A clay-rich Callovo-Oxfordian sedimentary formation was selected in the eastern Paris Basin (MHM site) to host an underground laboratory dedicated to the assessment of nuclear waste-disposal feasibility in deep geological formations. As described initially, this formation shows a mineralogical transition from an illite-smectite (I–S) mixed-layered mineral (MLM), which is essentially smectitic and randomly interstratified (R = 0) in the top part of the series to a more illitic, ordered (R ⩾ 1) I–S in its deeper part.

This description has been challenged by using the multi-specimen method developed by Drits et al. (1997a) and Sakharov et al. (1999). It is shown that all samples contain a physical mixture of an unusually (?) illitic (∼65% I) randomly interstratified I-Exp (illite-expandable MLM) and of a discrete smectite, in addition to discrete illite, kaolinite and chlorite. Structural parameters of the different clay phases vary little throughout the series. According to the proposed model, the mineralogical transition corresponds to the disappearance of smectite with increasing burial depth.

Comparison with clay minerals from formations of similar age (Oxfordian-Toarcian) throughout the Paris Basin shows that the clay mineralogy in the deeper part of the series originates from a smectite-to-illite transition resulting from a low-temperature burial diagenesis. The anomalous lack of evolution of clay minerals in the upper part of the series is thought to be related to specific interactions between organic matter and clay minerals.

The effect of a saline environment on illitization in volcanoclastic rocks is examined in deep boreholes in the East Slovak Basin. Based on X-ray diffraction analysis, it is concluded that illite-smectite (I–S) expandability is always less in the salt-bearing bentonites (SBB) than in the salt-free bentonites (SFB) for a given depth interval. These two lithologies can be distinguished easily by water-leachate chemistry. Within the depth interval 2100–2500 m, the expandability in SBB varies within the range 25–10% expandable with R1 and R3 ordering in SBB and 68–35% expandable with R0 ordering in SFB. In two shallow SBB samples the expandability is close to that of SFB, suggesting that salinity alone does not enhance the illitization; but salinity may enhance it when combined with higher burial temperature. Vitrinite reflectance and Tmax of RockEval pyrolysis measured in adjacent shales confirm that the increased illitization in SBB is not due to heating and/or erosion. The model of burial and thermal history calibrated by organic maturity suggests that the same thermal history produces two different expandabilities in the two lithologies (SBB and SFB). Particle thickness measurements and K-Ar data were used to deduce the crystal growth mechanism of illitization in SBB. Whereas surface-controlled growth is typical for SFB, simultaneous nucleation and growth played a more important role in the case of SBB. The effect of a salty environment on the illitization is not yet fully understood and may have severe consequences for the utilization of bentonites as engineering barriers in radioactive waste disposal sites if salt formations used as host rocks are taken into account.

The sea-cliffs of the Isle of Wight were deposited during a period of overall sea-level rise starting in the Barremian (Lower Cretaceous) and continuing into the Aptian and Albian. They consist of fluvial, coastal and lagoonal sediments including greensands and clays. Numerous episodes of erosion, deposition and faunal colonization reflect condensation and abandonment of surfaces with firmgrounds and hardgrounds. This study focused mainly on shallow marine cycles where variations in clay mineralogy would not be expected, because overall system composition, sediment source, and thermal history are similar for all the samples in the studied section. Instead we found a wide variety of clay assemblages even in single samples within a 200 m interval.

In this interval, distinct clay mineral assemblages were found and can be described as consisting of Al-rich, Fe-richand intermediate Fe and Al compositions withrespect to 2:1 and 1:1 layers in mixed-layer arrangements. Nearly pure glauconite-nontronite clays exist in the <2 µm fraction only when the bulk rock is free of K- and plagioclase feldspar. Conditions favorable to glauconite-nontronite formation are interpreted to result from a hiatus in volcanoclastic sedimentation, thus providing a stable substrate for glauconitization.

The Fe-bearing mixed-layer clay assemblages consist of glauconite, nontronite and berthierine-like layers in various proportions with several mixed-layer clays often coexisting in the same sample. In different samples, Al-richand Fe-Mg-rich mixed-layer clays are similar in their content and distribution of 1:1 and 2:1 layers. This suggests that the original clay assemblages were similar and later diagenesis affected certain horizons resulting in substitution of Al by Fe + Mg while preserving the original layer structure and arrangement.

