lawrence Livermore National Laboratory (LLNL). (author)

Kinetic and thermodynamic studies of uranium minerals. Assessment of the long-term evolution of spent nuclear fuel

Energy Technology Data Exchange (ETDEWEB)

Casas, I; Bruno, J; Cera, E [MBT Tecnologia Ambiental, Cerdanyola (Spain); Finch, R J; Ewing, R C [Department of Earth and Planetary Sciences, University of New Mexico, Albuquerque, NM (United States)

1994-10-01

We have studied the dissolution behavior of uraninite, becquerelite, schoepite and uranophane. The information obtained under a variety of experimental conditions has been combined with extensive solid phase characterizations, performed in both leached and unleached samples. The overall objective is to construct a thermodynamic and kinetic model for the long-term oxidation alteration of UO{sub 2}(s), as an analogy of the spent nuclear fuel matrix. We have determined the solubility product for becquerelite (logK{sub s0} 32.7{+-}1.3) and uranophane (logK{sub s0} = 7.8{+-}0.8). In some experiments, the reaction progress has shown initial dissolution of uranophane followed by precipitation of a secondary solid phase, characterized as soddyite. The solubility production for this phase has been determined (logK{sub s0} = 3.0{+-}2.9). We have studied the kinetics of dissolution of uraninite, uranophane and schoepite under oxidizing conditions in synthetic granitic groundwater. BET measurements have been performed for uraninite and uranophane. For schoepite, the measurement has not been performed due to lack of sufficient amount of sample. The normalized rates of dissolution of uraninite and uranophane have been calculated referred to the uranium release, as 1.97x10{sup -8} moles h{sup -1} m{sup -2} and 4.0x 10{sup -9} moles h{sup -1} m{sup -2}, respectively. For schoepite, the dissolution process has shown two different rates, with a relatively fast initial dissolution rate of 1.97x10{sup -8} moles h{sup -1} followed, after approximately 1000 hours, by a slower one of 1.4x10{sup -9} moles h{sup -1}. No formation of secondary phases has been observed in those experiments, although final uranium concentrations have in all cases exceeded the solubility of uranophane, the thermodynamically more stable phase under the experimental conditions. 24 refs, 45 figs.

Kinetic and thermodynamic studies of uranium minerals. Assessment of the long-term evolution of spent nuclear fuel

International Nuclear Information System (INIS)

Casas, I.; Bruno, J.; Cera, E.; Finch, R.J.; Ewing, R.C.

1994-10-01

We have studied the dissolution behavior of uraninite, becquerelite, schoepite and uranophane. The information obtained under a variety of experimental conditions has been combined with extensive solid phase characterizations, performed in both leached and unleached samples. The overall objective is to construct a thermodynamic and kinetic model for the long-term oxidation alteration of UO 2 (s), as an analogy of the spent nuclear fuel matrix. We have determined the solubility product for becquerelite (logK s0 32.7±1.3) and uranophane (logK s0 = 7.8±0.8). In some experiments, the reaction progress has shown initial dissolution of uranophane followed by precipitation of a secondary solid phase, characterized as soddyite. The solubility production for this phase has been determined (logK s0 = 3.0±2.9). We have studied the kinetics of dissolution of uraninite, uranophane and schoepite under oxidizing conditions in synthetic granitic groundwater. BET measurements have been performed for uraninite and uranophane. For schoepite, the measurement has not been performed due to lack of sufficient amount of sample. The normalized rates of dissolution of uraninite and uranophane have been calculated referred to the uranium release, as 1.97x10 -8 moles h -1 m -2 and 4.0x 10 -9 moles h -1 m -2 , respectively. For schoepite, the dissolution process has shown two different rates, with a relatively fast initial dissolution rate of 1.97x10 -8 moles h -1 followed, after approximately 1000 hours, by a slower one of 1.4x10 -9 moles h -1 . No formation of secondary phases has been observed in those experiments, although final uranium concentrations have in all cases exceeded the solubility of uranophane, the thermodynamically more stable phase under the experimental conditions. 24 refs, 45 figs

Dissolution of uranium oxide TBP-HNO3 complex

International Nuclear Information System (INIS)

Mizuno, Mineo; Kosaka, Yuji; Mori, Yukihide; Shimada, Takashi

2002-12-01

As a head end process for the pulverization of the spent fuel, the mechanical method (the shredder method) and the pyro-chemical method (oxidisation heat-treatment) have been examined. UO 2 is a main ingredient of Uranium oxide powder by the mechanical method, and U 3 O 8 is that by the pyro-chemical method. Moreover, the particle size of the pulverized powder depend on the conditions of the pulverizing process. As it was considered that the difference of dissolution rates of samples was caused by the difference of sample chemical forms and dissolution temperature, parametric surveys on chemical form and particle size of powder and dissolution temperature were carried out, and the following results were obtained. 1) The remarkable difference of dissolution rate between U 3 O 8 powder (average particle size 3.7 μm) and UO 2 powder (average particle size 2.4 μm) which have comparatively similar particle size was not observed. 2) It was confirmed that the dissolution rate became lower according to the particle size increase (average particle size 2.4 μm-1 mm). And it was considered that dissolution rate had strong dependency on particle size, according to the results that the powder with 1 mm particle size did not dissolute completely after 5 hours test. 3) The temperature dependency of the dissolution rate was confirmed by dissolution test with UO 2 powder (average particle size 2.4 μm-1 mm). The higher dissolution rate was obtained in the higher dissolution temperature, and 11 kcal/mol was obtained as activation energy of dissolution. 4) In the dissolution test of UO 2 powder, the nitric acid concentration started to change earlier than that of U 3 O 8 powder and concentration change range became larger compared with that in the dissolution test of U 3 O 8 powder. It was considered that those differences were caused by difference in mole ratio of Uranium and nitric acid which are consumed in the dissolution reaction (3:7 for U 3 O 8 , 3:8 for UO 2 ). 5) In case

Dissolution rate enhancement of piroxicam by ordered mixing.

Science.gov (United States)

Saharan, Vikas Anand; Choudhury, Pratim Kumar

2012-07-01

Micronized piroxicam was mixed with lactose, mannitol, sorbitol, maltitol and sodium chloride to produce ordered mixture in a glass vial by manual hand shaking method. The effect of excipients, surfactant, superdisintegrant, drug concentration and carrier particle size on dissolution rate was investigated. Dissolution rate studies of the prepared ordered mixtures revealed that all water soluble excipients increased the dissolution rate of piroxicam when compared to the dissolution rate of piroxicam or its suspension. Ordered mixture formulation PLF4, consisting of lactose as water soluble excipient, SSG (8% w/s) and SLS (1% w/w), released piroxcam at a very fast rate so much so that about 90% of the composition had passed into solution within 2 min. The order of the dissolution rate enhancement for ordered mixtures of various water soluble excipients was: lactose > mannitol > maltitol > sorbitol > sodium chloride. Carrier granules of size 355-710 µm were most effective in increasing the dissolution rate of drug from ordered mixtures. Decreasing the carrier particle size reduced drug dissolution from ordered mixtures. The dissolution rate of ordered mixtures consisting of 1-5% w/w piroxicam was superior to dissolution rate of piroxicam suspension. The dissolution data fitting and the resulting regression parameters indicated Hixson Crowell, cube root law, as the best fit to drug release data of ordered mixtures.

