At room temperature both Fe(III)-exchanged montmorillonite and Fe(III)-hectorite gave similar Mössbauer spectra, each consisting of a single doublet with parameters characteristic of ferric iron. At 77 K the Fe(III)-hectorite gave a spectrum similar to that observed at room temperature, but with the montmorillonite an additional distinct doublet, with relatively large values of both isomer shift and quadrupole splitting, was observed. The Fe(II)-exchanged samples behaved very differently at room temperature and 77 K. At 77 K well-defined doublets were produced; these had quadrupole splittings similar to those shown by the ion and appreciably greater than those observed for Fe(II) in the structural sites in layer-silicates. At room temperature, however, there was no absorption corresponding to ferrous ions in either of the specimens, because the recoil-free fraction was low as a result of the loose association between the ion and the mineral lattice.

Oxygen (18O/16O) and hydrogen (2H/1H) isotopic ratios were measured on 22 smectite separates from bentonite deposits of the Sierra de Gata and Serrata de Nijar, Almeria, Spain. In addition, 18O/16O and 2H/1H ratios were determined on some waters from springs and wells, and 18O/16O ratios were measured on quartz, plagioclase and biotite samples separated from the bentonites. The smectites displayed two distinct isotopic compositional groups which excluded an origin either by submarine alteration or weathering under normal surface conditions of the associated volcanic rocks. Bentonization processes caused by low-temperature fluids of meteoric origin could account for the stable isotopic contents. Argillization temperatures are estimated at ∼40°C and ∼70°C for the Serrata de Nijar and the Sierra de Gata deposits, respectively.

The Boom Clay is an important raw material for the Belgian structural clay products industry. It can be divided into several lithological sub-units. In order to obtain an insight in the parameters which characterize these different units, and which affect the overall properties of the clay, a detailed chemical, physical and mineralogical analysis was carried out. Pearson correlation coefficients were calculated between the variables, which were then placed in four correlation groups: a quartz/clay mineral group, a reducing component group, a carbonate group and a feldspar group. This treatment of the data allowed three analysis parameters to be selected: <2 µm fraction, organic carbon and CO2. The other variables could be calculated fairly accurately from these by means of regression lines.

Although natural Na-bentonite has little catalytic activity, various cation-exchanged bentonites have proved to be effective catalysts for a wide variety of organic reactions. In the presence of these catalysts alkenes can be induced to add (a) water, to yield branched-chain symmetrical ethers; (b) alcohols, to give a variety of ethers; (c) thiols, to yield thio-ethers; (d) carboxylic acids, to give esters. The number of products obtained in each reaction depends on the ease of rearrangement of the carbocation intermediates. High yields are obtained where a single carbocation intermediate is formed, A variety of elimination reactions is also catalysed by these sheet silicates. Water is eliminated from alcohols to produce ethers, ammonia is eliminated from amines to make secondary amines, and hydrogen sulphide is eliminated from thiols to give dialkyl sulphides. In most cases the ion-exchanged bentonites react as acidic heterogeneous catalysts.

En utilisant des méthodes diffractométriques avec des smectites mal cristallisées, il n'est pas possible de déterminer de façon précise la répartition des atomes dans le feuillet. Il est particulièrement difficile de confirmer si le mineral est di- ou trioctaédrique, ou de déterminer la position de la vacance (position cis ou trans) dans la couche octaédrique. De même la nature polytypique de ces minéraux est difficile à preciser. La détermination de ces paramètres est difficile car les modulations (hkl) obtenues par diffraction des rayons X avec les smectites sont faibles et très peu marquées. Ce travail montre qu'en utilisant le césium comme cation interfoliaire, il y a non seulement augmentation de l'ordre dans l'empilement des feuillets mais aussi que son grand facteur de diffusion augmente l'intensité des modulations (hkl). En supposant que la substitution par du césium ne modifie pas la répartition des atomes dans le feuillet (il affecte seulement la distorsion de la couche tétraédrique), il est alors possible de déterminer cette répartition.

An autochthonous origin for the bauxite deposits of the Eufaula district, south-eastern Alabama, appears to have received general acceptance but, compared with younger residual bauxites of the present day tropical regions of the world, the Eufaula deposits have a number of features that are difficult to reconcile with development in situ. In an attempt to resolve the enigma, a detailed study was undertaken of cores from three drill holes that intersected a complete succession through one of the Eufaula deposits. Although the results are not conclusive, it is believed that much of the observed phenomena can be explained on the basis of an essentially transported origin for the deposits.

