The thermal stability of bentonites is of particular interest for containment barriers in nuclear waste storage facilities. The kinetics of smectite reactions have been investigated under laboratory conditions for some time. The variables of time, chemical composition and temperature have been varied in these experiments. The results of such an assessment are that there are about as many kinetic values deduced from experiments as there are experiments.

Experiments using natural bentonite to study the smectite-to-illite conversion have been interpreted as a progressive transformation of montmorillonite to illite. It is highly probable that the initial reaction product is not illite but a high-charge beidellite + saponite + quartz mineral assemblage which gives, then, beidellite-mica interstratified mixed-layer minerals. These experimental reactions are noticeably different from those of diagenesis, being closer to reactions in hydrothermal systems.

Molecular simulations using the Cerius2 modelling environment have been used to investigate the structure of montmorillonite (MMT) intercalated with Zn cations. Basal spacing and bonding of Zn2+ cations in the interlayer have been investigated with regard to their dependence on the water content. In the first part of the work, Zn cations in the interlayer are coordined by six water molecules and the energy of the system is discussed. The energy discussion is focused on the influence of the different starting orientations of the Zn octahedron, and different positions of Mg atoms in the octahedral sheet. An energy scan at fixed d-spacing was carried out. Later the hydration simulation giving the hydration curve (i.e. the dependence of d-spacing on the number of water molecules in the interlayer) was also carried out. Two different hydration states were found — for certain humidity ranges there is almost constant d-spacing and between these intervals there is a sharp edge. Finally the structure of totally dehydrated Zn-MMT was simulated.

Goethite and maghemite are the stable species of Fe oxyhydroxides-oxides formed an acidic and alkaline environments from the oxidation of Fe(II) perchlorate solutions. The influence of montmorillonite on the oxidation products of 0.02 M ferrous perchlorate at pHs of 6.0 and 8.0 was studied by X-ray diffraction, infrared and transmission electron microscopic analyses. Increased rate of OH consumption during the oxidation at constant pH indicated that the presence of montmorillonite accelerated the rate of Fe(II) oxidation. The presence of montmorillonite, with high surface reactivity, at an initial montmorillonite/Fe (w/w) ratios of 1.4 and 3.4 retarded the formation of goethite, lepidocrocite and maghemite, and maghemite and goethite, and promoted the formation of ferrihydrite and lepidocrocite at pHs of 6.0 and 8.0, respectively. Kaolinite, on the other hand, with relatively low surface reactivity had no influence on the nature of the Fe(II) oxidation products formed at either pH.

A high-iron content saponite, of the variety griffithite, was reduced using sodium dithionite and hydrazonium sulphate solutions. An important amount of Fe3+ was reduced during the treatments. When using sodium dithionite as reducing agent, the reduction was accompanied by the substitution of Ca2+ by Na+ as the exchangeable cation. When using hydrazonium sulphate, the reduction was accompanied by acid activation of the clay, the protons being released in the oxidation reaction of the hydrazonium cation. The charge balance in the clay layers is affected by the reduction processes. These structural changes do not significantly affect the pillaring ability of the clay, which is similar in the reduced solids and in the natural griffithite.

Low molecular weight polycyclic aromatic hydrocarbons can intercalate from the solid phase into montmorillonite (Mt) saturated with quaternary alkylammonium ions. However, the interaction and relationship between guest and host organic molecules in the interlayer space of the clay are not well understood. We have intercalated phenanthrene into tetradecyltrimethylammonium (TDTMA)-montmorillonite by a solid-solid reaction. The basal spacing of the original TDTMA-Mt complex is close to 1.8 nm, indicating the presence in the interlayer space of a double layer of TDTMA ions with the alkyl (polymethylene) chains lying parallel to the silicate layers, and the carbon zig-zags adopting an all-trans conformation. After intercalation of phenanthrene the basal spacing increases to about 3.4 nm, indicating a change in orientation of the alkyl chains with respect to the silicate layers. 13C-NMR spectroscopy shows that adding phenanthrene to TDTMA-Mt leads to a displacement by -3 ppm of the -(CH2)n- signal for TDTMA. This signal and that for interlayer phenantbrene are also broadened relative to the respective pure compounds. These observations, together with measurements of nuclear spin relaxation time constants, strongly suggest that in the complex with phenanthrene the polymethylene chains of TDTMA extend away from the silicate layers, and no longer assume a rigid all-trans carbon zig-zag conformation. Rather, the TDTMA chains become relatively disordered and intimately mixed with phenanthrene.

The Ga for A1 substitution in kaolinites and smectites was studied using clay synthesis from initial gels having an (Al + Ga)/Si ratio of kaolinites and MGa = Ga/(Ga + A1) ratio ranging from 0 to 1. Only kaolinite was obtained for MGa in the range 0-0.10. For higher MGa, synthesized clays were both kaolinite and beidellite, or pure beidellites. The evolution of b cell parameters, and the appearance of a vAI-OH-Ga absorption band at 3600 cm-1 in FFIR spectra, proves the progressive substitution of AI by Ga in kaolinite. The low substitution of AI by Ga in kaolinite can be correlated with the large difference in ionic radii between Al3+ and Ga3+ which causes a large increase in cell dimensions. By contrast, the incorporation of Ga in smectites is easy and can be complete.

