Naturally occurring ammonium illites have been discovered in black shales surrounding a stratiform base metal deposit in the DeLong Mountains, northern Alaska. Infrared spectra of the samples exhibit pronounced absorption at 1430 cm−1, the resonant-banding frequency for NH4+ coordinated in the illite interlayer. X-ray powder diffraction characteristics of the ammonium illites include an expanded d(001) spacing, with values as large as 10.16 Å, and ratios for I001/I003 and I002/I005 of about 2. Infrared analyses of physical mixtures of NH4Cl with a standard illite, and comparisons with synthetic ammonium micas indicate significant substitution (>50%) of NH4+ for K+ in the illite interlayer position. Nitrogen determinations on two ammonium illites after removal of carbonaceous matter gave values of 1.48 wt. % NH4+ and 1.44 wt. % NH4+. A survey of more than 150 different shale horizons indicates that the NH4+ content of the illites increases in proximity to the stratiform base metal mineralization.

High-Mg chlorites from Vermont and Quebec and high-Fe chlorites from Michigan and New Mexico were equilibrated at room temperature in the near-neutral pH range. Gibbsite, kaolinite, and hematite of known stability were added to the samples to control unmeasurable variables at calculable levels. Equilibrium solution compositions were obtained from undersaturation and from supersaturation. Other indicators of equilibrium were good agreement between successive analyses over a long period of time, between duplicate samples, between independent systems, and between independent measures of equilibrium. All four chlorites were stable relative to brucite and, with a few exceptions, relative to talc under the conditions of study. When in equilibrium with gibbsite, the pH − ½Mg2+ value of the chlorites ranged from 6.3 to 6.5, at a pH4SiO4 value of 4.0. These values are in good agreement with prior estimates of chlorite stability. The calculated standard free energy of formation of the chlorites is dependent upon solution Fe2+ calculated from the sample Eh and assumed equilibrium with hematite, with the assumption that the Fe2+-Fe3+ couple is at the same Eh as the sample.

A layered double hydroxide with a chemical composition [Al2Li(OH)6]+X− · nH2O, where X− is an interlayer anion, has been synthesized hydrothermally at 130°C from aluminum-tri-(sec-butoxide) and lithium carbonate. Electron micrographs showed the product to have a platy morphology with distinct hexagonal symmetry, which has been corroborated by selected area electron diffraction patterns corresponding to a projection of the structure on its (001) plane. Evidence for a superlattice with a = 5.32 Å was obtained, indicating cation ordering among octahedral sites. X-ray powder diffraction data also can be interpreted by reference to a hexagonal supercell with dimensions a = 5.32 Å and c = 15.24 Å. The arrangement of the octahedral sites appears to be that of gibbsite, but with the vacancies filled with lithium cations. Anions must be present between the sheets to balance the charge. A complete assignment of the observed infrared lattice vibrations can be made for the anion [Al2LiO6] with the ideal D3d symmetry for motions within one octahedral sheet. The results show that [Al2Li(OH)6]+X− · nH2O is a hydrotalcite-like compound with the octahedral cations largely ordered. The general formula for hydrotalcite-like compounds, [M2+1−xM3+x(OH)2]x+Xm−x/m · nH2O, should be extended to include the monovalent lithium cation.

Bis-ethyl 2-hexylphosphoric acid (di-2 EHPA) dissolved in decane is chemisorbed on kaolinite and montmorillonite dispersed in an acidic aqueous solution. The adsorption results in the formation of complexes with the surface cations of the clays. The adsorption isotherms are of the Langmuir type and reveal a limiting value of adsorption on H+-kaolinite of 12.2 mg/g, comparable to that measured in the absence of water. For H+-montmorillonite, however, the limiting value in the presence of acid is somewhat less (20.6 mg/g vs. 23.8 mg/g). Di-2 EHPA does not react with the magnesium cations available at the surface. The isotherm is “stepped” and suggests the presence of adsorption sites with distinctly differentiated energies. The sites of di-2 EHPA adsorption can be masked by treating the two clay minerals with polyphosphate anions. Thus, with pyro- and tripolyphosphate anions, di-2 EHPA uptake in acidic medium is very low. Adsorbed di-2 EHPA can be recovered by treating the clays with fluoride, hydroxyl, and dihydrogenphosphate anions. Dihydrogenphosphate anions lead, however, to a state of equilibrium between the organic and inorganic phosphate anions adsorbed.

The Upper Pliocene sediments near Lebrija in southern Spain contain commercial deposits of palygorskite and sepiolite. These sediments of continental origin consist chiefly of carbonate, marl, and clay resting on marine Pliocene quartzose sand. The lowest unit, the “Marly-Calcareous Bed,” consists of sepiolite-rich marl associated with concretions and irregular layers of chert, <0.5 m thick, and local diatomite layers, as well as limestone, sandy limestone, marl, and clayey sandstones. This unit has a maximum thickness of 30 m and contains three clay-mineral suites as follows: (1) bottom—sepiolite ± palygorskite; (2) center—sepiolite and palygorskite ± illite; (3) top—palygorskite and illite, ± sepiolite and smectite. Sepiolite decreases and palygorskite and illite increase toward the top, reflecting the composition of detrital material supplied to the basin. Beds 0.5–1 m thick locally and containing 50 to 60% sepiolite have been called “Tierra del Vino” (wine earth) because the material formerly was used to clarify and purify wine. The sepiolite-rich beds are as much as 15 m thick in the eastern part of the area. The upper unit is called the “Palygorskite Bed” because certain layers, 0.3 to 3 m thick, contain 35 to 75% palygorskite. The palygorskite-rich layers are interbedded with limestone and marl, and the entire unit is 15 m thick. The total resource of palygorskite is estimated at about 9 million tonnes.

