An unusually complete sequence of pelitic rocks ranging from diagenetic to greenschist-facies metamorphic grades occurs in southern Sierra Espun˜a, Spain. Prograde and retrograde reactions have been studied by X-ray diffraction and electron microscopy (SEM, TEM and AEM). The prograde reaction series, with reactions facilitated by tectonic stress, includes: (1) R4 interstratified illite-smectite in the diagenetic Malaguide Complex that preserves the variable orientation of original smectite packets, and has 1Md polytypism; (2) chemically heterogeneous illite and Na-K dioctahedral white micas that progressively evolve toward chemical and textural equilibrium in the anchizonal Intermediate Units; and (3) thick, defect-free packets of phengite, paragonite and clinochlore which have a typical metamorphic texture, in the Alpujarride Complex. Two superimposed retrograde episodes produced: (a) sudoite at near-peak metamorphic conditions and (b) dioctahedral smectite during low-temperature retrograde diagenesis.

A nearly monomineralic 1.5 m thick bentonite bed sampled in Melo (Uruguay) appears to be a pure high-charge montmorillonite: [Si3.94Al0.06](Al1.40Fe3+0.11Ti0.02Mg0.49Mn0.01)O10 (OH)2Na0.01K0.08Ca0.18. However, contrasting swelling behaviours have been demonstrated by fitting the experimental X-ray diffraction patterns which were recorded on oriented preparations of the same sample in different saturation states. According to the expandability of the layers in the Ca-, K- and K-Ca-saturated (i.e. saturated first with K+ and subsequently with Ca2+) states, three ‘layer types’ were defined. Low-, intermediate-, and high-charge layers are fully, partly, and not expandable, respectively, after K-saturation. Collapse of high-charge layers is not reversible after subsequent Ca-saturation, probably because of tetrahedral substitutions. These three different layer types are segregated in two distinct randomly interstratified mixed-layer phases. Total surface area and cation exchange capacity are shown to depend on the interlayer cation composition.

Hydrotalcite-like compounds (HTlc) were found as secondary products in two corrosion experiments performed with Al plates in highly concentrated solutions (MgCl2-saturated brine) in the presence of metallic and soluble iron at 90ºC under an Ar atmosphere. The durations of the experiments were ∼10 and 13 months, respectively. To investigate the corrosion experiments, solution and gas samples were collected and the main parameters measured. The solid and liquid samples obtained were analysed by X-ray diffraction (XRD), scanning electron microscopy (SEM) and ICP-OES. The presence of the hydrotalcite-like phase was confirmed by XRD and SEM. In one experiment HTlc was found only after dialysis. Formation of the hydrotalcite-like phase was observed at lower pH than mentioned in the literature. These results are useful in understanding the long-term behaviour of corrosion products of reactor fuel elements in relation to their possible barrier function and to comprehend the long-term behaviour of this type of waste during its final disposal.

Alumina-pillared fluorine micas were prepared from synthetic highly layer-charged expandable fluorine mica and polyhydroxoaluminium solutions under different solution loadings (Al mmol in solutions per 1.0 g mica) in order to clarify the effects of solution loading on thermal durability and microporous properties. The intercalated Al content of the pillared micas increased with increased solution loading. The intercalated Al content (i.e. the pillar density) of the pillared micas influenced both the thermal durability and specific surface areas of the pillared micas. The pillared micas obtained from the high solution loadings showed better thermal durability than those obtained from the low solution loadings. Through micropore formation upon heating, the pillared micas exhibit cation exchangeability due to the liberation of residual Na+ ions from steric hindrance in the interlayer pillaring space. The amount of the exchangeable ions depends on the heating temperature of the pillared micas.

The alkali leaching of two aluminosilicates, kaolinite and metakaolinite, with aqueous NaOH has been studied. Both silicates gave hydroxysodalite (HS) with or without the evanescent zeolite NaA. X-ray diffraction and high-resolution 29Si and 27Al MAS-NMR spectroscopy provide information about the reaction sequence of the clay. The conversion starts with the formation of an amorphous gel precursor at a rate which depends on the alkali concentration but not on the choice of kaolinite or metakaolinite as starting material. The rate of zeolitization of this gel is much faster when it is obtained from kaolinite, probably because it is more homogeneous.

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.

