Weathering profiles developed on the top surface of a bentonite (containing Al-Mg montmorillonite) and a K-bentonite (containing mixed-layer illite-smectite (I-S)) under Central European temperate conditions were studied by XRD, HRTEM, FTIR, K-Ar and chemical analyses. Weathering of montmorillonite results in the decrease of cation exchange capacity (CEC), total surface area and Mg content. The process is interpreted as montmorillonite dissolution and precipitation of amorphous SiO2. Weathering of I-S produces an increase in CEC and total surface area. The XRD data suggest dissolution of I-S and appearance of smectite as a separate phase at intermediate depths. The fixation of ammonium is documented in the topmost sample. In both profiles, abundant aeolian contaminants, including mica, were identified and their migration was traced using K-Ar dating.

Quartz-hematite veins in the St. Austell pluton feature an assemblage of authigenic kaolin, illite, chlorite and hematite. Similar assemblages occur in altered granites adjacent to the veins. Complex textures in the veins and altered granites show that kaolin was an initial precipitate from hydrothermal fluids that was subsequently replaced by illite, hematite and chlorite. The sequence of mineral precipitation reflects a kinetic control on crystal growth, with early nonequilibrium precipitation of kaolin from fluids with compositions appropriate for the equilibrium formation of illite. Hematite formed under relatively oxidizing conditions that subsequently became more reducing to permit the late precipitation of chlorite. Illite associated with the quartz-hematite veins differs texturally, mineralogically and chemically from the coarsely crystalline hydrothermal muscovite (sericite or gilbertite) associated with quartz-tourmaline veins and greisen. Quartzhematite veins are thus considered to record a distinct mineralization event that is not related to the early greisenization or the economic kaolinization.

Clay mineral associations of Palaeocene and Eocene age, with special attention to the late Palaeocene thermal maximum, have been examined in ten sections from the Tethys (Egypt, Israel, Tunisia, Spain and Kazakhstan) and Atlantic (England). A widespread abundance of kaolinite in marine sediments at all locations suggests a warm and humid climate with high rainfall in the Tethys region during the early Palaeocene. In the coastal basins along the southern margin (Israel and southern Tunisia), kaolinite disappears gradually giving way to palygorskite and sepiolite, suggesting the progressive development of arid climatic conditions in this part of the Tethys from the late Palaeocene to the early Eocene. Remarkably, kaolinite increases strongly throughout most of the Tethys during the late Palaeocene thermal maximum (LPTM) reflecting an episode of humidity and warmth and coincident with a global maximum warmth of seawaters inferred from oxygen isotopic data.

Studies of the subsurface microbiology of the Äspö Hard Rock Laboratory, Sweden have revealed the presence of many different bacteria in the deep groundwaters which appear to maintain reducing conditions. Experiments were conducted to study the rock-water and microbial interactions. These used crushed Äspö diorite, Äspö groundwater and iron- and sulphate-reducing bacteria in flowing systems under anaerobic conditions. In column experiments, there was evidence of loss and mobilization of fine-grained crushed material (<5 μm) which had originally adhered to grain surfaces in the starting material. The mobilized fines were trapped between grains. The degree of mineralogical alteration was greater in the experiments when bacteria were present. In both column and continuously stirred reactor experiments, there is evidence for the formation of a secondary clay. These experiments have shown that microbial activity can influence rock-water interactions even in nutrient-poor conditions.

Rectorite crystals [[4](Si6.81Al1.19)[6](Al3.26Ti0.04Fe0.553+Mg0.18Mn0.01)[12](Na0.02K0.88 Mg0.16Ca0.01)O20(OH)4·0.75H2O] found in micaschist of the Sesia-Lanzo Zone (NW Italy) were studied using a variety of techniques including microprobe analysis, infrared spectroscopy, single crystal and powder X-ray diffraction, atomic force microscopy and thermal analysis. Chemical data and exchangeable cation determination indicate that K+ is the dominant non-exchangeable interlayer cation, and thus is believed to occupy the mica interlayer site; Mg2+ together with small amounts of Ca2+, Na+ and K+ represent the exchangeable cations and can therefore be related to the smectite-like component. The coefficient of variation, CV, of d(00l) values (CVnatural = 0.47; CVglycolated = 0.43) demonstrates the regularity of the mica-smectite interstratification, whereas the unit-cell parameters obtained by single crystal methods suggest different layer-stacking models.

