Scanning, transmission, and analytical electron microscopy studies of shales from the Salton Sea geothermal field revealed that phyllosilicates progress through zones of illite-muscovite (115°−220°C), chlorite (220°−310°C), and biotite (310°C). These phyllosilicates occur principally as discrete, euhedral to subhedral crystals which partly fill pore space. The structural and chemical heterogeneity, which is typical of phyllosilicates in shales subject to diagenesis, is generally absent. Textures and microstructures indicate that the mineral progression involves dissolution of detrital phases, mass transport through interconnecting pore space, and direct crystallization of phyllosilicates from solution.

Phyllosilicate stability relations indicate that either increase in temperature or changing ion concentrations in solutions with depth are capable of explaining the observed mineral zoning. Textural and compositional data suggest that the observed mineral assemblages and the interstitial fluids approach equilibrium relative to the original detrital suites. The alteration process may have occurred in a single, short-lived, episodic hydrothermal event in which the original detrital phases (smectite, etc.) reacted directly to precipitate illite, chlorite, or biotite at different temperatures (depths) without producing intermediate phases.

The thermal decomposition of a fibrous talc was studied by transmission electron microscopy (TEM) and selected-area electron diffraction (SAD). Small changes in the lengths of a and b unit-cell parameters were noticeable at 500°C, but the talc laths did not change morphologically until 800°C. At this temperature striations began to appear in the TEM image, and the talc SAD reflections began to develop faint satellite streaks. At 900°C the striations appeared to be crystallites, and reflections of orthorhombic enstatite were noted. Both TEM and SAD evidence showed that the enstatite crystallites were formed in three orientations corresponding to the three pseudohexagonal a axes of the talc. Thus, triple superposition of the electron diffraction pattern at the three equivalent angles explains the high symmetry star-shaped pattern. At 1000° to 1100°C the enstatite crystallites were shorter and thicker, and the streaks in the SAD pattern were nearly absent. Above 1200°C only one orientation of the enstatite crystallites was found. Noncrystalline regions were also detected at 900°C and became progressively scarce at 1000° and 1100°C. They were not detected at 1200°C. At 1300°C cristobalite was detected in some SAD patterns. The crystallographic axes and unit-cell parameters of the talc and enstatite were also topotactically related as follows: at (5.3 Å)//ce (5.2 Å); bt (9.16 Å)//be (8.8 Å); d(001)t (18.84 Å)//ae (18.2 Å). These results are compatible with an inhomogeneous decomposition mechanism as proposed by earlier workers.

Six standard polytypes of micas exist that have c-periodicities between 1 and 6 layers; these can be subdivided into groups A and B according to whether the octahedral cations are in the same set of positions in every layer or alternate regularly between I and II possible sets of positions (alternate slant directions), respectively. Correspondingly, 12 standard polytypes exist for 1:1 layers of the serpentine-type structures, which are divisible into four groups A-D. Groups A and B differ as in the micas, as do groups C and D. Groups A and B have ±a/3 interlayer shifts, whereas groups C and D have zero or ±b/3 interlayer shifts. Six structural types of semi-randomly or regularly stacked 1-layer chlorites exist that differ in the slant of the interlayer sheet (I or II) and its position (a or b) relative to 6-member rings in adjacent 2:1 layers.

Criteria have been established that permit the X-ray diffraction identification of the above-mentioned groups as well as the individual polytypes within each group. These criteria involve inspection of the strong X-ray diffraction reflections of index k = 3n for identification of the groups and of the generally weaker k ≠ 3n reflections for identification of the polytypes (assuming indexing on orthohexagonal axes throughout for convenience). In all hydrous phyllosilicates the octahedral cations and anions repeat at intervals of b/3 and thus contribute strongly to X-ray diffraction reflections of index k = 3n. The intensities of these reflections identify the two mica groups, the four serpentine-type groups, and the six chlorite groups. The periodicities of these reflections along Z* is that between identical octahedral sheets. The basal oxygen atoms do not repeat at intervals of b/3 and are a primary contributor to the intensities of k ≠ 3n reflections. The period along Z* for these reflections is that between identical basal oxygen planes, and the periodicity plus the symmetry identify the individual trioctahedral polytypes. For dioctahedral polytypes of the kaolin-group minerals and chlorites, the position of the vacant octahedral site must be considered also.

These general principles can be illustrated especially well by single-crystal precession photographs and extrapolated to powder photographs.