The layer charge characteristics of smectite from the Tertiary basins in the Pohang area, Korea have been studied in detail using the alkylammonium method. On the basis of layer charges, the smectite in the Pohang area can be classed as normal and high-charge (hc) smectite. The layer charge of the normal smectite averages 0.3, and ranges from 0.25 to 0.38/half unit-cell. The hcsmectite collapses on K saturation to become illite-like material and shows 10 Åseries reflections on X-ray diffraction. The layer charge of the hc-smectite ranges from 0.5 to 1. The layer charges do not appear to be related to stratification or to basins of occurrence. The diagenetic trend that may have existed in the region was probably disturbed by later volcanic activity. A systematic change in layer charge and geochemistry of smectite in Waeup illustrates that the heat and solutions associated with the volcanic activity may have played a role in the development of layer charge.

Clay from Fourges has been selected by the Commissariat à l'Energie Atomique as a support in radioactive waste disposal studies. This material was activated by adding Na2CO3, then compacted at 60 MPa. Subsequently, its swelling behaviour was monitored at 90°C and 145°C for 330 days and at the end of this period the samples were examined by transmission electron microscopy (TEM). For this, they were embedded in a resin then sectioned with an ultramicrotome for mineralogical and chemical analyses. The initial material is essentially composed of kaolinite and smectite. Addition of Na2CO3 at room temperature induces a replacement of Ca ions by Na ions and the precipitation of finely divided carbonates on the surface of the constituents. At the end of 330 days at 90°C under a hydraulic pressure of 1 MPa, the initial particles combine and the material exerts a swelling pressure of 20 MPa. A complete reorganisation of the clay crystallites is observed without significant dissolution of the solid phases. After the same time at 145°C under a hydraulic pressure of 10 MPa, in a basic medium, the combined conditions are such that a high proportion of the clay is dissolved with formation of amorphous aluminosilicates correlated with a marked drop in the swelling pressure to 5 MPa. This work establishes the advantages of following the macroscopic properties in parallel with the microstructure variations for understanding the changes in the properties of clays.

Although the kinetics of the dehydroxylation of kaolinite have been widely studied, there is no definitive explanation of its mechanism due to its dependence on a variety of parameters. In this study, the dehydroxylation of kaolinite has been studied using controlled-transformation rate thermal analysis (CRTA), allowing precise control of the reaction rate, and thus of both the temperature and pressure above the sample. Modelling of the experimental results obtained by CRTA as well as those from TEM and MAS-NMR show that two elementary processes (diffusion and firstorder) can occur in competition. At the start of the decomposition the diffusion mechanism is predominant, but as the reaction progresses, the first-order mechanism prevails. It would seem that the importance of each process depends, in particular, on the presence of defects as well as on the local vapour pressure.

Nitrogen adsorption isotherms were measured on synthetic 2-line and 6-line ferrihydrites heated to 400 K, 500 K, and 600 K under dry conditions for different times ranging from 4 to 3000 h. Evaluation of specific surface area, microporosity and fractal dimension revealed that 2-line and 6-line ferrihydrites are highly microporous powders consisting of aggregates with corrugated interior and exterior surfaces. Furthermore, the surfaces of the single particles forming the aggregates have a smaller fractal dimension, i.e. a smoother appearance, than those of the entire aggregate. The diffusion of water lost during the heating process is influenced by the size of the micropores. The initial stage of the dehydration of the ferrihydrites can be described as similar to the process of Ostwald ripening.

Reevesite, the Ni-Fe member of the hydrotalcite group, occurs as a secondary mineral in the serpentinized ultramafic rocks of the Kwangcheon area in Korea, replacing the pecoraitc-magnetite-millerite-polydymite assemblages in small veins lining cracks and fracture zones. Chemical analyses for the reevesites indicate the presence of the Co-analogue of reevesite and the complete solid-solution between Fe3+ and Co3+. The Co-analogue of the reevesite shows the approximate ratio of 3:1 of divalent to trivalent cations, which is in distinct contrast to the comblainite with the ratio of 2:1 reported by Piret & Deliens (1980). The presence of the complete solid-solution phase between Fe3+ and Co3+ is confirmed by synthesis at room temperature. On the basis of the results, the Co-analogue of the reevesite should be named as a new member of the hydrotalcite group, and thereby be distinguished from the comblainite. The partial substitutions of SO2-4 for CO2-3 in the interlayer region might affect the slight increase of the basal spacing in the reevesite. The synthesis performed suggests that the reevesite could be precipitated under either an alkaline or a neutral environment, if carbonate activity is high enough.

