Reactive Transport Modelling of CO2 Sequestration in Saline Aquifers

International audienceGeological sequestration of CO2 in deep saline aquifers may offer numerous opportunities for the mitigation of greenhouse gas emissions. In order to ensure good containment, a correct understanding of the evolution of such systems after a massive injection of CO2 is compulsory. For this purpose, coupled reactive transport modelling can provide useful information, by simulating chemical reactions likely to occur in the system coupled to reactive transport, at large time and space scales.This study aimed at investigating the possible benefits of reactive transport modelling in the context of CO2 sequestration. Two deep saline aquifers have been chosen to test the performance and limitationsof the codes: the carbonated aquifer of the Dogger (Paris Basin) and the sandstone aquifer of the Bunter (North Sea). The aquifers, with contrasting behaviours, have been chosen to illustrate the main expected phenomena: CO2 dissolution in the carbonated aquifer, carbonate mineral precipitation in the sandstone aquifer. The simulations highlight the performance of the reactive transport codes, particularly the possibility to represent in detail a source (or sink) term with the dissolution of the CO2 bubble (or the precipitation of carbonated minerals), coupled to the transport of the dissolved CO2. Furthermore, flux assessment at various points of the system illustrates the storage capacity of the systems. However, several shortages have been identified: a lack of data on the aquifers and on the reactivity of CO2 under sequestration conditions. Finally, developments are advisable to better estimate the transport, dissolution and reactivity of the supercritical CO2: This involves a two-phase coupled reactive transport code, and a coupling with the exchange between phases

Optimisation of accurate rutile TiO2TiO_2 (110), (100), (101) and (001) surface models from periodic DFT calculations

In this paper, geometric bulk parameters, bulk moduli, energy gaps and relative stabilities of the TiO2 anatase and rutile phases were determined from periodic DFT calculations. Then, for the rutile phase, structures, relaxations and surface energies of the (110), (100), (101) and (001) faces were computed. The calculated surface energies are consistent with the natural rutile powder composition, even if a dependence on the number of layers of the slab used to model the surface was identified. Internal constraints, consisting in freezing some internal layers of the slab to atomic bulk positions, were thus added to mimic the bulk hardness in order to stabilise the computed surface energies for thinner systems. In parallel, the influence of pseudopotentials was studied and it appears that four valence electrons for titanium atoms are sufficient. The aim of this study was to optimise accurate rutile TiO2 surface models that will be used in further calculations to investigate water and uranyl ion sorption mechanisms

Actinide diffusion in zirconium and the role of oxidation

AC

Fission Enhanced diffusion of uranium in zirconia

This paper deals with the comparison between thermal and Fission Enhanced Diffusion (FED) of uranium into zirconia, representative of the inner face of cladding tubes. The experiments under irradiation are performed at the Institut Laue Langevin (ILL) in Grenoble using the Lohengrin spectrometer. A thin $^{235}UO\_2$ layer in direct contact with an oxidized zirconium foil is irradiated in the ILL high flux reactor. The fission product flux is about 10$^{11}$ ions cm$^{-2}$ s$^{-1}$ and the target temperature is measured by an IR pyrometer. A model is proposed to deduce an apparent uranium diffusion coefficient in zirconia from the energy distribution broadening of two selected fission products. It is found to be equal to 10$^{-15}$ cm$^2$ s$^{-1}$ at 480$\circ$C and compared to uranium thermal diffusion data in ZrO$\_2$ in the same pressure and temperature conditions. The FED results are analysed in comparison with literature data

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]

Combined investigation of water sorption on TiO2TiO_2 rutile (1 1 0) single crystal face: XPS vs. periodic DFT

XPS and periodic DFT calculations have been used to investigate water sorption on the TiO2 rutile (1 1 0) face. Two sets of XPS spectra were collected on the TiO2 (1 1 0) single crystal clean and previously exposed to water: the first set with photoelectrons collected in a direction parallel to the normal to the surface; and the second set with the sample tilted by 70°, respectively. This tilting procedure promotes the signals from surface species and reveals that the first hydration layer is strongly coordinated to the surface and also that, despite the fact that the spectra were recorded under ultra-high vacuum, water molecules subsist in upper hydration layers. In addition, periodic DFT calculations were performed to investigate the water adsorption process to determine if molecular and/or dissociative adsorption takes place. The first step of the theoretical part was the optimisation of a dry surface model and then the investigation of water adsorption. The calculated molecular water adsorption energies are consistent with previously published experimental data and it appears that even though it is slightly less stable, the dissociative water sorption can also take place. This assumption was considered, in a second step, on a larger surface model where molecular and dissociated water molecules were adsorbed together with different ratio. It was found that, due to hydrogen bonding stabilisation, molecular and dissociated water molecules can coexist on the surface if the ratio of dissociated water molecules is less than ≈33%. These results are consistent with previous experimental works giving a 10–25% range

