MX-80 is a bentonite clay from the Clay Spur bed, Wyoming, USA, consisting of ~80 wt.% Na-rich montmorillonite and is a leading candidate material for use in engineered barriers within underground nuclear waste disposal sites in Switzerland and Sweden. The diffusive invasion of groundwater into the engineered barriers is likely to cause the dry high-density bentonite to swell and evolve into a less-dense, water-rich gel during re-submergence of the shafts and galleries. Data on H20 diffusivity within water-rich bentonite gels are therefore essential to the safe design of the engineered barriers. To address this need, the self-diffusion coefficient, D, of 1H2O molecules in water-rich MX-80 bentonite gels was measured using the pulsed-gradient spin-echo method of 1H nuclear magnetic resonance spectroscopy at 0.47 T; D was measured over a wide range of temperatures (20.6–70.1°C) and of bentonite volume fractions (0 to 17.2 vol.%). The results showed that D increased markedly to values of bulk water self-diffusivity as the bentonite volume fraction decreased towards 0 vol.%. The activation energy of the diffusion process for the gels was approximately equal to that for bulk water. As a result, the normalized H20 self-diffusivity, D/D0, was approximately independent of temperature, where D0 is D in bulk water. The D/D0 data for ≤6.39 vol.% bentonite fraction were successfully fitted to a porous clay gel model that involves unbound water molecules that diffuse in the pore space by avoiding randomly placed discoidal obstacles (clay particles) of a high aspect ratio. The D/D0 data for MX-80 were similar to data for SWy-2 (Wyoming bentonite from the Newcastle formation) and Kunigel-Vl (bentonite from Yamagata, Japan), suggesting that all three bentonites are equally suitable candidate materials, in terms of water diffusivity performance, for use within engineered barriers.

The formation of clay minerals was investigated in Spodosols developed in the subalpine belt, with similar exposure, climate and age, but deriving from different parent materials. All the soils were classified as Haplic Podzols and showed the characteristic eluviation and illuviation features of Fe, Al and organic carbon. However, varying parent material lithology led to different clay mineral assemblages in the soil. Smectite could be found in the E horizons of soils developed from granodiorite and tonalite materials. Its formation was strongly dependent on the presence of chlorite in the parent material. If nearly no other 2:1 mineral components, such as chlorite, are present in the lower soil horizons, then a residual micaceous mineral becomes the dominant clay mineral. The latter derives from a mica-vermiculite interstratified mineral.

The clay mineral assemblages and microtextures of a suite of mudrocks from the Lias Group of England and Wales indicate important regional differences in burial history.

Samples from the northern Cleveland Basin are characterized by illite-smectite (I-S, 90% illite) and little carbonate whilst samples from the southern Worcester and Wessex basins contain less mature discrete smectite and are often calcite- and dolomite-rich. Lias Group rocks have been buried to 4 km in the Cleveland Basin but to <2 km in the Worcester and Wessex basins. Burial in the Cleveland Basin is deeper than previously estimated and does not need a local heating event. Illite- smectite (80% illite) detected in samples from the East Midlands Shelf suggests burial to 3 km, again deeper than previous estimates for this region.

The Tarbert Formation on a north±south oriented structure along the eastern flank of the Viking Graben has been studied. The reservoir in the two wells studied is buried ~100 m deeper in the northern than in the southern well. The present reservoir temperature is ~130°C. The reservoir quality is good, but due to extensive illitization of kaolin, the northern well shows lower permeability values than the southern well, for similar porosity values. The initial composition of the analysed samples in the two wells is very similar. There are no significant differences in total clay content and both wells contain K-feldspars and kaolin. However, the diagenetic alteration is more advanced in the deeper well. Total porosity is about the same in both wells but, due to illitization, the ratio of micro- vs. macro-porosity is higher in the deeper well. Petroleum emplacement in the structure occurred in two phases: oil emplacement predates, whereas gas emplacement postdates, most of the quartz cementation. In the deeper well, illitization occurred after gas emplacement.

