Claystones of Kimmeridgian-Volgian(-Ryazanian) age are the main source rocks for oil in the Central Trough, North Sea, but they are too immature for oil generation in the Norwegian-Danish Basin. This paper describes the diagenesis of mixed-layer illite/smectite (I/S) in these source rocks as investigated by X-ray diffraction and high-resolution electron microscopy, interpretation for both methods being supported by computer simulations. Randomly-ordered I/S with ∼70% illite layers, together with discrete illite, kaolinite, and traces of chlorite and vermiculite, are detrital. The clay mineralogical data suggest the existence of an island at Gassum during part of the Upper Jurassic. Mixed-layer illite/smectite originating from volcanic ash is found in two wells in the Central Trough. The volcanism may be related to a period of stretching in the North Sea graben system during Jurassic-Lower Cretaceous time. Diagenesis has not altered the I/S in the Norwegian-Danish Basin. In the Central Trough, however, the amount of illite layers in I/S increases from ∼70% to ∼90% and the I/S becomes ordered. The volcanic clays have been changed to randomly ordered I/S with ∼50% illite layers. These changes occurred in the Central Trough simultaneously with oil generation.

When describing clay minerals of natural origin one often has to take into account the possibility that they contain other phases, e.g. iron oxides and hydroxides which may form a ‘coating’ on the clay mineral itself or occur as physically inseparable ultra-fine particles. These iron oxyhydroxides are sometimes difficult to detect by XRD as a consequence of their very small ‘domain volumes’ (Kodama et al., 1977). The iron oxyhydroxides are normally removed chemically prior to detailed characterization of the clay mineral. Removal of iron oxyhydroxide coatings facilitates dispersion and subsequent particle-size fractionation of minerals and soils and also enhances the parallel orientation, and therefore the intensity, of basal X-ray reflections of layer-silicates.

The thermal energy necessary for the removal of molecular water from Li+-, Na+-, Cs+-, Mg2+-, Ca2+-, Ba2+-, Alx(OH)yz+- and La3+-homoionic montmorillonite powders was determined by thermogravimetric analysis under atmospheric pressure. The weight loss curves and their derivatives exhibit one or several features related to the various populations of water molecules. The activation energy for water removal, which is the sum of the adsorption energy and the activation energy for diffusion, was calculated in each case using a simple first-order differentiation method. The results allow the physisorbed water and the water coordinated to the cations to be clearly separated. For the later population and with the exception of the Na-clay, a good correlation was found between the temperatures and activation energies for water removal and the polarizing power of the cations. Comparison with the results of mechanical tests performed on similar samples suggests that the creep of smectite clays is not controlled by mobility of the individual water molecules but by the mobility of the interlayer cations surrounded by their hydration shell.

Kaolinite-ferrihydrite and montmorillonite-ferrihydrite associations were prepared following a procedure based on the Russell method for the synthesis of ferrihydrite and the texture of the clay-ferrihydrite complexes was studied using different techniques. The textural properties of kaolinite were little affected by the Fe association, showing only a slight increase in the specific surface area measured by nitrogen adsorption and a decrease in the largest pores (>10 µm), as measured by mercury porosimetry. In contrast, the nitrogen specific surface area of the montmorillonite complexes was much higher than that of the clay without Fe and the pore structure depended on the amounts of Fe in the complexes. Application of the fractal approach to nitrogen adsorption data indicated that the surface roughness (microporosity) was greater for the complexes prepared from diluted Fe(III) solutions, in agreement with the information obtained from classical interpretation of the adsorption isotherms (shape of the isotherms and t-plots).

From leaching experiments with metallic uranium-aluminium material test reactor fuel elements in repository-relevant MgCl2-rich salt brines, a Mg-Al-layered double hydroxide with chloride as interlayer anion was identified as a crystalline secondary phase component. In the present study, this Mg-Al-Cl-layered double hydroxide (Mg-Al-Cl-LDH) was synthesized and its ability to adsorb iodine was evaluated. The adsorption of I– was rapid, and equilibrium for an initial concentration of 4.25 x 10-5 mole/l was obtained within 48 h. Further results indicated that the adsorption isotherm for I– retention could be fitted to Freundlich and Dubinin-Radushkevich equations. The values obtained indicate that iodine is adsorbed on Mg-Al-Cl-LDH by an anion- exchange process. The adsorption of I– was also studied as a function of pH. In the pH range between 3.5 and 8.5, the adsorption was independent of the pH. The effects of competiting anions were investigated using an MgCl2-solution instead of water, and indicate that chloride anions have a greater affinity towards the Mg-Al-Cl-layered double hydroxide than iodine.

Lower Cretaceous clay minerals suites of the Alava Block, analysed by XRD, are dominated either by illite or kaolinite. These assemblages are mainly inherited in origin, although textural evidence (SEM) indicates some diagenetic clay. Precipitation of blocky kaolinite took place in sandstones from the southern domain of the Block, characterized by low sedimentation and subsidence rates and by low vitrinite reflectance values (%Rr <0.8). In the northern domain, where sedimentation and subsidence rates were high (%Rr >3.3), illitization of kaolinite and smectitic clays and precipitation of authigenic chlorite occurred. Some chemical aspects of these reactions are discussed.

