Infrared spectroscopy in the mid-IR region was used to follow the structural changes occurring in five Li-saturated dioctahedral smectites upon heating. The smectites included three montmorillonites, an Fe-beidellite and a ferruginous smectite. Fixation of Li+ ions in the structure even upon heating at 120°C caused the appearance of an AlMgLiOH-stretching band near 3670 cm–1 in the spectra of all three montmorillonites. This band confirmed the presence of Li(I) in the previously vacant octahedral positions in montmorillonites. No similar band was observed in the spectra of ferruginous heated smectites with prevailing tetrahedral charge. A gradual upward frequency shift and decrease in intensity of the AlAlOH-bending band showed that Li(I) present in the hexagonal cavities causes pronouncedperturbation of this OH-bending mode. The Li(I) present in the octahedral sheets causes small perturbations of the OH-bending mode near 850 cm–1 and activation of a new OH-bending mode near 803 cm–1. Reversible changes in the positions of the stretching Si–O and bending OH bands in the spectra of Fe-beidellite and a ferruginous smectite proved that Li was present in these minerals primarily in the hexagonal holes of the tetrahedral sheets.

Diffuse reflectance spectra in the near-infrared region are presented for Li-saturated smectites heated up to 200°C. The smectites included three montmorillonites, an Fe-beidellite and a ferruginous smectite. Unheated samples showed a complex band near 7060 cm-1 assigned to the first overtone of the OH-stretching mode of structural hydroxyl groups and bound H2O. The OH combination bands appeared in the 4600-4300 cm-1 region. Spectra of heated montmorillonites showed an upward shift and splitting of the OH-overtone band into two components near 7170 and 7110 cm-1. The presence of a band near 7170 cm-1, assigned to the overtone of the AlMgLiOH-stretching vibration, implied that local trioctahedral domains were created upon Li(I) fixation in the previously vacant octahedral positions of montmorillonites. The OH combination bands were shifted to higher frequencies and a new band appeared near 4472 cm-1 in the spectra of montmorillonites heated to temperatures in excess of 130°C. No features indicating Li(I) in the structure of Fe-beidellite or ferruginous smectite were observed in the NIR spectra.

The changes of adsorption properties of uncalcined Al-pillared montmorillonite were studied. A soda-activated bentonite from Slovakia was reacted with polymeric hydroxoaluminium salt solutions. During storagein air at room temperature for three years, the basal spacing decreased by 0.15–0.2 nm; the specific surface area was reduced by 80% and the total pore volume by 40–60%. Adsorption experiments from ethanol-cyclohexane mixtures revealed the decreasing adsorption capacity and the increasing hydrophobicity. The changing surface character was also evident in the decrease in enthalpy of immersion in ethanol from 65.3 J/g to 8.3 J/g (sample B) and from 37.8 J/g to 5.2 J/g (sample C). The alteration probably arises from gradual formation of gibbsite-like interlayers and the redistribution of charges.

Thermal analysis (DTA-TG-DTG), X-ray diffraction (XRD), Fourier transform infrared (FTIR) spectroscopy, nitrogen adsorption and mercury intrusion porosimetry techniques were used to assess the structural changes induced upon heating of two hydrotalcite-phenol (trichloro- and trinitrophenol, HT-TCP and HT-TNP) complexes, and the results were compared with those obtained for the original hydrotalcite (HT) sample. The DTA revealed thermal effects that depended on the nature of the interlayer ion in the complexes. The total weight loss (TG-DTA) increased from 37% for the original HT to 40% for HT-TCP and 77% HT-TNP, as the amount of phenol increased. The XRD and FTIR spectroscopy showed that the calcination product (550°C) of the HT-phenol complexes was indistinguishable from that formed from the original HT. Since HT-phenol complexes were prepared by phenol adsorption on calcined HT, our results confirm the recyclability of HT-like compounds as sorbents for phenols.

The results of a new technique for the measurement of the thickness distribution of fundamental particles are reported. The technique is based on high-resolution transmission electron microscopy (HRTEM) of Na-saturated mixed-layer illite-smectite dispersed in polyvinylpyrrolidone (PVP-10). Intercalation of PVP-10 increases the spacing of expandable interlayers and changes the arrangement of particles so that the number of layers per fundamental particle can be counted easily on HRTEM images. The data obtained by HRTEM on PVP-10-intercalated illite-smectite of hydrothermal origin are compared with data from the Pt-shadowing technique. A good agreement between the two methods for the measured thickness distributions, mean thickness and expandability confirms the reliability of the new technique. The same technique is applied to a set of four sedimentary samples with different expandabilities (83-18%). The thickness of illite particles from shales and claystones has a lognormal distribution. Detrital anddiscrete illite particles can be distinguished from the thickness distribution of authigenic illite.