The clay mineral distribution in the Early Cretaceous depositional sequences along the Cameros Basin has been established on the basis of XRD traces and TEM/EDAX analyses. Samples from the Latest Berriasian-Barremian depositional sequences are characteristic of epimetamorphic conditions. Illite ‘crystallinities’ are broader than expected (0.35–0.490°Δ2θ), due to the consistent presence of K-mica-paragonite mixed-layer and discrete paragonite associated with the illite 10 Å peak. The Late Barremian-Early Aptian depositional sequence, around the depocentral sector of the basin, represents a sudden change to anchimetamorphic conditions, marked by the presence of pyrophyllite and rectorite and by a significant decrease in the A1IV content of the chlorites. Towards the northwestern border of the basin, this sequence was affected by deep diagenetic conditions, as deduced from the clay mineral association and the ‘crystallinity’ values (0.57°Δ2θ). The changes in the clay mineral assemblages and ‘crystallinity’ data can hardly be explained in terms of the varying burial depth and are related to changes in the circulation of fluids associated with varying facies (modal composition, grain size). Permeability is regarded as the main factor controlling the circulation of these migratory fluids.

White clayey geomaterials were collected from northeast of the Nefza region (northern Tunisia). These deposits belong to the Mio-Pliocene molassic basins (basin of Tamra-Sidi Dris, Boukhchiba) and Oligocene Numidien in the area of El Aouinet. Analysis by X-ray diffraction showed associations of halloysite and kaolinite (Tamra), kaolinite and illite (Aouinet zone) and mixed layers, kaolinite and feldspars (Boukhchiba zone). Semi-industrial processed bricks showed promising characteristics and were visibly free of defects. Ceramic tiles had a bending strength that met the required standards but water absorption was somewhat high. So, to achieve higher quality, optimisation needs to be carried out in the formulation of batches or in the processing conditions. Finally, the incorporation in whitish sanitary-ware glaze formulations generated smooth coating layers that showed the required strong brightness and were free of defects.

The effects of dry grinding on the structure, morphology and properties of imogolite have been investigated by means of X-ray powder diffraction analysis, IR, DTA, and measurements of CEC and specific surface area. Imogolite is very susceptible to alteration by grinding compared to layer silicate minerals such as halloysite, kaolinite and montmorillonite. In the earlier stages of grinding, the parallel array of imogolite tubular structure units is markedly disturbed. On further grinding, disruption of Si-O-Al linkages, polymerization of the silica component released and loss of structural OH groups proceed simultaneously, these changes eventually resulting in complete breakdown of the structure. Ground imogolite is reaggregated finally into granular particles of irregular shape. All these changes are associated with a decrease in water holding capacity, CEC and specific surface area.

The sequential development of kaolin by progressive alteration of smectite, involving kaolin-smectite interstratifications as a genetic link is described from a red and black complex. Mineral compositions were studied using XRD, DTA and XRF techniques. The basalt-derived soils are situated along a 600 m transect and grade in colour from dark grey (10 YR 3/1) to red (5 YR 3/3). The kaolin proportions in the interstratification increase almost linearly with increasing reddening up to ∼80%. Whole-soil chemical analyses exhibit no significant variations in the major element composition, but dithionite extractable Fe increases along the transect from 1% to 4·16%. Hematite and goethite are the only secondary iron phases. Topographic differences are slight but sub-surface bedrock contours plus appreciable variations in sand content between red and black soils could be genetically significant.

Clay-based nanostructures were prepared from kaolinites of varying structural order by two different methods. In the first method the kaolinite-urea precursor, obtained by dry grinding, was intercalated further with triethanolamine and the tetraalkylammonium salt was synthesized in the interlamellar space. Exfoliation was achieved by the use of sodium polyacrylate (PAS). In the second method, the kaolinite-potassium acetate (kaolinite-KAc) precursor, obtained via two different methods, was intercalated further with ethylene glycol (EG) and then n-hexylamine (HA). Intercalation with EG was also achieved by heating either directly or with microwaves. The morphology that results depends on the method of precursor preparation, the method of heat treatment and the degree of structural order of the original clay. Higher structural order facilitates the formation of a tubular morphology, while mechanical treatment and microwave agitation may result in broken tubes. Molecular mechanical (MM) calculations showed that organo-complexes may be exfoliated to a d value of 10–11 Å.

Aggregation of colloidal clay particles (Na-montmorillonite) by CaCl2 and anionic polysaccharide (succinoglycan) in turbulent conditions was investigated using time-resolved size measurements by laser diffraction on diluted (50 mg l –1) and stirred suspensions. Excess of Ca2+ ions promotes coagulation of the clay, reducing interparticle repulsions, and allows adsorption of succinoglycan, inducing bridging flocculation. Growth/breakage cycles, characteristic of the turbulent conditions, cause the macromolecules to be incorporated in the innermost of the flocs, where the morphological units are shown by confocal microscopy to be the micrometric Ca-clay particles. Such incorporation results in an increased floc tensile strength, depending on the amount of macromolecules adsorbed, with a maximum at polysaccharide concentrations of 2 wt.% with respect to clay mass.

