Examination of two volcanic and two precipitated allophanes by solid-state NMR, thermal analysis and X-ray powder diffraction shows three of the samples to contain structural features similar to both tubular imogolite and defect layer-lattice aluminosilicates such as kaolinite. The fourth allophane, a precipitated sample from New Zealand, had no imogolite-like features and contained tetrahedral as well as octahedral aluminum. The imogolite-like units in allophane are less stable thermally than tubular imogolite. The NMR spectra and their changes on heating can be accounted for by a structural model in which a two-sheet, kaolinite-like structure containing defects (holes in the tetrahedral sheet) is curved into a sphere in which imogolite-like orthosilicate units are anchored into the octahedral sheet and fit into the tetrahedral defects. Computer simulation shows that the model is crystallographically sound, and accounts for all the known facts, including the spherical morphology, the solid-state NMR spectra and the thermal dehydroxylation behavior of all except the New Zealand allophane, which is of a different structural type.

The Bingham yield stress for suspensions of illite-iron oxide complexes is examined as a function of pH and iron oxide content. Addition of iron oxides to illite increased the yield stress over a pH range of 3 to 10. With increasing pH the yield stress decreased for the complexes with iron oxides of 2 and 5% while the complexes with iron oxides of 7, 10, and 20% exhibited the maximum yield stresses at pH values from 6 to 8. The iron oxides which are not associated with the illite enhanced the yield stress more than the iron oxides precipitated on the illite surfaces. The yield stress for the complexes was correlated with their zeta potential, and the higher yield stress is considered due to smaller interparticle repulsion.

The extent of illite/smectite (I/S) reactions is linked with quantitative measurements of shale fabric in a suite of samples from a lower Frio Formation well. Greater illitization of the I/S clays is found in laminated shales that possess a larger pore surface area/pore volume (SA/V) of 3.21 × 106 cm−1 than the adjacent massive shale lithofacies with a SA/V of 1.97 × 106 cm−1. Mean pore diameter in both shale lithologies is 0.0145 micrometers, though in the laminated shale distributions are skewed towards more smaller-sized pores. While no direct permeability measurements were made, estimates of permeability that are based on simple physical models using SA/V suggest that lower permeabilities are associated with laminated shales. The trend of greater illitization at higher SA/V values is contrary to expectations that reaction extent is enhanced by greater permeabilities, such as created by silt laminations in shale. The limitations of estimated permeabilities emphasize that porosimetry measurements of shale fabric are useful for estimating the access of material to all reaction sites, and do not just describe the effect of a few large pores that dominate permeability. Greater reaction extent in the laminated shales is associated with the accessibility of fluids to more pore space than in the massive shales.

The heat capacities of kaolinite (7 to 380 K) and of dimethyl sulfoxide (DMSO) intercalated kaolinite (20 to 310 K) were measured by adiabatically shielded calorimetry. The third law entropy of kaolinite, S298, is 200.9 ± 0.5 J·mol−1K−1.

The “melting point” of the DMSO in the intercalate, 288.0 ± 0.2 K, is 3.7 K lower than that of pure DMSO, 291.67 K. The heat capacity of DMSO in the intercalate above 290 K is approximately 5.2 J·mol−1·K−1 smaller than that of pure liquid DMSO at the same temperature.

The adsorption of citrate, at 10 4−10−3 M initial concentration, by pseudoboehmite suspended in 0.02 M NaC1O4 was investigated at varying pH. Citrate shows a strong affinity for the pseudoboehmite surface, as seen in the adsorption isotherm at pH 6. Adsorption envelopes of adsorbed citrate vs. pH for a given initial citrate concentration are characteristic for the adsorption of a polyprotic acid by a variable-charge mineral. The envelope data were fit well by the Constant Capacitance Model assuming a ligand-exchange adsorption mechanism, three monodentate surface species of citrate, and a reactive surface OH density of 0.4 mol kg−1. Aqueous speciation calculations suggest that solubility equilibrium with pseudoboehmite was attained at pH > 9 and that particulate or polymeric Al may have existed at 6 < pH < 9. Dissolved Al appeared to reduce the adsorption of citrate at pH < 5.5 via solution complexation reactions.

