The synthesis of magnesium smectite from heated slurries of magnesium hydroxide, silica and lithium fluoride proceeds through ready formation of torroidal structures visible under the electron microscope. These are associated with the synthesis of a smectite-like material with, however, only half the expected requirement for silica. True smectite only forms significantly with Si/Mg ratios > 1 and reaction times (at reflux) > 1-3 days.

Bentonite deposits in Basoren Kutahya, West Anatolia, Turkey formed from alteration of perlite and pyroclastic rocks of Pliocene age. The distribution of bentonite deposits along faults in the study area indicates that the alteration solutions were hydrothermal. Although lateral zonation is observed in bentonite deposits in some regions (i.e. Demirli, Akyokus, Seklice- Sarıokuz, etc.), alteration zones are extremely irregular in the Cayırlık bentonite deposit.

X-ray diffraction studies have shown that Basoren bentonites contain dioctahedral Ca-smectite.

The Greene-Kelly test (Li-saturation and heating) showed that the Demirli and Akyokus bentonites consist of montmorillonite and that the Cayırlık bentonite consists of montmorillonite and/or beidellite. Spherulitic or hemispherical ‘crystals’ of opal-CT minerals formed from hydrothermal alteration of volcanic glass. The MgO, CaO and total Fe2O3 enrichment in bentonites, compared to parent rocks, is related to the chemical composition of hydrothermal solutions that passed through the ophiolitic rocks such as serpentinite.

We report a montmorillonite material with enhanced surface area but with very little alteration in cation exchange capacity (CEC) upon dealumination with para toluene sulphonic acid (p-TSA). The new material shows higher catalytic activity in comparison with mineral-acid-treated clay. Montmorillonite clay was treated with p-TSA for 10 minutes under microwave irradiation. The resulting clay was characterized by CEC, X-ray diffraction (XRD), BET analysis, Fourier transform infrared spectroscopy (FT-IR), temperature programmed desorption (TPD) of ammonia and cyclic voltametry (CV) techniques. XRD patterns show an unchanged structure of pristine matrix after the acid action. BET analysis revealed an increase in the surface area and pore volume on p-TSA treatment, indicating formation of voids in the octahedral layer which suggests dealumination. Nitrogen adsorption-desorption curves showed the creation of new micro porous regions, possibly in the octahedral sheets. In contrast to mineral acid treatment, p-TSA treated clay samples showed similar CEC which shows the absence of dissolution of isomorphously substituted Mg and Fe ions present in the octahedral layer. CV studies confirm the formation of an Al-p-TSA complex, suggesting dissolution of aluminium octahedral sheets. The complex subsequently hydrolyses, replacing interlayer cations with Al3+ ions. Similar treatment with mineral acid resulted in clay with enhanced surface area but with reduced CEC, evidently due to the removal of isomorphously substituted Fe and Mg. Further, the p-TSA treated clays showed relatively higher esterification activity under solvent-free microwave irradiation. The p-TSA treated clay retained its activity even after three subsequent runs and thus can be exploited for practical applications.

The magnetic susceptibilities of seven different nontronites in their natural oxidation states were measured between 5 and 100 K. Results revealed that the magnetic exchange interaction in all samples was antiferromagnetic, except no clear minimum occurred at the Néel temperature. Possible explanations for this phenomenon which are discussed include magnetic dilution due to isomorphous substitution, and antiferromagnetic frustration due to either non-centrosymmetric distribution of octahedral Fe3+ or tetrahedral Fe3+ substitution. A computer simulation model was developed to demonstrate the effects of these variables on long-range magnetic ordering. Magnetic dilution and tetrahedral Fe3+ content could explain the anomalous antiferromagnetic behaviour in some, but not all, samples. The non-centrosymmetric model is the only one which explains the behaviour of all samples. In this model, at least 13% of the octahedral Fe3+ would occupy trans-dihydroxide sites, with the balance in cis sites. Magnetic frustration occurs because two Fe3+ neighbours of a third Fe3+ ion are also neighbours to each other, making the simultaneous satisfaction of all antiferromagnetic exchange interactions impossible.

