Comparative approach of the solubility of protactinium oxy/hydroxides

RADIOCHThe hydrolysis constants and the solubility products of the oxide/hydroxides of Pa(IV) and Pa(V) have been first reviewed and re-evaluated through the application of three comparative methods: the simple Hard Sphere Electrostatic model (HSE), the Brown and Wanner Theory (BWT) and the Correlation between Solubility and Complex stability constants of a metal ion (CSC). The latter method is the most empirical one, but it gives coherent results, in agreement with the few published experimental values, for all the possible aqua species of protactinium (Pa4+, Pa5+, PaO2+ and PaO3+). The selected thermodynamic data have then been used to predict the protactinium solubility in non complexing media of various pH and redox potential

Reproducibility of the uptake of U(VI) onto degraded cement pastes and calcium silicate hydrate phases

http://www.radiochimacta.deInternational audienceThe U(VI) uptake in degraded cement pastes was undertaken in the laboratories of CEA/L3MR and SUBATECH in order to check the reproducibility of the study. Two well hydrated cement pastes, CEM I (Ordinary Portland Cement, OPC) and CEM V (blast furnace slag (BFS) and fly ash added to OPC) were degraded using similar protocols. Equilibrium solutions and solid materials were characterised for three degradation states for each paste. All samples are free of portlandite and the pH of the equilibrated cement solutions vary in the range 9.8–12.2. Three calcium silicate hydrate phases (C-S-H) were synthesised in order to compare the sorption properties of degraded cement pastes and of hydrate phases in similar pH conditions. In order to avoid precipitation processes, the operational solubility limit was evaluated before batch experiments. These solubility values vary significantly in the pH range [9–13] with a 2.4×10−7 mol/L minimum at pH close to 10.5. In batch sorption experiments, the distribution ratio Rd values are high: 30000–150000 mL/g. The uptake of U(VI) increases when comparing the least and the most degraded cement pastes whereas the initial composition of cement has relatively insensitive effect. Sorption isotherms, expressed as a log [U(VI)solid]/ log [U(VI)solution] plots are linear. A slope of 1 is calculated indicating the predominance of sorption processes. As sorption and desorption values are close, the uptake mechanism seems reversible. The Rd values measured in C-S-H suspensions are in good agreement with Rd values of degraded cement pastes, and C-S-H materials could be one of the cementitious phases which control U(VI) uptake in cement pastes

Europium retention onto clay minerals from 25 to 150 °C: Experimental measurements, spectroscopic features and sorption modelling

The sorption of Eu(III) onto kaolinite and montmorillonite was investigated up to 150 °C. The clays were purified samples, saturated with Na in the case of montmorillonite. Batch experiments were conducted at 25, 40, 80 and 150 °C in 0.5 M NaClO4 solutions to measure the distribution coefficients (Kd) of Eu as a trace element (<10−6 mol/L) between the solution and kaolinite. For the Na-montmorillonite, we used Kd results from a previous study [Tertre, E., Berger, G., Castet, S., Loubet, M., Giffaut, E., 2005. Experimental study of adsorption of Ni2+, Cs+ and Ln3+ onto Na-montmorillonite up to 150 °C. Geochim. Cosmochim. Acta 69, 4937–4948] obtained under exactly the same conditions. The number and nature of the Eu species sorbed onto both clay minerals were investigated by time resolved laser fluorescence spectroscopy (TRLFS) in specific experiments in the same temperature range. We identified a unique inner-sphere complex linked to the aluminol sites in both clays, assumed to be double bond; length as m-dashAlOEu2+ at the edge of the particles, and a second exchangeable outer-sphere complex for montmorillonite, probably in an interlayer position. The Kd values were used to adjust the parameters of a surface complexation model (DLM: diffuse layer model) from 25 to 150 °C. The number of Eu complexes and the stoichiometry of reactions were constrained by TRLFS. The acidity constants of the amphoteric aluminol sites were taken from another study [Tertre, E., Castet, S., Berger, G., Loubet, M., Giffaut, E. Acid/base surface chemistry of kaolinite and Na-montmorillonite at 25 and 60 °C: experimental study and modelling. Geochim. Cosmochim. Acta, in press], which integrates the influence of the negative structural charge of clays on the acid/base properties of edge sites as a function of temperature and ionic strength. The results of the modelling show that the observed shift of the sorption edge towards low pH with increasing temperature results solely from the contribution of the double bond; length as m-dashAlOEu2+ edge complexes. Finally, we successfully tested the performance of our model by confronting the predictions with experimental Kd data. We used our own data obtained at lower ionic strength (previous study) or higher suspension density and higher starting concentration (TRLFS runs, this study), as well as published data from other experimental studies [Bradbury, M.H., Baeyens, B., 2002. Sorption of Eu on Na and Ca-montmorillonite: experimental investigations and modeling with cation exchange and surface complexation. Geochim. Cosmochim. Acta 66, 2325–2334; Kowal-Fouchard, A., 2002. Etude des mécanismes de rétention des ions U(IV) et Eu(III) sur les argiles: influence des silicates. Ph.D. Thesis, Université Paris Sud, France, 330p]

