SWy-2 (Wyoming), Sap-Ca saponite (California) and SAz-1 (Cheto, Arizona) were exchanged with different cations (Al, Ni, Mg, Ca and Na). The catalytic activity of these ionexchanged clays was measured directly using the isomerization of α-pinene at 80°C for 2 h to yield camphene, limonene and other minor products. The order of activity for the different cationexchanged forms was Al > Ni > Mg > Ca > Na, which correlated well with the known polarizing power of these cations and the resulting interlayer acidity. Catalysts derived from Sap-Ca were the most active followed by SWy-2, with SAz-1 the least active by a considerable margin. The greater activity of Sap-Ca over SWy-2 was attributed to the high tetrahedral charge in the former. Reduction of the layer charge of SAz-1 using Li fixation caused a significant improvement in the catalytic activity of the Al-exchanged reduced-charge SAz-1.

A survey of the clay fraction at the surface of 86 loam and silt loam agricultural soils from the Central United States was undertaken to observe the possible influences of climate and parent material (dominantly phyllosilicates in this study) on the clay mineralogy of the upper portions of the soils, for the most part in Mollisol–Alfisol order soils.

Decomposed X-ray diffraction spectra show that the most abundant clay minerals are two disordered illite-smectite (I-S) minerals, one with ∼50% smectite layers and another, less abundant, disordered I-S phase with 20% smectite. These minerals usually co-exist in the same samples. The charge site in both of these I-S minerals is both beidellitic and montmorillonitic in the expanding layers. A relatively large proportion of these smectite layers (up to 20%) are of high charge.

There seems to be a convergence in mineralogy towards mixed-layer phases formed under a range of mid-Continent climates from a range of phyllosilicate parent materials.

Some recent works dealing with the concept of order-disorder in clay minerals are considered, including those aspects of order-disorder which appeared in the Brindley & Brown (1980) monograph, i.e. disorder in the distribution of cations, disorder in layer stacking, orderdisorder in mixed-layer systems and finite crystal size as a lattice disorder. Heterogeneity of samples and polymorphous transformations are also considered as other types of disorder. Most of these works emphasize that accurate structural characterization can only be obtained if several techniques are combined (e.g. XRD and IR, EXAFS and Mo¨ssbauer spectroscopies, etc.). Another conclusion is that accurate structural determination provides the key to the genesis of clays.

Mixed-layer illite-smectite from Lower Palaeozoic sedimentary rocks, on both sides of the Teisseyre–Tornquist tectonic zone (TTZ) in northern Poland, was studied by X-ray diffraction and dated by K-Ar means.

The percentage of smectite layers in illite-smectite (%S) indicates maximum palaeotemperatures of 125–135°C at the surface of Lower Palaeozoic rocks on the craton (NE of TTZ), and 110 to ≤180°C in different tectonic blocks to the SW of TTZ (area of Caledonian consolidation). The vertical changes in the %S indicate that the maximum palaeotemperatures were reached before Permian time on the craton, and before Jurassic, Triassic, Permian or Carboniferous periods but after the beginning of Devonian time in the Caledonian zone. The K—Ar ages of bentonites indicate that the maximum palaeotemperatures were reached by 370—390 Ma or even slightly earlier (Middle—late Devonian). A maximum of 3—6 km of Silurian–Devonian cover on the craton and in the TTZ is suggested by the data.

In this paper, the role of Cu in the adsorption of the cationic pesticide chlormequat (CCC) on montmorillonite is studied. The adsorption of CCC was measured in various media, e.g. water and aqueous solutions of NaCl, CaCl2 and Ca(NO3)2 at the same ionic strength (I= 0.01 mol l–1). The retention of CCC on montmorillonite in aqueous media is due principally to a cationic exchange process with inorganic cations which saturate the interlamellar positions on this mineral. However, the amount of inorganic cations liberated from montmorillonite was ∼15% less than the amount of CCC adsorbed. This indicates that not all the pesticide was adsorbed through cation exchange.