The rate of dissolution of akaganéite in HCl increased with time over the bulk of the reaction leading to a sigmoid dissolution vs. time curve. The bulk of the dissolution of lepidocrocite could be described by the cube root law. Transmission electron microscopy examination of partly dissolved crystals of akaganéite showed that acid attack proceeded mainly along the [001] direction. Initially, the tapered ends of the crystals became squared, and as dissolution continued the lengths of the crystals decreased steadily. At the same time, the crystals were gradually hollowed out. Acid attack was most pronounced at the edges of the crystals of lepidocrocite and appeared to involve a disruption of the hydrogen bonds that link the sheets of octahedra making up the structure. Defects also acted as sites for preferential acid attack. Dissolution of multi-domainic crystals involved preferential attack along the domain boundaries, as well as at the edges of the crystals. Single-domain crystals were well developed, but appeared to contain internal imperfections, which promoted the formation of holes on the otherwise unreactive (010) faces.

The stacking order of a 14.30-Å Mg-vermiculite from Santa-Olalla, Spain, has been determined from Weissenberg photographs. The results prove that the Mg-vermiculite structure is not a 2-layer polytype structure, but a semi-ordered one. Because the structure is semi-ordered, its resolution needed a dual approach: (1) a direct approach using an electron density projection along the y axis in conjunction with a one-dimensional electron-density projection onto the z axis; and (2) an indirect approach in which the observed intensities along the (0,k) and (1,k) reciprocal rods were compared to the calculated intensities given by model defect structures. The semi-ordered structure of the Mg-vermiculite results from ±b/3 shifts in the stacking of the silicate layers. The shifts are randomly either along +b or -b.

Gabbroic saprolite at Mont Mégantic, Quebec, was studied in detail mineralogically to gain a better understanding of the origin of ferruginous smectite reported previously from these rocks. The parent rock is a ferrogabbro composed of plagioclase, augite, calc-alkalic amphiboles, biotite, olivine, magnetite, ilmenite, and apatite. Extensive weathering has decomposed most of the mafic minerals and magnetite to goethite, lepidocrocite, and iron-rich clay minerals, which occur in numerous microcracks distributed irregularly in the outer shells of boulders and in cracks and fissures in the bedrock. Some of the felsic minerals have altered to kaolinite. The secondary minerals and the more resistant primary minerals, such as plagioclase, ilmenite, and apatite, have subsequently moved to the lower part of the saprolite. The major ferruginous clay minerals present are smectite and vermiculite, which are compositionally similar, except that the smectite is slightly richer in SiO2 and MgO and poorer in Fe2O3 than the vermiculite.

To establish a structural formula for the ferruginous smectite, the oxidation state of Fe in a sample treated with dithionite-citrate-bicarbonate was examined by Mössbauer spectroscopy. All structural iron was found to be ferric. The calculated structural formula of a Na-saturated sample is:

$$N{a_{0.61}}\left( {M{g_{1.39}} + Fe_{0.85}^{3 + }A{l_{0.17}}M{n_{0.03}}} \right)\left( {S{i_{3.49}}A{l_{0.51}}} \right){O_{10}}{\left( {OH} \right)_2},$$

Hollow spherical particles of aluminosilicate having diameters of 80 to 100 Å and high electric charge were synthesized by heating solutions containing Si and Al concentrations of about 2 mM (Si/Al molar ratio = 1.0–1.2; pH = 9.0) at 95°–100°C for 7 days. Electron microscopy, X-ray powder diffraction, and infrared spectroscopy suggested that the walls of the spherical particles consisted of monolayer aluminosilicate, most probably having a 1:1 layer structure. Chemical analysis supported this supposition but indicated modifications as shown in the formula (Si1.85Alo0.62)IV(Al1.38)VI(OH)4.10O4.96Na0.62, compared with (Si2)lv(Al2)VI(OH)4O5 for an ideal 1:1 layer silicate. High-resolution 29Si and 27A1 nuclear magnetic resonance spectroscopy indicated the substitution of Al for Si in the tetrahedral sheet, the presence of A1IV and A1VI, and the presence of Si bonded through oxygen to three Al atoms and one H. A natural counterpart of the synthesized aluminosilicate may be a precursor of halloysites formed by weathering of volcanic ash and pumice and have a close structural relation with allophane and imogolite

