Separate montmorillonite suspensions were treated with CrCl3 to give seven Cr(III) concentrations. Each suspension was then titrated with 0.1 N NaOH to give a NaOH/Cr3+ molar ratio of 2.5. Montmorillonite was an effective sorbent for hydroxy-Cr species up to 1200 cmol(+)/kg; above that concentration, sorption continued, though less efficiently. However, N2-BET specific surfaces and cation exchange capacity measurements indicated that the montmorillonite could sorb significantly more than 1200 cmol(+)/kg. There was virtually no exchangeable Cr in any of the clays, suggesting that this element was covalently bonded to the siloxane surface. Infrared spectroscopy revealed a vibration at 1015–1020 cm–1 in the Cr clays which was not present in the control. This new absorption band was attributed to an attenuation of the Si–O a11 vibration caused by inner-sphere complexation of the interlayer Cr with the siloxane oxygen. Because Cr was strongly held and efficiently sorbed, montmorillonite was shown to be an effective sorbent for hydroxy-Cr polymers.

Electron microscopy was used to study swollen samples of n-butylammonium vermiculite prepared in dilute aqueous solutions of n-butylammonium chloride. Three electrolyte concentrations were studied, 0.1 M, 0.01 M and 0.001 M. The 0.1 M samples studied were in a taetoid phase, exhibiting crystalline legions of about ten layers separated by large irregular aqueous regions. The dilute samples were studied in their gel phase, exhibiting regular spacings of 85 nm and 55 nm in the 0.001 M and 0.01 M solutions, respectively. These spacings are much larger than those measured previously by neutron scattering, probably due to an additional expansion of the interlayers during the freezing process employed in preparing the replicas. In all examples, the structures were found to be lamellar over regions of several microns.

Interaction between positively charged Fe-oxyhydroxide (β-FeOOH) particles and negatively charged particles of montmorillonite was studied as a function of particle concentration, pH and time. The results showed that the clay particles appear to bridge between FeOOH particles leading to associations in which the ratio of positive to negative particles varied between 1.4 and 2.56 depending on pH and particle concentrations. The data could be represented by isotherms of interaction of the high affinity type and, together with the interaction kinetics, could be described by Langmuir type formulations.

The surface/near-surface chemistry of allophane has been studied by X-ray photoelectron spectroscopy (ESCA) and the bulk material by 27A1 and 29Si solid-state NMR and other techniques. The surface/near-surface Si/Al ratio of allophane is c.1.0, similar to that for kaolinite, zeolite Na-A and sodalite. The core level binding energies for kaolinite and allophane are almost identical, but quite different from those for zeolite Na-A and sodalite, both framework aluminosilicates. The nature and size of these differences is consistent with the differences between the chemistry of sheet and framework silicates. The small variations in the Si(2p) spectra for kaolinite and allophane are discussed in terms of bonding of the tetrahedral units in the two materials.

Pecoraite and nepouite, Ni-serpentines, occur in the serpentinized ultramafic rocks in the Kwangcheon area, Korea, where the parent rock is classified as harzburgite and/or lherzolite. Pecoraite was precipitated twice from the solution; the early-formed pecoraite coexists with magnetite, millerite, and polydymite both in the Buk- and Nam-sites, while the late-formed pecoraite appears as well-grown colloform and opaque-free phase only in the Buk-site. The typical colloform texture of the late-formed pecoraite strongly indicates that it was precipitated from the solution in supergene conditions. Pecoraite is characterized by its extremely high Ni content and the difference in Fe content between the early- and late-formed pecoraite. Nepouite is distinguished from pecoraite by its prismatic morphology and the large degree of isomorphous substitution between Ni and Mg. The phase relations among coexisting magnetite-millerite-polydymite assemblage with the early-formed pecoraite suggest that the pecoraite might have precipitated in the extremely limited fO2 and fs2 environment from the highly Ni-concentrated solutions and is stable at 25°C and 1 bar.

The Carrión lacustrine basin (≈10 km2), central Spain, is filled with Neogene-Quaternary sediments (20–25 m thick) rich in palygorskite. Two clay units of ∼15 m thick are of particular interest in the basin. The lower one contains over 75% phyllosilicates (palygorskite up to 90%, smectites and illite) in marginal areas (facies A), and it is laterally bound by a distal facies (B) also rich in clay minerals (smectites and illite, and some palygorskite) and gypsum, and includes dolomitic marl intercalations. The composition at the top is primarily marly, with some gypsum (C). The upper clay unit, mainly clay-size material, (D) is rich in smectites, palygorskite and sepiolite, and contains carbonate intercalations near the top. A statistical treatment of the mineralogical and chemical composition data from 120 samples, using principal factor analysis, suggests that: (a) illite and smectite are detrital in origin; (b) palygorskite was formed by transformation of illite and smectite involving reaction with Mg; and (c) sepiolite was a neoformation product favoured by evaporation of silica- and Mg-bearing waters.

Rare earth elements are mobilized, fractionated and precipitated during weathering processes of basaltic rocks of the Lisbon Volcanic Complex. In general there is an increase in the REE contents in the whole samples with increasing weathering and fractionation between LREE and HREE. Cerium is partially oxidized and Ce4+ is retained resulting in negative Ce anomalies in the whole samples of the base and middle profile zones. In the clay fraction there is an increase in the REE contents from the top to the bottom of the profiles, except for Ce, giving rise to positive Ce anomalies in the top and negative anomalies of this element in the middle and bottom of the profiles. Significant positive Ce anomalies occur in the finer fractions of palaeoweathered (Upper Cretaceous/ Lower Eocene) basalts associated with low REE contents relative to the whole samples indicating more intense leaching conditions in the Upper Cretaceous/Lower Eocene than at the present day. However, in both cases no positive Ce anomalies were found in the whole samples. There appears to be a negative correlation between the (La/Yb)ch ratio variation and the clay mineralogy/drainage conditions.

In the region of Illapel, Chile, dioritic and andesitic rocks of Cretaceous to Paleocene age from the Unidad San Lorenzo Formation have suffered strong alteration resulting in the formation of a kaolin-rich zone, which is mined in the La Vanguardia open pit near Combarbalá. Detailed mineralogical and chemical investigations of channel samples from this mine, involving a combination of optical microscopy, XRD, SEM-EDX, XRF and TEM, permitted recognition of a zone of silicification and a zone of advanced argillic alteration, both of which contain alunite s.s. and aluminium-phosphate-sulphate (APS) minerals of the woodhouseite group with subordinate amounts of gorceixite, florencite and goyazite. These minerals are found to have originated from infiltration of meteoric waters. The passage from silicification into advanced argillic alteration was associated with an increase in sulphate activity as manifested by the increase of SO42— at the expense of PO43— in the alunite s.s. and by an increase of the Au content from 0.01 to 0.03 mg/kg Au. This high sulphidation type of wallrock alteration may be roughly compared with the Nansatu type of White (1991).

The definition of ‘clay’ was first formalized in 1546 by Agricola. It has been revised many times since, although the fundamentals involving plasticity, particle size, and hardening on firing were retained by most. For an exhaustive account of the history of the definition to 1963, the reader is referred to Mackenzie (1963). More recent developments may be found in Weaver (1989).

The definition of clay raises the important issue of clay constituents and, implicitly, the definition of ‘clay mineral'. Mackenzie (1963, p. 15) noted the inappropriateness of defining clay mineral as “any mineral which occurs in clay” since, among several reasons, it would include many accessory minerals that are not characteristic of clay.