The effect of electrolyte concentration, exchangeable sodium percentage (ESP), sodium adsorption ratio (SAR), and pH on the flocculation-dispersion behavior of 50/50 mixtures of reference illite with reference kaolinite or reference montmorillonite was investigated. The clays were Na- or Ca-saturated and freeze-dried before use. Critical coagulation concentrations (CCCs) were investigated in the range of pH 5.9 to 9.6, percent Na-clay 0, 10, 20, 40, 60, 80, and 100 and SAR 0, 10, 20, 40, 60, 80, and ∞. CCC values increased with increasing ESP, increasing SAR, and increasing pH. The pH dependence of illite/kaolinite was greater than that of illite/montmorillonite especially at high ESP and SAR. The presence of illite did not play a dominant role in determining flocculation-dispersion behavior of the 50/50 clay mixtures. The CCCs of illite/kaolinite resembled reference illite more than reference kaolinite for SAR 0 to SAR 60. Illite/montmorillonite exhibited CCCs more similar to reference illite than reference montmorillonite at SAR 40 and SAR 60. At the agriculturally desirable ESP and SAR values of 0 to 15, all the 2:1 clays and 2:1 clay mixtures demonstrated similar CCC values.

Iron phyllosilicates with 1:1 and 2:1 layer structures were prepared from silicic acid, ferrous sulfate and sodium hydroxide. Hydrothermal treatment at 100–200°C of a reaction mixture with an initial Fe/Si ratio of 1.5 gave the 2:1 iron phyllosilicate, whereas a Fe/Si ratio of 2.25 gave the 1:1 phyllosilicate. The 57Fe Mössbauer spectroscopy showed that 60% of the iron in the 1:1 phyllosilicate is ferrous, versus only 3% in the 2:1 phyllosilicate. The values of quadrupole coupling showed that the iron-oxygen tetrahedra and octahedra in the 2:1 phyllosilicate were more deformed than those in the 1:1 phyllosilicate.

Three gels of illitic composition having different octahedral substitutions were hydrothermally treated in distilled water at 300°C and 500 bars for 7 to 90 days. The gel of the composition K0.7Al2.0(Si3.3Al0.7)O10(OH)2, having no octahedral substitutions, yielded poorly crystalline and randomly interstratified illite/smectite (I/S) having possibly 30% or more expandability. These I/S particles occurred predominantly as foliated or compact lamellar aggregates having morphological features characteristic of common smectite. Laths having a morphology similar to that of diagenetic “fibrous illites” were also found in small amounts after the gel had been aged for 35 days. Their chemical composition was similar to that of the foliated aggregates of I/S in the same run.

Illitic gel having the composition K0.7(Al1.7Fe3+0.3)(Si3.3Al0.7)O10(OH)2 having octahedral Fe3+ substitutions yielded more and better crystalline I/S. The reaction products of the 7-35-day runs consisted mainly of randomly interstratified I/S having an expandability of 90 to 65%. The I/S particles occurred as foliated or compact lamellar aggregates having a smectite-like morphology, as described above. The Fe3+-bearing gel yielded, after 90 days of ageing, an Rl-ordered I/S having 25% expandability and a morphology of ribbons and hexagonal platelets.

Illitic gel of composition K0.8Al1.6Mg0.4)(Si3.6Al0.4)O10(OH)2 having octahedral Mg2+ substitutions produced no illite even after 90 days of ageing, but a pure smectite in the form of foliated aggregates.

Pierre shale samples from a thin stratigraphic zone within the contact aureole of the lamprophyric Waisen dike record changes due to thermal effects that are not influenced by detrital differences. Analyses of fixed-NH4, mineralogy, and Rock-Eval pyrolysis indicators of organic matter maturity provide new insights on the fixation process. Fixed-NH4 increases with the quantity of authigenic illite formed from illite/smectite, but the maximum fixation per unit of illite formed occurs within the “oil window” where thermal breakdown of organic matter is rapid. Extrapolation of these results to the burial diagenetic regime supports the potential use of fixed-NH4 as an indicator of organic maturity and hydrocarbon migration pathways.

The chemical compositions of chlorite-smectite mixed-layered minerals (C/S) from the Ohyu caldera (Inoue, 1985) are analyzed using M+-4Si-3R2+ diagrams. The assumed original saponite has the following composition: Si3.54Al0.46O10Al0.173Fe2+1.385Mg1.295Mn0.02(OH)2M+0.56. Random C/S minerals (100 to 80% expandable layers) are interpreted as an interstratification of the starting 2:1 smectite layer with a A1XR2+3−x interlayer. The 2:1 smectite layer charge remains constant but Ca, Na, K cations are replaced by a Al-R2+ complex ion. The brucitic layer (produced by the polymerization of the complex ions) and the 2:1 smectite layer form a 14 Å non-expandable phase having a composition different from a true chlorite.

