Abstract

57Fe Mössbauer spectra of the Na+- and Ca2+-saturated forms of four ferruginous smectites, displaying a range of compositions, have been fitted with Voigtian profiles to represent (principally) two correlated distributions of isomer shifts and quadrupole splittings for the Fe3+ sites. Correlating the areas and hyperfine parameters of these distributions with simulations of the octahedral array of cations based on chemical analyses and infrared spectroscopy has enabled identification of the Fe3+ ions that contribute to the outer quadrupole doublet. The octahedral Fe3+ sites are characterized as having at least one Mg2+ nearest-cation neighbour and probably a cis-configuration with respect to the OH ions.

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