The sediments are believed to have been deposited in a brackish, lacustrine environment. Originally, tectonic stability and an arid climate favored the formation of sepiolite at about pH 8. Later, after significant weathering of the source rocks, detrital illite was transformed to palygorskite in the Mg- and Si-rich waters. Here, palygorskite was also precipitated directly.

Electron spin resonance (ESR) analysis of Cu2+-hectorite suspensions provides evidence for the surface-induced hydrolysis of Cu(H2O)62+ at low pH and surface-inhibited hydrolysis (or precipitation) at high pH. Dehydration of the hectorite by heating to 110°C appears to promote hydrolysis in high pH clays further. Heating to even higher temperatures removes ligand water from Cu2+, allowing the metal ion to coordinate with silicate oxygen atoms. The planar Cu(H2O)42+ ion predominates in the interlamellar regions of hectorite that has been air dried or heated to temperatures of 110°C or lower, but more extreme thermal treatment changes the apparent orientation of the Cu2+-ligand axes as some or all of the four water ligands are removed, A loss in ESR signal intensity upon heating Cu2+-hectorite above 110°C is evidence for lowered symmetry of the dehydrated, surface-coordinated Cu2+ ion.

Ferruginous clay partings in limestones of the marine, largely evaporitic, Upper Triassic Mohila Formation (Makhtesh Ramon, Israel) contain hexagonal plates and cube-like bodies up to one millimeter across. Analyses by electron microscopy, infrared and Mössbauer spectroscopy, and X-ray powder diffraction indicate that the matrix contains Fe-rich anhedral kaolinite, up to 100 μm in size; the hexagonal plates are composed of euhedral, Fe-free kaolinite covered with well-developed acicular goethite and platy hematite (0.5 to 2 μm in size), and the cubes consist of fine-grained goethite with minor amounts of kaolinite. The anhedral kaolinite appears to be detrital, the hexagonal plates to be authigenic, and the cubes to be pseudomorphs after pyrite. Oxidation appears to have altered Fe-rich kaolinite and pyrite to Fe-free kaolinite, goethite, and hematite and was accompanied by recrystallization and pseudomorphic replacement. The alteration process was slow and was probably induced by a small increase in pH and in the Al/Fe ratio, resulting from oxidation of reduced components (pyrite, ferrous carbonate, organic matter) in a semiclosed, sediment-mud system. Overlying kaolinitic flint clay deposits may be the final product of a similar process.

The broad charge heterogeneity typical of nearly all smectites is not necessarily characteristic of vermiculites. In addition to vermiculites with pronounced heterogeneity, minerals with no or only limited charge heterogeneities are known. Layer charge and charge heterogeneity of 25 vermiculites were determined by alkylammonium ion exchange. The comparison of experimental basal spacings with dL/n-plots provided a simple determination of the average charge density. The spacings of high-charged vermiculites (≥0.8 eq/(Si,Al)4O10) with paraffin-type interlayers follow a straight line in the dL/n-plots. Lower-charged vermiculites were recognized by stepwise increasing spacings due to mono-, two-, or three-layer chain packings. Charge heterogeneity produced a superposition of the dL/n-curves for different charges, and the basal reflections of some of the alkylammonium derivatives became nonintegral.

The hydrolysis and decomposition of M-hectorite (M being Na, Li, Mg, or Ca) in dilute solutions of M-chlorides were studied by recording the changes in electrical conductivity (EC) of the clay suspensions with time, and by chemical analyses of the interclay solutions and resulting solid phases. The rate of hydrolysis of the hectorites in suspension, as evaluated by the change of EC with time, was found to decrease with increase in salt concentration (to zero for Na-hectorite in NaCl concentration of 47 meq/liter), and to decrease with increase in the valency of the adsorbed cation (the rate of hydrolysis of Ca-hectorite was one sixth of that of Na-hectorite). The rate of Na-hectorite hydrolysis was determined by the concentration of protons at the clay surface as calculated from the diffuse double layer theory.

Conversely, in suspensions of Al-hectorite saturated with Na, the hydrolysis rates were not dependent on the electrolyte concentrations. This result can be explained by assuming that the hydroxy-Al polymers at the clay surface determine the proton concentration at the clay surface. Hectorites saturated with structural cations (such as Mg and Li) are chemically more stable than those saturated with Na and Ca. The presence of Li and Mg at the clay surface slowed down the diffusion release of these octahedral ions to the clay surface, compared with Na and Ca hectorite, respectively.