The clay mineralogy of Upper Permian–Lower Cretaceous mudstones from East Greenland has been investigated by X-ray diffraction (XRD), atomic force microscopy (AFM) and thermal analysis in order to evaluate long-term trends in provenance and palaeoclimate and to detect possible volcanic events. The Upper Permian–Lower Triassic mudstones contain illite, chlorite, vermiculite, kaolinite and illite-smectite (I-S), whereas the Rhaetian–Sinemurian mudstones are dominated by kaolinite. Aalenian–Albian mudstones contain kaolinite and large amounts of I-S with ˜80% illite layers. Exceptions are three Kimmeridgian samples, which contain mainly I-S with 30% illite layers, and three Upper Barremian–Lower Aptian samples with large amounts of smectite layers. Discrete clay minerals in the Upper Permian–Jurassic mudstones are largely detrital. The smectite-rich I-S probably reflects episodes of volcanic activity in late Jurassic and late Barremian–early Aptian times. This is the first indication of Mesozoic volcanism from the Mesozoic rift basin of East Greenland. The main sediment source during late Permian–early Cretaceous times was weathered Precambrian and Caledonian crystalline basement. The only possibly climate-induced change is a change from chlorite, illite, vermiculite and kaolinite in Upper Permian–Lower Triassic mudstones to kaolinite and I-S in the Jurassic mudstones and is probably due to an increase in precipitation.

Late Cretaceous bentonitic clays in the Kelkit Valley region of Turkey are composed of an alternation of limestone lenses and silicified tuff nodule-bearing pyroclastic rocks and their alteration products. Quartz, feldspar, biotite, trace amounts of augite together with pumice and volcanic rock fragments comprise the volcanogenic components. Diagenetic minerals are represented by clay, calcite, opal-CT, zeoliteand dolomite. The clay fraction is dominated by smectite and lesser amounts of I-S, illite, chlorite and kaolinite. The d001 basal spacing of dioctahedral smectites ranges from 12.51 to 12.55Å in Na-smectites and 14.97 to 15.52 A˚in Ca-smectites. The CaO/Na2O ratio of smectites ranges from 0.15 to 19.50, and the interlayer Na and Ca contents are 0.22–0.30 in beidellitesand 0.02–0.09 while those in montmorillonites are 0.01–0.13 and 0.03–0.15, respectively. The data obtained indicate that bentonites formed in a marine environment by the alteration of volcanic ash of rhyodacitic/dacitic and intermediate/acidic composition.

There are two different views regarding the genesis of gibbsite in tropical acid soils: (1) direct weathering of primary Al-silicate minerals; and (2) transformation through clay mineral intermediates. We investigated the genesis of gibbsite in two representative Ultisols from northeastern India. Gibbsite in these Ultisols appears to be the remnant of earlier weathering products of aluminosilicate minerals formed in a neutral to alkaline pedochemical environment. The mere presence of gibbsite in these soils, therefore, does not indicate their advanced stage of weathering. The formation of typically rod-shaped and well-crystallized gibbsite in both the coarse and fine soil fractions in the presence of large amounts of 2:1 minerals indicates that the anti-gibbsite hypothesis may not be tenable in these tropical acid soils. A schematic model for the formation of gibbsite and kaolin in Ultisols is proposed.

Clay minerals from the tidal flat sediments along the coast of Youngjong Island, west of mainland Korea, were studied to ascertain their potential as an indicator of sea-level fluctuation. Semi-quantitative analysis of their clay-size fractions by XRD shows that the vertical distribution of clay minerals can be separated into four clay mineral assemblage units. Based on the relative contents of chlorite, four sedimentary units are distinguishable, and the abundance of chlorite is inversely related to that of smectite. The kaolinite content is constant, and so it is clear that chlorite originating from the Han River was transformed to smectite by pedogenesis during regression periods. Therefore, the relative contents of clay minerals from the unconsolidated materials in the tidal flat of Youngjong Island canbe used as indicators of transgression and regression in accordance with the sea-level fluctuation.