Composites based on ZnS nanparticles embedded in layered magadiite were synthesized via a three step process : protonation of Na-magadiite, ion exchange in order to introduce Zn(NH3)42+ in the interlayer space, and addition of Na2S to form ZnS particles in the interlayer space of magadiite. The composites obtained were characterized by X-ray power diffraction (XRD), Scanning Electron Microscopy coupled with Energy Dispersive Spectroscopy (SEM-EDS), Transmission Electron Microscopy (TEM), Raman spectroscopy, Photoluminscence spectra (PL), and UV-visible transmission spectra (UV-vis). Results indicated that ZnS nanoparticles embedded in magadiite presented different optical properties and photoluminescence enhancement properties compared with those of uncovered ZnS particles (without host magadiite).

A series of organo-silicates was obtained from synthetic Na-fluorotetrasilicic mica (Na-TSM) by ion exchange with dodecyl-, tetradecyl-, hexadecyl- and octadecyltrimethylammonium (C12, C14, C16 and C18) bromides. When the concentration of the alkylammonium ions has varied from 0.43 to 3.4 mmol/g of the silicate, the maximum amount adsorbed on the mica was 0.92 mmol/g. As shown by 23Na MAS NMR, ∼0.30 mmol/g of Na+ ions were non-exchangeable, even if a large excess of the organic ions was used. The XRD patterns of all the samples obtained show that alkylammonium ions are distributed inhomogeneously within the mica interlayers. As a consequence, the organo-micas contain several phases consisting of randomly and regularly interstratified layers differing in terms of the amount of alkylammonium ions adsorbed. These different layers swell in ethylene glycol in the same manner and form new interlayers with identical spacings. The d001 values of individual organo-TSMs after glycolation suggest that the alkylammonium ions are oriented perpendicular or almost perpendicular to the mica layers. The Na-TSM layers were not detected in organo-TSMs by XRD. The presence of organic and inorganic (Na) mixed-ion interlayers with spacings controlled by the arrangements of the organic ions is consistent with the results obtained. These data also suggest that the alkylammonium/Na+ ion ratios vary in alternate interlayers.

Tubular halloysite has many applications as a nanomaterial. Spheroidal halloysite (SPH) is the other most common form of halloysite. Its mode of formation has had different explanations, including association with allophane, or more generally, following weathering of volcanic glass. Some SPHs have formed from minerals in crystalline rocks, sometimes as an early stage of evolution into plates and/or tubes of halloysite and ultimately to kaolinite. Spheroidal halloysites can show a range of Fe contents and can occur with other forms of halloysite; they have often formed in confined environments whereas tubular halloysites apparently form in more open spaces. They have also formed on microbes or where there is a significant amount of organic matter. Generally, SPHs have often formed by rapid dissolution of volcanic glass and primary minerals. The SPHs can persist over time. They have fewactive edges, so interparticle interaction is poor, causing low viscosities in clay-water suspensions, poor soil stability and low adsorption capacities.

Hydrotalcites with heterogeneous distributions of anions between their layers were synthesized. Some synthesis parameters were studied to verify their influence on the anionic segregation properties of the hydrotalcites. The nature of the divalent cation and the crystallization method were most relevant. Zinc, in contrast to magnesium, assisted in discriminating carbonates and attracting nitrates to form hydrotalcites with heterogeneous distributions using microwave irradiation. Furthermore, the identification of this kind of hydrotalcite could be easily verified by determining the presence of a double reflection in the 003 X-ray diffraction (XRD) maximum, which definitively characterized a heterogeneous anion distribution. Finally, the reason as to why in some cases the hydrotalcite presented two reflections in the 003 XRD peak was elucidated.

In a study of wall-rock alteration in the 1.4 km long Würmtal adit at the Käfersteige hydrothermal vein deposit (northern Black Forest, Germany) illite was found to be the only clay mineral within the Bunter sandstone and intercalated claystone. Illite occurs mainly as a detrital mineral in the claystone, whereas it is hydrothermally neoformed in the sandstone, either in the pores or as an alteration product of K-feldspar. The extensive occurrence of authigenic illite along the entire 1.4 km long profile confirms that the fluids migrated far into the sandstone.