The true chlorite layers first appear in the ordered (corrensite) phase composed of a high charge saponite: Si3.35A10.65O10R2+3(OH)2M+0.65 and an octahedral vacancy-free chlorite Si2.90A11.10O10Al1.10R2+4.90(OH)8. The recrystallization of the original trioctahedral smectite into a high-charge saponite decreases the b-dimension difference with the chlorite component.

From these data, it is suggested that the trioctahedral smectite-to-chlorite conversion is controlled by three reactions: 1. fixation and polymerization of Al-R2+ complex ions in the interlayer region of the original smectite producing a 14 Å non-expandable phase (the interlayering of this phase with the original smectite gives the randomly interstratified C/S mineral. 2. dissolution of these random mixed-layered minerals and precipitation of corrensite. 3. dissolution of corrensite and growth of Fe-rich chlorite.

One-aminonaphthalene is sorbed onto the Na-saturated smectite clays, montmorillonite and hectorite, by cation exchange. In the presence of Fe3+, either in the clay structure or on the clay surface, sorption is followed by the formation of a blue-colored complex, with the continuous disappearance of aminonaphthalene from solution and the clay surface. The rate of aminonaphthalene disappearance decreases as pH increases. With time, four major products that appear to be structural isomers of N(4-aminonaphthyl)-l-naphthylamine are produced. A simplified model of this transformation is suggested to be the oxidation by Fe3+ of sorbed aminonaphthalene forming a radical cation-clay complex. A subsequent reaction between the radical-cation and a neutral aminonaphthalene molecule takes place, with the products being strongly sorbed to the clay surface.

The nature of the siloxane surface in smectites was investigated by measuring the adsorption of aromatic hydrocarbons from water by organo-clays. The organo-clays were prepared by replacing the hydrophilic, inorganic exchange cations of a series of smectites with the small, hydrophobic organic cation, trimethylphenylammonium (TMPA). Smectites with a range in charge densities were used that resulted in different TMPA contents in the organo-clays. Adsorption isotherms of benzene, alkylbenzenes, and naphthalene from water by the TMPA-smectites indicated that sorption was inversely related to TMPA content. The Langmuir form of the isotherms suggests that the aromatic compounds adsorb to the clay surface. Possible adsorptive sites in TMPA-smectites are limited to the TMPA cations and the siloxane oxygen surfaces. Because sorption increased as layer charge and TMPA content decreased, the organic compounds must adsorb to the siloxane surfaces.

Calculations based on an adsorbed compound monolayer, which was estimated by fitting adsorption data to the Langmuir equation, and the N2 specific surface area of each TMPA-clay, indicate that the surface area occupied by each adsorbed molecule increases as the planar area of the molecule increases. This strongly indicates that the planar surfaces of the compounds adsorb directly to the clay surface. Apparently, the TMPA cations function to keep the smectite interlayers open. Interactions between the phenyl groups of TMPA cations on opposing interlayer clay surfaces may act to increase the size of the adsorptive regions. These results show that the siloxane surfaces of smectites can effectively adsorb aromatic hydrocarbons from water if the hydrophilic, inorganic exchange cations are replaced with small, hydrophobic organic cations. The strong adsorption of hydrophobic organic molecules from water demonstrates the hydrophobicity of the siloxane surfaces in smectites.

Recent data in the biological literature suggest that the natural zeolite erionite may be more tumorigenic than asbestos minerals. Because of its potential biological importance, a technique has been developed to facilitate detection of erionite in tuffaceous rocks to a lower limit of detection (LLD) between 100 and 500 ppm. The method involves the use of automated X-ray powder diffraction instrumentation with long count times, as much as 360 s/step. The presence of interfering phases, such as smectite or clinoptilolite, raises the LLD. Ethylene glycol solvation of smectite improves the LLD, and profile fitting with clinoptilolite-bearing mixtures improves quantification. Application of these methods to tuffs from central Turkey allowed improved detection and more accurate quantification compared with previous scanning electron microscope examinations. Use of these methods with tuffs from Yucca Mountain, Nevada, the potential site for the nation's first high-level radioactive waste repository, showed that erionite occurs sporadically. Erionite is found only in the altered zone directly above the lower vitrophyre of the Topopah Spring Member. This altered zone is anomalous in that is contains a variety of zeolites that are either rare or absent in other Yucca Mountain tuffs. It appears that erionite is restricted to fractures and must have formed under unusual and variable conditions in the altered zone.