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.

Alunite-kaolinite deposits occur in argillized zones in acid volcanic rocks at Tolfa. Over seventy samples were examined by one or more of the following methods: thin section, DTA, X-ray, IR, TG, SEM, chemical, and hydrogen and oxygen isotope analysis. Kaolinite and dickite, of high structural order, are the dominant clays with micamontmorillonite and halloysite subordinate. In many samples kaolinite and dickite coexist; their relative amounts are variable but the dickite content tends to increase with depth. SEM studies show that dickite crystals—up to 30 µm—are bigger than kaolinite.

The D/H and 18O/16O ratios of six clays, a whole rock, two biotites from fresh host rock, two chalcedony veins and three local meteoric waters indicate that the clays formed in a meteoric-hydrothermal environment of acid hot spring type at about 80°C. The fresh volcanic host rocks are strongly enriched in 18O relative to ‘normal’ igneous rocks due to derivation from or exchange with 18O-rich sedimentary rocks at depth prior to hydrothermal and solfataric activity. In the absence of present-day geothermal activity the life of this hot spring system was less than 4 m.y.

Palaeoweathering profiles are widely represented in the Iberian meseta. Transmission electron microscopy (TEM) and analytical electron microscopy (AEM) were used to describe the mechanisms governing the processes involved in the formation of one of these weathering profiles developed over slates of the Iberian Hercynian Massif. Three well-differentiated weathering stages were distinguished, based upon well-defined mineralogical signatures characteristic of primary or secondary minerals. The lower stage is characterized by fresh green slates composed of Fe-chlorite, micas, quartz and feldspars. The soft slates represent an intermediate weathering stage. A confined environment has permitted the development of smectite from the different primary phyllosilicates, both by neoformation of montmorillonite and transformation into beidellite. In the upper part of the profile, the red slates are the most weathered. A tropical or subtropical climate has resulted in the formation of kaolinite and abundant iron oxides over several metres. The present study demonstrates that the three identified weathering stages were formed under the same climatic conditions. Such ‘toposequences’ are developed at the present time in tropical areas (Bocquier, 1971).

More than 50 samples from a Barents Sea borehole near the Mjolnir Structure (an extraterrestrial impact feature) were used to investigate changes in the clay assemblage associated with the submarine impact. Seismic evidence, the presence of shocked quartz and a prominent Ir anomaly restricted the potential impact affected zone to a 10 m interval, straddling the Jurassic/Cretaceous boundary.

Increased abundance (up to 30 wt%) of a smectite, a randomly interstratified smectite-illite with 85% smectite layers, forms the basis for a two-layer oceanic impact clay model that differs from published terrestrial cases. The smectite is assumed to represent seawater-altered impact glass from the ejecta blanket material that was mixed with resuspended shelf sediments by the collision generated waves. The smectite-rich interval is almost 5 m thick. It is overlain by a coarser unit (~2 m thick) containing abundant smectite, shocked quartz grains, and anomalous Ix contents at its base. The smectite-rich interval may have originated as a density/turbidity current, generated by the impact and the collapse and erosion of the crater rim. Seawater alteration of volcanic glass and changes in the tectonic regime of the provenance area, or changing oceanic current circulation patterns could produce similar variations in the clay mineral assemblage. The most compelling evidence for the possible impact derivation of this clay assemblage is the direct association with the Mjolnir Impact Structure and associated mineralogical and geochemical anomalies.

29Si, 27Al MAS NMR is used to characterize Laponite RD and synthetic saponites of variable interlayer charge. The Si/Al ratios are in good agreement with the calculated charge from chemical analysis except for the lowest-charged saponite. In contrast to the 29Si MAS NMR spectra in which resolved signals are detected, the 27Al MAS NMR spectra show one signal whose linewidth increases with the clay charge. The water content of the clay samples was obtained from 1H MAS NMR.

The 2D MQMAS NMR technique is required to obtain a high-resolution spectrum of nuclei with strong quadrupolar interaction. This method was applied to the 23Na nucleus of clay counterions and to the 27Al structural nucleus. One well-defined 23Na NMR signal is observed for all the clays studied except the highest-charged saponite. Possible explanations for this different behaviour are discussed. The calculated isotropic chemical shift evolves progressively with the clay charge whereas the deduced quadrupolar interaction does not change significantly. The 27Al 2D 3QMAS technique was not able to resolve more than one signal.

