Long-term corrosion of two nuclear waste reference glasses (MW and SON68): A kinetic and mineral alteration study

Powder samples of two inactive borosilicate glasses (MW and SON68), used as references for vitrified nuclear waste in Switzerland, were leached statically in pure water over more than 12a at 90 °C. Solution aliquots were taken at regular intervals in order to investigate the glass dissolution kinetics and the retention of elements representing radionuclides. At 5.7 and 12.2a, single tests were interrupted to investigate the corroded samples.Boron and Li concentration data indicate that the glass corrosion kinetics of the MW glass is about 10 times faster than for the SON68 glass, both in the transient and asymptotic phase of the leaching process. The alteration products were studied by X-ray diffraction (XRD), scanning (SEM) and transmission electron microscopy (TEM-STEM) coupled with energy dispersive spectrometry (EDS) analyses. Alteration of the MW glass produced abundant magnesian clay minerals, as well as nanoparticles of lanthanide and Zr phosphates, whereas only small amounts Ca–Zn–Fe–Ni clay minerals were formed as alteration product of SON68.Retention factors were above 99% for most trace elements, indicating almost quantitative fixation of many radionuclides in the secondary phases. Solution concentration data were used to calculate aqueous speciations and saturation indices of potential secondary solids. The solutions are close to saturation with respect to simple lanthanide phosphates (in agreement with the TEM data) and quartz. The presence of quartz in the altered SON68 samples is corroborated by XRD data.In conclusion, the corrosion and radionuclide retention properties of SON68 seem to be more favorable than those of the MW glass. A major finding of this investigation was that glass degradation may strongly depend on minor compositional changes in the glass composition. The presence of Mg in the MW glass triggers the nucleation of secondary clay minerals, thereby promoting glass corrosion via silica removal. In the Mg-free SON68 glass the formation of clays, and hence the glass degradation, were considerably slower.     

A simple way to constrain the stoichiometry of secondary smectites upon aqueous glass alteration

The comparison of the stoichiometry of several nuclear waste glasses and basaltic glasses with their associated secondary smectites evidenced that Si/Al ratios of secondary smectites are nearly equal to the Si/Al ratios of parent glasses. This information may be very useful in constraining secondary smectites structure and stoichiometry in cases where other identification methods are difficult to apply.     

The significance of intergranular diffusion to the mechanisms and kinetics of porphyroblast crystallization

The spatial disposition, compositional zoning profiles, and size distributions of garnet crystals in 11 specimens of pelitic schist from the Picuris Range of New Mexico (USA) demonstrate that the kinetics of intergranular diffusion controlled the nucleation and growth mechanisms of porphyroblasts in these rocks. An ordered disposition of garnet centers and a significant correlation between crystal radius and near-neighbor distances manifest suppressed nucleation of new crystals in diffusionally depleted zones surrounding pre-existing crystals. Compositional zoning profiles require diffusionally controlled growth, the rate of which increases exponentially as temperature increases with time; an acceleration factor for growth rate can be estimated from a comparison of compositional profiles for crystals of different sizes in each specimen. Crystal size distributions are interpreted as the result of nucleation rates that accelerate exponentially with increasing temperature early in the crystallization process, but decline in the later stages because of suppression effects in the vicinity of earlier-formed nuclei. Simulations of porphyroblast crystallization, based upon thermally accelerated diffusionally influenced nucleation kinetics and diffusionally controlled growth kinetics, quantitatively replicate textural relations in the rocks. The simulations employ only two variable parameters, which are evaluated by fitting of crystal size distributions. Both have physical significance. The first is an acceleration factor for nucleation, with a magnitude reflecting the prograde increase during the nucleation interval of the chemical affinity for the reaction in undepleted regions of the rock. The second is a measure of the relative sizes of the porphyroblast and the diffusionally depleted zone surrounding it. Crystal size distributions for the Picuris Range garnets correspond very closely to those in the literature from a variety of other localities for garnet and other minerals. The same kinetic model accounts quantitatively for crystal size distributions of porphyroblastic garnet, phlogopite, sphene, and pyroxene in rocks from both regional and contact metamorphic occurrences. These commonalities indicate that intergranular diffusion may be the dominant kinetic factor in the crystallization of porphyroblasts in a wide variety of metamorphic environments.     

Rock alteration in alkaline cement waters over 15 years and its relevance to the geological disposal of nuclear waste

The interaction of groundwater with cement in a geological disposal facility (GDF) for intermediate level radioactive waste will produce a high pH leachate plume. Such a plume may alter the physical and chemical properties of the GDF host rock. However, the geochemical and mineralogical processes which may occur in such systems over timescales relevant for geological disposal remain unclear. This study has extended the timescale for laboratory experiments and shown that, after 15 years two distinct phases of reaction may occur during alteration of a dolomite-rich rock at high pH. In these experiments the dissolution of primary silicate minerals and the formation of secondary calcium silicate hydrate (C–S–H) phases containing varying amounts of aluminium and potassium (C–(A)–(K)–S–H) during the early stages of reaction (up to 15 months) have been superseded as the systems have evolved. After 15 years significant dedolomitisation (MgCa(CO₃)₂ + 2OH⁻ → Mg(OH)₂ + CaCO₃ + CO₃²⁻_(aq)) has led to the formation of magnesium silicates, such as saponite and talc, containing variable amounts of aluminium and potassium (Mg–(Al)–(K)–silicates), and calcite at the expense of the early-formed C–(A)–(K)–S–H phases. This occured in high pH solutions representative of two different periods of cement leachate evolution with little difference in the alteration processes in either a KOH and NaOH or a Ca(OH)₂ dominated solution but a greater extent of alteration in the higher pH KOH/NaOH leachate. The high pH alteration of the rock over 15 years also increased the rock’s sorption capacity for U(VI). The results of this study provide a detailed insight into the longer term reactions occurring during the interaction of cement leachate and dolomite-rich rock in the geosphere. These processes have the potential to impact on radionuclide transport from a geodisposal facility and are therefore important in underpinning any safety case for geological disposal.     

