High-gradient magnetic separation (HGMS) performed on the clay fraction (< 1 µm) of acid soils facilitates the separation and concentration of mineral fractions according to their Fe and Mg contents. As a result, smectitic layers formed by weathering of a chlorite were identified although they were not detected in the bulk sample. The concentration in the non-magnetic fraction of minerals with an intergrade vermiculite-chlorite behaviour enabled more accurate information to be obtained on these minerals.

The Palaeocene Everest Complex, located in the Central Graben of the North Sea, comprises interbedded sandstones and mudrocks deposited in a submarine fan environment and overlies Cretaceous limestones. Depositional facies are the main influence on reservoir quality, although the latter is reduced significantly locally by ferroan calcite cementation, particularly in the lower part of the complex. Carbon and O stable isotope analyses have been made from cements in sandstones and mudrocks and from shear fractures and injection features within mudrock intervals. These indicate a marine source of detrital carbonate becoming mixed with HCO3− from decarboxylation higher in the succession. Petrographic observation and microprobe analyses indicate that dissolution of coccoliths and foraminifera in limestones are the principal sources of cementation. The similar composition of cements in sandstones, fractures and injection features suggests a common formation. Burial history modelling shows cement precipitation is synchronous with periods of excess pressure and therefore excess pressure release associated with rock failure is proposed as a prominent mechanism for initiating cementation.

The layered double hydroxide (LDH) Al2Li(OH)6[NiCl4]1/2 was synthesized by anion exchange of Al2Li(OH)6(NO3) and the coordination structure of [NiCl4]2− in the interlayers was investigated. The LDH had a hexagonal cell with a = 5.06 and c = 23.06 Å. Since the basal spacing of one layer was 7.7 Å, the interlayer distance was calculated to be 2.9 Å and was too narrow for the usual tetrahedral NiCl4 structure. From extended X-ray absorption fine structure (EXAFS) measurements, the first neighbour Ni-Cl distances in the LDH were 2.10 Å which was compatible with four-fold coordination. Since the electron spin resonance (ESR) spectrum of the LDH showed no absorption, the [NiCl4]2− structure was considered to be square planar, rather than the usual tetrahedral structure in the interlayers of LDH.

The occurrence of sepiolite and palygorskite in soils, Eocene limestones and the Asmari dolomitic limestone of Iran has been described by many workers (Bentor et al., 1963; Martin Vivaldi & Robertson, 1971; Abtahi, 1977, 1980). No studies have been carried out on the genesis of these minerals in Iranian soils, however, and the purpose of this note is to describe some experimental conditions under Which sepiolite can form, and which also could apply to the genesis of the mineral in Iranian soils.

Intercalation of the tris(2,2'-bipyridine)ruthenium(II) complex cation into a layered silicate (magadiite; the ideal formula for which is Na2Si14O29.nH2O) was investigated. Since the complex cation did not intercalate by a direct ion exchange reaction with the interlayer Na ions in an aqueous medium, dodecyltrimethylammonium exchanged magadiite was used as a precursor. Depending on the loading of the complex cations and the solvents employed for the reactions, two types of tris(2,2'-bipyridine)mthenium(II)-magadiite intercalation compounds formed. One has a basal spacing of ~2.9 nm due to a large amount of the dodecyltrimethylammonium ions which remained in the interlayer space of magadiite and coexisted with the intercalated tris(2,2'- bipyridine)ruthenium(II) complex cations. The other has a basal spacing of '2.0 nm because the intercalated tris(2,2'-bipyridine)ruthenium(II) complex ions form a monolayer in the interlayer space of magadiite.

Numerous studies focus on the relationships between chemical composition and OH-band positions in the infrared (IR) spectra of micaceous minerals. These studies are based on the coexistence, in dioctahedral micas or smectites, of several cationic pairs around the hydroxyl group which each produce a characteristic band in the IR spectrum. The aim of this work is to obtain the wavenumber values of the IR OH vibration bands of the (Al-Fe3+)-OH and (Fe3+-Fe3+)-OH local cationic environments of ‘pyrophyllite type’ in order to prove, disprove or modify a model of dioctahedral phyllosilicate OH-stretching band decomposition. Natural samples are characterized by powder X-ray diffraction (XRD), Fourier transform infrared (FTIR) and Raman spectroscopies and electron microprobe; the hydrothermal synthesis products are also analysed by powder XRD and FTIR after inductively coupled plasma measurements to obtain the chemical compositions of starting gel phases. Natural samples contain some impurities which were eliminated after acid treatment; nevertheless, a small Fe content is found in the pyrophyllite structure. The amount of Fe which is incorporated within the pyrophyllite structure is much more important for the synthetic samples than for the natural ones. The IR OH bands were clearly observed in both natural and synthetic pyrophyllites and assigned to hydroxides bonded to (Al-Al), (Al-Fe) and (Fe-Fe) cationic pairs. During this study, three samples were analysed by DTG to check the cis- or trans-vacant character of the layers and to determine the influence of this structural character on the OH-stretching band position in IR spectroscopy.

