Parallel-oriented and exceptionally long (> 10 μm) tubes of halloysite occur in the pallid zone of a deeply-weathered lateritic profile on granite in southwest Australia.

Transmission electron microscopy and selected-area electron diffraction of ultrathin sections showed that kaolinite plates within pseudomorphs of mica crystals had fractured at irregular intervals along the a crystallographic axis to produce laths elongated along the b axis. The laths near the edges of the pseudomorphs were less constrained by the pseudomorph and had rolled to produce halloysite tubes. The tubes varied in diameter and degree of roundness. Some tubes were polyhedral rather than cylindrical in cross section. The length and number of planar faces in a tube and the angle between faces varied, exhibiting no consistent pattern.

Tubes in dispersed clay samples showed two types of twinning. In the first type, tubes and associated laths were joined together side by side. In the second type, single tubes bifurcated into two individual tubes. It is proposed that the first type of twinning occurred by folding of adjacent laths that remained joined together while the second type occurred due to exfoliation of a thick lath followed by folding of the exfoliated lath fragments into tubes.

Analytical electron microscopy showed that the chemical compositions of halloysite tubes, laths, and kaolinite plates were similar with the average cation exchange capacity of single tubes being small (4.5 meq/100 g) but higher than values for laths (2.8 meq/100 g) and plates (1.9 meq/100 g).

The influence of tartaric acid and pH on chemical composition, morphology, surface area, and porosity of short-range ordered Al precipitation products was studied. Samples were prepared (1) at pH 8.0 and at the tartaric acid/Al molar ratios (R) ranging from 0 to 0.25 and (2) at R = 0.1 and in the pH range of 4.7 to 10.0. In Al precipitation products formed at pH 8.0, the organic C content increased from 8 g/kg (R = 0.01) to 93 g/kg (R = 0.25), whereas the Al content decreased from 363 g/kg (R = 0.01) to 271 g/kg (R = 0.25). The specific surface of the materials was particularly high (>400 m2/g) when samples were prepared at R < 0.1, but drastically decreased when samples were prepared at R > 0.1 (e.g., 78.6 m2/g at R = 0.25). When the C content was relatively high (>45 g/kg), aggregation between the particles was promoted, and the specific surface, thus, decreased. Electron optical observations showed that such samples were strongly aggregated. In the materials prepared at R = 0.1, but at different initial pH values, the C content decreased from 90 g/kg (pH = 4.7) to 25 g/kg (pH = 10.0). As a consequence, the lower the initial pH, the lower was the specific surface of the Al precipitation products. Tartaric acid plays an important role in both Pertubation of crystallization of Al hydroxides and promotion of aggregation of the reaction products. The two processes counteract in influencing the specific surface and pore volume of Al hydroxides.

Heating treatments greatly affected the specific surface and porosity of Al precipitation products. The specific surface and porosity of the samples generally increased by increasing the temperature up to 400°C and then decreased. Small amounts of C still remained after heating some samples for 12 hr at 600°C.

Expansion properties often homoionic smectites that differed in amount and location of layer charge were examined by X-ray powder diffraction analysis at various relative humidities, or after glycerol or ethylene glycol solvations. Except for K-samples with glycerol solvation, and Na- and Ca-samples with ethylene glycol, differences in the basal spacings are observed in samples having similar layer charge. These results show that the basal spacings are larger when the layer charge is located in octahedral sites than when it is in tetrahedral sites. This suggests that expansion is due to the combined effects of the charge location and amount.

The effects of layer charge magnitude and location on expansion were represented by an energy change (expansion energy: ΔEr) during the hydration and solvation processes. Plots of basal spacings versus ΔEr show a reasonable relationship; the spacings generally decrease stepwise as the value of ΔEr increases. The basal spacings of K-samples with glycerol solvation, Na-saturated and K-saturated samples at 100% RH are apt to contract stepwise with increasing value of ΔEr. For these samples, the figures showing the relationship between each expanded phase and the charge characteristics are obtained from the isoquants of ΔEr, given the boundary of the expanded phases. A behavior test using these figures may be combined with the Greene-Kelly test to estimate the amount and the location of the layer charge of common smectites.