Structural formulae for the berthierine-like phase and berthierine-like layers in these mixed-layer clays show their layer cation composition is intermediate between odinite and standard berthierine. The total sum of octahedral cations varies from 5.26 to 5.55 whereas the amount of Fe2+ cations varies from 2.12 to 2.22 per O10(OH)8. A feature of the berthierine-like phase as well as of berthierine-like layers is that they are di-trioctahedral and Fe2+ and Fe3+ are the prevalent cations. Moreover, in these berthierine-like components, the amount of Fe2+ is greater than that of Mg (in contrast to odinite) and Fe3+ cations prevail over Al (in contrast to berthierine). The presence of authigenic ferrous Fe clays and the relationship between glauconite-nontronite and bulk mineralogy has implications for sedimentological processes and geochemical conditions during and shortly after deposition.

The clay fraction of the sedimentary succession beneath the Mahakam Delta (eastern Kalimantan, Indonesia) consists mainly of mixed-layer illite-smectite, with minor amounts of kaolinite and/or dickite, discrete detrital illite and chlorite. On the near-shore anticline, evolution of this mixed-layer material is characterized by a decrease in expandability with depth. The mechanism of conversion of smectite to illite layers depends on the lithology of the host rocks: it evolves along a solid-state transformation in the shales and a dissolution-precipitation in the sandstones.

Illite fundamental particles from two sandstones buried at ∼4000 m in the Tambora field next to the Handil field on the same near-shore anticline yield a mean K-Ar age of 15.7±1.6 Ma (2σ), which is younger than the stratigraphic age but still slightly biased by minute amounts of discrete detrital illite. Recalculated after modeling, which takes into account the occurrence of the discrete detrital illite, this K-Ar age becomes 14.4±0.7 Ma. The K-Ar values of the fundamental particles from associated buried shales are significantly older, which can be explained by a mixture of (1) a precursor material similar to that presently deposited in the delta of the Mahakam River, and (2) authigenic fundamental particles incorporating Ar with a 40Ar/36Ar ratio above atmospheric value during nucleation and growth on the same detrital precursor.

Application of the modeling to the burial evolution of <0.4 µm particles from both the shales and the sandstones of the basin points to a contribution of detrital micaceous material in both lithologies, (1) in the sandstones as a detrital component dissolving progressively and mixed mechanically with the authigenic fundamental particles, and (2) in the shales as a detrital precursor progressively releasing radiogenic 40Ar by burial alteration, and at the same time acting as a support for the fundamental particles for the growth of authigenic fundamental particles that were found to incorporate Ar characterized by an excess of 40Ar.

A new method has been developed for quantifying smectite abundance by sorbing polyvinylpyrrolidone (PVP) on smectite particles dispersed in aqueous solution. The sorption density of PVP-55K on a wide range of smectites, illites and kaolinites is ∼0.99 mg/m2, which corresponds to ∼0.72 g of PVP-55K per gram of montmorillonite. Polyvinylpyrrolidone sorption on smectites is independent of layer charge and solution pH. PVP sorption on SiO2, Fe2O3 and ZnO normalized to the BET surface area is similar to the sorption densities on smectites. γ-Al2O3, amorphous Al(OH)3 and gibbsite have no PVP sorption over a wide range of pH, and sorption of PVP by organics is minimal. The insensitivity of PVP sorption densities to mineral layer charge, solution pH and mineral surface charge indicates that PVP sorption is not localized at charged sites, but is controlled by more broadly distributed sorption mechanisms such as Van der Waals’ interactions and/or hydrogen bonding. Smectites have very large surface areas when dispersed as single unit-cell-thick particles (∼725 m2/g) and usually dominate the total surface areas of natural samples in which smectites are present. In this case, smectite abundance is directly proportional to PVP sorption. In some cases, however, the accurate quantification of smectite abundance by PVP sorption may require minor corrections for PVP uptake by other phases, principally illite and kaolinite. Quantitative XRD can be combined with PVP uptake measurements to uniquely determine the smectite concentration in such samples.

