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.

The pink clays from the Tagus basin, Spain, were characterized by X-ray difraction (XRD), infrared spectroscopy (IR), scanning electron microscopy (SEM), and transmission electron microscopy (TEM). Chemical data were obtained by plasma emission spectroscopy and analytical electron microscopy (AEM), and specific surface and cation-exchange capacity were measured also. The data indicate that these pink clays are primarily stevensite. This Mg-rich smectite is characterized by poor crystallinity, a high degree of structural disorder, trioctahedral character (pure magnesian), a very low cation-exchange capacity, a very small crystal size (which generates an abnormally high specific surface area), and a deficiency of octahedral cations. On the basis of the very small crystal size, a large number of edge dislocations, the lack of periodicity (turbostratic) in the structure, and a cellular (spherical) texture observed by TEM, we consider this occurrence to be an early stage of crystallization. Unlike other precursor clay materials described in the literature, this clay is not an alteration of volcanic ash, but it was generated by precipitation from a Si- and Mg-saturated medium.

A sequence of interstratified illite-smectite (I-S) and illite in Paleozoic pelites and metapelites from the Iberian Range, Spain, was studied by X-ray diffraction (XRD), scanning electron microscopy (SEM), and transmission electron microscopy (TEM). The fine-grained matrix of diagenetic pelites is composed of I-S with sequences of illite- and smectite-like layers in a given sample. The Reichweite (R) values as determined by XRD and averaged over heterogenous I-S layer sequences increase with increasing grade, apparently continuously, in sharp contrast with TEM observations of other published sequences. Changes in I-S sequences along layers are rarely observed. In the higher-grade diagenetic pelites, I-S coexists with illite. Each I-S phase has a composition similar to that of illite, implying unique Al-Si distributions in contrast to smectite and muscovite. Selected area electron diffraction (SAED) patterns of I-S and illite are diagnostic of 1Md polytypism. Anchizonal metapelites consist of larger packets of well-crystallized muscovite, with SAED patterns corresponding to a two-layer polytype.

The continuous sequence of changes studied by TEM in I-S sequences and lateral transitions among these units is consistent with illitization by layer-by-layer replacement, although other processes are possible also. Replacement of individual layers probably occurs via fluids at reaction interfaces, in contrast to solid-state reactions, sensu strictu. The transition from the diagenetic to anchizonal rocks (transition in textures and formation of muscovite-2M1) occurred via dissolution/crystallization, however, presumably by tectonic stress. XRD and TEM data imply a consistent prograde trend in the sequence, the XRD data denning the average, long-range Reichweite ordering sequence, whereas the TEM data define the short-range layer sequences.

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.

Cetyltrimethylammonium- and tetradecyltrimethylammonium-intercalated magadiites were prepared by direct syntheses, starting from sodium metasilicate (Na2O/SiO2 = 1.0) and nitric acid. Total substitution of sodium by cetyltrimethylammonium or tetradecyltrimethylammonium cations was not achieved in the range of surfactant: silicon molar ratios used in this study. When a phosphoniun-based surfactant replaces the ammonium surfactants in the same procedure, the result of the synthesis is a mixture of quartz and unmodified surfactant. If dodecylammonium bromide is used, an MCM-41 molecular sieve is obtained. The substitution of the silicon source by tetramethylammonium silicate or of nitric acid by hydrochloric, hydrofluoric, or acetic acids also yields MCM-41 molecular sieves, indicating that the formation of magadiite is greatly dependent on the presence of sodium cations and nitrate anions.

The intercalation complex of a low-defect (“well-crystallized”) kaolinite from Cornwall, England, with hydrazine was studied by high-temperature X-ray diffraction (HTXRD), differential thermal analysis (DTA), and thermogravimetry (TG). The X-ray pattern at room temperature indicated that intercalation of hydrazine into kaolinite causes an increase of the basal spacing from 7.14 to 10.4 Å, as previously reported. Heating between 25-200°C produces a structural rearrangement of the complex, which initially causes a contraction of the basal spacing from 10.4 to 9.6 Å. In a second stage, the basal spacing reduces to 8.5 Å. Finally, in a third stage, a reduction in spacing occurs through a set of intermediate phases, interpreted as interstratifications of intercalated and non-intercalated 1:1 layers. Evidence for these changes was observed by DTA, where three endothermic reactions are observed at low temperature. This behavior suggests that intercalated molecules occupy several well-defined sites in the interlayer of the kaolinite complex. The intercalated molecules deintercalate in an ordered fashion, which explains the successive and discontinuous contraction of the basal spacing of the complex. Heating between 200-400°C caused a limited increase in stacking order of the kaolinite structure, whereas dehydroxylation of kaolinite and the disappearance of its X-ray reflections occurred between 450-640°C.