The structure of a disordered IIb Mg-chamosite was studied using Rietveld refinement techniques and powder X-ray diffraction (CuKα, 18–120° 2θ in 0.02° 2θ increments). The refinement in space group CĪ yielded high precision lattice parameters (a = 5.36982(5)Å, b = 9.3031(9)Å, c = 14.2610(6)Å, α = 90.315(5)°, β = 97.234(7)°, γ = 90.022(9)°) and atomic coordinates very similar to previous studies. However, the presence of semi-random stacking in this specimen created a situation in which not all atoms could be precisely located: the positions of the octahedral cations and anions which repeat at intervals of ±b/3 could be uniquely determined in three dimensions whereas only the z parameter of the other atoms could be refined. The reasonable appearance of the final model, despite the fact that many of the atom positions could be located in only one dimension, may have resulted because all of the atoms in this structure except O(5) repeat at intervals which are very nearly ±b/3.

A critical demand in environmental modeling and a desirable but elusive goal of research on the ion exchange properties of the charged solid surface has been to determine the selectivity coefficient from fundamental properties of the ions and surface. We developed a Hard and Soft Acid and Base (HSAB) Model to describe exchangeable cation selectivity on solid surfaces. Our previous work has shown that the model quantitatively describes alkali cation exchange on clay minerals in terms of the absolute electronegativity and softness of the exchangeable cations and two fitting parameters: α and β. This study was conducted to determine the relationship between α and β and surface charge characteristics of 2:1 clays. The layer charge and cation selectivity of seven smectites and one vermiculite were used. The regression of log Kvo against four combinations of charge properties was performed and the appropriate relationship between α, β, and surface charge was selected based on both statistical criteria (R2) and their consistency with the assumptions of the HSAB model. The selected model was then cross-validated using separate cation exchange data from the literature. It was found that α and β are linearly related to the amount of charge arising from mineral tetrahedral and octahedral sites, respectively. These results make it possible to predict the alkali cation selectivity of 2:1 clay minerals from their chemical composition data and the alkali cation properties.

Interaction of water with montmorillonite exchanged with Na+, K+, Co2+, and Cu2+ cations as a function of water content was examined using an FTIR/gravimetric cell designed to collect spectroscopic and sorption data simultaneously. Correlation of water desorption isotherms with infrared spectra of the clay-water complex showed that the position of the HOH bending band of water decreased as a function of water content. The largest decreases in frequency were observed for Cu2+ and Co2+; smaller decreases were found for Na+ and K+. In addition, the molar absorptivity of sorbed water increased upon decreasing the water content. The decrease in frequency and the concomitant increase in molar absorptivity were attributed to polarization effects on the sorbed water molecules by exchangeable cations. The interference fringes of a self supporting clay film permitted d-spacings to be determined optically and, therefore, changes in frequency, molar absorptivity, and water sorption behavior to be related directly to changes in interlayer spacing. The d-spacings obtained from the interference fringes were consistently larger by approximately 0.5 Å than those determined using powder XRD.

A new approach is described to computer simulate cation distribution in octahedral sheets of dioctahedral 2:1 layer silicates with vacant trans-octahedra. This approach makes use of the information on cation distribution at the one-dimensional level provided by integrated IR optical densities for the region of OH-stretching frequencies. By using this program it is possible to show that (1) the Mössbauer spectrum of glauconite B. Patom conforms to the structural model composed of celandonite-like and illite-like domains whose dimensions are limited by approximately 2 or 4 unit cells; (2) non-equivalency of “left” and “right” cis-positions (with fixed b-direction) with respect to R2+ and R3+ occupancy is a characteristic feature of a celadonite-like domain.

