Glass-iron-clay interactions in a radioactive waste geological disposal: An integrated laboratory-scale experiment

摘要

Glass-iron-clay setups were reacted at 90°C for 6-18months to investigate the coupled interactions between glass alteration, Fe corrosion and clay transformation. The reacted interfaces were probed at the microscopic level using complementary characterization methods (scanning electron microscopy coupled with energy-dispersive X-ray analysis, micro-Raman spectroscopy, micro X-ray diffraction, micro X-ray fluorescence spectroscopy, and micro X-ray absorption near-edge structure spectroscopy). The 10-μm thick Fe foil was fully corroded within 10months, exposing glass to the pore solution. Iron corrosion led to the formation of a layer containing mostly magnetite, siderite and Fe-rich phyllosilicates with one tetrahedral and one octahedral sheet (TO) or two tetrahedral and one octahedral (TOT) sheet per layer. The clay in contact with this corrosion layer was enriched in siderite (FeCO_3). Glass alteration resulted in the formation of a gel layer whose thickness increased with reaction time (from 20μm after 6months to 80μm after 18months) and a thin layer of secondary precipitates that concentrated lanthanides, P, and Mo. Assuming conservative behavior of Zr, the Si molar concentration in the gel is about 57% that in the glass. Glass dissolution remained at a rate close to the initial dissolution rate r0. The data are consistent with glass dissolution sustained by the uptake of dissolved Si and charge-compensating cations on secondary (corrosion) products, thus maintaining the gel porosity open and facilitating the leaching of easily soluble elements.