Submicroscopic intergrowths of K biotite, Na biotite and intermediate Na-K biotite from a schist near Málaga (Betic Cordilleras, Spain) were discovered using high-resolution transmission electron microscopy and analytical electron microscopy. The sample was also studied with X-ray diffraction, electron microprobe analysis, and scanning electron microscopy. Scanning electron microscopy revealed that the Na-enriched biotite is concentrated in albite-rich microdomains, albite being partially replaced by biotite. These images also revealed that both K and Na-K biotite grains appear locally retrograded to kaolinite. Transmission electron microscopic data indicated that K biotite, Na biotite and Na-K biotite form parallel or subparallel packets with interfaces parallel to the basal planes of biotite. Potassium biotite forms thick packets, chemically homogeneous, with a basal spacing of 10.1 Å. Sodium biotite also occurs as chemically homogeneous stacks of layers with a 9.78 Å periodicity. Sodium-K biotite shows, on the contrary, variable composition and basal spacings intermediate between K and Na biotites. Analytical electron microscopic data revealed important chemical differences between Na and K biotites, which affect both the tetrahedral and the octahedral sheets. Both electron microprobe analysis and analytical electron microscopy indicated that the trioctahedral micas show relatively low interlayer occupancy, suggesting the presence of H3O+ replacing the interlayer cations. Partial hydration of biotite explains the presence of a weak 14 Å reflection in the X-ray patterns. Both chemical and textural data suggested that these trioctahedral micas grew during a common prograde metamorphic episode, the phases with intermediate composition probably being metastable.

Cronstedtite is a member of the kaolin-serpentine group. It yields a wealth of more or less disordered polytypes. The crystals of polytype 1T (space group P31m, a = 5.512, c = 7.106 Å) contain, within coherently scattering blocks, variable concentrations of stacking faults so that domains of the basic 3D periodic structure can be shifted by 1/3 (a2 − a1) or 1/3(a1 − a2). These so-called OD parallel intergrowths have been confirmed by high-resolution transmission electron microscopy. The effect manifests itself in the diffraction pattern so that reflections with h-k = 3n — the family reflections — are always sharp, whereas remaining reflections — the characteristic polytype reflections — may be smeared out parallel to c*. The intensities of the latter are thus underestimated during diffractometer measurements. An analysis of such multiple OD intergrowths reveals that the moduli of structure factors for all characteristic (i.e. non-family) polytype reflections are reduced relative to those calculated for the non-intergrown basic structure, by a common factor. This fact usually leads to the appearance of ghost peaks in Fourier maps and to their erroneous interpretation. The structure of the basic model can, however, be refined much better if two scale factors are assigned to the family and non-family reflections, respectively.

Three petrographically distinct styles of altered glasses in two hyaloclastites and one hyalotuff were studied. The texture and chemistry of these samples were investigated using electron probe microanalysis, scanning electron microscopy and transmission electron microscopy in order to understand better the mechanism by which alteration of sideromelane and formation of palagonite occurred in these samples. The results show that clay minerals (primarily smectites) are present in three different microenvironments: (1) coating the surfaces of glass and crystals or vesicle walls; (2) as a relatively heterogeneous, but well crystallized, replacement product (i.e. reddened smectite grain replacement or RSGR) of glass or; (3) as a relatively homogeneous, amorphous to poorly crystalline replacement product (i.e. palagonite). Both the grain size and composition of these smectite-like materials vary considerably.

Crystalline smectites occur in both hyaloclastites and have an intermediate composition between the two end-members nontronite and saponite. This composition could correspond to a mechanical intergrowth and/or an interstratification of two different smectites: one dioctahedral (i.e. nontronite) and one trioctahedral (i.e. saponite or stevensite) or simply to a true di-trioctahedral smectite. The coating smectite appears to have precipitated by a paragenetically-early, dissolution-precipitation mechanism prior to the formation of the RSGR. The high Ti content found in RSGR is attributable to an amorphous Ti-rich material which is intergrown with smectite and which behaves as a sink for immobile elements and those not included in smectite.

Palagonite from both hyaloclastites and hyalotuff is poorly to non-crystalline and more aluminous than the coating smectites. Palagonite from the hyalotuff has an Fe-rich montmorillonite-like composition. The TEM images show a 30–50 nm thick leached layer formed by selective (non-stoichiometric) dissolution that takes place in the fracture domain. The hydration and replacement of glass during the palgonitization process is accompanied by the loss of Fe, Mg and Ca with a concomitant gain of Al. Both palagonites (from hyaloclastites and hyalotuff) show smilar textural and chemical characteristics.

