Some recent works dealing with the concept of order-disorder in clay minerals are considered, including those aspects of order-disorder which appeared in the Brindley & Brown (1980) monograph, i.e. disorder in the distribution of cations, disorder in layer stacking, orderdisorder in mixed-layer systems and finite crystal size as a lattice disorder. Heterogeneity of samples and polymorphous transformations are also considered as other types of disorder. Most of these works emphasize that accurate structural characterization can only be obtained if several techniques are combined (e.g. XRD and IR, EXAFS and Mo¨ssbauer spectroscopies, etc.). Another conclusion is that accurate structural determination provides the key to the genesis of clays.

Mixed-layer illite-smectite from Lower Palaeozoic sedimentary rocks, on both sides of the Teisseyre–Tornquist tectonic zone (TTZ) in northern Poland, was studied by X-ray diffraction and dated by K-Ar means.

The percentage of smectite layers in illite-smectite (%S) indicates maximum palaeotemperatures of 125–135°C at the surface of Lower Palaeozoic rocks on the craton (NE of TTZ), and 110 to ≤180°C in different tectonic blocks to the SW of TTZ (area of Caledonian consolidation). The vertical changes in the %S indicate that the maximum palaeotemperatures were reached before Permian time on the craton, and before Jurassic, Triassic, Permian or Carboniferous periods but after the beginning of Devonian time in the Caledonian zone. The K—Ar ages of bentonites indicate that the maximum palaeotemperatures were reached by 370—390 Ma or even slightly earlier (Middle—late Devonian). A maximum of 3—6 km of Silurian–Devonian cover on the craton and in the TTZ is suggested by the data.

The diagenetic evolution of clay minerals in a 4249 m sedimentary-magmatic sequence of the Zemah-1 drillhole in the Dead Sea Rift, Israel, was studied, mainly by X-ray diffraction (XRD). The parallel maturation of the organic matter was estimated by the thermal alteration index (TAI) method. Both parameters follow a progressive diagenesis with depth. The original clays, now encountered only at shallow depths, were dioctahedral, and mostly detrital. They transformed into Mg-rich trioctahedral clays starting with a saponite-dominated assemblage, followed by a saponite, ordered chlorite-smectite (C-S), and chlorite assemblage, and finally by a saponite, corrensite, chlorite and talc assemblage. Significant mineralogical composition gaps occur between saponite to corrensite and corrensite to chlorite. Short-range variations within the most evolved assemblage are controlled by bulk-rock composition. Depths of first occurrence and disappearance of minerals indicate a much higher geothermal gradient in the past whereas the TAI values suggest an even higher palaeogradient of ∼708C km–1.

The ODP Leg 171B drilled a transect of four sites at Blake Nose in the NW Atlantic providing an excellent record of the K-T boundary. At the deepest, Site 1049, the boundary is marked by a 9–17 cm thick layer formed mostly of green spherules composed of Fe-rich smectite resulting from the diagenetic alteration of tektites and impact glasses. Minor amounts of authigenic zeolites and palygorskite also occur. This association represents a notable break in the clay mineral composition of Cretaceous and Tertiary sequences. The clay mineral assemblages of the Cretaceous and Tertiary sediments are dominated by inherited clays. Aluminium-rich smectite of pedogenic origin is abundant in both Cretaceous and Tertiary sediments, indicating a relatively warm and hydrolysing climate across the K-T boundary. At Hole 1049A, where the oldest sediments of the interval were analysed, an increase in kaolinite and smectite down core suggests tectonic rejuvenation and distal transport of illite and kaolinite, probably accompanied by more hydrolysing conditions during the late Maastrichtian.

Saponitic bentonite mined in the Magan deposit (Toledo, Spain), has been classified as a suitable clay barrier in the storage of high-level radioactive waste. Several hydrothermal alteration assays have been carried out in Teflon reactors at 45, 60, 90, 120, 175 and 200°C for periods of up to 1 y. The mineral components of bentonite are stable below 175°C. At and above this temperature, the accessory sepiolite transforms into a monomineral phase of saponitic composition. The texture of the clay also changes. A rise in temperature above 120°C causes a decrease in the proportion of the <2 μm size-fraction, a reduction of BET and total surface areas and an increase in the relative volume of micropores (<20 Å). This process has been interpreted as the formation of granular aggregates that preserve a micropore network. This new arrangement of the aggregates produces a significant reduction in the free swelling volume.