Improvement of database on glass dissolution

International Nuclear Information System (INIS)

Hayashi, Maki; Sasamoto, Hiroshi; Yoshikawa, Hideki

2008-03-01

In geological disposal system, high-level radioactive waste (HLW) glass is expected to retain radionuclide for the long term as the first barrier to prevent radionuclide release. The advancement of its performance assessment technology leads to the reliability improvement of the safety assessment of entire geological disposal system. For this purpose, phenomenological studies for improvement of scientific understanding of dissolution/alteration mechanisms, and development of robust dissolution/alteration model based on the study outcomes are indispensable. The database on glass dissolution has been developed for supporting these studies. This report describes improvement of the prototype glass database. Also, this report gives an example of the application of the database for reliability assessment of glass dissolution model. (author)

Dating Last Interglacial Coastal Systems Using New Feldspar Luminescence Technologies

Science.gov (United States)

Lamothe, M.

2017-12-01

The recent explosion in new luminescence dating technologies offers new opportunities to explore Quaternary marine coastal facies and landforms. However, tectonic and climatic processes controlling the development of Pleistocene coastal lithosomes are commonly obscured by their poorly constrained geological age. Luminescence dating of feldspar probes one order of magnitude deeper into geological time than radiocarbon and more than 5 times the current age range of quartz optically-stimulated luminescence, routinely used in luminescence dating. However, feldspar luminescence stimulated by infrared photons (eg IRSL) is hampered by anomalous fading. Successful correction methods developed by us over the last 15 years did produce sound chronologies but the fading-corrected ages carried large uncertainties. New approaches initiated by other laboratories, mainly in Europe, have isolated high temperature post-IRSL luminescence as this signal seems to be only slightly affected by fading. However, the gain in stability seems to be lessened due to bleachibility issues, generating age overestimations. We developed a novel protocol known as post-isothermal IRSL dating (Pit-IR) that focuses on a dual system of luminescence signals, probing low (50C) and medium (225C) temperature IRSL signals following isothermal treatments of various intensities. These protocols have been tested on Last interglacial coastal sediments in strikingly different GIA contexts along the Atlantic coastal areas of SE USA as well as from Morocco, Brazil and LIG sites in the Mediterranean basin. A systematic analysis of these results would suggest that a) falling-stages sequences are more commonly preserved as the OSL/IRSL ages are preferentially dating from the end of the MIS5e high stand and b) MIS5a marine sediments may be detectable away from areas generally thought to be affected by peripheral bulge collapse.

Formation, transformation and dissolution of phases formed on surfaces

International Nuclear Information System (INIS)

Shoesmith, D.W.

1983-03-01

The basic mechanisms of film growth, transformation, and dissolution of phases formed on surfaces are discussed. Film growth can occur via solid-state processes or via substrate (usally metal or alloy) dissolution, followed by local supersaturation and precipitation of an insoluble phase. The phase(s) formed may be metastable and transform to a more stable phase, via either solid-state or dissolution-reprecipitation processes. Film dissolution reactions can also occur via a variety of mechanisms, including: (i) direct chemical dissolution when no oxidation state change occurs; (ii) redox dissolution when the film dissolves via a redox reaction involving a reducing or oxidizing agent in solution; and (iii) autoreduction, where film dissolution is coupled to metal dissolution. Such film-growth and dissolution processes, which often produce complex multilayer films, are common in the nuclear industry. A number of examples are discussed

Deformation of quartz and feldspar at mid-crustal depths in an extensional normal fault (Viveiro Fault, NW Spain)

Science.gov (United States)

López-Sánchez, M. A.; Llana-Fúnez, S.; Marcos, A.; Martínez, F. J.

2012-04-01

Metamorphic reactions, deformation mechanism and chemical changes during mylonitization and ultramylonitization of granite affected by a crustal-scale shear zone are investigated using microstructural observations and quantitative analysis. The Vivero Fault (VF) is a large extensional shear zone (>140Km) in NW of Iberia that follows the main Variscan trend dipping 60° toward the West. The movement accumulated during its tectonic history affects the major lithostratigraphic sequence of Palaeozoic and Neoproterozoic rocks and the metamorphic facies developed during Variscan orogenesis. Staurolite, and locally, andalucite plus biotite grew in the hangingwall during the development of VF, overprinted the previous regional Variscan greenschist facies metamorphism. Andalusite growth took place during the intrusion of syntectonic granitic bodies, such as the deformed granite studied here. The Penedo Gordo granite is coarse-grained two-mica biotite-rich granite intruding the VF and its hangingwall. This granite developed a localized deformation consisting of a set of narrow zones (mm to metric scales) heterogeneously distributed subsequently to its intrusion. Based on pseudosections for representative hangingwall pelites hosting the granite and the inferred metamorphic evolution, the shear zone that outcrops at present-day erosion surface was previously active at 14,7-17 km depth (390-450 MPa). Temperature estimates during deformation reach at least the range 500-600° C, implying a local gradient of 35±6°C/km. Microstructures in the mylonites are characterized by bulging (BLG) to subgrain rotation (SGR) recristallization in quartz with the increasing of deformation. Albitisation, flame-perthite and tartan twining are common in K-feldspar at the early stage of deformation. The inferred dominant deformation mechanisms are: i) intracrystalline plasticity in quartz, ii) cataclasis with syntectonic crystallisation of very fine albite-oligoclase and micas in K-feldspar, and

Accumulated phenocrysts and origin of feldspar porphyry in the Chanho area, western Yunnan, China

Science.gov (United States)

Xu, Xing-Wang; Jiang, Neng; Yang, Kai; Zhang, Bao-Lin; Liang, Guang-He; Mao, Qian; Li, Jin-Xiang; Du, Shi-Jun; Ma, Yu-Guang; Zhang, Yong; Qin, Ke-Zhang

2009-12-01

The No. 1 feldspar porphyry in the Chanho area, western Yunnan, China is characterized by the development of deformed glomeroporphyritic aggregates (GA) that contain diagnostic gravity settling textures. These textures include interlocking curved grain boundaries caused by compaction, bent twins, and arch-like structures. The GAs are accumulated phenocrysts (AP) and antecrysts. The unstable textural configurations such as extensive penetrative microfractures that are restricted within the AP and fractured cores of zircon grains, all suggest that the GAs are transported fragments of fractured cumulates that formed in a pre-emplacement magma chamber rather than form in situ at the current intrusion site. Compositions of minerals and melt as represented by different mineral aggregates formed at various stages of the magmatic process and their relations to the composition of porphyry bodies in the Chanho area indicate that the porphyritic melt for the No. 1 feldspar porphyry experienced two stages of melt mixing. Pulses of potassic melt flowed into a pre-emplacement magma chamber and mixed with crystallizing dioritic magma containing phenocrysts resulted in the first hybrid alkaline granitic melt. The mixing caused denser phenocrysts to settle and aggregate to form cumulates. Secondly, new dioritic melt was injected into the magma chamber and was mixed with the previously formed hybrid alkaline granitic melt to produce syenitic melt. Geochron data, including U-Pb age of zircon and 39Ar/ 40Ar age of hornblende and oligoclase phenocrysts, indicate that hornblende and oligoclase phenocrysts, as well as the core of zircon grains, were antecrysts that formed in a number of crystallization events between 36.3 and 32.78 Ma. Gravity settling of phenocrysts took place at about 33.1 to 32.78 Ma and melts with deformed GAs were transported upwards and emplaced into the current site at 32 Ma. Results of this research indicate that the No. 1 feldspar porphyry was a shallow

Investigations of the post-IR IRSL protocol applied to single K-feldspar grains from fluvial sediment samples

