Anisotropy of magnetic susceptibility (AMS) and X-ray diffraction studies on shale decollement horizons in the Western Helvetic nappes were conducted to delineate the interactions between clay particles and deformation during a non-coaxial thrusting deformation. The reorientation of magnetic lineations in the decollement horizons, from a NW—SW thrusting direction to a NE—SW oriented lateral escape, provides the opportunity to study the evolution of magnetic fabrics and clay mineralogy during a two-step deformation history. The AMS of these shales originates from paramagnetic phyllosilicate minerals: illite, phengite and chlorite. Clay mineral studies indicate that magnetic lineations parallel to the thrust directions correspond to the spatial organization of the basal planes of phengites, whereas those parallel to the lateral escape movement are caused by illites. This work indicates that the change in direction of magnetic lineations from orogenic contraction to lateral escape not only records the strain history but also the dissolution and neoformation of paramagnetic minerals.

Fuchsite and other Cr-rich phyllosilicates, paragenetic with dolomite, are present in some ultramafic enclaves from the ‘frailesca’ rock (a lapilli- to block-size pyroclastic lithic-tuff), in the Almadén mercury mining district, Spain. Analyses (EMPA and TEM) of fuchsite and Cr-chlorite showed a relatively large range in levels of Cr2O3. Petrographic relationships between these phyllosilicates and primary relics of Cr-spinel crystals, as well as their high Cr content, indicate that these Cr-rich minerals originated from primary chromian spinels through an early hydrothermal alteration stage. The hydrothermal fluids accounting for this early alteration would be of relatively high temperature, high aCO2 and aK, and variable aNa/K. In a later alteration stage, fuchsite was partially or totally replaced by illite and Cr-illite, giving rise to an argillitic alteration.

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 K/Ar characteristics of 53 clay assemblages (Triassic–Cretaceous), representing the detrital, volcanogenic and arid-facies clay mineral associations, are interpreted in relation to their mineralogy, chronostratic age and geological origins. The K-bearing mineral components of the 1–2 μm, 0.2–1 μm and <0.2 μm fractions of each clay assemblage together display one of two characteristic patterns of K2O and 40Ar values (the K/Ar signature of the assemblage) on a 40Ar/K2O correlation diagram. Interpretation of the K/Ar signatures indicates that: (1) all of these clay assemblages are apparently unaffected by burial diagenetic illitization; (2) the Jurassic and Cretaceous detrital clay assemblages are derived from the reworking of weathered Caledonian metasediments (420 500 Ma) and weathered kaolin-bearing sediments of Upper Devonian/ Carboniferous age; and (3) the role played by palaeoclimate in developing the pattern of clay minerals in the Mesozoic sediments of England is much less significant than previously believed.

X-ray photoelectron spectroscopy (XPS) was used to determine the surface-charge magnitude and distribution for some micas and high-illite I-S clays. Based on predictable layer by layer atomic ratios for margarite, muscovite and sericite it was possible to establish an escape depth of ∼15 Å for photoelectrons. After the replacement of surface ions by Ba2+, interlayer ion (Ca, K, Na)/Ba ratios are a measure of the relative layer charges on external surfaces and the first internal interlayer. These ratios can be used to assign charge magnitudes and ascertain layer charge asymmetry when it occurs. The O/Ba ratios determined by XPS serve the same purpose. Diagenetic I-S from the Vienna Basin gives an XPS-determined symmetrical layer charge of 0.41; in a similar clay from the Gulf Coast sequence, the outer surface is smectitic, with an external charge of 0.21, in contrast to an opposing silica layer with a charge of 0.31.

Ethyl cinnamate/montmorillonite intercalation complexes were obtained by gaseous adsorption of the drug on the clay surface. They were characterized by powder X-ray diffraction, differential thermal and thermogravimetric analyses and by visible-UV and IR spectroscopies. It was found that after 1 day of adsorption, most of the drug enters the interlayer space of the clay by substitution of water molecules, and is removed only after heating at high temperature. In addition, a portion is physisorbed on the external surface of the crystallites, being removed easily below 100°C. The interlayer complex improves the protecting ability of the pure clay or the pure drug against ultraviolet radiation, specially in the so-called ‘C’ range (290–190 nm).