Thermodynamics of hydration of MX80-Na: an experimental study of the hydration energies

Hydration properties of swelling clay minerals may be very variable depending on the chemical composition of the clay, on the nature of the interlayer cations and on the interlayer charge (Berend et al., 1995; Vieillard et al., 2011). The Wyoming smectite has been largely studied, notably for assessing its hydration behavior as a function of the interlayer cations, in connection with its structural characteristics (Ferrage et al., 2005; Salles et al., 2007). In the present work, carried out as part of a collaborative Andra/BRGM/HydrASA research program for ThermoChimie project, we propose an original experimental study, based on adsorption and desorption isotherms performed on MX80 clay samples. The goal is to determine energetic contributions to the reactions of hydration, which have been revealed to be non-negligible with respect to the stability of the clay minerals (Gailhanou et al., submitted). In particular, the present work addresses the problems of the hysteresis loop between adsorption and desorption isotherms and of the irreversibility of hydration reactions. This is directly related to the application of classical thermodynamics to the hydration reactions of clay minerals. In a first stage, an experimental study is dedicated to better understand the origin of the hysteresis loop which is systematically observed for the adsorption-desorption isotherms at 25°C. The development of the hysteresis loop has been studied by considering several kinetically related parameters: stabilization periods, temperatures (from 25°C to 60°C) and hydration steps (Figure 1). No sensible change was observed in the hysteresis loop. Therefore, the amount of adsorbed water depends on the followed reaction pathway (adsorption or desorption). The variations in microstructures and in the distribution of hydration layers (0/1/2 water layers; Ferrage et al., 2005) as a function of relative humidity (RH) could provide a possible explanation for this phenomenon

A study of the factors responsible for the difference in cesium adsorption by two geological clay samples

International audienc

Physico-chemical characterization of the colloidal hematite/water interface: experimentation and modelling

The surface of colloidal hematite (alpha-Fe2O3) of two different batches (synthesized in the present work or commercialized). is first characterized by electrophoretic measurements. The discrepancies about the IsoElectric Point (TEP) values are discussed. A correlation is pointed out between the aggregation of the particles and their surface charge, which is assigned to the importance of the electrostatic interactions in the stability of the colloidal suspensions. Potentiometric titrations are carried out in order to determine the concentration and acidity constants of the surface sites. The Point of Zero Charge (PZC) is in good agreement with the IEP value. The pK(a) values depend somewhat on the surface complexation model (diffuse layer model, constant capacitance model. model without electrostatic term) used to modelize the experimental curves. The parameters so obtained are compared to each others and to literature data

Sorption de molécules organiques sur une roche argileuse. Du mécanisme microscopique au transfert macroscopique.

National audienceL’argilite du Callovo-Oxfordien (COx) est étudiée par l’Andra comme barrière naturelle de confinement dans le cadre du stockage profond des déchets radioactifs de haute et moyenne activité à vie longue (HA-MAVL-projet Cigéo (fig.1)). La présence des molécules organiques anthropogéniques (MOA), générées par la dégradation de certains colis de déchets MAVL, pourrait perturber la roche et influencer la migration des radionucléides de façon plus ou moins significative en fonction des interactions géochimiques. L’objectif de cette étude est d’étudier le transport de ces MOA solubles dans la roche argileuse. Les paramètres detransport macroscopique des MOA, (D$_e$ , ε$_a$ , K$_d$ ) sur le COx sont déterminés par des expériences de diffusion et de sorption/désorption en $batch$. En complément, des mesures spectroscopiques sont prévues pour obtenir des données microscopiques sur les mécanismes de transport.Ces résultats seront utilisés comme données d’entrée pour valider les modèles de transport réactif des complexesorganiques dans la roche argileuse