The adsorption of CCC in aqueous media decreased in the presence of a heavy metal, compared with metal-free treatment. This behaviour indicates competition between the two cations for interlamellar positions. The adsorption of CCC in the presence of Cu also decreased in electrolyte media with the effect being highest in the presence of Ca electrolytes. The maximum CCC diminution was ∼30%. However, the isotherms derived in CaCl2 and Ca(NO3)2 media at different Cu concentrations were close to each other, indicating that Ca from background electrolyte exerts greater competition than Cu for montmorillonite planar positions.

Major and trace chemical elements from eleven Lower Pleistocene bentonite deposits from Eastern Milos Island, Aegean, Greece, were used for geochemical fingerprinting of the bentonites, by means of scatter binary and ternary plots and canonical discriminant analysis. The trace elements were selected according to their immobility during bentonite formation and subsequent hydrothermal alteration. The bentonites can be separated into at least four geographically distinct groups, each consisting of materials with similar geochemical affinities. The deposits of each group were derived from protoliths erupted from different volcanic centres, suggesting the existence of at least two distinct volcanic provinces, having rhyolitic and andesitic affinities respectively. Several deposits consist of more than one bentonite horizon, indicating that in some volcanic centres the character of volcanism changed with time. Geochemical fingerprinting, supplemented with geological, mineralogical, and textural evidence, may be useful for correlation and exploration of bentonites, in terrains with complex geological histories.

The main reason for the initial determinations of illite crystallinity (IC) was to support the exploration for liquid and gaseous hydrocarbons. The application in 1960 of the Weaver Sharpness Ratio to core materials of a borehole from eastern France indicated that it was not a reliable tool for identifying well-crystallized illite. This ratio was later replaced by the Full Width at Half-Maximum (FWHM), the value of which decreases regularly and consistently towards greenschist facies. The use of FWHM allowed a precise definition of the anchimetamorphic zone between the upper diagenesis and the epimetamorphism. Afterwards, analysis of weak-tointermediate diagenetic sequences showed that illite crystallinity decreases together with the amount of swelling interlayers in mixed-layer clay minerals. Technological improvements, such as computing and modelling of X-ray diffraction patterns, increased the analytical precision relative to measurements of the plain FWHM. Consequently, illite crystallinity went back to its initial use, namely detection of the transitions between diagenesis, anchi- and epi-metamorphism in smectitefree lithologies, where it can be used as a stratigraphic and mineralogic marker of alteration stages.

The diagenetic evolution of clay minerals in a 4249 m sedimentary-magmatic sequence of the Zemah-1 drillhole in the Dead Sea Rift, Israel, was studied, mainly by X-ray diffraction (XRD). The parallel maturation of the organic matter was estimated by the thermal alteration index (TAI) method. Both parameters follow a progressive diagenesis with depth. The original clays, now encountered only at shallow depths, were dioctahedral, and mostly detrital. They transformed into Mg-rich trioctahedral clays starting with a saponite-dominated assemblage, followed by a saponite, ordered chlorite-smectite (C-S), and chlorite assemblage, and finally by a saponite, corrensite, chlorite and talc assemblage. Significant mineralogical composition gaps occur between saponite to corrensite and corrensite to chlorite. Short-range variations within the most evolved assemblage are controlled by bulk-rock composition. Depths of first occurrence and disappearance of minerals indicate a much higher geothermal gradient in the past whereas the TAI values suggest an even higher palaeogradient of ∼708C km–1.

Mixed-layered phyllosilicates with composition intermediate between mica and chlorite were identified in very low-grade metaclastites from the Malàguide Complex (Betic Cordilleras, Spain), and studied by X-ray diffraction, and transmission and analytical electron microscopy. They occur both as small grains in the rock matrix, and associated with muscovitechlorite stacks. Transmission electron microscope observations revealed a transition from chlorite to ordered 1:1 interstratifications through complex 1:2 and 1:3 interstratifications. Analytical electron microscopy data indicate a composition slightly different from the sum of discrete trioctahedral chlorite and dioctahedral mica. The types of layer transitions suggest that mixed-layer formation included two main processes: (1) the replacement of a brucite sheet by a cation sheet in the chlorite structure; and (2) the precipitation of mica-like layers between the chlorite layers. The strongest diffraction lines in oriented X-ray patterns are: 12.60 Å (002), 7.98 Å (003), 4.82 Å (005) and 3.48 Å (007).

