The chemical and the mineralogical composition of a group of pumiceous tuffs associated with recent salic volcanic episodes from Tenerife (Canary Islands) have been studied. The investigation focused on the two main types of pyroclastic deposits of the zone: ash-flows and ash-falls. The samples can be classified chemically as trachytic and phonolitic rocks with an intermediate silica content and a high percentage of alkali cations (Na+ and K+). The mineralogical composition, determined by X-ray diffraction, scanning electron microscopy, and optical microscopy, shows the occurrence of zeolites (mainly phillipsite, with lesser chabazite and analcime), associated with the parent glass. K-feldspar (sanidine) and calcite are accessory minerals. Zeolites are significantly more abundant in the ash-flow deposits. Zeolite formation by hydrothermal weathering in closed-system conditions varies according to the nature and the origin of the pyroclastic deposits. Tenerife phillipsites differ from typical diagenetic, lacustrine, and deep-sea phillipsites, both in chemical and mineralogical features. Alkali cations exceed divalent cations in the unit-cell that, assuming a monoclinic symmetry, has the following parameters: a = 8.46–10.55 Å, b = 14.21–14.40 Å, c = 7.80–8.70 Å, and β = 105°–110°.

Columns for high pressure liquid chromatography were prepared from spray dried samples of montmorillonite that were heated with potassium halides (KTM) to increase both the cation density on the clay surfaces and the expandability of the interlayers. Some of the clay samples were exchanged with Cu before and/or after the potassium halide treatment.

Retention of nitrobenzene and its chloro and methyl derivatives, of methyl substituted phenols and of nitrophenols on these columns was studied, using eluents ranging in polarity from hexane to isopropanol. The retention of the aromatic molecules depends on their specific interaction with active sites on the clay surfaces and on steric effects which limit access to the clay interlayers. Both penetrability and surface interaction are controlled by the composition and method of preparation of the solid phase and by the polarity of the mobile phase. Very strong adsorption of some eluates and efficient chromatographic separations between related substituted benzenes were achieved. Mixtures of the three isomers of cresol, chloronitrobenzene, nitrotoluene or nitrophenol were completely resolved by a judicious combination of solid phase and eluent.

Consideration of XRD, TEM, AEM, and analytical data reported in the literature indicates that dioctahedral aluminous smectite and illite form two separate solid solutions that differ chemically from one another primarily by the extent of Al substitution for Si, the amount of interlayer K, and the presence of interlayer H2O. The data indicate that limited dioctahedral-trioctahedral and dioctahedral-vacancy compositional variations occur in both minerals. Excluding interlayer H2O and based on a half unit cell [i.e., O10(OH)2], natural dioctahedral smectite and illite solid solutions fall within the compositional limits represented by A0.3${\rm{R}}_{1.9}^{3 + }$Si4O10(OH)2-AR2+ R3+ Si4O10(OH)2-A0.25${\rm{R}}_{0.3}^{2 + }{\rm{R}}_{1.8}^{3 + }$Al0.25Si3.75O10(OH)2 for smectites and A0.8${\rm{R}}_{1.9}^{3 + }$Al0.5Si3.5O10(OH)2-A0.55${\rm{R}}_{0.45}^{2 + }{\rm{R}}_{1.55}^{3 + }$Al0.1Si3.9O10(OH)2-A0.9${\rm{R}}_{0.3}^{2 + }{\rm{R}}_{1.8}^{3 + }$Al0.9Si3.1O10(OH)2 for illites, where A represents either monovalent cations or divalent cations expressed as their monovalent equivalent (e.g., Ca2+/2); R2+ stands for the divalent cations Mg2+ and Fe2+ and R3+ refers to the trivalent cations Al3+ and Fe3+. Taking account of these compositional limits, smectite and illite solid solutions can be described in terms of nine and six thermodynamic components, respectively, all of which are consistent with both the law of definite proportions and the concept of a unit cell. Thermodynamic components that can be used to describe natural smectite solid solutions in terms of a half unit cell [i.e., O10(OH)2] can be expressed as NaAl3Si3O10(OH)2, NaAl3Si3O10(OH)2 ·4.5H2O, Al2Si4O10(OH)2, Fe2Si4O10(OH)2, Mg3Si4O10(OH)2, Fe3Si4O10(OH)2, K3AlSi4O10(OH)2, KAl3Si3O10(OH)2, and Ca0.5Al3Si3O10(OH)2. Of these, NaAl3Si3O10(OH)2 ·4.5H2O provides explicitly for the presence of interlayer H2O in the mineral. Thermodynamic components representing illite solid solutions in natural systems can be written for a half unit cell as KAl3Si3O10(OH)2, KMg3AlSi3O10(OH)2, KFe3AlSi3O10(OH)2, Al2Si4O10(OH)2, KFe2AlSi3O10(OH)2, and K3AlSi4O10(OH)2. The calculations and observations summarized below indicate that neither smectite nor illite occur in nature as stoichiometric phases and that the two minerals do not form a mutual solid solution corresponding to mixed-layered illite/smectite.