Three principal modes of formation are apparent for authigenic smectites in Recent marine sediments: alteration of volcanic rocks and glass, low-temperature combination of biogenic silica and Fe-oxyhydroxides, and direct precipitation from hydrothermal fluids. The latter two mechanisms are discussed with reference to new evidence from studies of sediments from the Bauer Deep of the equatorial eastern Pacific and the Atlantis II Deep in the Red Sea. In the Atlantis II Deep sediments, three sub-environments of smectite formation from hydrothermal fluids are recognized. In two of them nontronites are formed, whilst in the third an Fe-poor smectite, intermediate in composition between beidellite and montmorillonite, occurs.

The importance of a number of techniques (including 1H and 13C NMR, XRD and IR) in exploring the important catalytic properties of synthetic and natural clays is described. A clear distinction is observed between proven catalytically-active clays (e.g. Al-exchanged) and those which are generally less effective (e.g. Na-exchanged). 13C NMR spectroscopy is used to identify directly products formed within the interlayer regions, and temperature-controlled powder XRD serves as a useful tool for identifying whether or not intercalation occurs under variously defined conditions. High-pressure XRD is used to verify the formation of different products during reaction.

The sorption and transformation of phenol, 2-methylphenol, 3-methylphenol, 2,6-dimethylphenol, 3,5-dimethylphenol, and 2,4,6-trimethylphenol, by homoionic Na-, H-, Ca-, Cu-, Al-, and Fe(III)-montmorillonite from both vapour and aqueous phases were examined by IR spectroscopy. All the phenols were sorbed by the clays but were modified to different degrees depending on the exchangeable cations and on the amount and type of alkyl substitution of the phenols. Sorption of 2,6-dimethylphenol from aqueous solution was irreversible, and the extent of sorption followed the order Fe- > Al- > Cu- > Ca-clay. Both transition and non-transition metal cations were effective in transforming the phenol sorbates and heating the clay/phenol complexes further enhanced transformation. The results are discussed in terms of the nature of the transformation products and the likely role of radical reactions in their formation.

L'étude d'une vingtaine de cas montre que les caractéristiques principales du cortège d'éléments traces des roches éruptives et métamorphiques sont conservées par les fractions fines des produits d'altérations. On peut ainsi, à partir de l'ensemble des éléments traces contenus dans une fraction fine, identifier la famille pétrographique de la roche mère. La mémoire de la roche mère est partiellement conservée par la fraction fine après érosion des profils d'altération, et sédimentation des matériaux érodés dans des environnements divers. La conservation de la mémoire de la roche mère est cependant inversement proportionnelle à l'activité chimique du nouveau milieu de sédimentation. L'influence du milieu de sédimentation peut devenir prépondérante. Les exemples cités montrent que les éléments traces des argiles peuvent être interprétés, dans de nombreux cas, comme des marqueurs d'héritage: héritage direct d'une roche mère dans des conditions d'altération, héritage d'une histoire sédimentaire antérieure à des remaniements de dépôs; comme des marqueurs d'environnements sédimentologiques divers.

Transmission electron microscopy, X-ray radial distribution function analysis, chemical analysis, X-ray absorption edge spectroscopy, and Mössbauer spectroscopy combine to confirm an amorphous or gel structure for minerals of the hisingerite-neotocite series: (Fe,Mn)0.8SiO3.1.2H2O. A framework of (Fe,Mn)O6 octahedra and [SiO4] tetrahedra form hollow spheres, 50–100 Å in diameter, cross-bonded into a physically isotropic solid with as much as 10% interconnected pore space. The outer 10–20 Å of the spheres has a rudimentary structure, possibly marking the onset of segregation into Si-rich and (Fe,Mn)-rich layers. The Broken Hill mineral ‘sturtite’ is an intermediate member of the hisingerite-neotocite series.

Although seldom appreciated, the hydrocyclone offers several advantages over the more commonly used sedimentation/decantation method for clay separation. Large amounts of relatively concentrated clay suspensions may be separated in a matter of minutes. In addition, no dispersing agents are required and the shear conditions encountered by the suspension during passage through the hydrocyclone lead to particle disaggregation both in the silt and sub-micron size range. Formulae relating design factors of the hydrocyclone to separation performance exist but are of limited value as they are unable to predict the maximum particle size of the clay product or percentage recovery of any particular size of particle. Such data, determined from practical trials, are given for kaolinite, smectite and mixed-assemblage clay suspensions. Design limitations prevent the effective separation of clay products with ‘cut-off’ sizes finer than 5 µm.