The physicochemical properties of clays can be modified by acid treatment with inorganic acids. This treatment is usually referred to as ‘acid activation’, because it increases the specific surface area and the number of active sites of the solids. In the present study, the acid activation of saponite from Cerro del Aguila (Madrid, Spain) with HCl solutions was measured. Illite, quartz and small amounts of feldspar were found as impurities in the raw saponite.

Acid treatments were carried out with different concentrations of HCl solutions. The samples obtained were characterized by mineralogical and chemical analyses, XRD, FT-IR spectroscopy, N2 adsorption-desorption isotherms and TEM. The acid attack, under the conditions employed, produced a progressive destruction of the structure of saponite by partial dissolution of the octahedral Mg(II) cations. Amorphous silica coming from the tetrahedral sheet of saponite was generated. The specific surface area of the most intensely treated sample (2.5% for 24 h) was doubled with respect to that of natural saponite. This increase in the surface area is due to the increase in both the external and internal surface areas.

The ODP Leg 171B drilled a transect of four sites at Blake Nose in the NW Atlantic providing an excellent record of the K-T boundary. At the deepest, Site 1049, the boundary is marked by a 9–17 cm thick layer formed mostly of green spherules composed of Fe-rich smectite resulting from the diagenetic alteration of tektites and impact glasses. Minor amounts of authigenic zeolites and palygorskite also occur. This association represents a notable break in the clay mineral composition of Cretaceous and Tertiary sequences. The clay mineral assemblages of the Cretaceous and Tertiary sediments are dominated by inherited clays. Aluminium-rich smectite of pedogenic origin is abundant in both Cretaceous and Tertiary sediments, indicating a relatively warm and hydrolysing climate across the K-T boundary. At Hole 1049A, where the oldest sediments of the interval were analysed, an increase in kaolinite and smectite down core suggests tectonic rejuvenation and distal transport of illite and kaolinite, probably accompanied by more hydrolysing conditions during the late Maastrichtian.

Metamorphic isograd surfaces are mapped within the Morcles nappe using illite crystallinity (IC) and (clay-) mineral parageneses in 268 samples. The diagenesis-anchizone and the anchizone-epizone boundaries are nearly vertical surfaces which crosscut the present-day recumbent fold nappe structure. Frontal parts of the nappe are diagenetic (Tmax <200°C) whereas rear parts both in the normal and inverted limb are epizonal (Tmax >300°C). We demonstrate that the calcite content of shales, marls or limestones has no influence on the average IC. Deviations of individual samples from the mean IC of any given diagenetic and lower anchizonal site are very large, however, without it being possible to associate deviations with any obvious rock parameter. The standard deviations of populations of IC values decrease strongly with increasing metamorphic grade (toward smaller IC values). Mapping the diagenesis-anchizone boundary requires a much larger sampling effort than the same exercise for the anchizone-epizone boundary.

Experimental alteration of a rhyolitic obsidian by solutions containing variable concentrations of Mg was carried out at 100, 150 and 200°C, for 30, 60 and 90 days, to investigate the mechanism of smectite formation. The smectite exhibits two distinct morphologies: (1) small flakes (aggregates of a few crystals); and (2) large flakes (massive groups). The small flakes are the earlier alteration products. Both morphological types have distinct chemical compositions: the smallest laminae are dioctahedral and contain more Fe, whereas the particles from the rose-shaped aggregates contain Mg and are trioctahedral. Intermediate compositions have been observed between the extreme compositions.

It is suggested that the two morphologies are the result of two distinct genetic processes: (1) the small flakes (Fe-rich smectite) form by solid state rearrangements of the hydrated external layer of glass and/or via the formation of domains within the glass; (2) the rose-shaped aggregates (Mg-rich smectite) form by precipitation from solution.

