Characterization of homoionic Fe2+-type montmorillonite: Potential chemical species of iron contaminant

Fe2+-montmorillonite with Fe2+ ions occupying cation exchange sites is an ideal transformation product in bentonite buffer material. In our previous study on preparation and characterization of Fe2+-montmorillonite, the montmorillonite sample that adsorbed Fe2+ ions on almost all of the cation exchange sites was prepared using a FeCl2 solution under an inert gas condition [N. Kozai, Y. Adachi, S. Kawamura, K. Inada, T. Kozaki, S. Sato, H. Ohashi, T. Ohnuki, T. Banba, J. Nucl. Sci. Technol. 38 (2001) 1141]. In view of the unstable nature of iron(II) chemical species, this study attempted to determine the potential contaminant iron chemical species in the sample. Nondestructive elemental analysis revealed that a small amount of chloride ions remained dispersed throughout the clay particles. The chloride ion retention may be due to the adsorption of FeCl+ ion pairs in the initial FeCl2 solution and the subsequent containment of the Cl− ions that are dissociated from the FeCl+ ion pairs during excess salt removal treatment. Two explanations are advanced for the second process: the slow release of the remaining Cl− ions from the collapsed interlayer of the montmorillonite, and the transformation of a minor fraction of the remaining FeCl+ ion pairs to iron(III) hydroxide chloride complexes having low solubility.