The dehydration and rehydration processes of the clay mineral palygorskite (PFl-1) were studied by textural analysis, thermogravimetric analysis connected with mass spectrometry (TGA-MS), and 29Si and 1H solid-state NMR techniques. The TGA-MS results clearly reveal weight losses at maxima of 70°C, 190°C, 430°C and 860°C. PFl-1 is characterized by a micropore area of 93 m2/g, corresponding to a micropore volume of 47 mm3/g. These values are also obtained for the sample heated up to 200°C for 20 h. Further heating at 300°C produces a collapse of the structure, as shown by the almost complete loss of microporosity.

The 29Si NMR spectra of palygorskite show two main resonances at −92.0 and −97.5 ppm, attributed to one of the two pairs of equivalent Si nuclei in the basal plane. A minor resonance at −84.3 ppm is attributed to Q2(Si-OH) Si nuclei. The resonance at −92.0 ppm is assigned to the central Si position, while the resonance at −97.5 ppm is assigned to the edge Si sites. It is confirmed bysolid-state 29Si and 1H NMR that nearly complete rehydration is achieved by exposing palygorskite samples that have been partially dehydrated at 150°C and 300°C, to D2O or water vapor at room temperature. When the rehydration is accomplished with D2O, the atoms are disordered across all the protons sites.

The sorption of two sulfonylurea herbicides (SU), metsulfuron methyl and nicosulfuron, on pure clays and organoclays was investigated. Three clays (Arizona smectite, SAz-1, Wyoming smectite, SWy-2, and hectorite, SHCa-1), were treated with amounts of octadecylammonium (ODA) or dioctadecyldimethylammonium (DODMA) cations equal to ∼50 and 100% of the clays’ cation exchange capacity (CEC). Sorption isotherms were fitted to the Freundlich equation. While no measurable sorption was found on the pure clays (Kf = 0), organoclays prepared using both primary and quaternary amines were effective as SU sorbents. The metsulfuron methyl Kf values ranged between 196 and 1498 µmol1−1/n kg−1 L1/n, and Kf values for nicosulfuron, which were lower than those of metsulfuron methyl, ranged from 35 to 198 umol1−1/n kg−1 L1/n. As shown by sorption coefficients, Kd and KOC, SWy-2 treated with DODMA at ∼100% of the CEC was the most effective sorbent for metsulfuron, Kd = 684 L kg−1 and KOC = 2138 L kg−1. For nicosulfuron the most effective sorbent was SAz-1 with ODA at ∼ 50% of the CEC (Kd = 147 L kg−1 and KOC = 1233 L kg−1). In contrast to other weak-acid herbicides, such as phenoxy and picolinic acids, no clear relationships were found between sorption and layer charge, organic carbon content, and basal spacing of the organoclays for both sulfonylurea herbicides. Sorption of both herbicides on organoclays was assumed to involve hydrophobic and polar interactions for which the availability of interlayer room between organocations was a very important factor.

The ability of hydrotalcites to retain anionic wastes was studied. In particular, Cr(VI)-adsorbed hydrotalcites were heated to immobilize Cr(VI) in the solid sample. When the heating temperature increased up to 500°C, the lamellar structure of hydrotalcite was lost. At high temperatures (1200°C), the solids were recrystallized in the form of a spinel. Lixiviation with 1 N and 5 N NaCl solutions were utilized to simulate the effect of sea water and of concentrated NaCl solutions in salt mines on the immobilization of Cr. Radiation damage on the solid containing the immobilized Cr was studied by γ-irradiating with a 60Co source at 1000 and 6000 kGy. The Cr-containing samples heated at 1200°C, whether irradiated or not, safely immobilized Cr in the hydrotalcite mainly in the form of MgCr2O4 spinel. Irradiation of hydrotalcites revealed two different effects: (1) samples heated up to 1200°C evolved as a solid in which chromium was retained more firmly than in the non-irradiated material, irradiation enhancing the spinel formation; (2) the structure of samples heated at 1200°C developed a preferential crystallite orientation rather than a purely random one or new location of chromium ions, this effect did not affect Cr immobilization in the solid. Chromium lixiviation with 5 N NaCl solution was always less than the corresponding value with 1 N NaCl solution, probably due to the poor mobility of Cl− ions in the highly concentrated NaCl solution.