Neutron scattering studies have indicated that the non-coordinated water at smectite surfaces has a similar mobility to that of bulk water, but that the water coordinated to the cations is immobile on the time scale of the neutron measurements. Thus hydrophylic polymers can readily displace the non-coordinated water and bind to the silicate surface, and to the exchangeable cations through a water-bridge mechanism. Poly(ethylene oxide) molecules with molecular weights up to 4000 appear to be bound to Na-montmorillonite in flattened conformations at the clay surface. Poly(vinyl alcohol) is extensively bound by Na-montmorillonite and by Na-Laponite (a synthetic hectorite-like clay); as binding progresses fewer molecule segments can contact the surface and so at the higher levels of adsorption extensive loops of polymer extend away from the silicate surface. Some polyanions provide good protection for smectites against flocculation with salt. The abilities of such polymers to protect the clays is dependent both on the extents of the charges and on the solution conformations which these polymers can assume.

Des études expérimentales sont réalisées afin de préciser les relations entre la vermiculitisation des biotites (ouverture par NaCl N) et les phénomènes d'oxydation (par l'eau ou par H2O2). Les évolutions sont suivies par diffraction des rayons X et en spectroscopie d'absorption infra-rouge; l'oxydation du fer est appréciée sur l'échantillon par spectroscopie Mössbauer. Les résultats montrent que si une certaine oxydation accompagne normalement la vermiculitisation, une oxydation intense provoque une expulsion de fer et la formation de vermiculite hydroxy ferrique.

Seven natural clay minerals (two kaolinites, three montmorillonites, a hectorite and a palygorskite) were tested for their cytotoxicity in vitro using an established cytotoxicity assay. Cellular viability, levels of lactate dehydrogenase, N-acetyl-β-d-glucosaminidase, lactic acid and total cellular protein were measured in cells of the macrophage-like cell line, P388D1, after 48 h incubation with each clay. There was a significant relationship between BET/N2 surface area of the clays and cytotoxicity but in two cases the level of cytotoxicity was apparently influenced by the presence of quartz or cristobalite in the samples. Results are discussed in the light of the available animal and epidemiological data relating to clay minerals.

The exchangable cations present on certain montmorillonites can be replaced by long-chain quarternary ammonium cations, and the resulting clays have the important property of being able to swell and disperse in a variety of organic solvents. Organophilic clays have a wide range of industrial applications and are, for example, important constituents of oil-well drilling fluids, paints, plastics and greases; their role in these is discussed. Organophilic clays have been extensively studied for about 50 years, but neither the structure nor the mechanisms by which they swell and disperse in organic solvents are clearly understood. An attempt is made to interpret the industrial applicatons in terms of published ideas concerning the structure and swelling properties of organophilic clays.

Veins of intimately associated fibrous and granular saponitic clay occur in a basalt quarry at Orrock, Fife, Scotland. Preliminary X-ray diffraction studies suggested that both fibrous and granular forms consisted of pure saponite but chemical and thermal studies showed the presence of subsidiary amounts of interstratified chlorite. The fibrous clay, which is strongly oriented around the a axis but with a uniform distribution of the b and c poles, consists mainly of highly-crystalline laths with minor amounts of turbostratically-ordered particles. The granular clay consists of turbostratically-ordered particles only. The swelling behaviour of both types of clay in water and in ethylene glycol is similar to that of pure saponite. With glycerol, only the granular clay swells completely but the fibrous clay behaves similarly if first subjected to grinding or chemical pre-treatment. These observations are accounted for on the basis that the fibrous clay has better order than the granular form, thus enabling the interlamellar constituents to participate more fully in layer-to-layer bonding.

Measurements of water desorption and sorption on four Ca-saturated illitic clays show that the shapes of the isotherms are very similar to those for other oxide surfaces, indicating that the formation of water multilayers is quantitatively similar. This enables graphs of multilayer thickness against mass sorbed to be drawn and used to assess microporosity. Hysteresis occurs and this is attributed to loss of external surface as drying brings platy particles in close face-to-face contact. Mixed-layer mica-smectites, however, exhibit no microporosity by this test and behave as if all surfaces are freely accessible to multilayer formation. The reason for this is not at present understood.

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.