The absorption spectra of methylene blue ion exchanged on hectorite, Laponite B, Barasym, or sepiolite in dilute aqueous suspensions show the presence of the monomer, the protonated monomer, the dimer, and the trimer. Due to conformational differences, the absorption band maximum of the monomer with respect to its maximum in aqueous solution is red shifted when it is adsorbed on the external surface and blue shifted when it is adsorbed on the interlamellar surface. The availability of the interlamellar surface for methylene blue as a function of the type of clay and/or the counterion present thereby can be probed. The results indicate that 0.6–0.7% of the cation-exchange capacity of Barasym consists of acid sites capable of protonating methylene blue. Counterions of low hydration energy were found to induce a small number of similar sites in hectorite and Laponite B; hence, these sites must be situated on the external surface. Dimers formed on external surfaces show one absorption band. Dimers formed on the interlamellar surface of hectorite yield spectra having two absorption bands. The trimer was formed only at the external surface. With increasing loading of the clays, the spectra of methylene blue showed metachromasy. The metachromatic behavior can be fully explained by dye aggregation, which is the result of its concentration on the surface. No π-electron interaction with the surface oxygens need be invoked.

The onset of the mobilization of fine particles of quartz (fines) in sandpacks was determined by comparing the theoretically calculated hydrodynamic and colloidal forces acting on a fines particle near a representative sand grain. The results show that the mobilization of fines depends strongly on the chemistry of fluids present in the reservoir. Specifically, a critical electrolyte concentration exists for mobilization, which depends on the pH. For large particles of fines and relatively high fluid velocity, the mobilization of fines may depend on the fluid velocity, but in a narrow range of electrolyte concentration. The types of interactions between the fines and sand grain surfaces were corroborated by direct visual observations using a traveling microcell pack.

The mobilization of fines in sandstones leads to a reduction of permeability (i.e., a reduction of the hydraulic conductivity).

The solubilities of HCl-treated samples of corundum, gibbsite, boehmite, and diaspore in aqueous solutions at 298 K and one atmosphere pressure were determined from undersaturated and supersaturated initial conditions. Solution characteristics at apparent equilibrium were measured and used to calculate equilibrium constants (Kr) for mineral dissolution reactions:

$$\begin{array}{l} A{l_2}{O_3}\left( {corundum} \right) + 3{H^ + } = A{l^3} + 1.5\,{H_2}O,\\ Al{\left( {OH} \right)_3}\left( {gibbsite} \right) + 3{H^ + } = A{l^3} + 3\,{H_2}O,\\ and\\ AlOOH\left( {boehmite\,or\,diaspore} \right) + 3{H^ + } = A{l^3} + 2{H_2}O, \end{array}$$

A kinetic study of the oxidation of hydroquinone by aqueous suspensions of hausmannite at pH 6 was conducted using an on-line analysis system. Electron transfer between hydroquinone and the oxide was monitored by ultraviolet and electron spin resonance spectroscopy to measure the loss of hydroquinone and the appearance of oxidation products. Although hydroquinone oxidized on the surface of the oxide and the oxide surface was altered after the reduction, hydroquinone and its oxidation products did not adsorb strongly on the surface. At a high concentration of hydroquinone, p-benzosemiquinone free radicals persisted in aqueous solution and were oxidized by dissolved O2. Calculations based on the thermodynamic stabilities of the oxide and the organic species involved show that the formation of p-benzosemiquinone radical by Mn reduction is feasible. The presence of the radicals indicates that the oxidation of hydroquinone by the oxide proceeded by a one-electron transfer process. At high organic/ oxide ratios, an increase in the amount of hausmannite dissolved with increasing hydroquinone concentration suggests that the reduction of the oxide by the organic was not limited to the surface layer of the oxide. At a high concentration of hydroquinone, polymers were detected in solution, suggesting that radical-mediated reactions played a role in the polymerization process. A reaction scheme is proposed to explain the effect of the Mn oxide to hydroquinone ratio on the consumption of O2 and the appearance of quinone, p-benzosemiquinone, and polymers in solution.

Diffusion of K during analytical electron microscopy (AEM) results in anomalously low count rates for this element. As the analysis area and specimen thickness decrease, count rates become disproportionally lower. Adularia and muscovite show different diffusion profiles during AEM; for muscovite a strong dependence of diffusion on crystallographic orientation has been observed. Conditions giving rise to reliable chemical data by AEM are the use of a wide scanning area (>800 × 800 Å) and/or large beam size to reduce the effect of diffusion of alkali elements, a specimen thickness greater than about 1000 Å, constant instrument operating conditions, and the use of a homogeneous, well-characterized standard sample. The optimum thickness range was obtained by determining the element intensity ratio vs. thickness curve for given operating conditions. The standard and unknown should have a similar crystal structure and, especially for strongly anisotropic minerals such as phyllosilicates, a similar crystallographic orientation with respect to the electron beam.