The SEM, XRD, FFIR and DTA analyses of different size-fractions of clay material from sandstone reservoirs which have experienced a large range of burial conditions have been used to examine the different steps of the depth-related kaolinite-dickite reaction. Dickite progressively replaced kaolinite within a range of burial depths estimated between about 2500 m and 5000 m. The kaolinite-to-dickite reaction proceeds by gradual structural changes concomitant to crystal coarsening and change from booklet to blocky morphology. The crystallization of dickite proceeds by two distinct paths: (1) Accretion of new material from either dissolution of smaller unstable kaolinite crystals and/or detrital minerals (chiefly feldspars), on early-formed coarser metastable kaolinite crystals which exert extended morphological control on the growing crystals. (2) Neoformation of ordered dickite which will continue to grow by a dissolution-crystallization process. The kaolinite-todickite reaction is kinetically controlled and anomalies in the kaolinite/dickite ratio observed in certain sandstone reservoirs may be used to assess the timing of invasion by hydrocarbons.

Sandstones and shales from the southern flank of the Bilbao anticline in the Gordexola and Orozko valleys, northwestern Spain, have been subjected to a detailed sedimentological, mineralogical and geochemical study. They are composed of proximal frontdeltaic sandbars interbedded with silty-clayey sediments and correspond to a prograding sequence of a deltaic system. The clay mineral assemblages of doublets of sandstones and shales are composed mainly of illite, chlorite and illite-smectite mixed-layers R3 (ISII). The clay diagenesis consists of the transformation of smectite and I-S mixed-layers to illite, the precipitation of Fe-rich chlorite in the pore spaces, and the alteration of micas to chlorite. According to petrographic, mineralogical and geochemical analyses, chlorite is more abundant in sandstones than in shales in both the <2 µm and coarser fractions. The relative abundance of chlorite increases in the sandstones located at the top of coarsening upward sandbars. Furthermore, chlorite formation occurs preferentially in the coarser grained sansdstones previously cemented by ankerite. The geochemical and petrological investigations suggest that chlorite formed during burial diagenesis in a relatively closed system.

The Danian of the Provence basin (SE France) is characterized by a strong subatmospheric alteration processes throughout the basin. A wide range of facies, depositional and weathering, were recognized in an interval of 5 Myr and include floodplain fine-grained alluvium, palustrine limestones, playa dolostones, mottled palaeosols, vadose and phreatic calcretes, and phreatic dolocretes. Palygorskite was invariably found in laminar, massive and honeycomb vadose calcretes and phreatic dolocretes, as well as in playa dolostones, and only exceptionally in floodplain siltstones, nodular calcretes and palustrine limestones. Regardless of the facies, palygorskite is associated with smectites. An authigenic origin, based on the morphology of the fibres and the vertical distribution of clay minerals, is proposed for palygorskites in all of the facies. The simultaneous occurrence of palygorskite in these environments is interpreted as a sign of a stable seasonal semi-arid climate and low detrital input during a period of low lake level (-0.5 Myr). The occurrence of authigenic palygorskite in siltstones around the lake was attributed to the rising of the water table, retention of the already saturated water in the pore spaces of the sediment, and its subsequent evaporation in a confined environment. A hydrogeological model is proposed for the distribution of palygorskite. The elongated shape of the Provence basin enhanced the influence of lateral inflow of freshwater during the low lake period which explains the distribution of palygorskite in different environments of the Provence basin as well as spatial distribution of phreatic calcretes and dolocretes. During the high lake level, palygorskite formed in the few remaining ephemeral ponds and on the floodplain along the lake margin.

Nearly pure sepiolite clay crops out in a playa-like depression near El Bur, Central Plateau region of Somalia. The deposit is associated with the Lower to Mid-Eocene Taleh Formation that includes, besides limestone, dolomite and gypsiferous marls, extensive anhydrite and various evaporites, primarily gypsum. The material was examined by XRD, DTA, IR and EM. The XRD and DTA analyses indicated that from 40 cm down to a depth of 300 cm, the material consists of well crystallized sepiolite, accompanied in some layers by minor calcite and traces of quartz and halite. The chemical composition, determined by XRF, indicated a low-Fe mineral, with the formula: (Si11.888Al0.l12)(Mg7.313Al0.154Fe0.084)O30(OH2)4(OH2)4.x8H2O.

The fibres, arranged in the form of interwoven mats, are straight and have lengths varying between 2-6 µm and widths of 20-40 nm. Commonly, they are aggregated into units of two parallel-lying fibres, with a random orientation against each other, creating a dense network of pores. The high viscosity and external surface area (306-346 m2g-1) of the material, compared to those of the Spanish Vallecas sepiolite, suggest the high industrial suitability of this clay. The extent of the deposit is not known. Lithology and geomorphology indicate a lacustrine, closed basin evaporative environment of formation for this deposit. In contrast to the palaeolacustrine environments of formation of Spanish and Turkish sepiolite deposits, the E1 Bur sepiolite apparently is more recent.

Regularly interstratified mica-smectites and chlorite-smectites have been synthesized by Ueda & Sudo (1966), Frank-Kamenetskij et al. (1972), Matsuda & Henmi (1973, 1974) and by Eberl (1978). Only a few studies have been carded out, however, on regularly interstratified minerals whose spacings exceed 30 Å (Lazarenko & Korolev, 1970; Sato & Kizaki, 1972).