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Effects of Temperature, pH, and Iron/Clay and Liquid/Clay Ratios on Experimental Conversion of Dioctahedral Smectite to Berthierine, Chlorite, Vermiculite, or Saponite

Published online by Cambridge University Press:  01 January 2024

Regine Mosser-Ruck ,
Michel Cathelineau ,
Damien Guillaume ,
Delphine Charpentier ,
Davy Rousset ,
Odile Barres  and
Nicolas Michau
Regine Mosser-Ruck*
Affiliation:
G2R, Nancy-Université, CNRS, CREGU, Boulevard des Aiguillettes, B.P. 239, F-54506, Vandoeuvre-lès-Nancy, France
Michel Cathelineau
Affiliation:
G2R, Nancy-Université, CNRS, CREGU, Boulevard des Aiguillettes, B.P. 239, F-54506, Vandoeuvre-lès-Nancy, France
Damien Guillaume
Affiliation:
LMTG, UMR 5563 CNRS-UPS-IRD, Observatoire Midi-Pyrénées, 14 avenue Edouard Belin, 31400 Toulouse, France
Delphine Charpentier
Affiliation:
CNRS-Université de Franche-Comté/UMR 6249 Chrono-environnement, 16 route de Gray, 25065 Besançon, France
Davy Rousset
Affiliation:
G2R, Nancy-Université, CNRS, CREGU, Boulevard des Aiguillettes, B.P. 239, F-54506, Vandoeuvre-lès-Nancy, France
Odile Barres
Affiliation:
Laboratoire Environnement et Minéralurgie, CNRS UMR7569, 15 Avenue du Charmois, BP40, 54501 Vandoeuvre-lès-Nancy, France
Nicolas Michau
Affiliation:
ANDRA, Direction Scientifique/Service Matériaux, Parc de la Croix Blanche, 1/7 rue Jean Monnet, 92298 Châtenay-Malabry, France
*
* E-mail address of corresponding author: regine.ruck@g2r.uhp-nancy.fr
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Abstract

In deep geological repositories for high-level nuclear wastes, interactions between steel canisters and clay-rich materials may lead to mineralogical transformations with a loss of the confining properties of the clays. Experiments simulating the conversion of smectite to Fe-rich clay phases in contact with Fe metal have been carried out to evaluate such a possibility by taking into account the effects of a series of critical parameters, including temperature, pH, and Fe/clay (Fe/C) and liquid/clay (L/C) ratios. The mineralogical and chemical transformations observed in these experiments have been compared with data from the literature, and subsequently used to propose a conceptual model for the main mineralogical transformations which can be expected in clay formations surrounding high-level nuclear waste repositories. In the presence of Fe metal and under low oxygen fugacity (<-40) the main mineralogical sequences are as follows:

  1. (1) up to 150°C, under neutral pH, and L/C > 5: dioctahedral smectite (di-sm) → 7 Å Fe-rich phase (berthierine, odinite-cronstedtite) for large Fe/C ratios (>0.5), or di-sm → Fe-rich di-sm + Fe-rich trioctahedral smectite (tri-sm) for small Fe/C ratios (0.1)

  2. (2) up to 150°C, under alkaline pH (10–12), and L/C > 5: di-sm → Fe di-sm (±palygorskite) for a small Fe/C ratio (0.1)

  3. (3) at 300°C, Fe/C = 0.1, and L/C > 5: di-sm → Fe-rich saponite → trioctahedral chlorite + feldspar + zeolite (near-neutral pH); di-sm → Fe-rich vermiculite + mordenite (pH 10–12).

Low temperatures (<150°C) and large L/C and Fe/C ratios seem to favor the crystallization of the serpentine group minerals instead of Fe-rich trioctahedral smectites or chlorites, the latter being favored by higher temperatures. The role of L/C and Fe/C ratios and the competition between them at different temperatures is a crucial point in understanding the transformation of smectite in contact with Fe metal.

Keywords

BerthierineChloriteFe MetalNuclear WasteSaponiteSmectiteVermiculite

Information

Type
Article
Information
Clays and Clay Minerals , Volume 58 , Issue 2 , April 2010 , pp. 280 - 291
Copyright
Copyright © Clays and Clay Minerals 2010

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