Owing to their large and chemically active surface, hydroxy-intercalated and pillared clays can be potent sorbents for organic compounds. The sorption behavior of Al and Zr-hydroxy-intercalated bentonite (HAl-, HZr-MX80), Al and Zr-pillared bentonite (Al-MX80, Zr-MX80), and a commercial Al-pillared bentonite (EXM 534) for 3-chloroaniline (3-CA), atrazine (AT), and 3-chlorophenol (3-CP) was investigated. The results were compared with the sorption behavior of the untreated Na-rich bentonite (MX80) and granulated activated carbon (GAC). Also the influence of the salinity of the sorbate and the age of the sorbents was studied.

Al and Zr-hydroxy-intercalated and pillared bentonites sorbed higher amounts of 3-CA, AT, and 3-CP than the untreated bentonite. The quantities sorbed related to the electron-donating properties of the sorbate and the acidity of the sorbents. Sorbed quantities increased from the hydroxy-intercalated to the pillared species, and from the Al to the Zr forms. The organic bases, 3-CA and AT, were sorbed in higher quantities than the organic acid 3-CP. For AT, the sorbents exhibited a high affinity. Aging of the samples and a high ionic strength of the sorbate reduced the sorption of 3-CA, whereas the sorption of AT was not affected greatly. The sorption capacity of GAC for organic bases was generally higher than that of the hydroxy-intercalated and pillared bentonites.

The data suggest that at initial concentrations at a ppm level, 3-CA and AT can be entirely removed from aqueous solutions by Al and Zr-hydroxy-intercalated and pillared bentonites. These materials, especially Zr-pillared bentonites, represent potent alternative sorbents for atrazine, chloroanilines, and probably a wide range of other organic bases.

Self-diffusion coefficients of H2O molecules in Na-rich hectorite gel were measured by 'H nuclear magnetic resonance (NMR), Spin-echo pulse sequences with magnetic field gradient pulses for the translational diffusion measurement were applied to the hectorite gel at the Larmor frequency of 20 MHz. Effects of clay fraction (0-51.2 wt. %) and temperature (20.0-60.3°C) were studied. The results show: (1) Phenomenologically, the self-diffusion coefficient, D, of 1H2O in the clay gel is expressed by the normalized diffusivity, D/D0 = exp(−0.0257w), where D0 is the water self-diffusivity in bulk water at temperature and w is the weight fraction of the hectorite (wt. %). (2) The activation energy of H2O diffusivity in the hectorite gel is nearly equal to that in bulk water. Hence, the normalized diffusivity, D/D0, obeys a temperature-independent curve. (3) The exponential dependence of D/D0 on w for w <30 wt. % is explained by a random-walk model, in which free or unbound H2O molecules migrate in the geometrically complex and tortuous pore structure of randomly scattered clay-mineral grains.

A hydrothermally altered rhyolitic hyaloclastite from Ponza island, Italy, has four alteration zones with unique clay assemblages: (1) a non-pervasive argillic zone characterized by smectite; (2) a propylitic zone with interstratified illite-smectite (I-S) containing 10–85% illite (I); (3) a silicic zone composed of I-S with ≥90% I and pure illite; and (4) a sericitic zone with I-S ranging from 66% I to pure illite. Atomic force microscopy reveals abrupt changes in particle morphology with illitization, including initial changes from anhedral plates to laths and then to euhedral plates and hexagonal plates. I-S particles progressively thicken with illitization and mean particle area (basal plane) remains constant from pure smectite to I-S with 80% I. However, particle area increases from 90 to 100% illite. Computer modeling of I-S structural forms indicates octahedral cation ordering progressively changes from cis- vacant smectite to interstratified cis- and tnuis-vacant I-S, and then to trans-vacant illite. In addition, polytypes progressively change from 1 Md to 1M, and then to 2M, illite. Electron-microprobe and X-ray fluoresence analyses show that I-S chemistry progressively changes during illitization, evolving toward a phengitic composition with ∼0.89 fixed interlayer K+ per O10(OH)2. Octahedral Mg2+ shows little change with illitization, varying from 0.3 to 0.5 cations per O,10(OH)2. The layer charge of smectite is ~0.38 equivalents per O10(OH)2.