The authigenic illite formed during a first pulse of high-temperature fluids (Th of ~220°C) with a low salinity (~1 wt.% NaCleq). These fluids also dissolved Sr and Rb from detrital illite of the claystones at the vein. A later hydrothermal pulse with a lower temperature (~70–150°C) and higher salinity (21–28 wt.% NaCleq) silicified the sandstone adjacent to the vein and caused partial substitution of OH- by F- in the structure of the detrital and neoformed illite along the profile.

Within analytical error, the K-Ar dates for the neoformed illite of the <2 µm fraction are the same along the profile (~150 Ma). During this hydrothermal process, the age of the detrital illite within the claystone was reset from 310 to 190 Ma. The illite-rich <0.2 µm fractions yield ages of ~142 Ma (sandstone) indicating a Jurassic origin. The uniform age data for illite in the sandstone and in the claystone are probably due to extensive migration of hot fluids through the wall rocks.

The hydrothermal fluids are attributed to recycled meteoric water and brines that ascended from the basement into the cover rocks during the opening of the North Atlantic and/or the nearby Tethys area.

Dehydration curves have been obtained for vermiculite saturated with Mg2+, Ca2+, Sr2+, Ba2+ and Na2+. Three of the hydration phases of Mg-vermiculite give energies of hydration of −3·8±0·1, −5·5±0·1, and −18±3 K cal per mole of water. The heat of hydration of vermiculite has been found to vary with the saturating cation, and to decrease with decreasing energy of hydration of the cation. Values for the heats of hydration of vermiculite saturated with Mg2+, Ca2+, Sr2+, Ba2+ and Na+ are reported.

From measurements of dielectric losses as a function of frequency and temperature, as well as thermally stimulated depolarization currents, performed on a dry Na-montmorillonite, a qualitative description of the conduction mechanism has been proposed for this type of material. A representative approach related to the polarization phenomenon determined on this material led to the evaluation of the elementary energy Wj, connected with the reorientation of the dipoles during the hopping process. The results show the coherence between the polarization conductivity and the thermally stimulated currents methods.

Calcareous volcanic ashes (pumice–tuffs) occur among Ordovician rocks in Snowdonia, North Wales. The clays of these rocks and of the ecologically important soils derived from them are found to be almost mono-mineralic and to consist of chlorites. Chemical, differential thermal and X-ray analyses are given and discussed with particular reference to a clay-size chlorite from weathered pumice–tuff. There is no evidence for pedogenetic clay mineral transformations in the range of soils studied.

Palygorskite, associated with aragonite, occurs as a fracture filling in a dunite body that has been intruded by felsic pegmatites. The palygorskite formed by direct precipitation from solutions given off by the pegmatite. Aluminium, calcium and silicon were provided by the pegmatite solutions while magnesium was derived from the serpentinization of the dunite along the host fractures. No direct replacement took place.

The kinetic parameters of the thermal degradation of sepiolite were evaluated with a new method based on thermal analysis data. Thermogravimetric/differential thermal analysis curves were recorded for the natural and preheated sepiolite samples in the temperature range 25–800°C for 4 h. The temperature-dependent height of the exothermic heat flow peak for the thermal decomposition of sepiolite located at ~850°C on the differential thermal analysis curve was taken as a kinetic variable for the thermal degradation. A thermal change coefficient was defined depending on this variable because this coefficient fit to the Arrhenius equation was assumed as a rate constant for the thermal degradation. The Arrhenius plot showed that the degradation occurs in three steps. Two of these are due to stepwise dehydration and the third originated from dehydroxylation of sepiolite. Three activation energies were obtained that increase with the increasing temperature interval of the steps.