Purified kaolins from Thai soil on diverse parent materials were characterized using analytical transmission electon microscopy, X-ray diffraction, thermogravimetric analysis and chemical analysis. The properties of Thai soil kaolins appear to be more diverse than Indonesian and Western Australian soil kaolins investigated using the same analytical procedures; this difference may reflect the greater range of parent materials for the Thai soils. The kaolins show a variety of crystal morphologies including euhedral hexagonal to subhedral platy crystals, tubes and laths and several morphologies were present in most samples. TEM-EDS enabled analysis of single crystals of each morphology present within a sample. Tubular or lath-shaped crystals usually have lower %Fe2O3 contents than hexagonal platy crystals in the same sample. The relationships between crystal size and Fe content within morphological populations were also examined by TEM-EDS. Generally, smaller kaolin crystals display a wider range of Fe concentration than the larger kaolin crystals in the same sample. Increasing Fe concentration in bulk samples is closely correlated to decreasing coherently scattering domain size (R2 = 0.57), increasing cation exchange capacity (R2 = 0.44) and increasing specific surface area (R2 = 0.65). However the properties of the deferrated soil kaolins, including their Fe content, are not related to forms of Fe, (total Fe, amorphous or organic) in the untreated clay fraction of the soil.

Inhibited vermiculite is a common minor constituent of these clay fractions and its average structural formula derived from EDS data indicates that it was formed by Al replacing K in muscovite. One Al3+ ion occupies the interlayer space previously occupied by three K+ ions. As the distances between these Al3+ cations in the interlayer space is large it is proposed that isolated or loosely associated hydrated Al3+ groups such as Al(OH2)63+ exist that resist exchange by other cations due to hydrogen bonding with the adjacent tetrahedral oxygen surfaces

Residual clays that developed on Permian and Carboniferous glass-rich silicic volcanic rocks (pitchstones, ignimbrites) at the Seilitz and Kemmlitz kaolin deposits, Saxony, Eastern Germany, contain locally abundant lath-shaped illite-rich illite-smectite mixed-layer minerals (I-S). Analyses by XRD and TEM-AES reveal a large illite percentage (>∼90%) and R3 ordering in I-S from Seilitz (>∼90%) and smaller illite percentage (∼70%) and R1 ordering in I-S from Kemmlitz. The clays never suffered a deep burial and there is no geological, petrographic or fluid inclusion evidence for aeolian input or hydrothermal origin of I-S at either deposit. The I-S formed exclusively at the expense of volcanic glass and not from K-feldspar. Residual quartz phenocrysts in the clays still preserve primary glassy silicate melt inclusions and lack secondary aqueous fluid inclusion trails. The dD and δ18O values of kaolinite and I-S are suggestive of low formation temperatures (<40ºC). Rb-Sr and K-Ar dating of I-S-bearing clay separates yield Lower Cretaceous ages at Seilitz and indicates the presence of excess or inherited 40Ar in illite-rich I-S. In contrast, Triassic to Jurassic Rb-Sr ages are obtained for I-S from the Kemmlitz kaolin deposit.

Microanalytical data on Plio-Pleistocene sediments from a Salton Sea Geothermal Field well define the evolution of textures and mineral assemblages from sediment to metamorphic rock in an open hydrothermal system.

At shallow depths detrital grains occur within a fine-grained matrix of I-S and illite. As depth and temperature increase, grains lose their detrital characteristics; they subsequently form a continuous intergrown array of irregular domains, with phyllosilicates occupying the progressively decreasing pore space.

Illite and chlorite are authigenic phyllosilicates down to 2500 m, where biotite occurs. Authigenic phyllosilicates occur as subhedral crystals (200 –600 Å thick). Alkali feldspar has end-member compositions, implying exchange of alkalis with convected fluids. Changes in texture imply dissolution of detrital phases and neocrystallization of authigenic phyllosilicates directly from pore fluids. Changes with depth are not time-dependent for phyllosilicates: they formed simultaneously at all depths as a result of a single hydrothermal event in an open system.

This paper summarizes recent results obtained on chemical modifications of smectites. These include replacement of exchangeable cations with protons, a process connected with smectite autotransformation – attack of protons on the layers and liberation of central atoms from the octahedral and tetrahedral sheets, causing modification of the acid sites on the particles. More severe modifications occur during dissolution in inorganic acids, when the layers are dissolved and threedimensional amorphous silica is formed. The negative charge on the smectite layers can be increased via reduction of structural Fe(III) to Fe(II) or decreased via fixation of small exchangeable cations, such as Li+, upon treatment at elevated temperatures. Heating for 24 h at different temperatures between 100 and 300ºC leads to a series of chemically similar materials of different charge, prepared from the same parent mineral. Such series are suitable for investigation of the effect of the layer charge on selected properties of smectites. Fe(II) can be partly stabilized in reduced smectites by Li fixation upon heating.