Intercalation of macrocyclic compounds (crown-ethers and cryptands) in 2:1 charged phyllosilicates is a topotactic reaction, the lamellar structure of the pristine material being preserved. X-ray diffraction and spectroscopic (IR, NMR) results provide information on the main structural characteristics of the intercalates. Guest species, which form 1 : 1 or 2 : 1 ligand/cation intracrystalline complexes, lie flat or tilting between the host layers as can be deduced from the increase in the basal space of the silicate and the dichroic effect observed on the CH and NH IR vibration bands of the guest species, after intercalation. The chemical shift observed in 23Na NMR spectra of the solids is associated with the different environment of the cation before and after the intercalation process.

Porosity development in a sepiolite from Toledo, Spain, has been studied as a function of acid (0·25, 0·50, 0·75 and 1·0 m HNO3) and subsequent heat treatments (110–400°C). Adsorption isotherms of N2 at 77 K have been analysed by f-plot, t-plot, αs-plot and the Cranston & Inkley methods. Results are compared with those obtained on products heated without previous acid activation. Experimental conditions favouring porosity development are discussed.

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.

Copper-sepiolites exchanged at different levels have been studied by ESR, IR, and TG. The results indicate that in the unheated samples the Cu2+ ions are located in octahedral edge positions. After dehydration, the Cu2+ ions occur in two positions with different environments. Some of the Cu2+ ions lose the two molecules of coordinated water in one step, at low dehydration temperatures, and adopt a square pyramidal geometry. Other Cu2+ ions lose the coordination water in two steps, at lower temperature than the natural sepiolite, and adopt a tetrahedral symmetry.

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.

The process developed in the UK to produce magnesium hydroxide from seawater is described, together with the heat treatment that the hydroxide receives to produce the active oxide. Some of the characteristics required of the dolomite used in the process are also discussed. Impurities introduced by the seawater are noted and the means by which they can be reduced explained.

The mechanism whereby water is absorbed by soils and thereby causes expansion and “heave” is discussed. The dependence of expansiveness on occurrence of montmorillonitic and illitic clay types is shown. Rapid methods of analysis used, include a micro-desiccator method of deriving water vapour pressure isotherms and the technique of glycol retention.

Palaeozoic to early Mesozoic rocks of both autochthonous and allochthonous units of the Eastern Tauride Belt have different textural and mineralogical features related to their varying deposition regimes and thermal histories. The Devonian and Carboniferous formations in the allocthonous units have anchizonal to epizonal grades of metamorphism, whereas those of the autochthon experienced only early diagenetic conditions. A well-developed penetrative slaty cleavage is also found in Devonian formations of the allocthonous units, which is not observed in equivalent rocks of the autochthon. Phyllosilicates of the uncleaved diagenetic assemblages consist mainly of illite, chlorite, kaolinite, mixed-layer illite-smectite, chlorite-vermiculite and chloritesmectite, whereas in addition to these, metamorphic allochthonous units contain some index minerals such as dickite, paragonite, Na and K mica, pyrophyllite, stilpnomelane and chloritoid. These latter assemblages show a higher degree of textural and mineralogical maturation and lower b cell dimensions than the autochthonous rocks, suggesting that they originated in a relatively high heat flow basin such as an extensional setting.

Chemical and mineralogical analyses of fossil caliche profiles developed on top of Lower Pleistocene alluvial formations in the East-central sector of the Ebro basin indicate that they have high content of carbonate (average 84%) and high Ca/Mg ratios (average 136). The clay mineral assemblages vary slightly depending on the host material, and, therefore, on the alluvial formation in the source area. Inherited detrital minerals (illite, kaolinite and chlorite), transformed components (from chlorite to mixed-layers of chlorite-vermiculite, and from smectite to palygorskite) and a neoformed phase (palygorskite) have been observed. The contents of carbonate and magnesian clay minerals (smectite and palygorskite) increase from the bottom to the top of the profiles, in relation to hardpan laminated caliche facies. The amount of palygorskite is controlled by the concentration of Mg2+ which in turn depends on the absolute content of Mg2+ in the host material and on its relative concentration by processes of evaporation linked to decreasing permeability in the profile during the biogenic-pedogenetic carbonate accumulation stages. These processes form part of the development of caliche profiles in a semi-arid environment.

Purified kaolins from Thai soil on diverse parent materials were characterized using analytical transmission electon microscopy, X-ray diffraction, thermogravimetric analysis and chemical analysis. The properties of Thai soil kaolins appear to be more diverse than Indonesian and Western Australian soil kaolins investigated using the same analytical procedures; this difference may reflect the greater range of parent materials for the Thai soils. The kaolins show a variety of crystal morphologies including euhedral hexagonal to subhedral platy crystals, tubes and laths and several morphologies were present in most samples. TEM-EDS enabled analysis of single crystals of each morphology present within a sample. Tubular or lath-shaped crystals usually have lower %Fe2O3 contents than hexagonal platy crystals in the same sample. The relationships between crystal size and Fe content within morphological populations were also examined by TEM-EDS. Generally, smaller kaolin crystals display a wider range of Fe concentration than the larger kaolin crystals in the same sample. Increasing Fe concentration in bulk samples is closely correlated to decreasing coherently scattering domain size (R2 = 0.57), increasing cation exchange capacity (R2 = 0.44) and increasing specific surface area (R2 = 0.65). However the properties of the deferrated soil kaolins, including their Fe content, are not related to forms of Fe, (total Fe, amorphous or organic) in the untreated clay fraction of the soil.