Bayerite forms a cascading, travertine-like deposit over volcanic tuffs on Raoul Island in the South Pacific where it is produced from episodic discharge of spent, caustic aluminate solutions from a hydrogen generator. Textural evidence indicates microbial activity has possibly been involved in formation of the hydroxide, as well as sodium carbonate aluminate, present in minor amounts. X-ray powder diffraction and infrared spectral studies failed to give confident identification of the bayerite, the identity being confirmed by laser Raman spectroscopy. A high quality spectrum was obtained extending from 3280 to 3680 cm−1 and from 100 to 1000 cm−1.

The reactivity of an Al-pillared interlayered clay (PILC) (AZA) and a mixed Fe/Al-PILC (FAZA), used as references by the Concerted European Action-Pillared Layered Structure (CEA-PLS), was investigated in the selective catalytic reduction (SCR) of NO by NH3 or propane, as either catalysts or as supports of Cu ions. Both AZA and FAZA, either with or without Cu were found to be inactive in the reduction of NO with propane and oxygen. This is different from the behaviour with alumina with or without Cu, because of the different surface acidity properties. Good NO conversions were observed for both PILCs using NH3. The best catalytic performances were shown by FAZA, but the activity of AZA was also remarkable. The addition of Cu ions to both AZA and FAZA leads to an improvment in the activity in NO conversion and a reduction in the side formation of N2O. The catalytic behaviour was found to depend on the method of Cu addition, the Cu loading and the nature of the PILC. With AZA the best results were obtained for a Cu content up to 2 wt%, while further increases in the amount of Cu resulted in a considerable decrease in the conversion of NO. With FAZA, on the other hand, a high activity was observed at up to 3% of Cu introduced by ion exchange. By comparison with other Cu containing catalysts, Cu-FAZA allows operation in a wider range of reaction temperatures due to the reduced rate of side ammonia combustion. The surface acidity properties of AZA and FAZA were also characterized to interpret the above effects.

Bentonite clay is planned to form a part of deep-geological repositories of spent nuclear fuel in several countries. The extremely long operation time of the repository requires an indepth understanding of the structure and properties of used materials. In this work the microstructure of a simplified system of Ca-montmorillonite is investigated using a set of complementary methods: X-ray diffraction, small angle X-ray scattering, nuclear magnetic resonance, transmission electron microscopy and ion exclusion. The paper presents experimental results obtained from compacted, water saturated samples in the dry density range 0.6–1.5 g/cm3. It can be observed that different methods yield similar quantification of water present in the interlamellar space. Combined results support the multiple porosity concept of the bentonite structure.

Hydrothermal experiments were performed at 100 and 200°C and at different clay:water ratios in order to investigate the transformation of smectitic layers during the alteration of a montmorillonitic starting material. This study focused on three phenomena: (1) the amount and localization of charge within the layer of the newly-formed dioctahedral smectite; (2) the stacking of low- and high-charge layers in the dioctahedral smectitic material; and (3) the neoformation of trioctahedral smectites.

In all of the runs, the formation of beidellite from montmorillonite induced morphological changes in clay particles which suggests a reaction proceeding by a dissolution-crystallization mechanism. Illite layers were detected in K-saturated montmorillonite runs after the transformation of ∼50% of the starting montmorillonite into beidellite (i.e. after 5 months of reaction with distilled water at 200°C). These illite layers were interstratified with both high-charge and low-charge dioctahedral smectites in a hypothetical three-component mixed-layer mineral.

The K/Ar characteristics of 53 clay assemblages (Triassic–Cretaceous), representing the detrital, volcanogenic and arid-facies clay mineral associations, are interpreted in relation to their mineralogy, chronostratic age and geological origins. The K-bearing mineral components of the 1–2 μm, 0.2–1 μm and <0.2 μm fractions of each clay assemblage together display one of two characteristic patterns of K2O and 40Ar values (the K/Ar signature of the assemblage) on a 40Ar/K2O correlation diagram. Interpretation of the K/Ar signatures indicates that: (1) all of these clay assemblages are apparently unaffected by burial diagenetic illitization; (2) the Jurassic and Cretaceous detrital clay assemblages are derived from the reworking of weathered Caledonian metasediments (420 500 Ma) and weathered kaolin-bearing sediments of Upper Devonian/ Carboniferous age; and (3) the role played by palaeoclimate in developing the pattern of clay minerals in the Mesozoic sediments of England is much less significant than previously believed.