The clay mineral assemblages of the Tithonian and Berriasian sediments (Tera and Oncala Groups) in the eastern part of the Cameros basin are investigated at seven localities. The lowest-grade assemblage, located on the southern border of the basin, contains calcite + quartz + hematite + kaolinite + mixed-layer illite-smectite (R = 1, 65 85% illite layers) + discrete illite (IC = 0.5 0.65Δ°2θ). Systematic increases in the illite and chlorite crystallinities suggest increasing metamorphic grade from the northwest part of the basin to the southeast. This trend does not follow the pattern previously described for the overlying late Berriasian–early Aptian sediments (Urbión and Enciso Groups), which exhibit a higher metamorphic grade. This may result from local variations in sedimentary facies, as well as the circulation of hot migratory fluids. Tertiary compression occurring long after the main metamorphic event is considered to be responsible for the enhanced illite and chlorite crystallinities measured in the SE extreme of the basin.

Saponitic bentonite mined in the Magan deposit (Toledo, Spain), has been classified as a suitable clay barrier in the storage of high-level radioactive waste. Several hydrothermal alteration assays have been carried out in Teflon reactors at 45, 60, 90, 120, 175 and 200°C for periods of up to 1 y. The mineral components of bentonite are stable below 175°C. At and above this temperature, the accessory sepiolite transforms into a monomineral phase of saponitic composition. The texture of the clay also changes. A rise in temperature above 120°C causes a decrease in the proportion of the <2 μm size-fraction, a reduction of BET and total surface areas and an increase in the relative volume of micropores (<20 Å). This process has been interpreted as the formation of granular aggregates that preserve a micropore network. This new arrangement of the aggregates produces a significant reduction in the free swelling volume.

Clay mineral quantification by XRD is difficult when mixed-layer clay minerals and discrete clay types are both present. New procedures for peak decomposition and pattern simulation offer increased opportunities to obtain mineral abundance estimates. This proposed methodological sequence, for quantitative representation (QR) of complex clay samples, involves: (1) determination of layer type, mixed-layer proportion and order (R); (2) simulation of XRD patterns using MULCALC, an adaptation of NEWMOD; and (3) interpretation of the clay assemblage by fitting the whole pattern with CLAY++, a statistical program. The product is a QR of individual phases or a summation of layer types. The absence of quantitative reference standards means results cannot be checked for accuracy, but the statistical fit is highly reproducible and less prone to operator error. The QRs may be obtained with simulated or actual reference mineral patterns in the database. Results for freshwater marsh samples illustrate the approach.

The relationship between illite crystallinity (IC) and finite strain as well as lattice strain and crystallite size of illite is examined in a series of 27 deformed breccia samples from the inverted limb of the Morcles nappe. The IC is determined independently for limestone components and a red/green clay-silt matrix. The finite strain varies widely (D= 0.8–2.5). The IC values vary from diagenetic to epizonal, but no correlation with finite strain could be established. The spread of IC values is explained by heterogeneities within the protolith which have not been homogenized/ obliterated by the anchizonal to epizonal metamorphic overprint. While limestone pebbles display IC values in agreement with the regional metamorphic conditions, the clay-silt matrix has anomalously high IC values, even after deconvolution of the 10 Å peak to correct for the presence of paragonite/muscovite. No correlation could be established between finite strain, lattice strain and/or crystallite size of illite.

The chemical, textural and structural transformations of Al13-intercalated montmorillonite, resulting from the depolymerization of the interlamellar Al13 polycations by Na salicylate solutions, were studied. Nitrogen gas adsorption shows a dramatic decrease in specific surface area from 493 to 39 m2g–1, due to the loss of microporosity. Modelling of small-angle X-ray scattering (SAXS) curves shows that the final product contains two phases: a Na-exchanged swelling phase accounting for 40% of the clay, and a fixed interlayer distance (20.8 Å ) phase accounting for 60% of the clay. The Al remaining in the clay galleries (45% of the initial Al) is composed of 13% Al13– and 87% hexacoordinated Al, probably Al(OH)03 and oligomeric Al-salicylate complexes, as shown by 27Al NMR. The instability of Al13-intercalated montmorillonite towards organic ligands is related to the hydration shell of the tridecamer, revealed by SAXS. These results focus on the necessity to take into account the presence of organic ligands in natural media when using materials such as Al13-intercalated clays.