On the basis of abrupt changes in morphology and progressive changes in polytype and chemistry, smectite illitization on Ponza involved a dissolution and recrystallization mechanism with multiple stages of nucléation and crystal growth. In this multi-step model, temperature of alteration provided the major control for the layer composition, polytype, and morphology of I-S crystallites. Other factors that may play a secondary role include: K+ availability, water-rock ratio, and permeability. Alternatively, the mechanism of I-S and illite formation at Ponza and other hydrothermal environments may occur by direct precipitation of I-S crystallites from rhyolite glass and may not involve progressive reactions of smectite precursors.

Silanol groups in protonated magadiite (H-magadiite) were characterized by 1H and 2H solid-state nuclear magnetic resonance (NMR). H-magadiite and deuterated (D) magadiite were synthesized by the treatment of Na-rich magadiite with 0.2 N HC1 and 0.2 N DC1, respectively. In the 1H NMR spectrum measured at room temperature, silanol groups of H-magadiite showed two signals at 3.75 and 5.70 ppm, indicating that two types of silanol groups were present. The ratio of silanol groups associated with strong hydrogen bonding (5.70 ppm) to those with weaker hydrogen bonding (3.75 ppm) was 2 to 1. The 2H NMR spectra of deuterated magadiite were measured in the temperature range from 150 to 440 K. In the spectra measured at temperatures below 294 K, silanol groups showed Pake doublet patterns. These patterns were composed of two components corresponding to the two types of silanol groups shown in the 1H NMR analysis. Both silanol groups produced wobbling motions with increasing temperature. Above 294 K, the profile of the Pake doublet pattern was transformed gradually to a near triangular pattern, indicating that the silanol groups underwent other motions also, such as a two-site jump.

Two analogous inorganic-organic hybrids with a phyllosilicate-like structure SILMg1 and SILMg2, containing 3-aminopropyl- and N-propylethylenediaminetrimethoxysilane were synthesized through a sol-gel process. These hybrids adsorbed divalent cations of cobalt, nickel, copper, and zinc from aqueous solution to give the effectiveness of adsorption capacities in the sequence Cu2+ > Zn2+ > Ni2+ > Co2+. SILMg1 has a higher capacity of adsorption than SILMg2. Elemental analysis, X-ray diffractometry, thermal analysis, infrared and nuclear magnetic resonance spectroscopies, and energy dispersive system microscopy characterized all hybrids. The proposed adsorption mechanism involves dissolution of the precursor matrix, formation of a phyllosilicate around the adsorbed ion, and a complexation of the cation by the amino-pendant groups in the interlayer. These new phyllosilicates are more crystalline than the original hybrids. The adsorption of Co2+ increases the interlayer distance to maximum values of 1.81 and 2.24 Å for SILMg1 and SILMg2, respectively. Thermal analysis data showed a decrease of thermal stability with cation adsorption. Si-O-Si groups were detected by infrared spectroscopy in all hybrids and a band at 1384 cm-1 was assigned to the nitrate counter anion, which indicates the participation of this ion in the sphere of coordination of the interlayer complexes. The photomicrographs obtained by scanning electron microscopy showed the organized distribution of the sheet structure for these synthesized phyllosilicates.