X-ray diffraction chlorite crystallinity (ChC) indices and major element chemical compositions of chlorites and bulk rocks were determined and correlated in meta-igneous rocks from different Mesozoic formations in various tectonic units of the Bükk Mountains, NE Hungary. The rocks, of basic to acidic compositions, range from ocean-floor metamorphic prehnite-pumpellyite facies (diagenetic zone) through regional metamorphic prehnite-pumpellyite facies (anchizone) up to the regional metamorphic pumpellyite-actinolite and greenschist facies (epizone). As in the case of meta-sedimentary rocks, chlorite crystallinity can be applied as an empirical, complementary petrogenetic tool to determine relative differences in grades of low-temperature meta-igneous rocks. Electron microprobe and XRD data show that ChC is controlled mainly by the decreasing amounts of contaminants (mixed-layered components or discrete, intergrown phases of mostly smectitic composition) in chlorite with advancing metamorphic grade, up to the epizone. The apparent increase in calculated Aliv content of chlorite with increasing temperature is related to the decrease of these contaminants, as stated earlier by Jiang et al. (1994). On the basis of the significant correlations found between ChC and temperatures, derived by the chlorite-Aliv geothermometer of Cathelineau (1988), both methods may be used for estimating the approximate temperatures of metamorphism, in spite of the contrasting interpretation of chemical data from chlorites obtained by electron microprobe analyses. After determining the effects of changing bulk chemistry on chlorite composition and ChC, the chlorite crystallinity method may complement the correlation of the illite crystallinity-based zonal classification of meta-sediments and the mineral facies classification of meta-igneous rocks.

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.

Sorption of the polar insecticide imidacloprid on organic-saturated octadecylammonium (C18) and dioctadecyldimethylammonium (DOD) and inorganic- (Fe- ) saturated Wyoming (W) and Arizona (A) montmorillonites has been investigated. Sorption isotherms were fitted to the Freundlich equation. Imidacloprid-montmorillonite complexes were studied by X-ray diffraction and FT-IR techniques. Imidacloprid sorption coefficients, Kf, decreased in the order WC18> AC18> WFe> WDOD≥ ADOD. The low layer charge and saturation by primary alkylammonium cation facilitates sorption of imidacloprid in the interlayer of the smectite, corroborated by the increase in basal spacing observed in X-ray diffraction patterns and by the presence of absorption band shifts in FT-IR spectra. Imidacloprid sorbs in the interlayer space of smectite mainly by hydrophobic interactions with the alkyl chains in organic smectites and with the uncharged siloxane surface in Fe(III)-smectite. Further polar bonds between the NO2 group of imidacloprid and the NH of the primary alkyl cations and protonation of imidacloprid in Fe-smectites enhanced sorption in these cases.

The sedimentation characteristics of two commercial bentonites, Tixoton (organically treated) and Montigel-F (untreated), were investigated using a 3% w/v clay suspension at different concentrations (1, 3.5 and 10%) of NaCl and pH values (2, 7 and 12). Settling rates, floc diameters and sediment volumes were derived from changes in light transmittance using a Turbiscan Ma 2000 instrument.

Both bentonite suspensions were unstable (flocculated) in NaCl solutions. The settling rate increased with increasing concentration of NaCl and was directly related to floc diameter. The sediment volume reduced with increasing NaCl concentrations, a result of greater double layer compression caused by increased ionic strength. At comparable salt concentrations, the organically-treated bentonite (Tixoton) settled at a much slower rate and had a greater sedimentation volume. The suspensions of both organically-treated and untreated bentonites were stable (dispersed) above pH 7 and unstable in acidic conditions. The settling rate for Tixoton under acid conditions was much smaller than that for the Montigel-F. Differences in sedimentation characteristics between the two bentonite samples are probably due to the presence of an anionic polymer (carboxymethyl cellulose: CMC) in Tixoton.

The viscosity of the bentonite suspensions was also studied. The viscosity of the clay suspension is closely related to clay dispersivity in solution. The CMC was highly effective in increasing the viscosity of the bentonite suspensions, but only under neutral and alkaline conditions.

