Twenty two samples were studied to investigate the nature and evolution mechanism of mixed-layer kaolinite-smectite (K-S). We examined the <2 μm or <0.2 μm fraction of K-S formed by hydrothermal and hypergenic alteration of volcanic material. The samples are from three localities: 20 specimens from a Tortonian clay deposit in Almería, Spain; one specimen from weathered Eocene volcanic ash from the Yucatan Peninsula, Mexico; and one sample from a weathered Jurassic bentonite from Northamptonshire, England. The samples were studied using chemical analysis, X-ray diffraction (XRD) and Fourier transform infrared spectroscopy (FTIR). The XRD patterns of the oriented, glycolated mounts were modeled using NEWMOD and the proportion of smectite and kaolinite layers was determined, ranging between 0 and 80% kaolinite. The analysis of the OH-stretching region of the FTIR spectra at different temperatures (180–550°C) showed the progressive dehydroxylation of kaolinite domains and, perhaps, of smectite domains, but no detailed information could be obtained about the sequential OH loss in different cation environments. The abundance and short-range ordering of the octahedral cations were studied using the OH-bending bands. The chemical and FTIR-estimated octahedral cation abundances were broadly similar. Aluminum showed a tendency to mix with Fe and Mg rather than to form AlAl pairs. Al-for-Mg substitution accompanying kaolinization was evident from the increase in AlAl pairs and decrease in AlMg pairs. Iron is retained in the structure. No other octahedral cation rearrangement was observed. The intensity of the 750 cm −1band, assigned to translational vibrations of external OH groups in a kaolinitic environment, was quantified and modeled in relation to kaolinite layer proportion. The chemical data show that there are residual interlayer cations in kaolinite domains, which, in accordance with the model mentioned above, disturb external OH-translation vibrations. These results indicate the persistence of certain chemical and structural smectite features in kaolinite domains and thus support a smectite kaolinization process via a solid-state transformation. This confirms previous XRD, thermal, chemical and NMR analyses of the same sample set.

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