Palygorskite has been widely reported as a clay phase in the Recent sediments of the northern Arabian Gulf (e.g. Aqrawi & Sadooni, 1988). It is usually thought to have originated from the sediments and soils of the Mesopotamian flood plains introduced by northwesterly (Shamal) winds (e.g. A1-Bakri et al., 1984). A1-Rawi et al. (1969) and Eswaran & Barzanji (1974) have detected palygorskite within Mesopotamian soils. This paper describes the occurrence of palygorskite in the Recent sediments of southern Mesopotamia and its possible origins will be discussed.

Three samples have been selected to represent the sedimentary variations of the Basin of Autun. IR and ESR techniques have been used to study the sheet composition of the different kinds of clays. The kaolinites are fire clays with two different degrees of crystallinity. The illites have a muscovite origin and belong to the 1 M polytype with mainly tetrahedral Al3+ and Fe3+ substitutions but also with some octahedral Fe3+ substitutions. The dioctahedral phyllosilicates contain mostly divalent and trivalent octahedral substitutions.

Previous attempts to use illite as a geothermometer have failed: no general relation between the mineral's chemical composition and temperature of crystallization has been found. Here, chemical compositions of 27 illite samples from five different geothermal fields (the data on four of which were drawn from the literature) were compared with their crystallization temperatures. As previously reported by Cathelineau (1988), the K content was found to be the only variable yielding a suitable correlation, but only when applied to one geothermal field; when various geothermal systems were considered, the correlation weakened considerably. Introduction of a correction algorithm to the K content of the illite has made it possible to draw a single line to fit the data from all the studied samples, yielding a good correlation coefficient (r = 0.84).

The formation of kaolinite from Al hydroxy interlayered Garfield nontronite has been carried out at 225°C in hydrothermal conditions. The kaolinitization process, which proceeds through mixed-layer kaolinite/smectite intermediates, was followed by XRD, IR and ESR spectroscopy, chemical analysis and charge properties. The smectite content of the clay products decreases regularly with the duration of the hydrothermal treatment. The CEC and the structural Fe content of the deferrated products show a similar trend. IR features specific to nontronite disappear and are barely detectable as the smectite content of the mixed-layer clay falls below 30%. In contrast, the ESR spectrum of nontronite is characterized by a broad g2 signal that remains even after prolonged hydrothermal treatment. The calibration of the g2 ESR signal, due to Fe-smectite, shows that the synthetic kaolinites have low Fe contents (∼ 1% Fe2O3) indicating that the kaolinitization process involves destruction of the 2:1 layers and the subsequent neoformation of kaolinite and Fe oxides. As illustrated by the study of deferrated soil clay samples, representing a weathering sequence Fe-smectite → kaolinite + Fe oxides, ESR spectroscopy proved to be a powerful Fe probe for detecting Fe-rich smectite in kaolinite/Fe-smectite mixed-layer clays.

The interaction of chrysotile and crocidolite with water has been investigated in an attempt to identify the factors affecting the rate and the degree of dissolution of asbestos fibres within groundwater systems at landfill sites. Dissolution experiments were used to investigate rate laws and to obtain apparent activation energies for the dissolution of the two minerals. The activation energies related to transport-controlled processes, but as the overall dissolution occurred so slowly it was unlikely to be controlled by processes with such low activation energies. Congruent dissolution of both minerals tended to increase with temperature and time, suggesting that in the long-term environmental situation, congruent dissolution of these two asbestos minerals would occur. However these experiments show that, as the reaction was so slow, there is little likelihood of reduction of the asbestos pollution hazard by the complete dissolution of fibres on prolonged contact with natural waters.

Analyses of shales, mudstones and associated strata from the British Coal Measures reflect the general similarity of the clay mineralogy of the rocks studied. Variations in the Na+:K+ ratio appear to be due to variations in the Na+:K+ ratio in illite. It is suggested that degraded illite supplied to the site of sedimentation had a higher Na+:K+ ratio than the illite now present in the shales and that post-depositional changes have caused a fall in this ratio. Under conditions of rapid sedimentation such changes tend to be inhibited by rapid burial. In the seat earths, produced by very slow sedimentation, post-depositional changes continued to an advanced stage and resulted in low Na+:K+ ratio in the final sedimentary rock.

