Mineralogical and chemical analyses of fine clay fractions from in and around Lake Abert, Lake County, Oregon, show that the pyroclastic rocks supplying detritus to the lake weather to a suite of layer silicate clay minerals varying from high-charge dioctahedral montmorillonite to montmorillonite/intergrade smectite-chlorite interstratifications. In the lake these clays extract K, Mg, and Si to form authigenic interstratified illite and a trioctahedral, Mg-rich mineral resembling stevensite in composition. Both the neoformed interstratifications contribute little unambiguously to X-ray powder diffraction patterns, which are dominated by the reflections of detrital clays. From limited data it appears that the illite occurs below 0.8 m depth in sediments of a possibly somewhat fresher (brackish) lake and the trioctahedral interstratification between 0.4 and 0.2 m depth in sediments of a lake of about the same size and salinity (about 30–90 g/kg) as that of the present lake.

To test the hypothesis that berthierine in oolitic ironstones formed by diagenetic transformation of detrital kaolinite, laboratory experiments simulating the early diagenetic conditions were conducted. Representative sets of the initial sediment were prepared in distilled water and artificial seawater suspensions by mixing 4–13 g/liter kaolinite with Fe(OH)3 precipitated from 0.1-0.3 M FeCl3 solutions. Na2S2O4 was added to the suspensions as a reducing agent, and inert N2 atmospheres were used to maintain the required Eh between +100 and -400 mV. The pH of the suspensions was controlled between 8 and 5 with dilute HCl. Within 300 days, the iron content of the bulk kaolinite in the seawater suspensions progressively increased from 0.18 to 2.44% at pH = 7 and Eh between -250 and -350 mV. Energy dispersive X-ray analyses of individual clay platelets in the final products showed progressive, temporal increase in Fe, and concomitant decrease in Al and Si. X-ray powder diffractometry revealed small d(001)-d(002) shifts, marked intensity reversals o. (001) an. (002) reflections, and the development of additional characteristic berthierine reflections with time. These data suggest progressive transformation of kaolinite to berthierine. Microprobe analyses of natural berthierine in oolitic ironstones also showed parallel patterns, which substantiate such progressive transformation from the margin toward the core of the ooids. The transformation did not take place in distilled water. The addition of Mg2+ to the distilled water suspensions, however, promoted the transformation.

A 14-Å mineral coexisting with kaolin minerals, mica, and gibbsite in a Korean Ultisol and showing X-ray powder diffraction features of “chloritized” vermiculite was studied by a combination of methods. The 14-Å mineral collapsed on saturation with K+ after extraction with hot 1/3 M sodium citrate, but the Si/Al ratio of the extracted material was close to 1.0 and kaolin minerals dissolved, as indicated by difference infrared spectroscopy. The 14-Å mineral was also collapsed by heating at or above 350°C. The difference infrared spectra and the X-ray powder diffraction patterns indicated that two forms of kaolin mineral are present that differ in thermal stability; one decomposed by heating at or below 375°C and the other by heating above 375°C. The former kaolin mineral is probably associated with vermiculite and the latter is present as a discrete form. The 14-Å mineral was inferred to be an intergradient vermiculite-kaolin mineral, in which most vermiculite layers each partially transform into double kaolin layers, and to represent an intermediate phase during the transformation of 2:1 to 1:1 layer silicates in acid soils.

A method of clay mineral sample preparation for electron microprobe analysis has been developed in which a film of clay plus 10–12 wt. % colloidal graphite is deposited on a porous ceramic disc using a specially designed suction device. Correction procedures are used to obtain quantitative elemental analyses representing the average chemical composition of the prepared sample. A statistical technique is employed to estimate the most likely proportions of clay minerals representing the known composition. Chemical compositions of clay minerals are presented in terms of five coordinates (“Si,” “Al,” “Mg,” “K,” and “Fe”). Using literature data, the chemical compositions of 13 different clay mineral groupings were defined statistically by their multivariate means and variance-covariance matrices. A correlation parameter, χ2, was calculated to compare the chemical composition of a sample with that of any mixture of the defined clay mineral groupings, the minimum χ2 indicating the best-fit mixture.

