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Experimental study of the transformation of smectite at 80 and 300°C in the presence of Fe oxides

¹ Géologie et Gestion des Ressources Minérales et Energétiques (G2R), UMR 7566 CNRS-CREGU-INPL-UHP, Université Henri Poincaré, BP 239, 54506 Vanduvre-lès-Nancy, ² Laboratoire Environnement et Minéralurgie (LEM), UMR 7569 CNRS-INPL, Ecole Nationale Supérieure de Géologie, BP 40, 54501 Vanduvre-lès-Nancy, ³ Laboratoire de Chimie Physique et Microbiologie pour l’Environnement (LCPME), UMR 7564 CNRS-UHP, Université Henri Poincaré, 405 rue de Vanduvre, 54600 Villers-lès-Nancy, ⁴ Agence nationale pour la gestion des déchets radioactifs (ANDRA), Direction Scientifique/Service Matériaux, Parc de la Croix Blanche, 1/7 rue Jean Monnet, 92298 Châtenay-Malabry, France

^* E-mail: damien.guillaume{at}g2r.uhp-nancy.fr

(Received 6 January 2003; revised 26 July 2003)

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.

KEYWORDS: bentonite, smectite, saponite, magnetite, hematite, experimental synthesis, EDS-TEM, transmission Mössbauer spectroscopy, X-ray diffraction

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