Chromium(VI) in the environment is of particular concern because it is toxic to both plants and animals, even at low concentrations. As a redox-sensitive element, the fate and toxicity of chromium is controlled by soil reduction-oxidation (redox) reactions. In-situ remediation of chromium combines reduction of Cr(VI) to Cr(III) and immobilization of chromium on mineral surfaces. In this study, Fe-rich smectite, montmorillonite, illite, vermiculite, and kaolinite were examined to determine reactivity in sorption-reduction of Cr(VI). The clays were compared to forms that were reduced by sodium dithionite. Clays containing Fe(II) efficiently removed soluble Cr(VI) from solution. Chromium K-edge X-ray absorption near edge structure (XANES) suggested that clays containing Fe(II) reduced Cr(VI) to Cr(III), immobilizing Cr at the clay/water interface. Adsorption of Cr(VI) by the Fe(II)-containing clay was a prerequisite for the coupled sorption-reduction reaction. Sodium dithionite added directly to aqueous suspensions of non-reduced clays reduced Cr(VI) to Cr(III), but did not immobilize Cr on clay surfaces. The capacity of clays to reduce Cr(VI) is correlated with the ferrous iron content of the clays. For dithionite-reduced smectite, the exchangeable cation influenced the sorption reaction, and thus it also influenced the coupled sorption-reduction reaction of Cr(VI). The pH of the aqueous system affected both the amount of Cr(VI) reduced to Cr(III) and the partition of Cr(III) between aqueous and adsorbed species. A plot of pH vs. amount (adsorption envelope) adsorbed for the coupled sorption-reduction reaction of Cr by reduced smectite exhibited a similar pattern to that of typical anion-sorption.

Transmission electron microscopy (TEM) including high-resolution transmission electron microscopy (HRTEM) and analytical electron microscopy (AEM) were used to study the fine clay fraction (<0.1 μm) from the eluvial E horizon of podzols located in central Finland that had developed from till materials. Soils of increasing age (6500-9850 y BP) were selected to represent a chronosequence of soil development. Expandable phyllosilicates (vermiculite, smectites) are formed in the eluvial E horizon of podzols in a short time (6500 y). TEM observations show that dissolution and physical-breakdown processes affect the clay particles. As the age of the soils increases, fragmentation and exfoliation of large precursor minerals lead to thinner clay particles of two to three layers thick. The chemical compositions of individual particles obtained by AEM indicate that expandable phyllosilicates from the E horizon of podzols are heterogeneous, involving a mixture of vermiculite, Mg-bearing smectites, and aluminous beidellite. Results suggest that heterogeneity is related to the nature of their precursors. Vermiculite and Mg-bearing smectites are derived from biotite and chlorite weathering whereas phengitic micas alter to aluminous beidellite. Because the transformation of biotite and chlorite is more rapid than phengitic micas, biotite and chlorite contributes predominantly to smectites in the younger soils, as long as ferromagnesian phyllosilicates are present in the E horizons. If not, a larger proportion of smectites is derived from phengitic micas in the older soils. Direct measurement of d(001 ) values on lattice fringe images from alkylammonium-saturated samples shows that interlayer charge varies from high-charge expandable minerals (0.6–0.75 per half unit cell) in the younger soils to 0.5–0.6 per half unit cell in the oldest soils. Thus, the proportion of the components in the clay assemblage, as well as their chemistry and interlayer charge, change over time with soil evolution.

Molecular dynamics simulations were performed of the adsorption of methylene blue (MB) on model beidellite, montmorillonite, and muscovite mica surfaces, using a previously determined empirical force field developed for dioctahedral clays. The simulations show that the adsorption of MB on mineral surfaces can result in a variety of configurations, including single and double layers of MB parallel to the basal surface, and irregular clusters. The d(001) values of ~12.3 and ~15.7 Å are assigned to dry phases with parallel single and double layers of MB, respectively, in agreement with X-ray studies. At intermediate MB loadings, stacks inclined to basal surfaces are formed. The stacks of MB ions inclined by 65–70° relative to the (001) plane of muscovite are not found on dry surfaces, in contrast to previous studies. Configurations similar to those proposed by others form spontaneously in the presence of H2O, but the ions in the model systems are not quite as ordered and not ordered in exactly the same way as the ones previously described, and they display a mobility that is not compatible with strict atomic order. The formation of a triple layer of H2O interspersed with ions may occur in the interlayer. Overall, the results of the simulations confirm that the MB-ion method must be used with great caution in surface-area determinations, because of the multiplicity of possible configurations. At the same time, the ability for adsorption to occur as either single or multiple MB layers is useful to determine cation-exchange capacity over a wide range of surface-charge densities.