Natural aluminosilicates can contain Fe in tetrahedral or octahedral coordination. Amongst smectites, tetrahedral iron is known to occur in Fe-rich nontronites but few indications exist for the presence of tetrahedral Fe in smectites of the montmorillonite–beidellite series. A set of 38 different bentonites showed a correlation of tetrahedral charge and Fe content in their smectites. All materials with large tetrahedral charge were rich in Fe. This could be explained by a general tendency of Fe to enter the tetrahedral sheet. To investigate this correlation, nine materials were selected and investigated by Mössbauer, UV-Vis, Fe K pre-edge and EXAFS spectroscopy with respect to tetrahedral Fe (Fe[IV]). The latter two methods were at the detection limit but Mössbauer and UV-Vis spectroscopy provided consistent results indicating the significance of both methods in spite of some scatter caused by the overall small amount of tetrahedral Fe. The results indicate the absence of any relation between Fe content and tetrahedral Fe. Tetrahedral Fe can be present in Fe-poor smectites and absent in the case of Fe-rich materials. This means that Fe-rich montmorillonites have a larger tetrahedral charge which is not caused by Fe[IV] but by Al[IV]. A possible explanation for this indirect relation is based on: the coordination of Al3+ in the weathering/smectite-forming solutions determines the coordination in the precipitates; and the Al[IV/VI] ratio increases with increasing pH. The correlation could thus be explained if the pH of weathering solutions generally was higher in Fe-rich parent smectite rocks than in more acidic smectite parent rocks. The relation between tetrahedral charge and Fe content can probably be explained by different geochemical contexts throughout the formation of smectites which affect the coordination of dissolved Al.

The interaction of two different bulk bentonites (Na- and Ca-types) with three types of simulated cement waters (pH 9.7, 11.3 and 12.0) and one saline groundwater simulate (pH 8.3) as a reference, was studied in batch reactors at 25°C. The solution pH was monitored in order to keep the pH as steady as possible by replacing the leaching solution with fresh one when needed. After 554 days, one set of parallel samples was removed from the experiment in order to investigate the possible changes in the bentonite materials.

The buffering capacity of bentonite was clearly observed, especially at the beginning of the high-pH experiments, as the pH of the leaching solutions decreased quite dramatically due to interaction with bentonite. The solution chemistry results showed a decrease of Ca content in all leachate samples, but especially in pH 12.0 experiments. Small amounts of silica were released throughout the experiment. Both bentonites in pH 12.0 experiments also released detectable amounts of Al, while in the lower pH experiments the levels were below detection limit. These observations were also supported by chemical analyses of the bentonite materials. Only minor changes were detected in the mineralogy, and they were mainly concentrated on experiments at pH 11.3 and pH 12.0. The measured swelling pressure showed an increase in pH 12.0 experiments. The results obtained in this research may facilitate modelling of bentonite interaction with high-pH solutions.

The efficiency of removal of the free iron from kaolinite-group minerals by means of acid leaching was followed by chemical, AES, XRD and ESR analyses. Structural Fe responsible for the g = 4 ESR signal represented only a small fraction of Fe impurity in the natural samples. The remaining non-structural Fe was found to exist both as forms easily extractable with acid, as well as deposits that were moderately resistant to the acid treatment. At least part of the latter could be associated with the broad g ~- 2 ESR signal typical of clustered Fe 3+ ions, which in most samples persisted even after prolonged acid leaching. The data demonstrate that procedures commonly used to clean kaolinite of free iron are by no means 100% efficient. In particular, frequently encountered quantitative association of the Fe remaining in the deferrated solids with purely structural Fe, homogeneously distributed in the kaolinite matrix, is probably significantly overestimated and should be treated with great caution.

From mineralogical and chemical characterization of two waste-rock piles from Vigonzano and Libiola sulphide mines in the northern Apennines, two types of fine-grained weathering products were recognized, One, from the Vigonzano mine, has a typical blue colour and consists of the Cu-Al sulphate of the woodwardite group. Its formation is related to an alkaline geochemical barrier, it is rather stable in acidic solution, and it controls Cu and Zn dispersion in the surrounding environment. The other group of sediments has a typical ochreous colour. Vigonzano samples consist mostly of goethite, whereas ferrihydrite is abundant in the Libiola sample. The ochreous sediments are enriched in Co, As, Mo, Se and Mn, thus significantly reducing the potential environmental hazard of the site, whereas solubility tests indicated possible problems due to AI dissolution at Libiola.