The kinetics of hydroquinone oxidation by aqueous suspensions of pure hematite and goethite-ferrihydrite mixtures at pH 6.0, 7.4, and 9 was studied using an on-line analysis system. The electron transfer between hydroquinone and the Fe oxides was monitored by UV-visible and electron spin resonance spectroscopy. The adsorption of organics on the Fe oxide surface was detected by Fourier-transform infrared spectroscopy. For different Fe oxides, a higher surface area was correlated with a greater oxidizing ability and greater adsorption of organics, suggesting that the oxidation reaction was a surface process. A reversal of the initially rapid redox reaction was found in this system, suggesting a delayed release of Fe2+ into solution as the reduction of the Fe oxide proceeded. Redox potential calculations confirmed the thermodynamic favorability of the reaction reversal. A distribution of the reduced state over neighboring Fe atoms on the oxide surface probably was responsible for the initial suppression of Fe2+ release into the aqueous phase. Based upon these observations and detection of the semiquinone radical as an intermediate of hydroquinone oxidation, an inner-sphere one-electron transfer mechanism for the oxidation of hydroquinone at the oxide surface is proposed.

Polynuclear hydroxy-Al cations were prepared by partially neutralizing dilute solutions of aluminum chloride. These cations were introduced in the interlayer space of montmorillonite by cation exchange, which formed heat-stable pillars between the silicate layers. Polynuclear hydroxy-Al was preferentially adsorbed on montmorillonite compared with monomer-Al; the maximum amount adsorbed was ∼400 meq/100 g of montmorillonite. Of this amount 320 meq was non-exchangeable. The 001 X-ray powder diffraction reflection of the polynuclear hydroxy-Al-montmorillonite complex was at 27 Å, with four additional higher-order basal reflections, giving an average d(001) value of 28.4 Å. This complex was thermally stable to 700°C. An analysis of the basal reflections by the Fourier transform method indicated that the 28-Å complex had a relatively regular interstratified structure of 9.6- and 18.9-Å component layers with a mixing ratio of 0.46:0.54. This ratio implies that the hydroxy-Al pillars occupied every second layer. Considering the relatively small amount of Al adsorbed and the thermally stable nature of the structure, the hydroxy-Al pillars must have been sparsely but homogeneously distributed in the interlayer space.

The kinetics of the thermal decomposition of the kaolin: dimethylsulfoxide (kaolin: DMSO) and the kaolin: N-methylformarnide (kaolin: NMF) intercalates have been reexamined. Two different sample sizes (2 mg and 8 mg) and grain-size distributions (<45 μm and 45–63 μm were investigated using isothermal and dynamic gravimetry in the temperature range 100°–200oC. All sample configurations for the kaolin: DMSO intercalate (2 mg, <45 μm; 2 mg, 45–63 μm; 8 mg, <45 μm; 8 mg, 45–63 μm) followed the rate law -ln(1 - α) = kt to a value for α, the reaction fraction complete, of.6, yielding activation energies and standard deviations at the 99% confidence level of 85.5 ± 3.79 and 71.75 ± 8.75 kJ/mole for the isothermal and dynamic runs, respectively. The kaolin: NMF intercalate (2 mg, <45 μm) also followed the same rate law for α <.8, with activation energies and standard deviations at the 99% confidence level of 89 ± 5.05 and 79.25 ± 6.47 kj/mole for the isothermal and dynamic studies, respectively. In solution the rate law -ln(1 - α) = kt is known as first-order kinetics, but here it appears to represent the non-instantaneous nucleation of uniformly sized particles, followed by the inward movement of a reaction interface.

Synthetic 2-line and 6-line ferrihydrite samples prepared from ferric nitrate solutions have the bulk compositions Fe4(O,OH,H2O)12 and Fe4,6(O,OH,H2O)12, respectively. The composition depends on crystal size, which averages 20 Å for 2-line and 35 Å for 6-line ferrihydrite. X-ray absorption edge spectra indicate the presence of tetrahedral Fe3+, a conclusion supported by heating experiments which show the development of maghemite after heating to 300°C in the presence of N2, followed by the formation of hematite at higher temperatures. These two reactions are recorded on differential thermal analysis traces by exotherms at 350° and 450°C. Transmission electron microscopy shows that 2-line ferrihydrite has no Z-axis regularity but does show hexagonal 2.54-Å lattice fringes. Six-line ferrihydrite forms faceted crystals having 9.4-Å c-parameter only detectable in dark field. In bright field, 2.54-Å lattice fringes indicate greater atomic regularity than in 2-line ferrihydrite. Analysis of the X-ray powder diffraction pattern of 6-line ferrihydrite suggests a structure based on double-hexagonal close-packed oxygens, containing 36% Fe in tetrahedral sites. Selective chemical dissolution, surface area measurements, and magnetic susceptibility are consistent with the recorded properties of ferrihydrite.

