The internal fabric of glauconite pellets has been studied by high-resolution transmission electron microscopy (HRTEM) for a better understanding of the glauconitization process. Typical “lamellae” which make up the glauconite pellets showed a spindle-like arrangement of layered crystallite packets. Three main mineral phases were detected: (1) well-ordered glauconite sensu stricto (d(001) = 10 Å) generally in the middle of the spindles; (2) a poorly ordered and undetermined layered-phase “X” with d(001) ~ 12.5 Å, usually sandwiching glauconite such that the interface between the two materials is very sharp; and (3) a noncrystalline or gel-like phase located between the lamellae. A 14-Å smectite-like phase was rarely observed at the periphery of some grains. The glauconite crystallites clearly showed characteristic growth features (e.g., growth steps), whereas the unknown phase X exhibited destabilization characteristics. A structural analysis of the pure glauconite indicates that this dioctahedral mica was present in the IMd (disordered), 1M, and, to a much lesser extent, 2M1 polytypic forms. HRTEM revealed no interlayering of glauconite with the other layered phases. Rather, it appeared to have formed by a layer-growth mechanism at the expense of the unknown phase X which apparently converted into non-crystalline matter before converting to glauconite. The precursor function of the interlamellae “gel” phase during the evolutive process of glauconitization is not understood.

The vibrational modes of clay minerals in aqueous suspension are uniquely accessible to Raman spectroscopy, but this potentially powerful approach has not been applied heretofore to study clays in aqueous samples. In this paper, Raman spectra in the 100- to 4000-cm−1 region were obtained for kaolinite in aqueous suspension and in air-dry samples. Contact with water perturbed the low-wavenumber Raman spectrum (100 to 1000 cm−1) significantly with respect to relative band intensities and resulted in a pH dependence of the integrated intensity in the OH-stretching region. Comparison of the Raman and infrared (IR) spectra of air-dry kaolinite samples confirmed five Raman-active OH-stretching modes at 3621, 3652, 3668, 3688, and 3696 cm−1, in contrast to four IR-active modes at 3621, 3652, 3668, and 3695 cm−1. The Raman spectra of two kaolinites of different origin showed differences in band positions and intensities. These results suggest that Raman spectroscopy may provide a useful method to study clay mineral-water interactions, colloidal behavior in clay suspensions, and variations in clay mineral structure.

The crystal structure of the kaolinite: dimethylsulfoxide (DMSO) intercalate (P1, a = 5.187(2), b = 8.964(3), c = 11.838(4) Å, α = 91.53(1)°, β = 108.59(2), γ = 89.92(1)°) has been determined using spectroscopic and X-ray and neutron powder diffraction data. Both the X-ray and neutron powder diffraction patterns were refined. Solid-state 13C, 29Si, and 27Al nuclear magnetic resonance data and previously collected infrared spectroscopic data provided a useful starting model for structural refinement. Due to the extreme overlap of reflections of this low-symmetry unit cell, the Rietveld method proved inadequate, and quasi-single crystal methods were employed. Each DMSO molecule was found to be triply hydrogen bonded above the octahedral vacancy in the gibbsitic sheet of the kaolinite layer. One methyl group is keyed into the ditrigonal hole in the tetrahedral sheet with the other S-C bond parallel to the sheet. The DMSO molecules are accommodated by significant horizontal displacement of individual kaolinite layers to achieve almost perfect overlap of the octahedral vacancy by the adjacent ditrigonal hole.

Nineteen drill core samples of lower Dogger opalinum shale from wells drilled in connection with a tunnel project near Brugg, northern Switzerland, were investigated. The shale is a well known swelling rock that has caused problems in underground construction work. Swelling pressures determined under constant volume conditions to obtain maximum values were 0.7 to 2.2 N/mm2. The samples contained 37–59% clay-size material and about 35% quartz, 7–18% carbonate minerals, and about 5% feldspar, pyrite, and organic matter. In addition to kaolinite, illite, and chlorite, the clay-size fraction also contained mixed-layer illite/smectite with about 30% swelling layers. The specific surface area of the clay fraction was 135 m2/g. The specific surface charge of the clay (6.7 × 104 esu/cm2), the ion concentration in the pore fluid of the specimen after the swelling test (10−2 mmole/cm3), the valence of the ions in the double layer of the clay particles (+1), and the half distance between the clay plates in the specimen (8–15 Å) allowed the calculation of the swelling pressure for each sample according to the Gouy double layer theory.

The mean value of the calculated swelling pressures was found to be of the same order of magnitude as the measured values, indicating that the technique can be used where cylindrical or rectangular specimens are not available for direct measurement.

The adsorption and oxidation of 3,3′,5,5′-tetramethyl benzidine (TMB) on hectorite has been investigated using X-ray powder diffraction, ultraviolet-visible spectroscopy, electron spin resonance, and infrared spectroscopy. The molecule adsorbed by cation exchange at low adsorption levels and oxidized to the monomeric radical cation (yellow). At higher adsorption levels, intercalation of TMB occurred in amounts greater than the cation-exchange capacity of the hectorite, and the π-π charge-transfer complex (blue) became much more evident. The TMB monomers appeared to lie flat in the layer silicate interlayers, whereas the molecules in the charge-transfer complexes assumed a near-vertical orientation relative to the surface. The oxidation of adsorbed TMB was probably due to diffusion of O2 to the surface, because the structural Fe3+ content of the hectorite was too low to facilitate a significant quantity of direct Fe3+-TMB electron transfer.