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 reaction of a Wyoming-type bentonite with pH 13.5 solutions was investigated experimentally at 35 and 60°C for periods of 1 to 730 days. Some crystal properties of the starting montmorillonitic clay remain unchanged, i.e. stability of the octahedral sheet, total cation exchange capacity (CEC) and CEC after neutralization of the octahedral charge, full expandability in the Casaturated state, and size distribution. Other properties are changed, e.g. there is an increase in the expandability after octahedral charge neutralization; a slight increase in the average layer charge; a decrease of the total surface area; and a particle morphological change from flakes to hexagonal shape.

The composition and the structure of the smectite layers did not change significantly during the reaction. The increasing number of expandable layers after octahedral charge neutralization is attributed to modifications in the stacking sequence. The number of interlayers surrounded by two charged tetrahedral sheets increases with reaction time.

The clay fraction of the deposits of the Otjomongwa Pan, southwestern Kalahari, is dominated by Mg-smectite. This mineral formed as an authigenic precipitate in a groundwater-fed lake, without involving the transformation of a precursor mineral. During the earliest recorded period, Mg-smectite formed together with sepiolite and dolomite in a shallow lake. This period was ended by a change in environmental conditions that led to an increase in the depth of the lake and a decrease in salinity and Mg content of the water. This resulted in a transition to a mineral association without sepiolite and including calcite, together with Mg-smectite and dolomite. The depth of the lake gradually decreased after this event, while the lake water progressively became depleted in Mg.

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.

Ten montmorillonites of different origins with variable Fe contents were analysed using transmission IR spectroscopy. Special attention was devoted to the OH-bending region to obtain information about the distribution of octahedral cations. For low to medium Fe contents (≤0.56 per Si8 formula unit), a linear relationship between the position of the δAlFeOH band and Fe content was observed. Such correlation might be explained by changes in the cis-trans occupancy of Fe in the octahedral sheet. Deconvolution of the OH-bending domain allows us to discriminate three components (δAlAlOH, δAlMgOH and δAlFeOH) which are correlated with cation abundances derived from chemical analysis. The relative area of each band can then be compared with theoretical areas calculated assuming a fully random distribution of cations in the octahedral sheet. Using such treatment, eight of the 10 montmorillonites studied presented a nearly randomized octahedral distribution. The two samples from Wyoming were clearly different as they exhibited a strong ordering tendency.

Hydrothermal experiments were performed at 100 and 200°C and at different clay:water ratios in order to investigate the transformation of smectitic layers during the alteration of a montmorillonitic starting material. This study focused on three phenomena: (1) the amount and localization of charge within the layer of the newly-formed dioctahedral smectite; (2) the stacking of low- and high-charge layers in the dioctahedral smectitic material; and (3) the neoformation of trioctahedral smectites.

In all of the runs, the formation of beidellite from montmorillonite induced morphological changes in clay particles which suggests a reaction proceeding by a dissolution-crystallization mechanism. Illite layers were detected in K-saturated montmorillonite runs after the transformation of ∼50% of the starting montmorillonite into beidellite (i.e. after 5 months of reaction with distilled water at 200°C). These illite layers were interstratified with both high-charge and low-charge dioctahedral smectites in a hypothetical three-component mixed-layer mineral.

The use of solid-laden emulsions (Pickering emulsions) provides an interesting alternative to normal emulsions because the need for organic surfactants is removed or reduced. Combination of a bentonite with a layered double hydroxide represents an effective emulsifying system and provides high stability against coalescence. Solid contents as low as 0.1% (w/w, related to the total mass of the emulsion) are sufficient to prepare very stable O/W emulsions; the mass ratio of hydroxide/bentonite is not critical but should vary between 0.25 and 4 (corresponding to mass fractions of the hydroxide between χ = 0.2 and 0.8). With large hydroxide contents, stabilization is mainly caused by the envelope of hydroxide particles around the oil droplets. This shell provides a mechanical barrier against coalescence, typical of Pickering emulsions described so far. Addition of increasing amounts of bentonite provides an additional stabilization by building-up a threedimensional network consisting of both types of particles spanning the coherent phase. A high storage modulus at mass fractions of the hydroxide between 0.2 and 0.8 indicates high flexibility for the inorganic framework which is considered to be an important factor in the high stability of these emulsions.

