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Cation mass-valence sum (CM-VS) approach to assigning OH-bending bands in dioctahedral smectites

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Clays and Clay Minerals

An Erratum to this article was published on 01 April 2008

Abstract

The assignments of OH-bending bands in the infrared (IR) spectra of dioctahedral smectites (montmorillonites, ferruginous smectites, and nontronites) have been revisited using a cation mass-valence sum (CM-VS) approach to quantify octahedral cation occupancy. The CM-VS approach enabled prediction of OH-bending band positions (in wavenumbers) related to OH-sharing octahedral cation pairs that had valence sums of 4 and 5, and cation masses associated with Fe(II) and Mg. Application of rules for the relationship enabled determination of the location of OH-sharing octahedral cation pairs containing Mg and Fe(II) for which previous assignments have been considered controversial, e.g. Fe(III)Mg-OH and MgMg-OH, or for which assignments have been missing due to lack of spectroscopic evidence, e.g. AlFe(II)-OH, Fe(III)Fe(II)-OH, Fe(II)Mg-OH, and Fe(II)Fe(II)-OH. Examples of these bands from several natural ferruginous smectites and nontronites are discussed. Quantification of IR spectra was used to develop a better understanding of the octahedral cation occupancy of this important class of Fe(III)-enriched smectites. While Fe(II) contents may be somewhat overestimated by the IR technique, those for four of the six ferruginous smectites studied here agree well with data from Mössbauer spectroscopy.

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  1. Department of Civil Engineering, Monash University, Clayton, 3800, VIC, Australia

    Will P. Gates

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Correspondence to Will P. Gates.

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Gates, W.P. Cation mass-valence sum (CM-VS) approach to assigning OH-bending bands in dioctahedral smectites. Clays Clay Miner. 56, 10–22 (2008). https://doi.org/10.1346/CCMN.2008.0560102

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  • DOI: https://doi.org/10.1346/CCMN.2008.0560102

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