Transmission electron microscope-analytical electron microscope analyses have been carried out on secondary minerals from pillow basalts with various degrees of alteration from the Juan de Fuca Ridge (ODP Leg 168). The electron microscopic data indicate that the alteration products consist mainly of phyllosilicate mixtures. The least altered sample shows poorly crystalline phyllosilicates occurrring as flakes with 10 Å -spaced lattice fringes. They have compositions of celadonite mixed with smectite and/or Fe oxyhydroxides and Mg-rich smectite. Proceeding towards older, more altered basalts, the alteration products consist of: (1) poorly crystalline celadonite mixtures and Mg-rich smectite; and (2) phyllosilicates with a higher degree of crystallinity, showing lattice fringes with 9.1 Å -spacing and with a talc-like composition. Changes in phyllosilicate association occur as the type of alteration changes from an oxidizing, water-dominated system (occurrence of celadonite mixtures with Fe hydroxides) to a reducing, rock-dominated system (occurrence of Fe-smectite and talc-like mixtures).

The alteration and transformation behaviour of Ceca smectite in two acid and saline solutions (NaCl and KCl) was studied in batch experiments. This type of smectite is proposed as potential backfill material for nuclear waste storage sites. The initial solution was enriched with 500 ppm of U, Th and Eu. The evolution of pH and solution concentrations were measured over a period of 25 months. The mineralogical and chemical evolution of the clays was also studied. X-ray diffraction revealed a significant loss of diffraction intensity and the clays became amorphous to Xrays with increasing reaction time. Deconvolution of the XRD data indicated a continuous collapse of the smectite layers but no illitization. Infrared spectroscopy revealed unchanged smectite spectra at the end of the experiment. Thorium precipitated as amorphous ThO2, but showed an incipient crystallization after 500 days. The Th, Eu and U were neither adsorbed onto the clays nor incorporated into a secondary phase.

The increase in specific surface of kaolinite (K) and pyrophyllite (P) induced by dry grinding in an oscillatory mill, proceeded during storage in water vapour. The average particle thickness, δ, changed from 42 nm (K) and 66 nm (P) in the original materials to 12 nm (K) and 20 nm (P) after water sorption (20 days at relative humidity RH = 1.0, at room temperature and pressure) and to similar values of 13 nm (K) and 16 nm (P) after grinding for 10 min (in agreement with some published data). The action of water molecules on ground clays (at the conditions indicated) resulted in a further decrease in δ. In pyrophyllite, prolonged grinding (30 min) and prolonged action of water molecules (36 days) caused a particle collapse. After pre-storing at RH = 0.5 the successive decrease in δ at RH = 1.0 was smaller.

Dioctahedral smectites (Cheto- and Wyoming-type montmorillonites and a beidellite) were treated with two hydrolysed OH-Al solutions (0.02 M in Al) containing different OH-Al complexes. The ratio of ∼3.25 mmol of Al per gram of smectite was used. The total Al and the presence of OH-Al species in solution before and after reaction with smectites were determined by the kinetics of Al-Ferron reaction colour development. The composition of the Al species retained by smectites was not the same as that present in the original solution added. The slow-reacting complexes present in the solution were preferentially adsorbed by dioctahedral smectites. Smectites prepared from slow-reacting polymer solutions showed changes in interlayer separation, b–dimension, order along the c axis and spectroscopic properties, after storage at room temperature. The OH-Al Cheto-type montmorillonite prepared from both solutions showed more retention of Al, best stability at room temperature and after thermal treatment at 550°C than interlayered OH-Al Wyoming-type montmorillonite and OH-Al beidellite smectites.

The pillaring of smectites (two saponites and a montmorillonite) with various Ti precursors was studied. The minerals were intercalated with ‘classical ’ Ti precursors, such as titanium tetrachloride and titanium tetraethoxide, and also with new precursors, such as solutions of titanium tetraisopropoxide in acetic acid, or titanium (bis (ethylacetoacetato) diisopropoxide) in acetone. A complete characterization of the intercalated solids was carried out and a comparison of the properties of the solids as a function of the precursors used in the intercalation established. The influence of the severe conditions in which the intercalation with Ti oligomers is usually carried out (low pH and/or high temperature) on the properties of the intercalated solids was analysed. Intercalation with TiCl4 and Ti(EtO)4 strongly affected the structure of the clays, not by acid attack on the octahedral sheet, but mainly by disaggregation of particles. Ti(isop)4 was found to be less aggressive for the clays, while Ti(etacet)2(isop)2 did not form pillared solids but organo-clays, and therefore was of no use as a pillaring agent. The solids were thermally stable up to 300°C, showing a high specific surface area.