Two-line ferrihydrite samples were synthesized following conventional procedure. Detailed characterizations of freeze-dried and untreated samples – prepared from direct inclusion of the fresh precipitates in hydrophilic resin – were made by high resolution transmission electron microscopy to investigate in detail their structural organization and to compare the two types of preparations.

Only highly disordered chain-like aggregates of 2 5 nm diameter size nano-particles were revealed within the untreated samples. Conversely, in freeze-dried samples, domains with different degrees of order were recognized, from poorly ordered 2-line ferrihydrite to 3-line ferrihydrite particle aggregates that revealed lattice fringes. Associated with these aggregates, a goethite phase with a modified crystal morphology was also observed.

These HRTEM observations revealed that freeze-drying techniques induce artifacts by disturbing ferrihydrite aggregates while direct inclusion in hydrophilic resin preserves the primary organization of such poorly ordered phases.

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 relationship between the K-Ar dates of mixed natural clays and the ratios of detrital and diagenetic components follows in most cases a linear trend, which agrees with the theory when the K2O contents of the end-members are similar. However, significant deviations from a linear trend may occur and take the form of poorly-defined concave curves. The absence of a linear trend is less likely to be due to the imprecise determination of the ratio between the two end-members than to heterogeneities of the natural samples which may arise from complex K-Ar evolutions of the detrital and diagenetic end-members. The straight-line approach is of limited use in the definition of diagenetic ages in shales by extrapolating linear trends to diagenetic end-members.

Kaolinite-rich rocks are widespread in Chinese coal-bearing strata. Three main types of deposits are recognized. Those deposits identified as flint clays are several metres thick and show lateral variations in bed composition. The kaolinite is thought to have formed mainly on the adjacent landmass, but some crystallization of gels within the basin is not ruled out. Tonsteins, which formed from the in situ alteration of airfall volcanic ashes, are very common in the coal measures and are up to 0.5 m thick. Finally, kaolinite deposits are described where the development of kaolin is related to weathering of coals either close to or at the present land surface.

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.

Smectites from the E horizon of podzols dated at 1200–10,000 y in central and northern Finland were studied. Clay minerals in the fine (<0.1 μm) and coarse (0.1–2 μm) fractions were examined by X-ray diffraction. The distribution (octahedral or tetrahedral) and magnitude of the layer charge of expandable minerals were estimated using intercalation of alkylammonium ions (nC = 12) associated with the Hofmann & Klemen effect. In addition, charge alteration following desaturation (H+ exchange) and autotransformation was investigated. Smectites from the E horizons of podzols are not homogeneous but constitute a mixture of several populations with various layer charges. Smectites with lower layer charge are present in podzols having a longer effective time of pedogenesis, suggesting alteration of the high-charge smectites with time. Experimental alteration of the smectites by autotransformation shows that a decrease of the layer charge is easily produced by desaturation of the smectite clays.

Tectonic observations in the Tethyan Himalaya reveal an important extensional event that succeeds the emplacement of SW-verging nappes. A major thrust, called the Kum Tso Thrust, has been backfolded and reactivated by normal faulting associated with this event.

Measurements of the Kübler index, coupled with characterization of clay-size paragenesis show the effect of normal faulting on the regional metamorphic zonation and indicate that important extension zones, like the Sarchu-Lachung La Normal Fault Zone (SLFZ), exist within the Tethyan Himalaya. Diagenetic limestones from within the SLFZ are characterized by the occurrence of mixed-layered clay phases, kaolinite and an illite with a 001 peak >0.4 Δ°2θ. This zone is bordered by two anchizonal-to-epizonal zones, where illite peaks become narrower. Further to the NE the successive appearance of biotite, chloritoid, garnet and garnet-staurolite-kyanite assemblages testifies to an increase in metamorphic grade. The cataclastic samples from the normal faults contain kaolinite, smectite and a ‘broad’ illite, indicating that extension occurs under diagenetic conditions.