Under the influence of a pulsed field, dilute clay sols become birefringent as the particles undergo orientational order. The rate of decay of the birefringence on removal of the field is characteristic of the particle geometry. Measurement of the decay rates under two specific experimental conditions provides sufficient information from which the particle-size distribution can be evaluated in terms of a two-parameter function. Experimental data are reported and analysed in terms of a log-normal distribution of particle sizes for attapulgite (rods), kaolinite (discs) and halloysite (ellipsoids) sols and compared with success to electron microscopic data. The ability of the method to determine size distributions in terms of the major dimensions of the clay particles, rather than those of the often used equivalent sphere, is highlighted.

Soil kaolins from Indonesia and Western Australia and a range of reference kaolins were studied using Mössbauer spectroscopy, electron paramagnetic resonance (EPR) spectroscopy and SQUID magnetometry. Mössbauer spectra indicate that the Fe within the kaolins is in the highspin Fe3+ oxidation state and that a large fraction of the Fe is present as dispersed atoms residing within the octahedral sites of the kaolinite crystal structure. The EPR spectra are typical for soil kaolins except for the absence of radiation-induced defects for the Indonesian kaolins. The Fe(I) spectra are dominant with a strong symmetric peak at g= 4.3, the presence of Fe(II) spectra is shown by a shoulder on this peak at g= 4.9 and a small phase up peak at g= 9.2.

Low-temperature (5 K) magnetization (M) measurements over large field (H) sweeps (±70 kOe) yielded M(H) curves which are fitted well with Brillouin functions indicating the paramagnetic nature of the kaolins at temperatures down to 5 K. A very small remanent magnetization was detectable in the kaolins. Remanent magnetization to saturation magnetization ratios ranged from 10–4 to 10–3 for the Indonesian kaolins and were all ∼10–3 for the Western Australian kaolins, indicating that at high fields the vast majority of the magnetization of the kaolins is due to paramagnetic ions.

Zero-field-cooled and field-cooled magnetization measurements in small fields (500 Oe) indicate that the Indonesian kaolins are generally free from magnetically-blocked material down to a temperature of 5 K. The magnetic susceptibility of the Indonesian kaolins shows Curie Law behaviour indicating paramagnetic behaviour over all temperatures down to 5 K. Measurements on the Western Australian kaolins indicated the presence of some magnetic material that is magnetically blocked at temperatures below ∼200 ­ 250 K. As a consequence, the magnetic susceptibility showed large deviations from Curie Law behaviour.

In Argentina, the only halloysite deposits found so far are located in the southwest of the province of Rio Negro. The areas are named Mamil Choique and Buitrera, separated by 50 km in a W–E direction. The deposits are located in pyroclastic rocks, rhyolitic tuffs and ignimbrites.

The aim of this paper is to determine the origin of the alteration, any relationship between the processes in Mamil Choique and Buitrera, and the factors which controlled the halloysite formation. The work was based on field work, mineralogical and geochemical studies, form and distribution of the alteration. Fresh as well as altered rocks were collected. The first were studied by petrographic and chemical methods. In altered samples, the clay mineralogy was determined by XRD and textures by SEM and TEM. Chemical analyses on fresh and altered samples were used to characterize the alteration process and the rock composition.

It was concluded that halloysite has been formed by weathering in a time range from Middle Eocene to Middle Oligocene and extended along 50 km in a W-E direction, independent of the source rock. Particle morphology depends on the original texture of the rock. Spheroidal halloysite is related to rocks with low porosity and tubular particles are related to rocks with open spaces.

A comprehensive study of weathering in plagioclase-hornblende rock (amphibolite) from La Roche-l'Abeille, Massif Central, using optical and classical methods of clay mineralogy and electron microprobe determinations demonstrates the mineral reactions which can occur as amphibole and plagioclase weather. Both minerals decompose ultimately into beidellitic smectites but of different lattice compositions. It appears, depending on the host mineral, that an aluminous ‘intergrade’ mineral, similar to a hydroxy-complexed vermiculite, forms first, recrystallizing into the beidellites. Exchangeable ion composition of the beidellites suggests that all smectites were in equilibrium with waters of similar chemical activity for Ca and Mg ions at equivalent depths in the profile. The activities of the exchangeable interlayer ions of the newly-formed smectites are similar, regardless of the host mineral. Very local chemical potentials evidently dictate the lattice composition of the phases, ferribeidellite formed from amphiboles, aluminous beidellite formed from plagioclases, but longer range equilibria (centimetric) dictate the type of phase which will crystallize, i.e. smectite.

