Clay mineral abundances and illite-smectite (I/S) compositions have been determined by X-ray diffraction (XRD) in shales of Permo-Triassic to Quaternary age from seven wells in the Viking Graben and Moray Firth. Chemical analyses of size fractions provide evidence that diagenetic illitization of smectite has occurred during burial by uptake of Al and K, and release of Si. K-feldspar was probably the main source of K for illitization. The depth at which random I/S disappears occurs at similar temperatures (mean 93°C) in each well for which reliable measurements are available. Vitrinite reflectance measurements at this depth are also similar (mean 0·64% R0) and correspond to early oil generation. I/S diagenetic levels may have been imprinted by a Tertiary heating event.

Illite/smectite mixed-layered minerals (I/S) occurring in hydrothermally altered dacite from the island of Martinique were studied using X-ray powder diffraction, electron microprobe and CEC measurement techniques. Microprobe analyses and X-ray identification of high- and low-charge smectite layers indicate that the I/S hydrothermal alteration operates from wall-rock to hydrothermal veins, with conversion of high-charge to low-charge smectite and formation of illite layers. The overall alteration reaction can be expressed as: mixed-layered high-charge smectite + Si4+ + K+ → mixed-layered low-charge smectite + illite. This reaction requires Si and K from external sources and differs from the currently invoked mechanisms for diagenetic illitization where Si is released. The proposed reaction appears, therefore, to be the first step of I/S alteration under low-temperature hydrothermal conditions, prior to the crystallization of newly-formed I/S.

Mössbauer spectra of several smectites demonstrate the existence of at least three phases with distinct Fe populations: (i) a component with very low Fe content (< 1%), which shows slowly-relaxing paramagnetic hyperfine structure at both 4·2 K and 77 K; (ii) a component with intermediate Fe content (∼ 1–10%) which is seen as doublets in the spectra at 4·2 K, 77 K and ambient temperature; (iii) an Fe-rich phase (> 30% Fe), which shows magnetic ordering at 4·2 K and 77 K. These data are consistent with components (i) and (ii) corresponding to Fe incorporated in aluminosilicate structures from distinct phases, whereas (iii) is characteristic of an iron oxide phase, probably goethite in most cases. These conclusions are supported by EPR measurements which show magnetically-dilute Fe in more than one type of structural environment plus an additional component with magnetically-interacting ions.

Mössbauer spectra of three natural ferrihydrites of different crystallinities were collected between 295 and 4·2 K. Optimal fits of the room-temperature spectra were obtained using distributions of quadrupole-split doublets; half-widths of the distributions (0·71–0·86 mm/s) increased, and maxima (at 0·62–0·78 mm/s) shifted to higher quadrupole splittings with decreasing crystallinity. Rather poorly-defined magnetically-ordered spectral components appeared and gradually replaced the superparamagnetic doublets as temperatures were reduced. Blocking temperatures between 115 and 28 K, derived from the relative areas under the doublets and magnetic sextets, indicated average particle sizes between ∼ 5 and 3 nm. The sextets were relatively broad and could be fitted with distributions of hyperfine fields. These distributions narrowed and their maxima shifted to higher fields as temperatures decreased; the influence of superparamagnetism was no longer apparent at 4·2 K.

Imogolite, protoimogolite and two synthetic allophanes (A and B) with very different Si/Al ratios have been pyrolysed over a range of temperatures, and the reactions followed by high-resolution solid-state 27AI and 29Si nuclear magnetic resonance (NMR) spectroscopy. The Si(OAloct)3OH groups of protoimogolite are destroyed at relatively low (∼ 200°C temperatures, whereas the same structures in imogolite are stable to ∼ 300°C. During pyrolysis of both materials there is little change in the observed coordination of AI at temperatures of < 500°C but at 500°C or higher, ∼25% of the NMR-visible Al is converted to tetrahedral coordination. The mechanism of decomposition of both protoimogolite and imogolite is shown to involve the formation of highly branched Si-O-Si chains. As far as can be discerned by 27Al and 29Si NMR, allophanes A and B both appear to produce products similar to protoimogolite on pyrolysis.

The degree of distortion of the calcite endotherm on differential thermal analysis (DTA) curves for kaolinite-calcite mixtures depends on the kaolinite sample used as well as on the factors previously established. Although no two of the ten kaolinite samples employed, even if from the same general locality, produced identical effects under all experimental conditions, a general relationship between locality of origin and degree of distortion was noted. The crystalline species detected in the products of heating, after standing in air at room temperature, included portlandite, calcite, aragonite, vaterite and the high-temperature phases gehlenite, α′-Ca2SiO4, and 12CaO. 7Al2O3. The actual species present again depended on the kaolinite sample. Although the results cannot be directly related to the volatiles evolved along with water on dehydroxylation of the different kaolinites, a tentative explanation is offered on the basis of the effects of the volatiles on the surfaces of the particles present.

The photo-oxidation of tryptophan (TRP), photosensitized by methylene blue (MB) exchanged on hectorite, Wyoming bentonite and laponite is strongly influenced by three factors: (i) Fe(III) in the structure, which quenches the excited state of MB; (ii) the adsorption site of MB, as photo-oxidation only takes place with MB on the external surface; (iii) dye aggregation, which reduces the yield. Rose bengal (RB), chemically anchored on the external surface of Barasym does not sensitize the photo-oxidation of TRP.

The interactions between and higher molecular weight hydroxy-Al species with homoionic Na- and Ca-montmorillonite have been studied by measuring adsorption of the hydroxy-Al on to the clay, turbidity of the resulting suspensions, electrokinetic potential, and d(001) basal spacing. The isolated “Al13” ions are adsorbed according to a cation-exchange process which causes flocculation of the tactoids at low concentrations. At higher concentrations, the adsorption of either isolated “Al13” or/and higher molecular weight species is mainly responsible for the dispersion of clay particles with a net positive surface charge (ζ ∼ + 50 mV). Consequently, the tactoids are destroyed.

High-gradient magnetic separation (HGMS) performed on the clay fraction (< 1 µm) of acid soils facilitates the separation and concentration of mineral fractions according to their Fe and Mg contents. As a result, smectitic layers formed by weathering of a chlorite were identified although they were not detected in the bulk sample. The concentration in the non-magnetic fraction of minerals with an intergrade vermiculite-chlorite behaviour enabled more accurate information to be obtained on these minerals.