The expert system described in the first part of this paper has been applied to the identification of mixed-layer phyllosilicates (mica-smectite, mica-vermiculite, chlorite-smectite, chlorite-vermiculite, chlorite-swelling chlorite, chlorite-mica, chlorite-talc, kaolinite-smectite, talc-smectite), and to the determination of their structural parameters (Reichweite, R, and proportions of constituting layers, Wi). The expert system has been run utilizing the data extracted from (1) experimental XRD patterns for which structural parameters had been evaluated by comparison with calculated patterns, or (2) patterns calculated using pre-selected values of the structural parameters. In all cases examined, the expert system provided correct conclusions concerning the identification of a mixed-layer phyllosilicate and the value of the Reichweite, while the abundances of the component layers were evaluated with a margin of error usually <5%.

The effect of diagenesis on shale petrophysical characteristics is being investigated as part of a study on shale sealing capacity because of its significance for modelling hydrocarbon charge histories of sedimentary basins. Results to date indicate that diagenesis (degree of cementation and dissolution) significantly affects porosity and inter-connectivity of the nano-pores (0.3–60 nm), the pores constituting the main pore-throats for tight shales. Diagenesis causes tight shale permeabilities to vary over a range exceeding an order of magnitude (10−21 − 6 × 10−20m2) and porosities to vary between 1 and 12%. In addition, diagenesis significantly influences shale nano-pore resistance to collapse during compaction and burial, mainly at depth > 2–3 km, affecting hydrocarbon trapping, overpressure and sealing capacities. Dissolution tends to delay the timing of excess pressure pulses, while cementation has a reverse effect. The significance of diagenesis is reduced at shallower depths.

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.

Intrinsic surface acidity constants (Kalintr, Ka2intr) and surface complexation constant for adsorption of orthosilicate onto synthetic ferrihydrite (Ksi for the complex ≡FeOSi(OH)3) have been determined from acid/base titrations in 0.001-0.1 M NaClO4 electrolytes and silicate adsorption experiments in 0.01 M NaNOi electrolyte (pH 3-6). The surface equilibrium constants were calculated according to the two-layer model by Dzombak ' Morel (1990). Near equilibrium between protons/hydroxyls in solution and the ferrihydrite surface was obtained within minutes while equilibration with silicate required days-weeks, both reactions probably being diffusion controlled. Applying the values for specific surface area and site densities for ferrihydrite used by Dzombak ' Morel (1990) (600 m2 g–1, 3.4 μmole m–2) the constants pKalintr = 6.93 ± 0.12, pKa2intr = 8.72 ± 0.17 and log Ksi = 3.62 were calculated by using the FITEQL optimization routine. Use of the specific surface area actually measured (269 m2 g-1) gave a poorer fit of the experimental data. Due to the slow adsorption of silicate and hence long shaking times, changes in the surface characteristics of the ferrihydrite seem to take place, probably a decrease in the concentration of surface sites. Adsorption isotherms calculated using the derived equilibrium constants showed that approximately twice the amount of silicate was adsorbed at pH 5 compared with pH 3.

Infrared spectroscopy of silica adsorbed to ferrihydrite showed Si-O stretching absorption maxima in the range 940-960 cm-1. The shift of the absorption maximum to higher wavenumbers with increasing amount of silicate adsorbed is probably due to an increase in the frequency of Si-O-Si bonds between orthosilicate adsorbed at adjacent sites. Small amounts of goethite were identified in the adsorption products.

Different types of heterogeneity were shown in F/OH/A1 pillared fluorohectorite by combined use of X-ray and selected area electron diffraction, high-resolution transmission electron microscopy (HRTEM) and energy dispersive X-ray (EDX) methods: interlayer distances heterogeneity (layer stacking order imperfections); domain structure heterogeneity; and phase heterogeneity (formation of secondary phases from pillaring solutions). The role of ageing of pillaring solutions and pillared smectites was revealed and discussed.