The formation of bentonites via alteration of volcanic glassy rocks is associated with apparently contradictory mineralogical, geological and geochemical characteristics, which remain poorly understood. This contribution attempts to answer some of the questions based on the work carried out in our laboratory over the past 15 y. The first question concerns the formation of opal-CT-free bentonites from acidic precursors. It is suggested that the formation of opal-CT-free bentonites is closely related to the mechanism of eruption and emplacement of parent volcanic rocks if the temperature of the parent glass after emplacement is high and/or the establishment of hydraulic gradients coupled with high permeability after deposition of volcanic glass (i.e. diagenetic alteration) if the temperature of the parent glass is low. The second question pertains to the behaviour of Fe during bentonite formation. Based on mineralogical and geological characteristics of different bentonite deposits, it is suggested that Fe is present mainly as Fe2+ and hence may be mobilized during alteration. Oxidation of Fe may take place when bentonites are exposed to more oxidizing conditions close to the surface. Assignment of Fe as Fe2+ increases the layer charge of smectites and decreases significantly the range of layer charge. Thus the smectites may have considerably different properties when formed compared with their counterparts on the surface. The third question considers the possible influence of parent-rock chemistry on the crystal chemistry of smectites. It is proposed that the parent rock may affect the chemistry of the neoformed smectites to some degree; therefore the smectite chemistry may provide indications about the geochemical affinities of the parent rock.

L'étude de l'adsorption des α amino-acides à leur point isoélectrique par la montmorillonite saturée en cations minéraux de valences différentes montre que la quantité fixée dépend de la réactivité de l'acide aminé pour le cation minéral saturant la smectite. La fixation des α amino-acides est plus forte avec les cations bivalents qu'avec les cations monovalents; elle s'accompagne d'une libération des cations minéraux (échange).

Nous avons pu mettre en évidence l'existence de relations linéaires entre les quantités d'amino-acide fixé et les quantités de cations incorporés dans le minéral. Ces relations permettent de connaître à priori le comportement d'un acide aminé donné vis-à-vis de la montmorillonite saturée en un cation donné. Elles permettent de classer les amino-acides en trois familles: (1) les amino-acides qui sont incorporés sous une forme cationique simple par échange d'ions; (2) les amino-acides qui forment des sels et/ou des complexes de coordination avec les cations métalliques; (3) les amino-acides qui présentent un comportement compliqué et dont l'incorporation dans la smectite se conjugue avec une polycondensation.

A method of analysing the colloidal stability of variable-charge mineral suspensions as a function of pH is described, which combines light scattering with soluble element and surface charge measurements. The absorbance of the suspensions closely follows the A = k−m equation, where m = −dlgA/dlgλ is an aggregate light-scattering index which is inversely related to the limiting sedimentation speed v = dA600nm/dt. Usually, suspensions of variable-charge minerals scatter less near their point of zero charge where the aggregation process is a maximum, in contrast to environments where they are charged and well-dispersed. Although the morphology of goethite is that of elongated needles, kaolinite plates, and imogolite tubes, the coalesced sphere approach of the Mie theory allows rapid correlation of the absorbance at 600 nm with aggregate-size distribution, indirectly measured by the light- scattering aggregate-size index m confirmed by electron microscopy experiments. Kaolinite and goethite suspensions obey the diffraction scattering law with a variation in size of 2–20 µm from the dispersed to the aggregated particles. Imogolite and alumina gel suspensions possibly obey the anomalous diffraction scattering law and are present as 0·05–1 µm aggregates of their 50–100 Å structural units. Silica gel and the more dispersed imogolite suspensions possibly obey the anomalous Rayleigh scattering law with a variation of aggregate size from 700–3000 Å.

It is usually assumed that the oxidation state of the small proportion of Mn sometimes present in micas is +2, although there is evidence from electronic spectroscopy (Burns, 1970) for at least the occasional occurrence of Mn(III) in manganophyllite. We describe here X-ray photoelectron spectroscopic (XPS) measurements on the Mn in a Norwegian lepidolite which was the subject of a concurrent structural study by X-ray photoelectron diffraction (Evans & Raftery, 1982). To establish the Mn oxidation state we have compared the Mn2p core-electron binding energies (BE), the Mn2P3/2-O ls BE differences, and the Mn2p XPS peak profiles from the four common oxides of manganese (MnO, Mn3O4, Mn2O3 and MnO2) with those from the lepidolite. A re-examination of these oxides was undertaken because the agreement between reports in the literature was unsatisfactory, and uncertainty existed concerning the integrity of some of the surfaces previously examined.

A previous classification scheme for clay minerals is revised and extended; the underlying principles are analyzed in detail.