International Nuclear Information System (INIS)

Nian, Xiaomei; Bailey, Richard M.; Zhou, Liping

2012-01-01

The post-IR IRSL protocol with single K-feldspar grains was applied to three samples taken from a fluvial sedimentary sequence at the archaeological site of the Dali Man, Shaanxi Province, China. K-feldspar coarse grains were extracted for measurement. Approximately 30–40% of the grains were sufficiently bright to measure, and after application of rejection criteria based on signal strength, recuperation, recycling ratio and saturation dose, ∼10–15% of the grains were used for D e calculation. The relationship of signal decay rate and form of D e (t) with the recovery dose were investigated. The dose recovery ratios of the samples after initial bleaching with the four different light sources were within uncertainties of unity. No anomalous fading was observed. The over-dispersion of the recovered dose and D e values were similar, suggesting neither incomplete resetting of the post-IR IRSL signals nor spatially heterogeneous dose rates significantly affected the natural dose estimates. The values of D e obtained with the single K-feldspar grain post-IR IRSL protocol were in the range ∼400–490 Gy. Combining all of the measured single-grain signals for each of the individual samples (into a ‘synthetic single aliquot’) increased the D e estimates to the range ∼700–900 Gy, suggesting that the grains screened-out by the rejection criteria may have the potential to cause palaeodose over-estimation, although this finding requires a more extensive investigation. Thermally transferred signals were found in the single K-feldspar grains post-IR IRSL protocol, and the proportion of thermally transferred signal to test-dose OSL signal (stimulation at 290 °C) from the natural dose was higher than from regenerative doses, and the proportion was grain- and dose-dependent. As such, TT-post-IR IRSL signals at 290 °C have the potential to cause dose underestimation, although this may be reduced by using larger test-dose irradiations. Our study demonstrates

Study of the thorium phosphate-diphosphate (TPD) dissolution: kinetic aspect - thermodynamic aspect: analysis of the neo-formed phases; Etude de la dissolution du phosphate diphosphate de thorium: - aspect cinetique - aspect thermodynamique: analyse des phases neoformees

Energy Technology Data Exchange (ETDEWEB)

Thomas, A.Ch

2000-10-06

The aim of this work is to study the aqueous corrosion of the thorium phosphate-diphosphate (TPD), of the formula Th{sub 4}(PO{sub 4}){sub 4}P{sub 2}O{sub 7}, in the framework of the actinides immobilization. In order to complete the anterior studies concerning solid solutions where thorium is substituted by a tetravalent ion (uranium (IV) or plutonium (IV)) in the TPD structure, compounds of thorium and neptunium phosphate-diphosphate, of formula Th{sub 4-x}Np{sub x}(PO{sub 4}){sub 4}P{sub 2}O{sub 7}, have been prepared. Furthermore, a new chemical way of synthesis has been investigated in order to sinter solids solution of thorium and uranium phosphate-diphosphate (TUPD) in good conditions. The TPD dissolution study showed two principals steps. The first one corresponds to the control of element concentration by the material dissolution whereas the second corresponds to the formation of secondary precipitates for which thermodynamic equilibrium controls the concentration of the species in solution. Leaching tests have been performed varying several independent parameters in order to determine the TPD dissolution rate. The partial orders related to the protons or to the hydroxide ions have been found between 0.35 and 0.45 whereas the apparent dissolution rate constants are in the range 1.10{sup -5} for 9.10{sup -5} g.m{sup -2}.j{sup -1} for acidic and basic media. The neo-formed phases have been characterized after the dissolution of TPD and TUPD. We found that the TPD leaching in acidic medium leads to the formation of the crystallized thorium phosphate-hydrogen-phosphate (TPHP), of formula Th{sub 2}(PO{sub 4}){sub 2}(HPO{sub 4}), x H{sub 2}O, whereas the TUPD dissolution leads to the TPHP and an other compound, of formula (UO{sub 2}){sub 3}(PO{sub 4}){sub 2}, 5 H{sub 2}O. We calculated its solubility product which is in good agreement with those found in the literature. The phases formed during the leaching of solids containing plutonium; americium or curium (Th

The investigation of the kinetics of hydrochemical oxidation of metal sulphides with the aim of determination of the optimal conditions for the selective extraction of molybdenum from ores

Directory of Open Access Journals (Sweden)

Lutsik V.

2005-01-01

Full Text Available The kinetics of the oxidation of molybdenyte, pyrite and sphalerite in solutions of nitric acid, hydrogen peroxide, and sodium hypochlorite was studied by the rotating disk method. The influence of the molar concentration of reagent, pH of solution, temperature, disk rotation frequency, and duration of measurements on the specific rate of hydrochemical oxidation of sulpfides was determined. The kinetic models allowing to calculate the dissolution rate of sulphides when these parameters change simultaneously were obtained. The conditions of kinetically and diffusion-controlled processes were detected. The details of mechanism of the studied processes were revealed. The nature of intermediate solid products, the reasons and the conditions of their formation as well as the character of their influence on the kinetics of dissolution processes were determined. The probable schemes of interactions corresponding to the observable kinetic dependences were offered. The conditions of the effective and selective molybdenum leaching directly from ore without its concentration were found.

Siderophore-mediated iron dissolution from nontronites is controlled by mineral cristallochemistry

Directory of Open Access Journals (Sweden)

Damien eParrello

2016-03-01

Full Text Available Bacteria living in oxic environments experience iron deficiency due to limited solubility and slow dissolution kinetics of iron-bearing minerals. To cope with iron deprivation, aerobic bacteria have evolved various strategies, including release of siderophores or other organic acids that scavenge external Fe(III and deliver it to the cells. This research investigated the role of siderophores produced by Pseudomonas aeruginosa in the acquisition of Fe(III from two iron-bearing colloidal nontronites (NAu-1 and NAu-2, comparing differences in bioavailability related with site occupancy and distribution of Fe(III in the two lattices. To avoid both the direct contact of the mineral colloids with the bacterial cells and the uncontrolled particle aggregation, nontronite suspensions were homogenously dispersed in a porous silica gel before the dissolution experiments. A multiparametric approach coupling UV-vis spectroscopy and spectral decomposition algorithm was implemented to monitor simultaneously the solubilisation of Fe and the production of pyoverdine in microplate-based batch experiments. Both nontronites released Fe in a particle concentration-dependent manner when incubated with the wild-type P. aeruginosa strain, however iron released from NAu-2 was substantially greater than from NAu-1. The profile of organic acids produced in both cases was similar and may not account for the difference in the iron dissolution efficiency. In contrast, a pyoverdine-deficient mutant was unable to mobilise Fe(III from either nontronite, whereas iron dissolution occurred in abiotic experiments conducted with purified pyoverdine. Overall, our data provide evidence that P. aeruginosa indirectly mobilise Fe from nontronites primarily through the production of pyoverdine. The structural Fe present on the edges of Nau-2 rather than Nau-1 particles appears to be more bio-accessible, indicating that the distribution of Fe, in the tetrahedron and/or in the octahedron

Kinetics of dissolution of {alpha}-Fe{sub 2}O{sub 3} and {gamma}-Fe{sub 2}O{sub 3} in EDTA and NTA-based formulations

Energy Technology Data Exchange (ETDEWEB)