Homoionic Ca-saturated clay pastes were prepared and drying curves were obtained by applying suction pressures from 1 kPa to 100 MPa, A transmission device was used to study particle orientation by placing the clay in a cell specially designed to obtain diagrams corresponding to different sample orientations. The 00l and hk0 reflections were compared to determine the best reflections for studying clay-particle orientation. Depending on the clay, 00/ reflections or the 020 reflection and/or hkl bands can be used to analyze orientation. In many cases the 020 reflection is preferred because the intensity of the peak is high and appears to be independent of the H2O content and the degree of stacking order of layers along the [001] direction.

For interstratified clays, the conditions required to obtain 00l reflections depended on several factors, the most important of which is the water content. Also, the intensity relating to particie orientation depends on (1) particle extension (size) in the (001) plane and (2) the crystal structure. Illite crystals of <1000 A gave a poorly oriented clay matrix. In contrast, large aggregates of illite, smectite, and kaolinite particles (>10,000 Å) showed a strongly oriented system. The particles of smectites may be curved and the dry material was poorly oriented owing to weak cohesion forces between the layers in comparison to illite.

The study of the orientation of particles by X-ray diffraction on hydrated samples may be affected by sample mounting techniques. Any change in the content or the way the sample is mounted may modify the microstructure of a material.

Clay containing a high water content affects the disorientation of particles, whereas, for the dry samples, pore size, pore volume, and solid continuity are associated with the geometry and crystal structure of the clay matrix.

Lechuguilla Cave is a hypogene cave formed by oxidation of ascending hydrogen sulfide from the Delaware Basin. A unique sediment deposit with characteristics suggesting derivation from the land surface, some 285 m above, was investigated. At this location, the observed stratigraphy (oldest to youngest) was: bedrock floor (limestone), cave clouds (secondary calcite), calcite-cemented silstone, finely laminated clay, and calcite rafts. Grain-size analysis indicates that the laminated clay deposits are composed of 59-82% clay-size minerals. The major minerals of the clay were determined by X-ray diffraction analysis and consist of interstratified illite-smectite, kaolinite, illite, goethite, and quartz. Scanning electron microscopy observations show that most of the clay deposit is composed of densely packed irregularshaped clay-size flakes. One sample from the top of the deposit was detrital, containing well-rounded, silt-size particles.

Surface soils are probably the source of the clay minerals. The small amount of sand- and silt-size particles suggests that detrital particles were transported in suspension. The lack of endellite and alunite is evidence that the clays were emplaced after the sulfuric-acid dissolution stage of cave formation. Fossil evidence also suggests a previously existing link to the surface.

The persistence of many seemingly metastable mineral assemblages in sediments and soils is commonly attributed to their sluggish transformation to the stable-phase assemblage. Although undoubtedly kinetics plays a major role, this study shows that thermodynamic factors, particularly surface energy, significantly influence the free energy. Enthalpies of formation of boehmite samples with variable surface area were derived using high-temperature oxide-melt calorimetry. The average surface enthalpy for all faces terminating boehmite particles was calculated at +0.52 ± 0.12 J/m2. This value represents the surface enthalpy for surfaces exposed to vacuum assuming that H2O adsorbed on the surface of boehmite is loosely bound. These results show that the enthalpy of formation of boehmite may vary by ≤8 kJ/mol as a function of particle size. An overview of published values of surface energies of gibbsite, γ-Al2O3, corundum, and the results here indicates that the hydrated phases (boehmite, gibbsite) have lower surface energies than the anhydrous phases (corundum, γ-Al2O3). Lower surface energies allow the hydrated phases to maintain high surface area, i.e., small particle size. Similar surface energies of boehmite and gibbsite suggest kinetic control favoring the crystallization of boehmite or gibbsite from aqueous solution. The enthalpy of formation of bulk boehmite from the elements was calculated at −994.0 ±1.1 kJ/mol. Combining this result with the data in existing thermodynamic databases, we confirm that bulk boehmite is metastable with respect to bulk diaspore at ambient conditions.