Glaukonitglimmer von 10 kretazischen Gesteinen werden mineralogisch und chemisch untersucht. Die von den Glaukonitkòrnern und Glimmern der Kolloidtonfraktion errechneten Strukturformeln der Glaukonitglimmer bestàtigen die Glaukonitglimmer als exakt dioktaedrische Minerale. Die Strukturformeln geben nur Mittelwerte der Verteilung der chemischen Hauptbestandteile und der Kationenladung der Glaukonitstruktur an. Innerhalb des Konzentrationsdreieckes Muskowit-Seladonit-Pyrophyllit deckt sich das Areal der Glaukonite mit dem der Illite, wenn auf den Seiten des Dreieckdiagrammes die Kationenladungen der Tetraeder-, Oktaeder- und Zwischenschichten aufgetragen werden. Entsprechend der iibereinstimmenden Verteilung der Kationenladungen in der Glaukonit- und Illitstruktur kònnen die Glaukonite als die eisenreichen Àquivalente der Illite angesehen werden. Der Gehalt an Spurenelementen in Glaukoniten ist, abgesehen vom Bor, deutlich geringer als in Biotiten und Muskowiten. Die chemische und strukturelle Inhomogenitat der Glaukonite in den Gesteinen wird am besten durch eine Entstehung der Glaukonite aus Gelen im Sediment erklàrt.

According to multivariate analysis, the following were established (a) kaolinite crystallinity index (KCI) values determined by XRD are highly correlated to one another and seemingly influenced by kaolin impurities; (b) kaolin minerals are concentrated mainly in the fractions <4 µm; (c) the kaolin surface area as determined by the BET (nitrogen adsorption) method is more markedly affected by kaolin impurities than by kaolin minerals themselves; (d) BET surfaces increase when kaolinite crystallinity decreases; (e) brightness is inversely correlated with kaolin impurities; (f) the more ordered the kaolinite and the greater the proportion in the <4 µm fraction of the kaolin, the greater the brightness; and (g) KCI values are particle size-distribution dependent for sedimentary-residual kaolins. The correlations obtained were better when kaolins were selected according to their origin because the kaolin minerals and their impurities, particle size-distribution and texture were more alike. The industrial properties of kaolin can not be predicted from other basic properties such as mineralogy, KCI, etc., because they are intricately related to one another.

Laponite RD forms stable, coherent films which adhere strongly to glass slides. Such films are capable of supporting liquid drops allowing the direct measurement of contact angles for five liquids of which, two were apolar (0:-bromonaphthalene and diiodomethane) and three were polar (water, formamide, glycerol); surface tension components and parameters (γLw, γ⊕ and γ⊖) were determined by solving the Young equation. These determinations were made for homoionic samples saturated with Li, Na, K, Rb, Cs, Mg, Ca, Sr, Ba and NH4 as well as the natural material. Whereas the values of γLw (the apolar Lifshitz-van der Waals component) varied only within narrow limits (41-44 mJ/m2), the Lewis base parameter varied comparatively widely (24-41 mJ/m2). The Lewis acid parameter was small and relatively constant (1·3-3·0 mJ/m2). The variation of γ⊖ as a function of the exchangeable cation suggests that the divalent cations are shielded from the silicate surface by the water molecules of their sphere of hydration, whereas the monovalent cations are in direct contact with the oxygen atoms of the silicate surface. Furthermore, the divalent cations may screen the Lewis base sites to a greater degree than do the monovalent cations. Lithium behaves anomalously and this may indicate that it physically enters into the ditrigonal hole in the silicate layer.

The detection of the plastic limit of clays is subject to human error. Several attempts have been made to correlate across studies the geotechnical properties of fine-grained soils (water content, liquidity index, shear strength, etc.). Based on the premise that the liquidity index and water content ratio can be correlated directly, an alternative method to obtain indirectly the plastic limit is suggested here. The present study investigated 40 natural clayey samples of various mineralogies and origins and other publicly available data, where Atterberg limits and undrained shear strength values obtained with the vane shear tests were given. The liquidity index and water-content ratio correlate very well for defined undrained shear strength values of the clays. Solving the liquidity index equation for the plastic limit, estimated plastic limit values obtained by the liquidity index/water-content ratio relationship were compared with laboratory plastic-limit values. Preliminary results based on 62 values show an exponential trend with a multiple regression coefficient of 0.79. The data need to be confirmed on a larger database, however.

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.

A modified HGMS system is described in which the inclusion of a peristaltic pump to continuously circulate a suspension of a soil clay through the magnetic trap greatly facilitates the operation of the technique. Application of this purely physical method of mineral separation to a variety of soil clays—using IR spectroscopy to monitor the progress of the separation—illustrates the ease with which magnetic fractions comprising different iron-containing clay minerals may be separated from a single soil clay, thereby making these minerals more accessible for further study by other techniques.