Ranganathan, S. [Dept. of Chemical Engineering, Univ. of New Brunswick, Fredericton, N.B. (Canada); Srinivasan, M.P. [Water and Steam Chemistry Lab. of Bhabha Atomic Research Centre (BARC) (India); Narasimhan, S.V. [Bhabha Atomic Research Centre (India); Raghavan, P.S. [Madras Christian Coll., Chennai (India); Gopalan, R. [Dept. of Chemistry, Madras Christian Coll., Chennai (India)

2004-06-01

The dissolution studies were carried out on haematite ({alpha}-Fe{sub 2}O{sub 3}) and maghemite ({gamma}-Fe{sub 2}O{sub 3}) in two different formulations of ethylenediaminetetraacetic acid (EDTA) and nitrilotriaceticacid (NTA). The rate constants were calculated using the ''inverse cubic rate law.'' The leaching of the metal ions from the oxide is controlled partly by the Fe(II)-L{sub n} (L is a complexing ligand and n is the number of ligands attached to Fe{sup 2+}), a dissolution product arising from the oxides having Fe{sup 2+} in the lattice. The addition of Fe(II)-L{sub n} along with the formulation greatly increased the initial rate of dissolution. The effect of the addition of Fe(II)-L as a reductant on the dissolution of {alpha}-Fe{sub 2}O{sub 3} was not the same as in the case of {gamma}-Fe{sub 2}O{sub 3}. The rate constants (k{sub obs}) for the dissolution of {alpha}-Fe{sub 2}O{sub 3} and {gamma}-Fe{sub 2}O{sub 3} in the presence of ascorbic acid were less in the EDTA formulation than in the NTA formulation. The studies using Fe(II)-NTA and Fe(II)-EDTA with varying compositions of citric acid and ascorbic acid revealed that a minimum quantity of the chelant is sufficient to initiate the dissolution process, which can be further controlled by the reductants and weaker chelants such as citric acid. (orig.)

Dissolution rate of BTEX contaminants in water

International Nuclear Information System (INIS)

Njobuenwu, D.O.; Amadi, S.A.; Ukpaka, P.C.

2005-01-01

Benzene, toluene, ethylbenzene and xylenes (BTEX) and substituted benzenes are the most common aromatic compounds in petroleum. BTEX components are the most soluble and mobile fraction of crude oil and many petroleum products, and frequently enter soil, sediments and aquatic environments because of accidental spills, leaks and improper oil waste disposal practices. The mass transfer process of hydrocarbons in aquatic mediums has received considerable attention in the literature. This paper focused on the molecular mass transfer rate of BTEX in water, with the aim of understanding and predicting contaminant fate and transport. A comprehensive model was developed to simulate the molecular dissolution rate of BTEX in a natural water stream. The model considered the physicochemical properties of the BTEX compounds and physical processes relevant to the spreading of contaminants in the sea. The dissolution rate was a function of oil slick area, dissolution mass transferability and oil solubility in water. The total dissolution rate N was calculated and the dissolution mass transfer coefficient K was given as the point value of mass transfer coefficient. Results for the dissolution rate based on the solubility of the components in the water were compared with analytical solutions from previous studies and showed good agreement. The model showed that benzene had the largest dissolution rate, while o-xylene had the lowest rate because of its lower fraction. Benzene dissolution rate was approximately 2.6, which was 20.6 times that of toluene and ethylbenzene. It was concluded that the model is useful in predicting and monitoring the dissolution rate of BTEX contaminants in soil and water systems. 22 refs., 2 tabs., 3 figs

Interaction Between Second-Phase Particle Dissolution and Abnormal Grain Growth in an Austenitic Stainless Steel

Directory of Open Access Journals (Sweden)

Dutra J.C.

2002-01-01

Full Text Available The continuing development of stainless steels has resulted in complex steel compositions with substantial amounts of alloying elements. The benefits of such additions invariably come attached to unavoidable disadvantages. One of the most critical item is the potential microstructural instability of the material. Alloying elements may be in a supersaturated solid solution, in which the precipitation of carbides, nitrides, borides and intermetallic phases occurs in a wide range of temperatures. In order to dissolve the mentioned precipitates, solution annealing is commonly performed. However, at the temperature range in which this treatment is carried out, the onset of abnormal grain growth can occur. The interaction between the dissolution of these second-phase particles and the occurrence of abnormal grain growth is investigated in this work. This study also shows that the thermodynamics and the kinetics of dissolution of precipitates may be used to predict whether abnormal grain growth takes place.

Determination of parameters dissolution of yellow-cake. Production of uranyl nitrate - Gas precipitation of AUC

International Nuclear Information System (INIS)

Mellah, A.

1987-07-01

The different stages of the purification cycle of yellow-cakes have been studied thoroughly in order to obtain an ammonium uranyl carbonate (AUC) as an intermediate product of uranium dioxide (UO 2 ). The optimal parameters of yellow-cake dissolution, filtration, extraction by solvent, scrubbing and stripping were determined. An original program of thermodynamic calculation was developed for the determination of the free energies of yellow-cake dissolution reactions. Different numerical methods were used to determine the kinetic constant, the reaction order and correlation equations of uranyl nitrate density as a function of U and H + concentrations, before and after the extraction cycle. For the first time, Algerian filteraids were used for the filtration of uranyl nitrate solutions with satisfactory results. A laboratory designed installation enabled the precipitation of AUC by injection of ammonia and carbon dioxide gases. Interesting results have been obtained and further investigations should be carried out in order to optimize all the paremeters of the gas precipitation of AUC

Kinetics of electrodialytic extraction of Pb and soil cations from a slurry of contaminated soil fines

DEFF Research Database (Denmark)

Jensen, Pernille Erland; Ottosen, Lisbeth M.; Ferreira, Célia

2006-01-01

-removal was obtained. During the first phase dissolution of carbonates was the prevailing process, resulting in a corresponding loss of soil-mass. During this phase, the investigated ions accounted for the major current transfer, while, as remediation proceeded hydrogen-ions increasingly dominated the transfer. During......The objective of this work was to investigate the kinetics of Pb removal from soil-fines during electrodialytic remediation in suspension, and study the simultaneous dissolution of common soil cations (Al, Ca, Fe, Mg, Mn, Na and K). This was done to evaluate the possibilities within control...

Bottom-up and Top-down Approaches to Explore Sodium Dodecyl Sulfate and Soluplus on the Crystallization Inhibition and Dissolution of Felodipine Extrudates.

Science.gov (United States)

Chen, Jiali; Chen, Yuqi; Huang, Wencong; Wang, Hanning; Du, Yang; Xiong, Subin

2018-05-05

The objectives of this study were to explore sodium dodecyl sulfate (SDS) and Soluplus on the crystallization inhibition and dissolution of felodipine (FLDP) extrudates by bottom-up and top-down approaches. FLDP extrudates with Soluplus and/or SDS were prepared by hot melt extrusion (HME), and characterized by PLM, DSC and FT-IR. Results indicated that Soluplus inhibited FLDP crystallization and the whole amorphous solid dispersions (ASDs) were binary FLDP-Soluplus (1:3) and ternary FLDP-Soluplus-SDS(1:2:0.15∼0.3 and 1:3:0.2∼0.4) extrudates. Internal SDS (5%-10%) decreased Tgs of FLDP-Soluplus-SDS ternary ASDs without presenting molecular interactions with FLDP or Soluplus. The enhanced dissolution rate of binary or ternary Soluplus-rich ASDs in the non-sink condition of 0.05%SDS was achieved. Bottom-up approach indicated that Soluplus was a much stronger crystal inhibitor to the supersaturated FLDP in solutions than SDS. Top-down approach demonstrated that SDS enhanced the dissolution of Soluplus-rich ASDs via wettability and complexation with Soluplus to accelerate the medium uptake and erosion kinetics of extrudates, but induced FLDP recrystallization and resulted in incomplete dissolution of FLDP-rich extrudates. In conclusion, top-down approach is a promising strategy to explore the mechanisms of ASDs' dissolution, and small amount of SDS enhances the dissolution rate of polymer-rich ASDs in the non-sink condition. Copyright © 2018. Published by Elsevier Inc.

