Isomorphous substitutions of Mg and Fe for Al generally appear in the octahedral sheets of montmorillonite, whereas they are infrequent in kaolinite. Therefore, the release of Mg and Fe from the octahedral sheets probably happens during the transformation of montmorillonite into kaolinite, which could affect the migration of Mg and Fe from clay minerals into surrounding environments. The objective of the current study was to investigate the relationship between Mg and Fe release during the transformation of montmorillonite into kaolinite. The results showed that the d060 value of clay minerals decreased slightly, and the intensities of both the AlMg–OH and AlFe–OH bending vibrations also decreased gradually. In addition, the (Mg+Fe)/Al (major octahedral ions) atomic ratio of kaolinite was lower than that of montmorillonite, especially in identical hydrothermal products. These results indicated that Mg and Fe ions were released progressively from the octahedral sheets during the transformation of montmorillonite into kaolinite. Moreover, the changed relative concentrations of Mg and Fe ions in the supernatant solutions after hydrothermal reactions suggested a random distribution of Mg and/or Fe in the octahedral sheets of the montmorillonite. These results improve understanding of the release relationship between Mg and Fe during clay mineral evolution and of the distribution of these two ions in the octahedral sheets, as well as the chemical composition of clay minerals as an indicator of geological environments.

Many studies of the chemical composition of sepiolite and palygorskite have been carried out using analytical electron microscopy (AEM). According to the literature, a compositional gap exists between sepiolites and palygorskites, but the results presented here show that they may all be intermediate compositions between two extremes. The results of >1000 AEM analyses and structural formulae have been obtained for the samples studied (22 samples of sepiolite and 21 samples of palygorskite) and indicate that no compositional gap exists between sepiolite and palygorskite. Sepiolite occupies the most magnesic and trioctahedral extreme and palygorskite the most aluminic-magnesic and dioctahedral extreme. Sepiolite and palygorskite with intermediate compositions exist between the two pure extremes: (1) sepiolite with a small proportion of octahedral substitution; (2) palygorskite with a very wide range of substitution (the pure dioctahedral extreme is unusual); and (3) intermediate forms, Al-sepiolite and Mg-palygorskite with similar or the same chemical composition. The chemical compositions of the intermediate forms can be so similar that a certain degree of polymorphism exists between Al-sepiolite and Mg-palygorskite.

The structure of an illite-smectite (I-S) sample (HSI) from the Tertiary–Cretaceous boundary layer at Stevns, Denmark, i.e. the so-called Fish Clay, is investigated in order to discuss the origin of this clay and its similarity to clays from Maastrichtian-Danian chalk of Denmark and the North Sea. The phase compositions and layer sequences have been determined by X-ray diffraction. The structural formulae are determined from chemical analysis and solid-state 27Al magic-angle spinning (MAS) nuclear magnetic resonance (NMR) spectroscopy. The octahedral vacancy pattern has been determined by thermal analysis and the particle shape by atomic force microscopy. The HSI sample I-S consists of two phases, a high-smectitic (HS) phase (70%) having 95% smectite and 5% illite (leucophyllite) layers, and a low-smectitic (LS) phase (30%) having 50% smectite and 50% illite (leucophyllite) layers. Both phases have trans-vacant dioctahedral sheets and contain only traces of IVAl, the charge of the illite (leucophyllite) layers being provided predominantly by octahedral Mg for Al substitution. The structure of the tetrahedral and octahedral sheets for the HSI are compared to the structure of an I-S sample (GRI) from the Maastrichtian chalk at Stevns below the Tertiary-Cretaceous boundary and to the standard smectite SAz-1 from Arizona. For all three samples the 27Al MAS NMR spectra show the presence of two resolved IVAl resonances, which indicate the presence of two different IVAl sites. The NMR, infrared spectroscopy and chemical data show that both HSI and GRI have highly ordered Mg for Al substitution in the octahedral sheet, each Al having one Mg and two Al neighbours, whereas substitution of Mg for Al in SAz-1 is random. For the HSI sample, both the HS and LS phases are probably formed from volcanic ash. The structural similarity of the phases in HSI and GRI shows that GRI formed from a material similar to HSI by illitization of the HS phase and chloritization of the LS phase.