On the basis of neutron diffraction studies, the two inner-hydroxyl ions in highly ordered kaolinite were recently shown to be differently oriented. One of the inner-hydroxyl ions points generally toward a hole in the octahedral sheet and the other toward a hole in the tetrahedral sheet. These orientations and the locations of the other atoms in the primitive triclinic unit cell have now been determined for a sample of Keokuk kaolinite with improved precision compared with that reported earlier. Rietveld structure refinement was carried out for the entire crystal structure simultaneously (99 atom positional and 17 other parameters) with each of two newly collected sets of high-resolution neutron powder diffraction data. The different orientations of the inner-hydroxyl ions are the most marked evidence that the unit cell is not C centered. The positions of the inner-surface hydrogen atoms provide further evidence in that all differ from a C-centered relationship by six to eight estimated standard deviations in their y coordinates. The cell is, therefore, not centered. The space group is P1.

Due to their unique polarity, pore-size distribution, and high surface areas, pillared and delaminated clays are potentially useful materials for the adsorption of environmental toxicants. To determine their properties for adsorption of chlorinated phenols, alumina-pillared montmorillonite (APM), chromia-pillared montmorillonite (CPM), and alumina-delaminated Laponite (ADL) were reacted with aqueous pentachlorophenol (PCP) solutions in batch equilibrium experiments. An hydroxy-Al Laponite (HAL) in which the Na+ exchange ions were replaced by ions of the type Al13O4(OH)(24+x)(H2O)(12-x)(7-x)+ was included in the study. With ADL as the adsorbent, the extent of PCP adsorption increased with decreasing pH, and then became constant at pH ≤ pKa. Thus, the neutral phenol was preferred over the phenolate form. Binding of neutral PCP at pH 4.7 to all adsorbents never reached saturation values, and the loadings achieved were limited by the water solubility of the adsorbate. Among the pillared and delaminated clays investigated, ADL exhibited the largest capacity for physical adsorption of PCP at pH 4.7. Differences in the PCP binding capacities for APM, CPM, and ADL suggested that adsorption was dependent on the pore structure and surface composition of the modified clay adsorbent, not on surface area alone. HAL exhibited quantitative uptake of PCP at the 8 µmole/g level, indicating that a chemi-sorption mechanism may operate for PCP binding to this adsorbent. Adsorption of 3-chlorophenol, 3,5-dichlorophenol, and 3,4,5-trichlorophenol by ADL at pH 7.4 increased as the degree of hydrophobicity and chlorination of the phenol increased; hence, the binding capacity was not limited by the molecular size of the adsorbate. In contrast to the adsorption properties observed for pillared, delaminated, and hydroxy-interlayered clays, Na+-montmorillonite and Na+-Laponite did not adsorb PCP from aqueous solution.

Modifications of the external surface area and the two types of microporosity of sepiolite (structural microporosity and inter-fiber porosity) were examined as a function of the temperature of a vacuum thermal treatment to 500°C. The methods used included: reciprocal thermal analysis, N2 and Ar low-temperature adsorption microcalorimetry, gas adsorption volumetry (for N2, Ar, and Kr at 77 K and CO2 at 273 and 293 K), water-vapor adsorption gravimetry, and immersion microcalorimetry into liquid water at 303 K. If the sample was not heated >100°C, only 20% of the structural microporosity was available to N2, whereas 52% was available to CO2 at 293 K. In both experiments, the channels filled at very low relative pressures. At >350°C, the structure transformed to anhydrous sepiolite, which showed no structural microporosity. The inter-fiber microporosity decreased from 0.031 to 0.025 cm3g (as seen with N2), and the external specific surface area decreased from 120 to 48 m2/g. The water adsorption isotherms showed a lower and lower affinity of the external surface of fibers for water as the temperature of thermal treatment increased. The thickness of the bound water on the external surface was estimated to be ≤ 3.5 monolayers, i.e., less than 10 Å.