Chapter 9: Model Systems for Formation and Dissolution of Calcium Phosphate Minerals

Energy Technology Data Exchange (ETDEWEB)

Orme, C A; Giocondi, J L

2006-07-29

Calcium phosphates are the mineral component of bones and teeth. As such there is great interest in understanding the physical mechanisms that underlie their growth, dissolution, and phase stability. Control is often achieved at the cellular level by the manipulation of solution states and the use of crystal growth modulators such as peptides or other organic molecules. This chapter begins with a discussion of solution speciation in body fluids and relates this to important crystal growth parameters such as the supersaturation, pH, ionic strength and the ratio of calcium to phosphate activities. We then discuss the use of scanning probe microscopy as a tool to measure surface kinetics of mineral surfaces evolving in simplified solutions. The two primary themes that we will touch on are the use of microenvironments that temporally evolve the solution state to control growth and dissolution; and the use of various growth modifiers that interact with the solution species or with mineral surfaces to shift growth away from the lowest energy facetted forms. The study of synthetic minerals in simplified solution lays the foundation for understand mineralization process in more complex environments found in the body.

Hydroxylamine a potential reagent for dissolution off gas scrubbing in nuclear spent fuel reprocessing: kinetics of the iodine reduction

Energy Technology Data Exchange (ETDEWEB)

Cau Dit Coumes, C.; Devisme, F. [CEA Centre d`Etudes de la Vallee du Rhone, 30 - Marcoule (France). Dept. d`Exploitation du Retraitement et de Demantelement; Chopin, J.; Vargas, S.

1996-12-31

Iodine, which can be released inside the containment buildings when accident occurs, can be traced, in normal operating conditions, at the back end of the fuel cycle. Hydroxylamine has been selected as a regent of potential interest to trap iodine in the dissolution off gas treatment. The kinetics of the reaction between hydroxylamine and iodine has been studied in a narrow range of pH(1-2), with hydroxylamine in excess (ratios of hydroxylamine to iodine initial concentrations varying from 2 to 40), at constant temperature (30 deg. C) and ionic strength (0.1 mol/l). Spectrophotometry and voltametry have been coupled for analytical solved using a investigation. The problem of the rapid mixing of the reactants has been solved using a continuous reactor. Tri-iodine has been shown non reactive towards hydroxylamine. An initial rate law have been proposed, pointing out the first order of the reaction with respect to hydroxylamine and iodine, and the inhibitory effect and hydrogen ions. Nitrous acid has been identified as a transitory product. Nitrous oxide and nitrogen monoxide have been detected by gas chromatography, the ratio of the amounts of products formed depending on acidity. The complexity of the overall reaction has been ascribed to the competition of hour reactions (I{sub 2} + I <=> I{sub 3}{sup -}NH{sub 3}OH{sup +} + 2 I{sub 2} + H{sub 2}O ->HNO{sub 2} + 4 I{sup -} + 5 H{sup +}; NH{sub 3}OH{sup +} + HNO{sub 2} -> N{sub 2}O + 2 H{sub 2}O + H-+ 2HNO{sub 2} + 2 I{sup -} + 2H-+ -> 2 NO + I{sub 2} + H{sub 2}O). (authors). 12 refs.

Effects of tablet formulation and subsequent film coating on the supersaturated dissolution behavior of amorphous solid dispersions.

Science.gov (United States)

Sakai, Toshiro; Hirai, Daiki; Kimura, Shin-Ichiro; Iwao, Yasunori; Itai, Shigeru

2018-04-05

The effects of tablet preparation and subsequent film coating with amorphous solid dispersion (ASD) particles that were composed of a drug with poor water solubility and hydrophilic polymers were investigated. ASD particles were prepared with a drug and vinylpyrrolidone-vinyl acetate copolymer (PVPVA) or polyvinylpyrrolidone (PVP) at a weight ratio of 1:1 or 1:2 using a melt extrusion technique. Tablets were prepared by conventional direct compression followed by pan coating. A mathematical model based on the Noyes-Whitney equation assuming that stable crystals precipitated at the changeable surface area of the solid-liquid interface used to estimate drug dissolution kinetics in a non-sink dissolution condition. All the ASD particles showed a maximum dissolution concentration approximately ten times higher than that of the crystalline drug. The ASD particles with PVPVA showed higher precipitation rate with lower polymer ratio, while PVP did not precipitate within 960 min regardless of the polymer ratio, suggesting the ASD particles of 1:1 drug:PVPVA (ASD-1) were the most unstable among the ASD particles considered. The dissolution of a core tablet with ASD-1 showed less supersaturation and a much higher precipitation rate than those of ASD-1 particles. However, a film-coated tablet or core tablet with a trace amount of hydroxypropylmethylcellulose (HPMC) showed a similar dissolution profile to that of the ASD-1 particles, indicating HPMC had a remarkable precipitation inhibition effect. Overall, these results suggest that tablet preparation with ASD may adversely affect the maintenance of supersaturation; however, this effect can be mitigated by adding an appropriate precipitation inhibitor to the formulation. Copyright © 2018 Elsevier B.V. All rights reserved.

Estimate of long-term dissolution rate of basaltic glass. A case study on Mt. Fuji area

Energy Technology Data Exchange (ETDEWEB)

Shikazono, Naotatsu; Takino, Akitsugu [Keio Univ., Environmental Geochemistry, Tokyo (Japan)

2002-03-01

Bulk compositional, mineralogical and physical properties of weathered basaltic ash soil ('Andisol') derived mainly from Mt. Fuji were studied. Mineralogical studies revealed that the dominant primary material and weathering products are volcanic glass, allophane and halloysite and the sequence of weathering is volcanic glass {yields} allophane {yields} 10A halloysite {yields} 7A halloysite. X-ray fluorescence analysis indicates that the relative elemental mobilities during the weathering is Na, Ca>K>Mg>P>Si>Ti, Fe>Al>Mn. The trends of soilwater chemistry (H{sub 4}SiO{sub 4} concentration) with depth were calculated based on dissolution - precipitation kinetics - fluid flow coupling model. In order to calculate the trends, the data on present-day annual rainfall, solubility of basalt glass, porosity and specific weight of soil, deposition rate of volcanic ash and grain size of volcanic glass were used. The calculated results were compared with analytical trends of soilwater chemistry. From this comparison the dissolution rate constant of basalt glass was estimated to be 10{sup -9.4} - 10{sup -9.2} (mole Si m{sup -2} s{sup -1}). This value is consistent with previous experimental dissolution rate constant of basalt glass reported in the literature. (author)

Monitoring the hydrolyzation of aspirin during the dissolution testing for aspirin delayed-release tablets with a fiber-optic dissolution system

Directory of Open Access Journals (Sweden)

Yan Wang

2012-10-01

Full Text Available The purpose of this study was to investigate the hydrolyzation of aspirin during the process of dissolution testing for aspirin delayed-release tablets. Hydrolysis product of salicylic acid can result in adverse effects and affect the determination of dissolution rate assaying. In this study, the technique of differential spectra was employed, which made it possible to monitor the dissolution testing in situ. The results showed that the hydrolyzation of aspirin made the percentage of salicylic acid exceed the limit of free salicylic acid (4.0, and the hydrolyzation may affect the quality detection of aspirin delayed-release tablets. Keywords: Aspirin delayed-release tablets, Drug dissolution test, Fiber-optic dissolution system, UV–vis spectrum

Effects of interface formation kinetics on the microstructural properties of wear-resistant metal-matrix composites

International Nuclear Information System (INIS)

Ilo, S.; Just, Ch.; Badisch, E.; Wosik, J.; Danninger, H.