A white calcium bentonite (CaB) from the Kütahya region, Turkey, contains 35 wt. % opal-CT and 65 wt. 9c Ca-rich montmorillonite (CaM). Samples were heated at various temperatures between 100–1300°C for 2 h. Thermal gravimetric (TG), derivative thermal gravimetric (DTG), and differential thermal analysis (DTA) curves were determined. Adsorption and desorption of N2 at liquid N2 temperature for each heat-treated sample was determined. X-ray diffraction (XRD) and cation-exchange capacity (CEC) data were obtained. The change in the <d(001) value and the deformation of the crystal structure of CaM depend on temperature. Deformation is defined here as changes of the clay by dehydration, dehydroxylation, recrystallization, shrinkage, fracture, etc. The activation energies related to the dehydration and dehydroxylation of CaB calculated from the thermogravimetric data are 33 and 59 kJ mol−1, respectively. The average deformation enthalpies, in the respective temperature intervals between 200–700°C and 700–900°C, were estimated to be 25 and 205 kJ mol−1 using CEC data and an approach developed in this study. The specific surface area (S) and the specific micropore-mesopore volume (V) calculated from the adsorption and desorption data, respectively, show a “zig zag” variation with increasing temperature to 700°C, but decrease rapidly above this temperature. The S and V values were 43 m2 g−1 and 0.107 cm3 g−1, respectively, for untreated bentonite. They reach a maximum at 500°C and are 89 m2 g−1 and 0.149 cm3 g−1 respectively. The XRD data clearly show that, at 500°C, where the irreversible dehydration is completed without any change in the crystal structure, the porosity of CaM reaches its maximum.

Microporous materials, (materials with pore sizes with widths <2 nm) were prepared by pillaring of smectites obtained from different soil deposits. The materials were prepared by intercalation with oligomeric cations of aluminum, which were transformed to aluminum-oxide pillars by calcination. The adsorption of n-hexane in the pillared clays was studied by the determination of heats of adsorption. Heats of adsorption were measured using either a static microcalorimeter or differential scanning calorim-etry coupled with thermogravimetry (TG-DSC). In this latter case, two different procedures were used that differ on the introduction of the (n-hexane) molecules that are to be adsorbed. The results obtained by the (standard) static microcalorimeter method and the TG-DSC method were compared. This comparison showed the heats of adsorption obtained by TG-DSC are differential heats of adsorption, and it showed the range of adsorption. Characterizing the texture of pillared clays, especially microporosity, is important for monitoring the intercalation process and for determining potential applications of these materials. Correlations between the obtained heats of adsorption and the dimensions of micropores suggest that TG-DSC is a semi-quantitative method for characterizing micropores in aluminum-pillared clays.

Oxygen-isotope data were obtained for synthetic aluminum-hydroxide phases precipitated over 65–125 mo and have been compared to results from similar experiments conducted for 3–56 mo. The Al(OH)3 polymorphs, gibbsite, nordstrandite, and bayerite, were synthesized, but gibbsite was dominant in most samples, and commonly the only phase present. Using pure gibbsite samples, the following oxygen-isotope fractionation factors, ${\alpha }_{gibbsite-H_{2}O}$, were obtained: 1.0167 ± 0.0003 (9 ± 1°C), 1.0147 ± 0.0007 (24 ± 2°C), 1.0120 ± 0.0003 (51 ± 2°C). These values, and the associated equation for an oxygen-isotope geothermometer for the interval 0–60°C 103ln ${\alpha }_{gibbsite-H_{2}O}=2.04\times {10}^6/T^2-3.61\times {10}^3/T+3.65$ (T in K), are not significantly different from those obtained from experiments of much shorter duration. These results, and the good agreement with ${\alpha }_{gibbsite-H_{2}O}$ values obtained for well-constrained natural systems, suggest that the experimentally determined fractionation factors describe equilibrium conditions for gibbsite that has precipitated directly from solution.

As also proposed by others using a modified-increment calculation, our synthesis experiments suggest that ${\alpha }_{Al(OH{)}_3-H_{2}O}$ is polymorph-dependent at low temperatures and that a significant temperature-dependent trend exists in the values of ${\alpha }_{Al(OH{)}_3-H_{2}O}$. However, previously calculated fractionation factors obtained using the modified-increment method are higher than those obtained from the experiments, with this discrepancy becoming larger as temperature decreases.