All possible polytypes of hydrotalcite-like minerals with a periodicity along the c axis of one-, two- and three-layers, as well as the simplest six-layer polytypes, were derived on the basis of the concept of closely packed brucite-like layers. Multilayer structures were found to be possible in several polytype modifications—three two-layer, nine three-layer, and a set of six-layer polytypes. The neighboring layers may be stacked in two different ways, building two kinds of interlayers: P-type where OH sheets lie one above another forming prisms and O-type where OH groups forms octahedra. Based on the kind of interlayer space, all polytypes may be separated into three groups: homogeneous interlayers of O-, or P-type, and alternating interlayers of both types. For the members of the first two groups, powder XRD patterns were calculated and criteria for distinguishing polytypes with the same number of layers per unit cell are suggested.

Polytype diversity of hydrotalcite-like minerals is mainly a function of the nature of the interlayer anion. Among the varieties with CO32− anions, only two- and three-layer polylypes having the same structure as manasseite and hydrotalcite have been confirmed. Stichtite and reevesite, which have been previously identified as six-layer polytypes, are in fact three-layer polytypes.

Among SO42− varieties, one-layer and three-layer polytypes have been identified, but the one-layer types are only present in more hydrated minerals with larger interlayer spacings. The three-layer varieties are of three different polytypes, with both P- and O-types of interlayers. Both rhombohedral and hexagonal varieties exist. Interlayer type may change during hydration-dehydration or anion exchange. Thus, in contrast with the CO32−-bearing minerals, a complete description of the polytype of the SO42−-bearing minerals cannot be made by simply indicating the number of the brucite-like layers in the unit cell.

The two-layer unit cell seen in refined crystal structures of some minerals with SO42− interlayers is not due to a doubled periodicity of alternation of brucite-like layers but to periodicity of interlayer anions, or layer cations.

Electron paramagnetic resonance (EPR) and Fourier transform infrared (FTIR) spectroscopy in combination with X-ray diffractometry and thermal methods were used to determine the coordination of residual exchangeable Mn(II) in an untreated sample of Wyoming montmorillonite. At room temperature, Mn(II) in a single-layer-hydrate interlayer was proposed to be coordinated directly with oxygen ions of the siloxane surface on one layer and to form water bridges to the oxygens on the siloxane surface of the opposite layer. Dehydration and collapse of the interlayer entrapped and thereby stabilized the partially solvated Mn(II) up to 600°C. A change to Mn(II) in highly symmetric coordination occurred during dehydroxylation of the montmorillonite structure between 600°C and 700°C. Manganese(II) remained coordinated at the surface but positioned in a bicapped trigonal antiprism formed by oxygens of the silicate structure. This coordination was metastable at 800°C when the structural decomposition of the clay mineral began.

The lower Permo-Triassic sediments of the Maláguide Complex contain abundant dickite. Whole rocks were studied by optical microscopy, scanning electron microscopy, and X-ray powder diffraction. The 2–20 µm and < 2 µm size fractions were extracted and analyzed by scanning and transmission electron microscopy, X-ray powder diffraction, infrared spectroscopy, differential thermal analysis, and thermogravimetry.

In the coarse-grained samples, the 2–20 µm size fraction consisted of well-crystallized dickite associated with minor quantities of kaolinite, illite, quartz, and hematite. XRD patterns of the fine-grained samples and the <2 µm fractions showed the existence of well-crystallized minerals in which several reflections of dickite (11l, 02l) were absent and the 132/13$\bar 2$ reflections were shifted. These patterns suggest the presence of an intermediate member between well-crystallized dickite and well-crystallized kaolinite. Only locally high-order reflections are present at 10.5 Å and 18–22 Å. DTA and IR data agree with those from XRD.

The observed compositional and structural variations are a function of the lithology and the particle size of the sample. The sequence kaolinite → kaolinite/dickite → dickite is proposed for the development of these materials during Alpine metamorphism.

