A chlorite-smectite interstratified mineral in a pottery stone from Niwatorizawa mine, Izushi-Cho, Hyogo Prefecture (Japan), has been studied by means of Fourier transform methods, together with interlamellar sorption of ethylene glycol and glycerol. The calculations were carried out with the INTER program (using an Olivetti M-24 personal computer with MS-DOS operating system) which allows the analysis of two-component interstratified structures by two Fourier transform based methods: the X-ray diffraction intensity function method, and the interlayer distances distribution function method. The material studied contains a 1:1 chlorite-smectite interstratification and shows a marked tendency to alternation, i.e., the interstratification is almost regular.

Maghemite with acicular morphology occurs as an oriented growth on fresh quartz surfaces in the magnetic sandy fraction of the B horizon of a Typic Rhodoxeralf from southern Portugal. The maghemite was characterized by Mössbauer spectroscopy, X-ray diffraction and electron microscopy (scanning and transmission), and on the basis of a structural similarity between quartz and maghemite, a mechanism has been proposed for the formation of the oriented overgrowth. Correlation with an interpretative chemical model is discussed, assuming active sites over quartz surfaces. Infrared absorption data agree with the proposed models.

Pillared smectites in which the pillars consist of iron oxide are expected to have interesting and unusual magnetic properties. Several possible routes by which such materials might be made have been investigated, namely intercalation of hydroxy-Fe(III) polycations, mixed hydroxy-Fe(III)/Al polycations, phenanthroline-Fe(II) cations, and trinuclear Fe(III) acetato cations into Na-montmorillonite. Only the last of these yielded a pillared clay (PILC) on calcination. The products have been characterized using X-ray powder diffraction and 57Fe Mössbauer spectroscopy. The precursor Fe-PILC has a d-spacing of 21 Å and expands to 23 Å on solvation with glycol. The calcined Fe-PILC has a d-spacing of 19 Å (gallery height 9·4 Å) and does not expand with glycol, confirming cross-linking of the layers. From Mössbauer spectra at 4·2 K it is estimated that there are of the order of some hundred Fe atoms per pillar.

Decomposition of decylammonium cations on vermiculite surfaces as a result of acidity has been studied. The vermiculite-decylammonium complex was treated with solutions of HCl in water and butanol, and solutions of chlordimeform in butanol. X-ray powder diffraction and IR spectroscopy data showed the presence after treatment of ammonium cations in addition to aliphatic chain compounds in the interlamellar space. The ammonium cation is produced by breaking of the C-N bond of alkylammonium due to the low pH of the medium and, when using butànol as solvent, to the dissociation of the scarce water molecules on the clay surface. The influence of the different solutions on the period of decomposition of alkylammonium cations is discussed. Vermiculite-decylammonium complex treated with HCl solutions for a year released structural Mg2+ due to the acidity of the medium. This Mg2+ partially displaced ammonium cations from the interlamellar space.

The effects of dry grinding on the structure of sepiolite were studied by XRD, surface area measurement, TG-DTA and IR spectroscopy techniques. The results show that the sepiolite framework is rather resistant to mechanical stress and its alteration by dry grinding occurs through three successive, overlapping processes: (i) thinning of the fibrous particles without structural alteration; (ii) distortion of the parallel units of sepiolite fibres, affecting essentially the particle surface which transforms into an amorphous protective coating; (iii) disruption of the inner structure and a prototropy effect, producing an amorphous phase with some residual order.

Dry grinding of pyrophyllite (Hillsboro, USA) has been studied by X-ray diffraction (XRD), specific surface area measurements (BET) and scanning electron microscopy (SEM). At the beginning of the grinding process, some effects such as delamination, gliding and folding of the layers, and decrease in particle size were detected by SEM and XRD, resulting in a large increase in specific surface area, up to a maximum of ∼60 m2·g−1. Marked changes in the structure take place between 30 and 32 mins grinding. Longer grinding times increase the degree of disorder and SEM and specific surface area data suggest that aggregation occurs. XRD results indicate that some residual order persists in the degraded structure.

Samples of two lenticular clay bodies from a Cretaceous deposit near Padrão (Lousã basin) were characterized by INAA, XRD and Mössbauer spectroscopy. This clay is believed to be the raw material used to manufacture the Iron Age and Roman fine grey pottery from Conímbriga. The differences observed in the chemical and mineralogical compositions of the clay samples and of different size fractions are consistent with the high variance found in the compositional group corresponding to that archaeological site.