This paper examines the ion-exchange properties of synthetic zeolite Na-Pc, which was produced from perlite-waste fines and has a SiO2:Al2O3 ratio of 4.45:1 and a cation-exchange capacity (CEC) of 3.95 meq g−1. Although equilibrium is attained rapidly for all three metals, exchange is incomplete, with Ac(max) (maximum equilibrium fraction of the metal in the zeolite) being 0.95 for Pb, 0.76 for Zn, and 0.27 for Ni. In both Na → ½Pb and Na → ½Zn exchange, the normalized selectivity coefficient is virtually constant for NAC (normalized equilibrium fraction of the metal in the zeolite) values of ≤0.6, suggesting a pronounced homogeneity of the available exchange sites. The Gibbs standard free energy, ΔG°, of the Na → ½Pb exchange calculated from the normalized selectivity coefficient is −3.11 kJ eq−1 and, for the Na → ½Zn exchange, it is 2.75 kJ eq−1.

Examination of the solid exchange products with X-ray diffraction (XRD) revealed a possible decrease in crystallinity of zeolite Pb-Pc as suggested by the significant broadening and disappearance of diffraction lines. This decrease is associated with a reduction of pore opening, as indicated from Fourier-transform infrared analysis (FTIR), which in turn results in a decrease of the amount of zeolitic water. Thermogra-vimetric-differential thermogravimetric (TG-DTG) analysis showed that water loss occurs in three steps, the relative significance of which depends on the type of exchangeable cation and subsequently on the type of complex formed with the cation and/or the zeolite channels. Zeolite Na-Pc might be utilized in environmental applications, such as the treatment of acid-mine drainage and electroplating effluents.

The Mössbauer and infrared spectra of Li- and Rb-saturated nontronites from Washington, USA (SWa-1), heat treated at different temperatures, were measured. The Mössbauer results show that diffusion of Li+ into the 2:1 layer by heat treatment at 250-300°C does not affect the magnetic hyperfine interactions of the octahedral iron centers. In contrast, significant changes were observed by calcination at temperatures >300°C for Li-saturated nontronites. The main features of the Mössbauer spectra recorded at different temperatures reveal superparamagnetic behavior with a blocking temperature of ~5 K. The superparamagnetic behavior is related to small magnetic domains created by partially broken Fe-O-Fe bonds upon heat treatment. The infrared spectra of Li-rich nontronite, heat treated at 300°C, show changes attributed to Li migration into the hexagonal cavities. Heating to higher temperatures, produced changes in the spectra of the Li- and Rb-saturated nontronites owing to the dehydroxylation of the layer structure. The dehydroxylation process begins with the loss of OH groups in the FeOHFe bridges and is completed with the disruption of the Al-O bonds at >600°C.

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.

The dielectric behavior of kaolinite, montmorillonite, allophane, and imogolite samples adjusted to a water potential of 33 kPa was examined using a time-domain reflectometry method over a wide frequency range of 103-1010 Hz. A dielectric relaxation peak owing to bound H2O was observed. The observation of this peak required the precise determination of the contributions of dc conductivity. The peak is located at 10 MHz, indicating that the relaxation time of the bound H2O is approximately ten times longer than the relaxation time of bound H2O with organic polymers, such as an aqueous globular-protein solution. The structure of bound H2O differs between phyllosilicates and amorphous phases, based on differences in relaxation strength and the pattern of distribution of the relaxation times. The dielectric process involving rotation of bulk H2O molecules was also observed at 20 GHz. The relaxation strength of bulk H2O increased with an increase in the water content. The interfacial polarization in the diffuse double layer occurred only in montmorillonite and kaolinite, indicating that mechanisms involving the Maxwell-Wagner and surface-polarization effects cannot be extended to include allophane and imogolite. Although these results suggest that additional work is required, a tentative conclusion is that a tangential migration of counter-ions along clay surfaces may be important.

Tertiary weathered sediments located immediately to the west of the harbor at Newhaven, Sussex, UK, were investigated by examination of major and trace elements by scanning electron microscope (SEM), microprobe, and inductively coupled plasma mass spectrometer (ICP-MS), and the mineralogy was studied by optical petrography, X-ray diffraction (XRD), transmission electron microscope (TEM), selective leaching, and thermodynamic modeling. Studied outcrops experienced acid leaching by sulfuric acid percolating downward through Tertiary sediments overlying Cretaceous chalk. The progressive neutralization of the percolating acid fluids resulted in “sequentially” layered neoformation of minerals: jarosite, iron oxides, aluminous minerals (sulfates, oxyhydroxides), gypsum, and Fe-Mn oxides. Substantial agreement was found between field observations and mineral assemblages obtained by modeling with the program CHILLER. These results suggest that the initial assumptions on the weathering process and mechanisms are correct. The relevance and implications of this study in the modeling of future denudation and weathering processes of radioactive waste-disposal sites (both deeply buried sites for high-leveI waste and surface sites for low-level waste) are discussed. Neoformed phases, such as jarosite, aluminous minerals, and silico-aluminous gels may play a significant role in the efficient trapping of mobilized pollutant radionuclides.