Intercalation of an ammonium amphiphile having an azobenzene chromophore, 4-dodecyloxy-4 ‘-(trimethylammoniopentyloxy)azobenzene and 4-(ω-trimethylammoniodecyloxy) -p’- (octyloxy)azobenzene bromide, into the layered silicate magadiite (ideal formula Na2Si14O29·nH2O) was carried out by a conventional ion exchange reaction in an aqueous medium. An intercalation compound with the ideal formula {(C12AzoC5N+)1.4H0.6·Si14O29·nH2O} was obtained. Based on the change in the basal spacing (to 4.21 nm) after the reaction and the visible absorption spectrum of the product, the intercalated azo dyes appear to form a J-aggregate in the interlayer space of magadiite. Under UV and visible light irradiation, the intercalated azo chromophore exhibited reversible transcis isomerization in the interlayer space of magadiite. This is the first successful report of photochemical reactions of guest species in the interlayer space of magadiite.

The clay mineralogy of a set of Tertiary marine sediments from the Internal Subbetic of the Betic External Zone was examined. Two types of sedimentary environment were distinguished: a platform environment consisting of limestones, marls, organogenic limestones, conglomerates and silexites distributed heterogeneously in time and space; and deep environments, where the sedimentation consisted of marls, marly limestones, marly clays and silexites, with no sedimentary gap. A third group of sediments studied belongs to the Águila Complex, with mineralogical and stratigraphic characteristics very similar to the platform sediments. This third type of sediment is found in the sediments of the Campo de Gibraltar Complex as large, disperse blocks resulting from tectonic activity. A very similar mineral association was observed in all three domains, consisting of smectite, illite, mixed-layer I-S, kaolinite and lesser amounts of palygorskite and chlorite. Materials mainly derive from the erosion of Mesozoic sediments, and sedimentation was controlled by the compressive tectonics of the region.

Sorption of the polar insecticide imidacloprid on organic-saturated octadecylammonium (C18) and dioctadecyldimethylammonium (DOD) and inorganic- (Fe- ) saturated Wyoming (W) and Arizona (A) montmorillonites has been investigated. Sorption isotherms were fitted to the Freundlich equation. Imidacloprid-montmorillonite complexes were studied by X-ray diffraction and FT-IR techniques. Imidacloprid sorption coefficients, Kf, decreased in the order WC18> AC18> WFe> WDOD≥ ADOD. The low layer charge and saturation by primary alkylammonium cation facilitates sorption of imidacloprid in the interlayer of the smectite, corroborated by the increase in basal spacing observed in X-ray diffraction patterns and by the presence of absorption band shifts in FT-IR spectra. Imidacloprid sorbs in the interlayer space of smectite mainly by hydrophobic interactions with the alkyl chains in organic smectites and with the uncharged siloxane surface in Fe(III)-smectite. Further polar bonds between the NO2 group of imidacloprid and the NH of the primary alkyl cations and protonation of imidacloprid in Fe-smectites enhanced sorption in these cases.

Plans to close a German radioactive waste repository in rock salt include as one alternative the construction of a ‘Cross Section Closure (CSC)’ sealing barrier. The proposed material for the sealing barrier is highly compacted bentonite. To investigate the swelling behaviour of a highly compacted bentonite, a large number of laboratory tests were performed. In addition, large scale model tests were carried out to demonstrate the development of a nearly homogeneous and isotropic swelling pressure. The results of the large scale model tests were interpreted numerically based on the models for stress-strain behaviour and water uptake which are implemented in the finite element computer codes FEST03 and HYDOPO. The investigations show good agreement between the results of the model tests and the corresponding analyses and show that the theoretical models are capable of describing the behaviour of sealing structures based on highly compacted bentonite.

Variegated palaeosols, which formed from weathering of clays, silts and brackish to freshwater limestones, are present in the Late Eocene–Early Oligocene Solent Group of the Hampshire Basin, southern UK. The composition and origin of the clay in three segments of the lower part of the Solent Group have been investigated by X-ray diffraction, microprobe analysis, inductively coupled plasma-mas spectrometry, K/Ar dating, high resolution scanning electron microscopy, analytical transmission electron microscopy and wet chemistry. The detrital clay mineral suite is dominated by illite and smectite with minor kaolinite and chlorite. Seasonal wetting and drying in gley soils has resulted in replacement of smectite by Fe-rich, or illite-rich illitesmectite. Illite has also formed with gypsum and calcite in ephemeral hypersaline alkaline lakes that periodically dried out. This illite may have precipitated directly from solution. X-ray diffraction data and probe analyses indicate that the neoformed illite is Fe-rich. The K and Fe for the illitization are thought to be derived from weathered glauconite reworked from the underlying Bracklesham Group and Barton Beds.