Dioctahedral smectite samples of a wide range of compositions (beidellites, montmorillonites, nontronites, Fe-rich montmorillonites and Al-rich nontronites) were studied by infrared (IR) spectroscopy. A special sample-preparation technique was used to eliminate the contribution of molecular water. The OH-stretching regions of the spectra were decomposed and curve-fitted, and the individual OH-stretching bands were assigned to all the possible types of OH-bonded cation pairs that involve Al, Mg and Fe. The integrated optical densities of the OH bands were assumed to be proportional to the contents of the specific types of OH-linked cation pairs with the absorption coefficients being the same for all individual OH bands. Good agreement between the samples’ octahedral cation compositions calculated from the IR data and those given by crystal-chemical formulae was obtained for a representative collection of samples in terms of a unique set of individual OH-band positions that vary within narrow wavenumber intervals. This has allowed us to minimize the ambiguity in spectra decomposition caused by the poor resolution of smectite spectra and confirmed the validity of the resulting band identification.

The bands associated with specific OH-bonded cation pairs in the spectra of smectites are, on the whole, shifted to greater wavenumbers with respect to the corresponding bands in micas. In addition to OH bands that refer to the smectite structure, AlOHAl and AlOHFe bands of the pyrophyllite structural fragments were identified. The band-position variation ranges overlap in a few cases (AlOHFe and MgOHMg; AlOHAl of smectite and AlOHFe of pyrophyllite-like component).

Unambiguous interpretation of the OH-stretching vibrations was found to be possible only for smectite samples with known chemical compositions, so that IR data cannot be used for quantitative determination of octahedral cation composition of mixtures of dioctahedral 2:1 phyllosilicates. In the case of the studied monomineral smectites with known chemical compositions, IR data provided information on the short-range order/disorder in the distribution of octahedral cations along cation-OH-cation directions. This information can be employed, in conjunction with the data of other spectroscopic and diffraction techniques, in the analysis of short-range octahedral cation distribution.

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