The basal spacings of complexes of saponite with five cationic dyes, 1,1′-diethyl-2,2′-cyanine, crystal violet, methylene blue, 1,1′-diethyl-2,2′-carbocyanine, and 1,1′-diethyl-2,2′-dicarbocyanine, varied with degree of saturation of each dye. At low loading of dye to saponite, each cationic dye showed nearly the same absorption spectrum in the UV-visible region as that of its dilute aqueous solution, whereas the spectrum changed distinctly at high loading. With increasing degree of dye loading, the absorption band shifted to longer wavelength for 1,1′-diethyl-2,2′-cyanine (J band) and to shorter wavelength for the others (D, H bands). On the basis of the basal spacing of each respective dye-clay complex, the orientation of the intercalated dye molecules is proposed as follows: the major plane of the cationic dye lies horizontal to the 2:1 layer surface at low loading. With increasing loading, the dye molecules interact with adjacent dye molecules and orient vertically to the 2:1 layer at high loading near the cation-exchange capacity.

The structural transformation of dioctahedral 2:1 layer silicates (illite, montmorillonite, glauconite, and celadonite) during a dehydoxylation-rehydroxylation process has been studied by X-ray diffraction. thermal analysis, and infrared spectroscopy. The layers of the samples differ in the distribution of the octahedral cations over the cis- and trans-sites as determined by the analysis of the positions and intensities of the 11l, 02l reflections, and that of the relative displacements of adjacent layers along the a axis (c cos ß/a), as well as by dehydroxylation-temperature values. One illite, glauconite, and celadonite consist of trans-vacant (tv) layers; Wyoming montmorillonite is composed of cis-vacant (cv) layers, whereas in the other illite sample tv and cv layers are interstratified. The results obtained show that the rehydroxylated Al-rich minerals (montmorillonite, illites) consist of tv layers whatever the distribution of octahedral cations over cis- and trans-sites in the original structure. The reason for this is that in the dehydroxylated state, both tv and cv layers are transformed into the same layer structure where the former trans-sites are vacant.

The dehydroxylation of glauconite and celadonite is accompanied by a migration of the octahedral cations from former cis-octahedra to empty trans-sites. The structural transformation of these minerals during rehydroxylation depends probably on their cation composition. The rehydroxylation of celadonite preserves the octahedral-cation distribution formed after dehydroxylation. Therefore, most 2:1 layers of celadonite that rehydroxylate (~75%) have cis-vacant octahedra and, only in a minor part of the layers, a reverse cation migration from former trans-sites to empty octahedra occurred. In contrast, for a glauconite sample with a high content in IVA1 and VIAl the rehydroxylation is accompanied by the reverse cation migration and most of the 2:1 layers are transformed into tv layers.

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.

Smectites synthesized from experiments at 5.5 GPa and 1500°C are of high quality, crystals are large at >10 μm, and the 2:1 layers may have a homogeneous charge distribution. Smectite was exchanged with various cations (Na+, Li+, K+, Ca2+, and Mg2+) and the hydration behavior of each sample was observed by an in situ powder X-ray diffraction method under precisely controlled relative humidity (RH). The smectite showed distinct stepwise (discontinuous) hydration versus RH. During the transition between two hydration states, the coexistence of the two states was observed. Randomly interstratified structures with one and two planes of H2O are time-dependent phenomena and relate to hydration and dehydration processes.

The intercalation complex of a low-defect dickite from Tarifa, Spain, with hydrazine was studied by high-temperature X-ray diffraction (HTXRD) differential thermal analysis (DTA), and ther-mogravimetry (TG). The X-ray diffraction (XRD) pattern obtained at room temperature indicated that the intercalation of hydrazine and H2O into dickite caused an increase of the basal spacing from 7.08 to 10.24 Å, which is slightly lower than the 10.4-Å spacing commonly observed after intercalation into kaolinite. Heating between 25–50°C produced a structural rearrangement of the complex, which decreased the basal spacing from 10.24 to 9.4 Å, and the resulting 9.4-Å complex was stable between 50–90°C. Heating between 90–300°C caused a gradual reduction in spacing, which occurred through a set of intermediate phases. These phases were interpreted to be interstratifications of intercalated and non-intercalated layers. These changes were also observed by DTA and TG. Two main endothermic reactions and two main stages of mass loss, respectively, were indicated in the DTA and the TG curves in the temperature range 25–200°C. This behavior suggests that intercalated molecules, hydrazine and H2O, occupied well-defined sites in the interlayer of the dickite. The intercalated molecules were lost in an ordered fashion as confirmed by the infrared analysis of the decomposition products; H2O was lost in the first stage and ammonia was identified in the second stage. Above 300°C, complete removal of the intercalated molecules restored the basal spacing of the dickite. However, the basal reflections were broadened, the relative intensities were changed, and changes in the dehydroxylation temperature indicated that the intercalation-desorption process induced some stacking disorder in the dickite structure.