The thermal behaviour of sepiolite and palygorskite treated with pyridine (Py) was investigated by DTA, TG, DTG and EGA (by MS) under a flow of air and inert gases (N2 or Ar). The thermal analysis showed that the organic base was adsorbed by the clays, penetrating into the clay pores and replacing zeolitic and bound water. Its presence in the pores shifted the dehydroxylation peak to temperatures higher than the corresponding peak in the untreated clays. Under N2 and Ar, thermal desorption of Py from sepiolite was observed at 260 and 650°C whereas for palygorskite only traces of Py were detected in the evolved gases. In addition to desorption, reactions of pyrolysis and condensation to coke were detected by the evolution of ammonia, methane and hydrogen, respectively. In air, oxidation of the organic matter led to the appearance of exothermic peaks. The profile of the DTA curve and the temperatures of the most intense exothermic peaks were determined by the rate of the carbon oxidation.

Transformations of clay minerals were studied in a sequence of podzols (Entic Cryorthods) of increasing age (5500-10000 years BP) developed from till materials in central Finland. The age of the soils was estimated according to altitude above the present sea level, with reference to the age of ancient shorelines and the rate of land uplift. Clay minerals in fine (<0.1 µm), coarse (0.1-2 µm) clay and fine silt (2-5 µm) fractions were studied by X-ray diffraction. The layer charge of expandable minerals was estimated on the basis of their re-expansion with ethylene glycol following K-saturation and heating to 110°C Pedogenic transformations of clay minerals occur essentially in the E horizons of the podzols. Smectites and illite-smectite mixed-layers are the dominant clay minerals in the E horizons of soils older than 6500 years. The number of mixed-layers decreases with evolution of the soil, leaving a nearly pure smectite phase in the oldest soil (10000 years). The smectites are dioctahedral with a tetrahedral charge. Groups of low-charge and highcharge interlayers are both present in the samples, but low-charge smectite layers were found only in the two older soils (9500-10000 years). This suggests alteration with time of the high-charge smectites.

The mineralogy of the clay fractions (<2 µm) of the major soils of England and Wales is reviewed, and the data presented in terms of the 1:250 000 National Soil Map. Most soils developed in pre-Rhaetic sediments are dominated by mica with lesser amounts of chlorite and kaolin. Exceptions are soils developed in calcareous Coal Measure shales which have significant smectite contents, and freely drained soils in Keuper Marl which contain swelling chlorite, sepiolite and palygorskite. Soils developed in post-Triassic sediments are dominated generally by expansible minerals, except for those developed in Lower Lias and Estuarine Series rocks (Jurassic) which are dominated by mica and kaolin respectively. The presence of loess in soils seems to be associated with the occurrence of a complex interstratified mineral with X-ray diffraction properties akin to vermiculite. Weathering of soil clays is most marked in the wetter uplands, but over most of lowland England is detectable only by slight changes in non-exchangeable potassium content and cation-exchange capacity towards the soil surface. Applications of soil clay mineralogy in the fields of plant nutrition and soil mechanics are discussed, in particular the production of maps showing mineralogical provinces.

Anisotropy and compositional and structural heterogeneity in clays are causes of considerable deviations from homogeneous diffusion, in particular in terms of direction-dependent transport rates and preferred transport zones. Conventional diffusion experiments, in which the sample is treated as a homogeneous black box in a concentration gradient, are interminable and insensitive to spatial effects. In contrast, tomographic imaging methods are capable of both reducing the amount of observation time required and revealing space-dependent features of the diffusion process.

In the present study, positron-emission-tomography (PET) was applied as the most sensitive quantitative spatiotemporal tomographic modality for direct observation of positron-emitting radiotracers in opaque media at reasonable resolution (1 mm) on a laboratory scale (100 mm).

Geoscientific applications of PET, or GeoPET, have revealed anisotropic and heterogeneous effects in diffusion experiments that have been conducted on Opalinus clay samples of different sizes, as well as on other rock types. Applying the Comsol Optimization Module to 2D-image sections of the PET tomograms, effective parameter values were derived, thereby quantifying the anisotropic diffusion.