The alteration and transformation behaviour of montmorillonite (Wyoming bentonite) was studied experimentally to simulate the mineralogical and chemical reaction of clays in contact with steel in a nuclear waste repository. Batch experiments were conducted at 80 and 300°C, in low-salinity solutions (NaCl, CaCl2) and in the presence or otherwise of magnetite and hematite, over a period of 9 months. The mineralogical and chemical evolution of the clays was studied by XRD, SEM, transmission Mössbauer spectroscopy and EDS-TEM. Experimental solutions were characterized by ICP-AES and ICP-MS. The main results are that no significant change in the crystal chemistry of the montmorillonite occurred at 80°C, while at 300°C, the presence of Fe oxides leads to a partial replacement of montmorillonite by high-charge trioctahedral Fe2+-rich smectite (saponite-like) together with the formation of feldspars, quartz and zeolites.