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

► A glass-iron-clay setup has been reacted at 90 °C for up to 18 months. ► The reacted interfaces were characterized with micro-spectroscopic techniques. ► Glass was altered at a rate close to the initial rate over a period of 18 months. ► P, Mo, and REE from glass precipitated as a thin layer. ► Oxidized Fe precipitated as a Fe-rich layer of siderite and Fe-phyllosilicate. Glass–iron–clay setups were reacted at 90 °C for 6–18 months 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 10 months, 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 20 μm after 6 months to 80 μm after 18 months) 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 r 0. 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.