2010-01-01

Research highlights: The dissolution reaction kinetics and the formation of intermediate layers of tungsten carbides in Ni-(Cr)-B-Si matrices were studied in liquid-phase sintering with well-defined temperature/time relationship. → The internal intermediate layer formation, close to the original primary tungsten carbide showed diffusion-controlled kinetic (∼t 0.5 ), whereas the outside layer thickness formation, proportional to the processing time (∼t), was formed by the subsequent eutectic reaction of the Ni-(Cr)-B-Si matrix with the WC/W 2 C component. → Cr-addition in the matrix highly influences the inner layer thickness caused probably by increasing the C-diffusion rate, whereas the outer layer thickness was not dependent on the initial Cr-content in the matrix. Generally, the Cr-addition in the Ni-based matrix increased the hardness and elastic modulus of the intermediate phases along the carbide/matrix interface. → The different microstructure gradients are depended mainly on the interface growth kinetics. → The intermediate layers are hard phases (carbides, borides or carbo-borides). → The hardness of the carbide/matrix interface area is significantly lower as the hardness of the original primary tungsten carbides. - Abstract: Hard-particle metal-matrix composites (MMC) are generally used to increase the lifetime of machinery equipment exposed to severe wear conditions. Depending on the manufacturing technology, dissolution reactions of hard phases undergo different temperature/time profiles during processing affecting the microstructure and mechanical properties of the MMCs. Therefore, quantification of the carbide dissolution effects on the microstructure and micro-mechanical properties is the key to success in the development and optimisation of MMCs. Dissolution kinetics of WC/W 2 C in Ni-based matrices were determined in the liquid-sintering with a well-defined temperature/time profile. Microscopic evaluation of the samples showed two

Heterogeneous Fenton-like discoloration of methyl orange using Fe3O4/MWCNTs as catalyst: kinetics and Fenton-like mechanism

Science.gov (United States)

Xu, Huan-Yan; Wang, Yuan; Shi, Tian-Nuo; Zhao, Hang; Tan, Qu; Zhao, Bo-Chao; He, Xiu-Lan; Qi, Shu-Yan

2018-03-01

The kinetics and Fenton-like mechanism are two challenging tasks for heterogeneous Fenton-like catalytic oxidation of organic pollutants. In this study, three kinetic models were used for the kinetic studies of Fe3O4/MWCNTs-H2O2 Fenton-like reaction for MO degradation. The results indicated that this reaction followed the first-order kinetic model. The relationship of reaction rate constant and temperature followed the Arrhenius equation. The activation energy and frequency factor of this system were calculated as 8.2 kJ·mol-1 and 2.72 s-1, respectively. The quantifications of Fe ions dissolution and •OH radicals generation confirmed that the homogeneous and heterogeneous catalyses were involved in Fe3O4/MWCNTs-H2O2 Fenton-like reaction. The reaction rate constant was closely related with Fe ions dissolution and •OH radicals generation. Fe3O4/MWCNTs nanocomposites had typical ferromagnetic property and could be easily separated from solution by an external magnet after being used. Furthermore, Fe3O4/MWCNTs nanocomposites exhibited good stability and recyclability. Finally, the Fenton-like mechanisms on homogeneous and heterogeneous catalyses were described.

Use of partial dissolution techniques in geochemical exploration

Science.gov (United States)

Chao, T.T.

1984-01-01

Application of partial dissolution techniques to geochemical exploration has advanced from an early empirical approach to an approach based on sound geochemical principles. This advance assures a prominent future position for the use of these techniques in geochemical exploration for concealed mineral deposits. Partial dissolution techniques are classified as single dissolution or sequential multiple dissolution depending on the number of steps taken in the procedure, or as "nonselective" extraction and as "selective" extraction in terms of the relative specificity of the extraction. The choice of dissolution techniques for use in geochemical exploration is dictated by the geology of the area, the type and degree of weathering, and the expected chemical forms of the ore and of the pathfinding elements. Case histories have illustrated many instances where partial dissolution techniques exhibit advantages over conventional methods of chemical analysis used in geochemical exploration. ?? 1984.

Stoneware tile manufacturing using rice straw ash as feldspar replacement; Fabricacion de gres porcelanico empleando ceniza de tamo de arroz en sustitucion del feldespato

Energy Technology Data Exchange (ETDEWEB)

Alvaro Guzman, A.; John Torres, L.; Martha Cedeno, V.; Silvio Delvasto, A.; Vicente Amigo, B.; Enrique Sanchez, V.

2013-07-01

In this research are presented the results of using rice straw ash (RSA) in low proportions as substitute of feldspar for manufacturing stoneware tiles. Specimens of semidry triaxial mixtures, where feldspar was substituted for different percentages (25 % and 50 %) of RSA, were prepared by uniaxial pressing, followed by drying and sintering. Physical and mechanical properties of sintered bodies were evaluated. Porcelain stoneware tile specimens C0 and CF25 reached bending strength and water absorption values were in accordance with standard ISO 13006 (Annex G, BIa) ( {>=} 35 MPa and {<=} 0.5 %, respectively). However, in porcelain stoneware tile specimens CF50 due to bloating phenomenon was not possible obtain commercial tiles in accordance with standard ISO 13006. By using Scanning Electron Microscopy (SEM) needles of primary and secondary mullite were identified in a vitreous phase; and by using X-Ray Diffraction (XRD) mullite and quartz phases were identified. It was concluded that feldspar can be substituted positively by RSA in stoneware tile pastes. (Author)

Jarosite dissolution rates in perchlorate brine

Science.gov (United States)

Legett, Carey; Pritchett, Brittany N.; Elwood Madden, Andrew S.; Phillips-Lander, Charity M.; Elwood Madden, Megan E.

2018-02-01

Perchlorate salts and the ferric sulfate mineral jarosite have been detected at multiple locations on Mars by both landed instruments and orbiting spectrometers. Many perchlorate brines have eutectic temperatures bearing rocks and sediments may have been altered by perchlorate brines. Here we measured jarosite dissolution rates in 2 M sodium perchlorate brine as well as dilute water at 298 K to determine the effects of perchlorate anions on jarosite dissolution rates and potential reaction products. We developed a simple method for determining aqueous iron concentrations in high salinity perchlorate solutions using ultraviolet-visible spectrophotometry that eliminates the risk of rapid oxidation reactions during analyses. Jarosite dissolution rates in 2 M perchlorate brine determined by iron release rate (2.87 × 10-12 ±0.85 × 10-12 mol m-2 s-1) were slightly slower than the jarosite dissolution rate measured in ultrapure (18.2 MΩ cm-1) water (5.06 × 10-12 mol m-2 s-1) using identical methods. No additional secondary phases were observed in XRD analyses of the reaction products. The observed decrease in dissolution rate may be due to lower activity of water (ɑH2O = 0.9) in the 2 M NaClO4 brine compared with ultrapure water (ɑH2O = 1). This suggests that the perchlorate anion does not facilitate iron release, unlike chloride anions which accelerated Fe release rates in previously reported jarosite and hematite dissolution experiments. Since dissolution rates are slower in perchlorate-rich solutions, jarosite is expected to persist longer in perchlorate brines than in dilute waters or chloride-rich brines. Therefore, if perchlorate brines dominate aqueous fluids on the surface of Mars, jarosite may remain preserved over extended periods of time, despite active aqueous processes.