From chemical analyses of artificial mixtures only approximate clay mineral proportions could be determined when the various clay mineral groupings had been defined statistically from literature analyses. The best results were obtained when the actual compositions of the end-members forming the artificial mixtures replaced the statistical definitions. Tests of the estimation procedure on clay mineral mixtures for which chemical compositions and corresponding clay mineral proportions were found in the literature, indicate that the technique has appreciable merit.

A vermiculite-aniline intercalate with a basal spacing of 14.78 Å was investigated by one- and two-dimensional X-ray diffraction methods. The intercalate, prepared by ion exchange between Na-saturated vermiculite from Llano, Texas, and a 1% aniline hydrochloride solution, contains only one aniline cation per single layer cell. A reduced effective cell-charge is believed to be responsible for this. Structure factor calculations were made in space group C2/c and with unit cell dimensions of a = 5.33, b = 9.18, c = 29.78 Å, and β = 97.0°. However, extra reflections in the a*b* plane, which are similar to those in a vermiculite-benzidine intercalate, showed that after aniline intercalation the true unit cell became primitive. The aniline cations are distributed statistically over equivalent crystallographic sites in the interlayer space. The organic molecules are orientated with their planes vertical and their nitrogen atoms over the projected centers of the ditrigonal cavities into which they key. The aniline cations form ordered arrays upon the silicate layers by packing into rows. Perpendicular to [010], populated and vacant rows alternate. Along populated rows aromatic ring planes are alternately parallel and perpendicular to [010]. With small adjustments this model is similar to that of benzidine-vermiculite.

The activities of thermodynamic components of clay minerals corresponding in composition to pyrophyllite, muscovite, paragonite, and margarite were computed from chemical analyses reported in the literature assuming ideal mixing of atoms on homological sites in the minerals. These activities were then used to generate stability fields for smectites, illites, and mixed-layer clays on logarithmic activity diagrams representing equilibrium among minerals and aqueous solutions at 25°C and 1 bar. Comparative analysis indicates that the approach affords close approximation of both mineral and water compositions in geologic systems.

The electrostatic lattice energy of polar phyllosilicates can be calculated when a correction term Ecorr equal to -2πμ2/V is taken into account, where μ is the dipole moment of a slice d(001) and V is the molecular volume. The interlayer bonding energy can be obtained by Giese's method, if the energy of separation of the layers over a distance A is plotted againts 1/[d(001) + Δ]. Thus, for a polar chlorite the interlayer bonding energy is 69.8 kJ/unit cell. Using the Madelung method, the interlayer bonding energy of slices of kaolinite having a thickness of d(001) is 84 kJ/mole. Similarly the interlayer bonding energy of slices having a thickness d(020) is 2520 kJ/mole. To avoid the instability of the outer slices of the crystal caused by the cooperating dipole moments of all slices, the hypothesis was made that the atoms have in reality reduced charges and that the charge reduction is such that the dipole moment becomes zero. The adopted charges lower the interlayer bonding energy to as little as 14 kJ/mole. The interlayer interaction of slices of fluorkaolinite with thickness d(001) is repulsive. Crystals of a polar chlorite must be bounded either by incomplete hydroxide layers or by layers onto which charge-compensating anions are adsorbed. Polarity makes cleavage in chlorite more difficult.

Electron spin resonance (ESR) spectra of Cu2+-hexadecylpyridinium (HDP) montmorillonites were investigated as a function of HDP+ content and the hydration state of Cu2+ at relative humidities of p/p0 = 0.52-8 × 10-7 at 298°K. The symmetry of the Cu2+ ESR spectra and the intensity of the ESR signal increased upon dehydration of the complex. The HDP+ cation caused an increase in the hydration state of Cu2+ at a given p/p0 and an increase in the covalency of the Cu-O bond.