Inhibited vermiculite is a common minor constituent of these clay fractions and its average structural formula derived from EDS data indicates that it was formed by Al replacing K in muscovite. One Al3+ ion occupies the interlayer space previously occupied by three K+ ions. As the distances between these Al3+ cations in the interlayer space is large it is proposed that isolated or loosely associated hydrated Al3+ groups such as Al(OH2)63+ exist that resist exchange by other cations due to hydrogen bonding with the adjacent tetrahedral oxygen surfaces

The clay mineral associations in the Cretaceous-Tertiary Boundary (KTB) and in the Danian and Maastrichtian levels of sections from the Mediterranean and the Atlantic Domains have been studied. The Mediterranean sections have a single mineral association consisting of smectiteiltite and kaolinite, whereas the Atlantic sections have several associations: illite-chlorite, illite-R1 I-S-kaolinite and illite-R 1 I-S-chlorite. Data are presented relating to the influence of K-feldspars and Fe oxide sphemles on the clay mineral associations. Study of rare-earth elements shows that regional geological factors affect the clay mineralogy of the KTB, examples showing significant anthigenesis in the Mediterranean sections, and important detrital supply in all the Atlantic sections. We propose that the KTB studied in these marine sections is equivalent to the uppermost layer of the two-layered clay unit originating in a cloud of a vapourized bolide. Regional tectonic conditions have been responsible for differences in clay sedimentation in these geological domains and among the stratigraphic sections of the Atlantic Domain.

Concepts for geological disposal of high-level radioactive waste usually include bentonite buffer materials. Numerous studies have been performed with most usingWyoming bentonite. Gaomiaozi (GMZ) bentonite has been selected as a potential buffer/backfill material for the deep geological repository of high-level radioactive waste in China. In this context, the highly alkaline environment induced by cementitious materials in the repository is likely to alter montmorillonite, the main clay mineral in GMZ bentonite. This alteration may result in deterioration of the physical and/or chemical properties of the buffer material. To acquire quantitative data which would allow us to assess the dissolution of montmorillonite and changes in the diffusivity of hydroxide ions as well as their effects on the swelling pressure and permeability of the compacted GMZ bentonite, an experimental study was conducted under highly alkaline (NaOH solutions with various pH values were used), simulated groundwater conditions. The GMZ bentonite also contains cristobalite which may also have been dissolved. The microstructure of the compacted bentonite samples after the experiments was determined by mercury intrusion porosimetry (MIP) and scanning electron microscopy (SEM). Energy dispersive spectroscopy (EDX) was carried out to identify mineralogical changes. At pH >13, the permeability of specimens increased significantly; the swelling potential decreased with increasing pH. Furthermore, the pore volume and pore size of GMZ bentonite changed when exposed to alkaline solution, resulting in an increase in porosity and permeability. The main alteration mechanisms of compacted GMZ bentonite undergoing infiltration by highly alkaline solution are likely to be dissolution and modifications in terms of the microstructure and mineralogy.

Le paramètre b des smectites, à charge faible et empilement désordonné, est déterminé dans les diagrammes de diffraction X à partir des maxima d'intensité de la bande (06,33); ce paramètre montre une très bonne corrélation avec la teneur en fer et magnésium des feuillets. Les équations de régression proposées sont applicables à tous les échantillons renfermant une ou plusieurs variétés minéralogiques du groupe. La méthode semble particulièrement bien adaptée aux études des transformations chimiques des sédiments, au cours, par exemple, de leur diagénèse.

The smectite-to-illite reaction (illitization) was examined in a dilute suspension of Wyoming bentonite in the presence of oxalate and acetate. Experiments were performed using fluidsampling apparatus at 200°C, 50 MPa, in which progressive changes in both clay mineralogy and fluid composition were monitored. The presence of K-oxalate and K-acetate under neutral-alkaline conditions produced significant reaction of smectite to either R1 or R2 ordered illite-smectite with 60–70% illite layers. Experiments at the same temperature with KCl, or oxalic acid plus KCl, produced no reaction. Fluid chemistry showed that K-oxalate and K-acetate resulted in the establishment of aK+/aH+ conditions within the muscovite stability field, favouring the formation of illite. The extent of dissolution and precipitation indicated by fluid data is insufficient to account for the amount of illitization evident in the mineralogy. This implies that a localized dissolution-precipitation process occurs, perhaps on the scale of a single clay particle. These experiments highlight the importance of pH as a control over illitization and show that organic anions can buffer fluid composition into the optimum aK+/aH+ condition for illitization. These findings are highly significant for the smectite-to-illite reaction occurring in organic bearing sediments where organic acid anions are generated during kerogen maturation.