The kaolinization of bauxite has generally been thought to be a simple process of epigenetic resilification. A study of the karstic boehmitic bauxites in the Vlasenica region of Yugoslavia, however, shows that kaohnization took place in a rather complex manner, in which the alteration was caused by the percolation of siliceous water descending through the deposit by means of cracks, fissures, etc. The matrix of one such Vlasenica deposit was found to be more highly kaolinized than the oolitic fraction. Based on a mineralogical and geochemical examination of matrix material, the following pattern of zoned alteration was identified: kaolinitic zone-boehmite enrichment zone-original bauxite. In the kaolinitic zone, well-crystallized kaolinite, formed by the reaction of dissolved silica with boehmite, has replaced all other minerals in the matrix. This Si metasomatism was accompanied by an outward migration of Al and resulted in the formation of a transition zone in which new boehmite partly replaces both kaolinite and hematite (Al remobilization). A thermodynamic model of the process has been established on the basis of stability diagrams calculated for the mineral assemblages in the alteration zones and in the deposit as a whole.

A mineralogical investigation by X-ray powder diffraction and optical, scanning, and transmission electron microscopy of partially weathered petrified wood in the Yegua Formation (Eocene) of east-central Texas revealed that microcrystalline quartz present in the unaltered petrified wood has been gradually dissolved and replaced by disordered silica polymorphs (mainly opal-CT) as a result of weathering. This replacement suggests that the reaction sequence: opal-A → opal-CT → quartz, which has been described elsewhere to occur during diagenetic alteration of petrified wood, is apparently reversed when the petrified wood is exposed to low-energy weathering conditions. The relatively high rate of dissolution of the quartz in the petrified wood appears to be related to its small crystallite size. The silica released by the dissolution of the quartz is subsequently reprecipitated as disordered cristobalite-tridymite (opal-CT) and poorly crystalline silica (opal-A) that, in turn, probably converts to opal-CT on aging. Opal-CT is the major silica phase in the completely altered powdery material enclosing the partially weathered petrified wood. The intermediate zone between the altered and unaltered zones contains both quartz and opal-CT.

Manganiferous karst bauxites are rare on a worldwide scale. One such body, recently mined at Kincsesbánya, Hungary, has been studied by chemical, petrographic, X-ray powder diffraction, scanning electron microscopic, and energy dispersive X-ray analytical techniques. The bauxite deposits of Kinesesbánya are of Paleocene to Lower Eocene age; however, the enrichment of manganese in them was a much later, epigenetic process. Lithiophorite is the main Mn mineral in this bauxite and occurs chiefly in dusters of < 1-μm size crystallites. Well-developed crystallites, however, 5–10 μm in size, line the walls of many microfissures and voids.

The oxidation of pyritic bauxite and lignitic clays in the overlying beds apparently mobilized finely disseminated Mn and Fe. Downward-migrating acidic solutions were gradually neutralized, and Mn and Fe minerals precipitated. The manganiferous bauxite was found only along the eastern rim of heavily eroded Middle Eocene sedimentary rocks. Here, epigenetic oxidation and mobilization were optimum. Farther to the east, pyrite-rich overburden and bauxite were apparently eroded away before Fe and Mn could be mobilized.

The effects of reduction and reoxidation of octahedral Fe3+ on the exchange of structural hydrogen in nontronite were determined using tritium (3H) as a label element. The uptake of H from the surrounding solution of nontronite suspensions increased as the reduction of structural Fe3+ increased. Similarly, the loss of H from the structure increased as the reduction increased. The results are generally consistent with a reduction mechanism involving the loss of structural OH, leaving the affected Fe sites with less than six-fold coordination. The attenuation of increased negative charge on the clay layer, however, was less than predicted by such a mechanism.

During the reoxidation of reduced nontronite in suspension, about one-third of the H remaining as part of the structure following reduction was lost, whereas twice that amount of H was incorporated into the structure from the surrounding solution. A reoxidation mechanism is proposed whereby H2O from the surrounding solution is incorporated into the mineral structure followed by the elimination of a hydrogen ion, returning the Fe to six-fold coordination. This mechanism implies the reversibility of Fe reduction in nontronite.

Multivariate analysis of variance and discriminant analysis were used to establish the crystal chemistry of several Al-rich smectites. The statistical analyses were carded out on 78 samples taken from the literature which were classified on the basis of their physicochemical properties. A strong discrimination exists between beidellites and montmorillonites, ‘non-ideal’ montmorillonites and ‘ideal’ montmorillonites, and Wyoming-type and Cheto-type montmorillonites. Of the Cheto-type montmorillonites, the Tatatilla-type samples are strongly discriminated, whereas the distinction between Chambers- and Otay-types is not strong. AlIV, AlVI, Fe, Mg, and Ca are generally important discriminating variables, whereas the tetrahedral portion of the layer charge, commonly used as a discriminating factor among these minerals, is only moderately significant.