The weathering of a trachytic pumice within a pyroclastic flow underlying an andic-brown soil on the volcano Vico has been studied. The main mineral formed is a spherical 10 Å halloysite which has been shown by SEM and in situ microprobe analysis to have formed directly from the glass. The major mineralogical characteristics as determined by XRD, IR, DTA, TEM and microdiffraction are typical of 10 Å halloysite. However, some minor mineralogical properties and the high Fe and K contents, suggest that it is an interstratification of 74% halloysite and 26% illite-smectite. The calculated formula of the hypothetical 2:1 minerals reveals an Fe- and K-rich clay, with high tetrahedral substitution, like an Fe-rich vermiculite, but the detailed structure of this mineral remains uncertain.

A statistical comparison has been made of chemical data for terra rossa and carbonate-free residues of Cretaceous limestones and dolostones in Apulia in order to evaluate the hypothesis that the terra rossa is a product of weathering of the underlying carbonate rocks. It has been shown that the differences in chemical composition between the residue of the carbonate rocks and the terra rossa are consistent with the former being the parent material of the latter. The transformation from carbonate rock residue to terra rossa was governed mainly by chemical weathering which produced a marked decrease in the K2O/Al2O3 (i.e. illite/kaolinite) ratio. The geochemical pattern of the Apulian terra rossa has been influenced by sedimentary processes which have led to a characteristic distribution of mineralogical components and a moderate contamination by biogenic silica.

In the Recent sediments of the Congo River estuary, the green Fe-bearing peloids containing 7 Å phases are nearer to the river mouth than the 10 Å phyllosilicates. Measurements of d060 for 7 Å minerals in various density fractions indicated a progressive transformation of kaolinite into trioctahedral 1:1 phyllosilicates in the zone with a high sedimentation rate. Projection of the chemical composition from the approximate crystallochemical formula on to a classification field confirmed the transformation of kaolinite into a 7 Å Fe-rich phase via substitution of Fe2+ and Mg for Al in the octahedral sheet, with insignificant changes in the tetrahedral sheet. The resultant transition phase has a composition closer to greenalite than berthierine. The possible advancement of the evolution process was stopped by massive formation of goethite. The 10 Å minerals formed in the grains deposited in the off-shore sediments have a homogenous composition and occur in association with goethite and quartz. These peloids show an enrichment in Al although no kaolinite is present.

Chlorite belonging to subfamily C, vermiculite 2MB-VII-meso, talc and a monoclinic amphibole were identified in rocks from a contact zone between highly tectonized granite and serpentinite at Jordanów, Lower Silesia, Poland. K-saturated vermiculite readily produced a phlogopite-like structure 1M-I (3TA-IV) indicating trioctahedral mica to be its precursor. Spatial relations of the mineral assemblages were compared with published experimental data and used to produce a tentative model of the geological evolution of the rocks and minerals, which include four episodes of mineral development separated by three tectonic events.

The relationships between the composition and the crystallization temperature of chlorites and illites have been investigated in different geothermal fields and in particular the Los Azufres system in Mexico, considered to be a natural analogue to experimental laboratories, as the main changes in physical and chemical conditions and mineralogy are related to progressively increasing temperature with depth. Temperature was estimated from combined geothermometric approaches, and especially from fluid inclusion studies on quartz coexisting with clays. The Al(IV) content in the tetrahedral site of chlorites, and the K content and total interlayer occupancy of illites increase with temperature. These chemical changes are mainly related to the marked decrease in the molar fraction of the Si(IV)-rich end-members (kaolinite for chlorites, and pyrophyllite for illites) which become negligible at ∼300°C. Other chemical changes, such as the variation in Fe and Mg contents, are partly influenced by temperature, but are strongly dependent on the geological environment, and consequently on the solution composition. The empirical relationships between chemical variables and temperature were calibrated from 150–300°C, but extrapolations at lower and higher temperatures seem possible for chlorites. Such geothermometers provide tools for estimating the crystallization temperature of the clays, and are important for the study of diagenetic, hydrothermal and low-T metamorphic processes.