Use of time-domain electromagnetic (TDEM) method to investigate seawater intrusion in the Lebna coastal aquifer of eastern Cap Bon,Tunisia

A multi-method geophysical survey, using time-domain electromagnetic (TDEM) fields, is conducted on the north-eastern coastal aquifer of Cap Bon, Tunisia. The aim of the study is to investigate the inland extent saltwater intrusion, to estimate the fresh-saltwater transition zone, and to characterize the lithologic spatial variability of the underground layers. Moreover, the TDEM is used to determine both fluid resistivity and bulk resistivity which are required to calculate the porosity by applying the Archie’s equation. The survey of TDEM profiles is carried out along the left and right overbanks of the Lebna river from the coast until the Lebna dam. The interpretation and the analysis of these profiles allow us to better identify the flux exchanges between the river and the underlying aquifer. On the basis of the 1D and 2D longitudinal and transversal resistivity profiles as well as the existing boreholes data and groundwater quality, it seems that the freshwater-saltwater interface is moving forward inland. Furthermore, electromagnetic results combined to the Archie’s law show that the porosity values are at the ranges of 12–36 and 5–31% for the Quaternary outcropping and Pliocene formation, respectively.     

An improved SPH method for saturated soils and its application to investigate the mechanisms of embankment failure: Case of hydrostatic pore‐water pressure

The method of smoothed particle hydrodynamics (SPH) has recently been applied to computational geomechanics and has been shown to be a powerful alternative to the standard numerical method, that is, the finite element method, for handling large deformation and post‐failure of geomaterials. However, very few studies apply the SPH method to model saturated or submerged soil problems. Our recent studies of this matter revealed that significant errors may be made if the gradient of the pore‐water pressure is handled using the standard SPH formulation. To overcome this problem and to enhance the SPH applications to computational geomechanics, this article proposes a general SPH formulation, which can be applied straightforwardly to dry and saturated soils. For simplicity, the current work assumes hydrostatic pore‐water pressure. It is shown that the proposed formulation can remove the numerical error mentioned earlier. Moreover, this formulation automatically satisfies the dynamic boundary conditions at a submerged ground surface, thereby saving computational cost. Discussions on the applications of the standard and new SPH formulations are also given through some numerical tests. Furthermore, techniques to obtain the correct SPH solution are also proposed and discussed throughout. As an application of the proposed method, the effect of the dilatancy angle on the failure mechanism of a two‐sided embankment subjected to a high groundwater table is presented and compared with that of other solutions. Finally, the proposed formulation can be considered a basic formulation for further developments of SPH for saturated soils. Copyright © 2011 John Wiley & Sons, Ltd.     

Use of micro-XRF chemical analysis for mapping volcanogenic massive sulfide related hydrothermal alteration: Application to the subaqueous felsic dome-flow complex of the Cap d'Ours section,Glenwood rhyolite,Rouyn-Noranda,Québec,Canada

A new analytical method using micro-X-ray fluorescence (XRF) is presented for the in situ analysis of major elements in rock samples. This approach has allowed for a separate study of hydrothermal alteration of matrix versus fragments in volcaniclastic material (i.e. flow breccia). This is particularly important for volcanogenic massive sulfide (VMS) exploration in subaqueous felsic dome-flow complexes, where brecciated facies are omnipresent and the imprint of hydrothermal alteration is typically heterogeneous. In this study, eleven elements are measured with a 1.7 by 1.3 mm window considered to be representative of each sample, based on replicate analyses. An average is calculated for the analyzed window and yields a nearly complete analysis with the exception of loss of ignition (LOI). Micro-XRF data were validated using whole rock XRF analyses performed on the same sample block. The application of this chemical method has been tested successfully on thin sections from the Cap d'Ours section of the Glenwood rhyolite in the Rouyn-Noranda region of Québec, Canada. With 58 samples spaced at approximately 50 m intervals, two styles of alteration zoning were recognized: (1) a lateral and concordant zoning expressed by vent-proximal silicification in the west grading toward vent-distal chlorite–sericite alteration to the east, and (2) vertical and discordant zoning expressed by stronger sericitization in the upper part of later volcanic quartz- and feldspar-phyric endogenous lobes. The former is typical of cooling induced by seawater interaction at the lava–water interface at temperatures greater than 400 °C, whereas the latter is related to lower temperature (< 300 °C) hydrothermal mineralization associated with endogenous lobe emplacement within the volcanic pile. The presented results clearly demonstrate the potential use of the micro-XRF data for characterizing weak to intense hydrothermal alteration in highly fragmented volcanic rocks.