The stacking order of a bi-ionic K/Mg vermiculite from Malawi (Nyasaland), has been determined from Weissenberg data. The sample corresponds to a K/Mg interstratified vermiculite containing 50% K layers (dK = 1.01 nm) and 50% Mg layers with two layers of water (dMg = 1.44 nm). The observed intensities along (0, 0), (h, 0), (0, k) and (1, k) reciprocal rods were compared to the calculated intensities given by model defect structures. It was found that: 1) The (h, 0), (0, k) and (1, k) rods reveal the interstratification phenomenon which was previously observed on the (0, 0) rod; 2) The exchange of Mg by K does not occur randomly in a single interlayer, but occurs in interlayer domains sufficiently extensive to allow the reorganisation of the layer stacking and development of the ordered K-vermiculite structure from the semi-ordered structure characteristic of magnesium vermiculites; 3) For this sample, the interlayer water of the Mg phase occurs in two coexisting configurations; one configuration has water molecules forming octahedral coordination around the Mg2+, the other has water which is not linked to the Mg2+ cation forming two planes.

Substantial studies have been carried out to investigate the mechanism of the formation of Al(OH)3 polymorphs. The influence of the nature of Al precipitation products on the formation of Al(OH)3 polymorphs still remains obscure. In this study, X-ray diffraction, infrared and thermal analyses, and electron microscopic observations of the Al precipitates formed at the initial pH 8.2 and at a citric acid/Al molar ratio of 0.01 and aged for 3 hr to 60 days revealed that the transformation from the initially formed noncrystalline materials to pseudoboehmite occurred through the formation of intermediate materials with various degrees of ordering and sizes of particles that apparently had a wide range of solubility. By increasing the pH of the suspension of precipitation products of Al to 10.0 after 3 hr and 3, 11, 31, and 60 days or longer, the crystalline precipitation products were hayerite, nordstrandite and bayerite, nordstrandite and pseudoboehmite, pseudoboehmite and gibbsite, and pseudoboehmite, respectively. This work shows evidence that, as the nature of the starting Al precipitates changed, the rate of their dissolution apparently changed, and various Al(OH)3 polymorphs consequently formed. Therefore, the data substantiate the hypothesis that the mechanism of the formation of an Al(OH)3 polymorph is determined by the rate of its nucleation, which is, in turn, influenced by the rate of dissolution of the noncrystalline or poorly ordered Al-oxides initially formed.

Saponite, hectorite, and laponite have been pillared with cationic Al clusters, and special attention has been given to the solution chemistry or Al. Pillared saponite is obtained after exchange with refluxed Al solutions; while for hectorite, Al solutions treated with ammonium acetate give a pillared product with 1.8–1.9 nm spacing and thermal stability up to 873 K. In both types of solutions, the Keggin ion Al cluster is a minority species or totally absent. The typical 1.8–1.9 nm spacing is only obtained after washing. The quality of the pillared material can be judged from its thermal stability, its surface area, and the width of the d001 line before and after pillaring. The width should not exceed 0.3 nm before calcination and 0.5 nm after calcination. The latter criterion reflects the importance of the crystallinity of the parent clay for successful pillaring. Pillaring in concentrated conditions occurs by a combination of ion exchange and precipitation of Al and gives materials that exhibit poor thermal stability.

The destruction of the crystal structure of kaolinite caused by mechanical forces was investigated by X-ray diffraction, thermal analysis, infrared spectroscopy, and specific surface area determination. Attention was also directed to the change of thermal reactions of milled kaolinite. Grinding experiments for 5 min, 10 min, and 1, 2, 4, 6, and 10 h were carried out in an AGO I planetary mill. After 1 h of grinding, the crystalline order of kaolin is destroyed; but the amorphization continues in the course of prolonged grinding. Grinding for 1 h produces a favorable state for forming mullite-type crystals after heating even at 1000°C.

The Clay Minerals Society Source Clay kaolinites, Georgia KGa-1 and KGa-2, have been subjected to particle size determinations by 1) conventional sedimentation methods, 2) electron microscopy and image analysis, and 3) laser scattering using improved algorithms for the interaction of light with small particles. Particle shape, size distribution, and crystallinity vary considerably for each kaolinite. Replicate analyses of separated size fractions showed that in the <2 µm range, the sedimentation/centrifugation method of Tanner and Jackson (1947) is reproducible for different kaolinite types and that the calculated size ranges are in reasonable agreement with the size bins estimated from laser scattering. Particle sizes determined by laser scattering must be calculated using Mie theory when the dominant particle size is less than ∼5 µm. Based on this study of two well-known and structurally different kaolinites, laser scattering, with improved data reduction algorithms that include Mie theory, should be considered an internally consistent and rapid technique for clay particle sizing.

Weathering of spodumene in a lateritized pegmatite in Western Australia was studied by investigating in situ samples by electron-beam techniques. The spodumene had mostly altered to smectite. However, some non-crystalline material adjacent to smectite and intermixed with smectite was also observed. No crystallographic orientation between spodumene and smectite was observed by high resolution techniques. The spodumene dissolved to produce etch pits similar to those observed on hornblende grains. The etch pits were almost completely filled with smectite. Most of the Li in the spodumene was lost during its weathering to smectite.