Comparative study of ice nucleating efficiency of K-feldspar in immersion and deposition freezing modes

Science.gov (United States)

Hiron, T.; Hoffmann, N.; Peckhaus, A.; Kiselev, A. A.; Leisner, T.; Flossmann, A. I.

2016-12-01

One of the main challenges in understanding the evolution of Earth's climate resides in the understanding the role of ice nucleation on the development of tropospheric clouds as well as its initiation. K-feldspar is known to be a very active ice nucleating particle and this study focuses on the characterization of its activity in two heterogeneous nucleation modes, immersion and deposition freezing.We use a newly built humidity-controlled cold stage allowing the simultaneous observation of up to 2000 identical 0.6-nanoliter droplets containing suspension of mineral dust particles. The droplets are first cooled down to observe immersion freezing, the obtained ice crystals are then evaporated and finally, the residual particles are exposed to the water vapor supersaturated with respect to ice.The ice nucleation abilities for the individual residual particles are then compared for the different freezing modes and correlation between immersion ice nuclei and deposition ice nuclei is investigated.Based on the electron microscopy analysis of the residual particles, we discuss the possible relationship between the ice nucleation properties of feldspar and its microstructure. Finally, we discuss the atmospheric implications of our experimental results, using DESCAM, a 1.5D bin-resolved microphysics model.

Aqueous dissolution rates of uranium oxides

International Nuclear Information System (INIS)

Steward, S.A.; Mones, E.T.

1994-10-01

An understanding of the long-term dissolution of waste forms in groundwater is required for the safe disposal of high level nuclear waste in an underground repository. The main routes by which radionuclides could be released from a geological repository are the dissolution and transport processes in groundwater flow. Because uranium dioxide is the primary constituent of spent nuclear fuel, the dissolution of its matrix in spent fuel is considered the rate-limiting step for release of radioactive fission products. The purpose of our work has been to measure the intrinsic dissolution rates of uranium oxides under a variety of well-controlled conditions that are relevant to a repository and allow for modeling. The intermediate oxide phase U 3 O 8 , triuranium octaoxide, is quite stable and known to be present in oxidized spent fuel. The trioxide, UO 3 , has been shown to exist in drip tests on spent fuel. Here we compare the results of essentially identical dissolution experiments performed on depleted U 3 O 8 and dehyrated schoepite or uranium trioxide monohydrate (UO 3 ·H 2 O). These are compared with earlier work on spent fuel and UO 2 under similar conditions

Dissolution of metallic uranium in alkalis

International Nuclear Information System (INIS)

Mondino, Angel V.; Wilkinson, Maria V.; Manzini, Alberto C.

1999-01-01

The dissolution of U metallic foils has been studied in the framework of the development of an improved 99 Mo-production process. The best conditions for the dissolution of uranium foils of approximately 150 μm are the following: a) NaClO concentrations of 0.20 and 0.23 M with NaOH of 0.27 and 0.31 M respectively; b) temperature of the solution, 70 C degrees; c) volume of the solution, 15 ml / cm 2 of uranium foil; d) dissolution time, 30 minutes. (author)

Development and Validation of a Dissolution Test Method for ...

African Journals Online (AJOL)

Purpose: To develop and validate a dissolution test method for dissolution release of artemether and lumefantrine from tablets. Methods: A single dissolution method for evaluating the in vitro release of artemether and lumefantrine from tablets was developed and validated. The method comprised of a dissolution medium of ...

Low temperature dissolution flowsheet for plutonium metal

Energy Technology Data Exchange (ETDEWEB)

Daniel, W. E. [Savannah River Site (SRS), Aiken, SC (United States). Savannah River National Lab. (SRNL); Almond, P. M. [Savannah River Site (SRS), Aiken, SC (United States). Savannah River National Lab. (SRNL); Rudisill, T. S. [Savannah River Site (SRS), Aiken, SC (United States). Savannah River National Lab. (SRNL)

2016-05-01

The H-Canyon flowsheet used to dissolve Pu metal for PuO₂ production utilizes boiling HNO₃. SRNL was requested to develop a complementary dissolution flowsheet at two reduced temperature ranges. The dissolution and H₂ generation rates of Pu metal were investigated using a dissolving solution at ambient temperature (20-30 °C) and for an intermediate temperature of 50-60 °C. Additionally, the testing included an investigation of the dissolution rates and characterization of the off-gas generated from the ambient temperature dissolution of carbon steel cans and the nylon bags that contain the Pu metal when charged to the dissolver.

Study of sensitivity change of OSL signals from quartz and feldspars as a function of preheat temperature

DEFF Research Database (Denmark)

Jungner, H.; Bøtter-Jensen, L.

1994-01-01

and as a result, the equivalent dose (ED) would be underestimated. A study of sensitivity changes in feldspars and quartz was carried out with emphasis on the effect of preheat and annealing on the OSL signal. Measurement results obtained are presented, and possible elimination of errors in dating caused...

Electrons in feldspar II: A consideration of the influence of conduction band-tail states on luminescence processes

DEFF Research Database (Denmark)

Poolton, H.R.J.; Ozanyan, K.B.; Wallinga, J.

2002-01-01

consider what influence the band tails have on the luminescence properties of feldspar, where electrons travel through the sample prior to recombination. The work highlights the dominant role that 0.04-0.05-eV phonons play in both the luminescence excitation and emission processes of these materials...

Kinetic study of the annealing reactions in Cu-Ni-Fe alloys; Estudio cinetico de las reacciones de recocido en aleaciones de Cu-Ni-Fe

Energy Technology Data Exchange (ETDEWEB)

Donoso, E.

2014-07-01

The thermal aging of a Cu-45Ni-4Fe, Cu-34Ni-11Fe and Cu-33Ni-22Fe alloys tempered from 1173 K have been studied from Differential Scanning Calorimetry (DSC) and microhardness measurements. The analysis of DSC curves, from room temperature to 950 K, shows the presence of one exothermic reaction associated to the formation of FeNi{sub 3} phase nucleating from a modulate structure, and one endothermic peak attributed to dissolution of this phase. Kinetic parameters were obtained using the usual Avrami-Erofeev equation, modified Kissinger method and integrated kinetic functions. Microhardness measurements confirmed the formation and dissolution of the FeNi{sub 3} phase. (Author)

Physical heterogeneity control on effective mineral dissolution rates

Science.gov (United States)