The influence of kaolinite and montmorillonite on the identification of pseudoboehmite was studied by X-ray diffraction (XRD), differential thermal analysis (DTA), infrared absorption (IR), and transmission electron microscopy (TEM). In the randomly oriented samples containing different proportions of the clay minerals and pseudoboehmite, pseudoboehmite was not easily detectable by XRD even in a sample containing 40% of pseudoboehmite. Preheating of the samples at 110-300°C improved the detection limit to 30%. In samples obtained by mixing suitable amounts of the suspensions of the clay minerals (<2 μm) and pseudoboehmite, the identification of pseudoboehmite was even more difficult. In oriented samples, pseudoboehmite was detectable only when present in amounts >30%, at low full-scale counts per second (1000-400 cps), on preheated samples in the presence of kaolinite, or on the samples that were Mg-saturated and solvated with ethylene glycol in the presence of montmorillonite. Identification of pseudoboehmite in the presence of kaolinite or montmorillonite by DTA, IR or TEM failed, even in samples containing 50% pseudoboehmite. In the presence of both kaolinite and montmorillonite (1:1 w/w), the identification of pseudoboehmite became much more difficult than in the presence of either mineral alone. The presence of pseudoboehmite in soils may, thus, be undetectable by standard clay mineralogical analyses.

Fluid inclusion studies from two contrasting fields in the Northern North Sea reveal hydrostatic pressure conditions during the formation of secondary quartz overgrowths which trapped both brine and petroleum inclusions. In these fields, dating of authigenic illite, part of the diagenetic sequence and broadly coeval with quartz cementation, permits comparison with modelled pressure conditions. Pressure modelling indicates the likelihood of several periods of overpressure in the past, interspersed with normal pressure. The timing of diagenesis coincides with one of these periods of hydrostatic pressure. Furthermore, as both fields are now highly overpressured, the cause and timing of overpressure generation post-date the diagenesis. A model is proposed to link the pressure history and diagenesis.

The clay deposits in fractures of the metamorphic basement under the Paris Basin sedimentary formations at Sancerre-Couy (France) are composed of trioctahedral species which are exceptionally well crystallized. Three samples were chosen in order to study the chemical composition of 100% expandable saponite, 50% expandable corrensite and 10% expandable chlorite-saponite mixed-layer mineral C90–S10 Two sets of microchemical analyses were performed in order to determine the variations of the composition on large and small numbers of particles. X-ray diffraction (XRD) and Mössbauer spectrometry were performed on purified samples.

The mathematical decomposition of Si, Al and Mg histograms established from microanalyses of a large number of crystals of saponite, corrensite and C90–S10 evidences bimodal populations. The total Fe content of the three species is unimodal whatever the chemical composition of the surrounding rock and the Fe2+/Fe3+ ratio. The structural formulae established from a large number of microanalyses of a few particles show that there are no parental relationships between saponite, corrensite and C90–S10. The expandable layer of corrensite is characterized by a high charge. It is proposed that the tetrahedral sheets adjacent to the brucitic sheet and the exchangeable interlayer in a 2 : 1 unit are identical in corrensite.

To investigate the long-term stability of bentonite under final disposal conditions of highly radioactive waste, K-bentonites from Kinnekulle (Sweden) and from the Marias River Formation in the Montana disturbed belt (USA) were studied. After separating the mixed-layer illite-smectite (I-S) from the K-bentonite samples, the interlayer charge was calculated from the cation exchange capacity (CEC) and the amount of fixed interlayer K+ ions (Kfix). The interlayer charge was also determined by the alkylammonium method. According to both methods the interlayer charge was in the range for smectite. The results show that the amount of exchangeable cations increased linearly with decreasing Kfix. A small increase in the interlayer charge with increasing Kfix was observed as was a linear correlation between the intracrystalline swelling up to the second water layer, the CEC and the content of Kfix. Divalent exchangeable cations were then found to be surrounded by approximately 24 water molecules per cation. Fixed interlayer K+ ions were unhydrated. Forming the third and fourth water layer, swelling was presumably limited by free silica formed by the vitrification of the volcanic ash.