Detailed clay mineralogical and chemical analyses of well cuttings of Tertiary sediments from two wells, Uruan-1 and Uda-1, on the eastern flank of the Niger delta, have been made in an attempt to investigate clay mineral burial diagenesis. The clay mineralogy indicates a transformation of smectite to an interstratified illite-smectite (I/S) phase. The relationship between ordered and random interlayering, however, is nonsystematic. The chemistry of the <0·1 µm size fraction shows some tendency towards a net gain in K2O and Al2O3 and a net loss in SiO2 with depth, but the relationship does not correlate well with the thermal gradient. The distribution of kaolinite and chlorite in both wells appears to be unrelated in any regular way to smectite transformation and these two minerals are considered to be either the products of other diagenetic reactions affecting various stratigraphic levels, or the result of primary sediment deposition. In well Uda-1, kaolinite decreases in relative abundance with depth. This trend has been interpreted elsewhere as indicative of a transition from nonmarine to marine facies. The results of this study indicate that lack of ion mobility, rather than availability, is a significant factor in retarding the formation of ordered I/S with depth, and that lithology, overpressuring, carbonate cement, and original smectite layer charge may be controlling factors in the smectite → illite transformation.

The chemical method for preparing pseudo-chlorite from montmorillonite suffers from the disadvantage that the magnesium hydroxide is soluble in the ammonium chloride formed. The electrolytic method described overcomes this difficulty and, in addition, gives preparations with up to five brucite layers between the montmorillonite sheets. Ions other than magnesium may also be used. A simple technique for overcoming difficulties associated with preferred orientation in the Brindley powder X-ray camera is described.

Acid mine-drainage from an abandoned Cu-S mine adit, located in the Avoca–Avonmore catchment in the southeast of Ireland, results in low-value ochre deposition. Ochre found on-site had similar physical (particle size 97.7% <2 mm and dry bulk density 0.8 g cm3), but dissimilar maximum P-retention characteristics (16–21 g P kg–1) to coal-mining ochre found in the UK. Stereomicroscopy identified oolites and diatoms in the ochre that were indicative of acidic environments. X-ray diffraction showed Fe mineralogy consisting of goethite, jarosite and minor amounts of ferrihydrite. Investigations by inductively coupled plasma-mass spectrometry and bulk energy-dispersive spectroscopy showed potentially toxic concentrations of Fe, Zn, Pb, As and Cu. Rapid mobilization of metals occurred during P-adsorption tests, which makes Avoca ochre unsuitable for use in a surface-water environmental technology.

A method of precipitation in homogenous solution has been used for the synthesis of kaolin minerals at room temperature. The method consists essentially in producing conditions for which a sufficiently slow rate of precipitation is maintained. In the particular case described in this paper, the conditions for homogenous precipitation are obtained by addition of an anion exchange resin in the OH form to an acidic solution (pH ≈ 4) of sodium silicate and aluminium chloride or acetate.

The mineral species synthesized in each particular case depend on the kind of anions present in the original solution (chloride or acetate) and also on the nature of the exchange resin used.

Experiments on a number of clays from different formations show that heating at 375°C for 16 hours removes 90 per cent. or more of the carbonaceous material without removing combined water from the clay mineral. A close relationship is found between percentage loss at 375°C and percentage carbon determined in the carbon-hydrogen furnace.

Dioctahedral smectites (Cheto- and Wyoming-type montmorillonites and a beidellite) were treated with two hydrolysed OH-Al solutions (0.02 M in Al) containing different OH-Al complexes. The ratio of ∼3.25 mmol of Al per gram of smectite was used. The total Al and the presence of OH-Al species in solution before and after reaction with smectites were determined by the kinetics of Al-Ferron reaction colour development. The composition of the Al species retained by smectites was not the same as that present in the original solution added. The slow-reacting complexes present in the solution were preferentially adsorbed by dioctahedral smectites. Smectites prepared from slow-reacting polymer solutions showed changes in interlayer separation, b–dimension, order along the c axis and spectroscopic properties, after storage at room temperature. The OH-Al Cheto-type montmorillonite prepared from both solutions showed more retention of Al, best stability at room temperature and after thermal treatment at 550°C than interlayered OH-Al Wyoming-type montmorillonite and OH-Al beidellite smectites.