Jung, Heewon; Navarre-Sitchler, Alexis

2018-04-01

Hydrologic heterogeneity may be an important factor contributing to the discrepancy in laboratory and field measured dissolution rates, but the governing factors influencing mineral dissolution rates among various representations of physical heterogeneity remain poorly understood. Here, we present multiple reactive transport simulations of anorthite dissolution in 2D latticed random permeability fields and link the information from local grid scale (1 cm or 4 m) dissolution rates to domain-scale (1m or 400 m) effective dissolution rates measured by the flux-weighted average of an ensemble of flow paths. We compare results of homogeneous models to heterogeneous models with different structure and layered permeability distributions within the model domain. Chemistry is simplified to a single dissolving primary mineral (anorthite) distributed homogeneously throughout the domain and a single secondary mineral (kaolinite) that is allowed to dissolve or precipitate. Results show that increasing size in correlation structure (i.e. long integral scales) and high variance in permeability distribution are two important factors inducing a reduction in effective mineral dissolution rates compared to homogeneous permeability domains. Larger correlation structures produce larger zones of low permeability where diffusion is an important transport mechanism. Due to the increased residence time under slow diffusive transport, the saturation state of a solute with respect to a reacting mineral approaches equilibrium and reduces the reaction rate. High variance in permeability distribution favorably develops large low permeability zones that intensifies the reduction in mixing and effective dissolution rate. However, the degree of reduction in effective dissolution rate observed in 1 m × 1 m domains is too small (equilibrium conditions reduce the effective dissolution rate by increasing the saturation state. However, in large domains where less- or non-reactive zones develop, higher

Detailed Modelling of Kinetic Biodegradation Processes in a Laboratory Mmicrocosm

Science.gov (United States)

Watson, I.; Oswald, S.; Banwart, S.; Mayer, U.

2003-04-01

Biodegradation of organic contaminants in soil and groundwater usually takes places via different redox processes happening sequentially as well as simultaneously. We used numerical modelling of a long-term lab microcosm experiment to simulate the dynamic behaviour of fermentation and respiration in the aqueous phase in contact with the sandstone material, and to develop a conceptual model describing these processes. Aqueous speciation, surface complexation, mineral dissolution and precipitation were taken into account also. Fermentation can be the first step of the degradation process producing intermediate species, which are subsequently consumed by TEAPs. Microbial growth and substrate utilisation kinetics are coupled via a formulation that also includes aqueous speciation and other geochemical reactions including surface complexation, mineral dissolution and precipitation. Competitive exclusion between TEAPs is integral to the conceptual model of the simulation, and the results indicate that exclusion is not complete, but some overlap is found between TEAPs. The model was used to test approaches like the partial equilibrium approach that currently make use of hydrogen levels to diagnose prevalent TEAPs in groundwater. The observed pattern of hydrogen and acetate concentrations were reproduced well by the simulations, and the results show the relevance of kinetics, lag times and inhibition, and especially that intermediate products play a key role.

Reaction of hydrogen peroxide with uranium zirconium oxide solid solution - Zirconium hinders oxidative uranium dissolution

Science.gov (United States)

Kumagai, Yuta; Takano, Masahide; Watanabe, Masayuki

2017-12-01

We studied oxidative dissolution of uranium and zirconium oxide [(U,Zr)O2] in aqueous H2O2 solution to estimate (U,Zr)O2 stability to interfacial reactions with H2O2. Studies on the interfacial reactions are essential for anticipating how a (U,Zr)O2-based molten fuel may chemically degrade after a severe accident. The fuel's high radioactivity induces water radiolysis and continuous H2O2 generation. Subsequent reaction of the fuel with H2O2 may oxidize the fuel surface and facilitate U dissolution. We conducted our experiments with (U,Zr)O2 powder (comprising Zr:U mole ratios of 25:75, 40:60, and 50:50) and quantitated the H2O2 reaction via dissolved U and H2O2 concentrations. Although (U,Zr)O2 reacted more quickly than UO2, the dissolution yield relative to H2O2 consumption was far less for (U,Zr)O2 compared to that of UO2. The reaction kinetics indicates that most of the H2O2 catalytically decomposed to O2 at the surface of (U,Zr)O2. We confirmed the H2O2 catalytic decomposition via O2 production (quantitative stoichiometric agreement). In addition, post-reaction Raman scattering spectra of the undissolved (U,Zr)O2 showed no additional peaks (indicating a lack of secondary phase formation). The (U,Zr)O2 matrix is much more stable than UO2 against H2O2-induced oxidative dissolution. Our findings will improve understanding on the molten fuels and provide an insight into decommissioning activities after a severe accident.

DNAPL remediation with in situ chemical oxidation using potassium permanganate - Part I. Mineralogy of Mn oxide and its dissolution in organic acids

Science.gov (United States)

Li, X. David; Schwartz, Franklin W.

2004-01-01

Previous studies on in situ chemical oxidation of trichloroethylene (TCE) with potassium permanganate indicated that the solid reaction product, Mn oxide, could reduce the permeability of the porous medium and impact the success of dense non-aqueous phase liquid (DNAPL) removal. In order to address the issue of permeability reduction caused by precipitation, this study investigated the mineralogy of Mn oxides and the possibilities of removing the solid precipitates by dissolution. The solid reaction product from the oxidation of TCE by permanganate is semi-amorphous potassium-rich birnessite, which has a layered mineral structure with an interlayer spacing of 7.3 Å. The chemical formula is K 0.854Mn 1.786O 4·1.55H 2O. It has a relatively small specific surface area at 23.6±0.82 m 2/g. Its point of zero charge (pzc) was measured as 3.7±0.4. This birnessite is a relatively active species and could participate in various reactions with existing organic and inorganic matter. The dissolution kinetics of Mn oxide was evaluated in batch experiments using solutions of citric acid, oxalic acid, and ethylenediaminetetraacetic acid (EDTA). Initial dissolution rates were determined to be 0.126 mM/m 2/h for citric acid, 1.35 mM/m 2/h for oxalic acid, and 5.176 mM/m 2/h for EDTA. These rates compare with 0.0025 mM/m 2/h for nitric acid at pH=2. Organic acids dissolve Mn oxide quickly. Reaction rates increase with acid concentration, as tested with citric acid. The dissolution mechanism likely involves proton and ligand-promoted dissolution and reductive dissolution. Citric and oxalic acid can induce ligand-promoted dissolution, while EDTA can induce ligand-promoted and reductive dissolutions. At low pH, proton-promoted dissolution seems to occur with all the acids tested, but this process is not dominant. Reductive dissolution appears to be the most effective process in dissolving the solid, followed by ligand-promoted dissolution. These experiments indicate the significant

Dissolution rates of DWPF glasses from long-term PCT

International Nuclear Information System (INIS)

Ebert, W.L.; Tam, S.W.

1996-01-01

We have characterized the corrosion behavior of several Defense Waste Processing Facility (DWPF) reference waste glasses by conducting static dissolution tests with crushed glasses. Glass dissolution rates were calculated from measured B concentrations in tests conducted for up to five years. The dissolution rates of all glasses increased significantly after certain alteration phases precipitated. Calculation of the dissolution rates was complicated by the decrease in the available surface area as the glass dissolves. We took the loss of surface area into account by modeling the particles to be spheres, then extracting from the short-term test results the dissolution rate corresponding to a linear decrease in the radius of spherical particles. The measured extent of dissolution in tests conducted for longer times was less than predicted with this linear dissolution model. This indicates that advanced stages of corrosion are affected by another process besides dissolution, which we believe to be associated with a decrease in the precipitation rate of the alteration phases. These results show that the dissolution rate measured soon after the formation of certain alteration phases provides an upper limit for the long-term dissolution rate, and can be used to determine a bounding value for the source term for radionuclide release from waste glasses. The long-term dissolution rates measured in tests at 20,000 per m at 90 degrees C in tuff groundwater at pH values near 12 for the Environmental Assessment glass and glasses made with SRL 131 and SRL 202 frits, respectively

Overview of chemical modeling of nuclear waste glass dissolution