Addition of methanol, ethanol, and n-propanol to aqueous dispersions of Namontmorillonite (2% w/w) reduces the apparent viscosity and the yield value. In the presence of NaCl the flow parameters increase to a maximum at medium alcohol concentration. Thus, the gel strength of Nabentonite dispersions can greatly change with the alcohol content of the dispersion. This is probably caused by the transition of dispersed clay mineral particles (individual silicate layers or lamellae of a few of these layers) to band-type networks with optical homogeneity and weakly attractive particle-particle interaction. When attraction between the particles becomes too strong at high alcohol concentrations, the bands are condensed to short fragments and, eventually, freely moving particles, reducing the viscosity and the yield value.

The interparticle interaction energy is calculated for the constant charge model by van Olphen's (1977) method. Agreement with the experimental results is only obtained when the Stern layer adsorption is governed by a specific adsorption energy μ, which increases with decreasing dielectric constant.

The flow behaviour of Wyoming bentonite dispersions was studied in water and water-alcohol mixtures (methanol, ethanol, n-propanol) with or without the addition of NaCl. The yield value τo and relative apparent viscosity τ*rel (= τ* (dispersion/τ* (medium) at γ = 94.5 s-1) increase to a maximum and then decrease with increasing alcohol content. The increase of the flow values is caused by face-to-face aggregation. Formation of band-type networks is a consequence of the enhanced attraction between the silicate layers in water-alcohol mixtures. At higher alcohol contents the bands are contracted to discrete particles. Both effects are considerably strengthened by calcium ions which are present in the crude bentonite.

Much emphasis has been placed recently on the role of Ostwald-type processes (both ripening and the step rule) in the formation of interstratified illite-smectite clay minerals during diagenesis. Closer investigation of the relationships between illite particle thickness (as defined in terms of the fundamental particle theory) and particle chemistry show that simple Ostwald ripening is too simplistic a mechanism to describe observed changes in illite thickness and composition. In addition, available thermodynamic data on clay minerals suggest that the conventional notion of metastability associated with Ostwald's step rule is an inaccurate description of the relationship between illitic clay minerals and their macroscopic 2 : 1 phyllosilicate analogues.

A sepiolite from Vallecas (Spain) was treated with solutions of HC1 (1.25, 2.5, 5.0, 10.0 and 20.0 wt%) at 25°C for 2, 6, 24 and 48 h, respectively. The resulting solids were characterized by XRD, FT-IR and thermal analyses, along with SEM, TEM and nitrogen adsorption isotherms at 77 K. The free silica was digested and determined in all samples. Several samples were seen to have specific surface areas up to 450 m2/g, with a maximum value of 549 m2/g in the sample treated with 1.25 wt% HCl for 48 h. A sudden decrease in specific surface areas was observed when free silica was digested.

Empirical porosity/depth trends from the Norwegian Continental Shelf are discussed in the light of models on compactional processes during burial. Linear best-fit lines are useful as a first approximation, illustrating the general decline in porosity with depth. Porosity increases non-linearly with pore-pressure, and notably higher than normal porosity is found in very high overpressure reservoirs. Hydrostatic pressure sandstones from the Haltenbanken area are on average more porous than equivalents from the northern Viking Graben. This may be related to the burial history, as generally more subsidence occurred in Late Pliocene and Pleistocene in the Haltenbanken basins. The porosity/depth data show considerable scatter, and this is to a large degree related to the initial mineralogical composition. Correlated with mineralogical analyses, the reservoir sandstones show a trend towards lower porosity with increasing clay content at shallow burial, probably due to more extensive mechanical compaction. At depths >3.0–3.5 km, the porosity loss is highest in sandstones with low clay contents. This may be explained by a lower rate of quartz cementation in sandstones with abundant intergranular clays or clay coatings around quartz grains. These data show that pre-burial mineralogy is a very important factor in porosity prediction of sandstones, in many cases more important than the degree of overpressure.

The uptake of Ba2+ and K+ by a synthetic Na-phyllomanganate has been studied by chemical analysis, X-ray diffractometry and X-ray photoelectron spectroscopy. The changes in basal spacing arising from cation exchange have been used to monitor the progress of the exchange reaction and confirm the selectivity measured by bulk chemical analysis. However, the selective uptake of Ba2+ over Ca2+ is much greater than that of K+ over Na+ and it is suggested that charge distribution in the interlayer is important. The results are discussed in the light of recent advances in our understanding of the phyllomanganate structure.