Zirconium oxidation under high energy heavy ion irradiation

This paper concerns the study of zirconium oxidation under irradiation with high energetic Xe ions. The irradiations were performed on the IRRSUD beam line at GANIL (Caen). The oxygen partial pressure was fixed at 10$^{-3}$ Pa and two temperature conditions were used, either 480$\circ$C reached by Joule effect heating or 280$\circ$C due to Xe energy deposition. Zirconia was fully characterized by Rutherford Backscattering Spectrometry, Transmission Electron Microscopy and Grazing Angle X-ray Diffraction. Apparent diffusion coefficients of oxygen in ZrO2 were determined from these experiments by using a model which takes into account a surface exchange between oxygen gas and the ZrO2 surface. These results are compared with thermal oxidation data

Experimental study of pure mineral phases/supercritical CO2 reactivity. Implications for geological CO2 sequestration

International audienceCarbon dioxide sequestration in deep aquifers and depleted oilfields is a potential technical solution for reducing green-house gas release to the atmosphere: the gas containment relies on several trapping mechanisms (supercritical CO2, CO2(sc), dissolution together with slow water flows, mineral trapping) and on a low permeability cap-rock to prevent CO2(sc), which is less dense than the formation water, from leaking upwards. A leakproof cap-rock is thus essential to ensure the sequestration efficiency. It is also crucial for safety assessment to identify and assess potential alteration processes that may damage the cap-rock properties: chemical alteration, fracture reactivation, degradation of injection borehole seals, etc. The reactivity of the host-rock minerals with the supercritical CO2 fluid is one of the potential mechanisms, but it is altogether unknown. Reactivity tests have been carried out under such conditions, consisting of batch reactions between pure minerals and anhydrous supercritical CO2, or a two-phase CO2/H2O fluid at 200 °C and 105/160 bar. After 45 to 60 days, evidence of appreciable mineral-fluid reactivity was identified, including in the water-free experiments. For the mixed H2O/CO2 experiments, portlandite was totally transformed into calcite; anorthite displayed many dissolution patterns associated with calcite, aragonite, tridymite and smectite precipitations. For the anhydrous CO2 experiments, portlandite was totally carbonated to form calcite and aragonite; anorthite also displayed surface alteration patterns with secondary precipitation of fibrous calcite

PWR iodine speciation and behaviour under normal primary coolant conditions: An analysis of thermodynamic calculations, sensibility evaluations and NPP feedback

Iodine is one of the most important fission products due to its high fission yield, significant radiobiological hazard and potential volatility. Its environmental and biological risks have been extensively studied in case of a severe reactor accident. Nevertheless, little information is available about iodine behaviour under normal Pressurize Water Reactor (PWR) operating conditions. The work reported explores the behaviour of different iodine species (I−, I3, I2, HOI and IO−) during full power periods, transient periods (power reductions and depressurizations) and shutdowns. Thermodynamic calculations were conducted, and their results are compared with previous predictions and with the experimental data provided by nuclear power plants (NPP). Based on thermodynamic calculations and NPP feedback, it was concluded that iodine speciation depends primarily on the redox potential and water radiolysis. * The experimental values confirm that the iodine ionic form I− is the major species during normal operation (I2 < 2%) and shutdowns (I2 < 9%). * During shutdowns: - High [I2] (20-40%) can be observed in the presence of fuel failures following an iodine spike during power or pressure variations. The fuel oxidation by radiolysis products can lead to I2 formation inside the gap and its subsequent release through cladding defects. - Once in the primary coolant, I2 is transformed into I− or View the MathML source, depending on the water oxidation conditions. * The lithium concentration and the primary coolant temperature seem to have a secondary influence on iodine speciation, while the existence of a redox potential threshold appears to be the main factor controlling the formation of volatile and non-volatile iodine forms. This paper summarizes the major results of the iodine thermodynamic studies and PWR feedback, permitting some possible recommendations for inclusion in the NPP guidelines in order to master iodine's behaviour. Future work is proposed. Redox potential measurements at high temperatures, coupled with thermodynamic estimations and radiolysis analysis, should be considered as useful tools to specify the optimal conditions for limiting iodine volatisation and I2 absorption