The <2 µm clay fractions from low-grade metabasalts of eastern North Greenland are mixtures of mafic phyllosilicates and celadonite that show complex X-ray diffraction (XRD) patterns. Interpretation of such patterns is difficult and subjective using only visual examination of peak positions and shapes. Deconvolution analysis offers a less subjective means of identifying peak positions for overlapping peaks and is applied to several composite peaks in a pattern; the peaks identified are then rationalized in terms of specific mixed-layer phases. Comparison against NEWMOD patterns of the identified clay mixture provides an additional constraint on the phases identified. Three mafic phyllosilicates, discrete chlorite and two chlorite-smectites with 60:40 and 80:20 proportions are demonstrated in the same XRD pattern. Modelling using NEWMOD of a mechanical mixture between these mineral shows an excellent match to the observed XRD pattern. The recognition in low-grade metabasalts of chlorite and random and different varieties of regular mixed-layer chlorite-smectite offers support for the classical model of a tri-smectite to chlorite transition. This is in contrast to an alternative model proposing smectite and chlorite end-members with corrensite as a discrete phase crystallizing directly without intervening mixed-layer chlorite-smectite.

The adsorption of the insecticide methomyl (S-methyl N-(methylcarbamoyloxy)thioacetimidate) by smectites with different layer charge (SWy and SAz montmorillonites and SH-Ca hectorite) has been determined. Adsorption has been expressed as the adsorbent/adsorbate distribution coefficient Kd, which increased when the layer charge of the smectite decreased. The Kd values for homoionic SWy montmorillonite samples increased when the ionic potential of the interlayer cation decreased, except for SWy-Fe3+. Infrared (IR) spectra and X-ray diffraction (XRD) analysis of the SWy-K+ and SWy-Na+ montmorillonites treated with methomyl suggest that pesticide molecules interact through polar bonds with the interlamellar cation. In the case of SWy-Fe3+, kinetic studies, high performance liquid chromatography (HPLC), IR and XRD data indicated that adsorption and degradation both account for the high Kd value obtained.

Ammonium-rich illite was identified in shales from the meta-anthracite coalfields of Zemplinicum (the Western Carpathians) together with K-illite and Na-illite using X-ray diffraction (XRD), infrared absorption and chemical analyses. The NH4-abundance in illite was quantified by the position of the 005 XRD reflection and by chemical analysis. Ammonium-bearing illite was probably formed in the temperature interval 200-270°C by illitization of a kaolinite precursor in the presence of ammonium.

By modelling a range of rock-forming processes such as compaction and various styles of cementation, a new understanding of how they affect pore-system geometry, and hence permeability, has been gained. For example, almost identical permeability-porosity trends result from progressive compaction or grain overgrowth cementation in a clean sandstone, and these trends are curvilinear on the traditional log-linear plot. The steepening which defines the curve marks the onset of pore-throat blocking. Other cement styles, such as pore-filling carbonates or grain-rimming clays, show different porosity-permeability trends. This new understanding can be used predictively (predicting permeability from predictions of grain size and diagenetic style), or as a tool for identifying the important permeability controls in a set of field data. This latter application is presented and illustrated using data from a variety of sandstone types. This approach has important advantages over commonly used multivariate statistical analysis approaches. It can quickly provide a good understanding of what are (and are not) the important controls on permeability. It also provides a basis for more focused and meaningful statistical analysis to quantify these controls.

The <2 µm fraction from the eluvial horizon of a humus-iron podzol is composed predominantly of a dioctahedral mineral with a basal spacing of 14.7 Å which contracts to 13.7 Å on solvation with glycol, and to 11.4 Å on heating to 300°C. The interlayer region is partially filled with an amorphous organo-Fe-Al complex which is very unstable and is affected by every treatment employed, even homoionic cation saturation. The mineral has a mica-like morphology, contains 3.4% non-exchangeable K2O and is considered to be an interstratified mica-vermiculite formed by the weathering of mica. The contraction of the basal spacing with glycol is probably due to water being removed from the interlayer region of the vermiculite component, leaving only the natural organo-complex in the interlayer; alternatively, the contraction may be more apparent than real, resulting from an interstratification effect. Treatment with H2O2 results in partial expansion with glycol.