The objectives of the study were to determine the chemical composition and layer charge of smectite found in calcareous till of the Interior Plains region of western Canada and to examine the effects of acidification on alteration of the smectite. Samples of acidified and non-acidified (calcareous) late-Wisconsin till were obtained from four soil pits located immediately adjacent to an elemental sulfur block located in southern Alberta. Samples of the surface material (0–10 cm depth) had been subjected to extreme acidity for 25 years due to the oxidation of elemental sulfur and displayed pH values of about 2.0. Samples of the till obtained at depth (65–75 cm) remained calcareous with pH values between 7.3 and 7.6. A combination of analytical methods was used to determine the chemical composition of the smectite found in the samples. The layer charge of the smectite was determined independently using X-ray diffraction data for n-alkylammoniurn saturated specimens. Smectite found in the non-acidified calcareous material was characteristic of montmorillonite with a low content of Fe and very little substitution of Al for Si in the tetrahedral sheet. The smectite had a structural formula of M+0.40(Si3.96Al0.04)(Al1.56Fe3+0.10Mg0.33)O10(OH)2, which compared well with a mean value for layer charge of 0.399 mol(−)/O10(OH)2 determined using X-ray diffraction data for n-alkylammonium treated specimens. Smectite remaining in the till material subjected to extreme acidity underwent incongruent dissolution with a net loss of layer charge and preferential loss of octahedral Mg.

A synergistic effect of reductant and complexant is observed in the dissolution of goethite by dithionite and citrate or EDTA. The rate data are interpreted using the surface complexation approach to describe the interface of the reacting oxide. Adsorption of both S2O42− (D) and complexant (L) generates three surface complexes that define the dissolution behavior: ≡ Fe-D, ≡ Fe-L, and dimeric surface complexes. The initial rate increases at lower pH values because of increased surface complexation conditional formation constants. At pH values below 4, however, the fast decomposition of S2O42− gives rise to a rapid depletion of reductant, and total dissolution is not observed. It is shown that for best analytical results in soil analysis, EDTA is a better complexant than citrate; the iron extracted in one dithionite-EDTA treatment at pH 5–6, under N2 at 315 K is not increased by increasing the number of extractions, and is equivalent to the total extractable iron found by previous procedures.

In a hitherto unpublished manuscript dated 1794–95, H.-B. de Saussure described three types of rudimentary laboratory experiments on weathering, each one lasting about 4 hours, undertaken on samples of jade, serpentine, feldspar, and mica schist. He submitted these samples to dry heating, heating with continuous addition of water, and heating with periodic addition of water. Experimentation was performed at temperatures of the order of 200–250°C, and Saussure seems to have realized that a reasonable increase of temperature was necessary for laboratory simulation of long-lasting geological processes. No changes were observed during dry heating whereas increasing alteration was noticed in the presence of water, particularly when heating was combined with periodic wetting. He concluded that these tests demonstrated his preconceived idea that weathering of minerals (mostly silicates) resulted from alternating periods of drying and wetting. This concept is basically very close, if not identical, to that underlying modern ideas on seasonal weathering.

The gold decoration technique of electron microscopy was used to observe the microtopography of natural (001) surfaces of 1:1 regularly-interstratified mica/smectite minerals (expandable layer: 40–45%) collected from four different pyrophyllite deposits in Japan. The specimens are characterized by parallel growth steps of malformed, circular or polygonal forms with varying step separations. Many particles exhibit paired steps that seem to show spiral growth. Microtopographic observations suggest that the growth of regular interstratification (at least for the specimens investigated in this study) normally takes place by an interlacing of paired steps. If the height of a single step corresponds to that of a mica or a smectite layer, the particles are estimated to be normally 40–300 Å in thickness. If the particles on which a spiral center is observed are single crystals of interstratified mica and smectite, then some crystals investigated in this study are far thicker than fundamental particles. The results of this study are interpreted to suggest that these regularly-interstratified mica/smectites were formed by hydrothermal metasomatism from their respective host rocks.

A new chemical, Peldri II, is evaluated as a compound for drying soft clay materials. Peldri II, a fluorocarbon (1,1-difluorotetrachloroethane), is a solid at room temperature and is a liquid above 25°C. Clay gels are embedded in Peldri II by immersing them in the liquid and allowing it to solidify. Once solidified, Peldri II will sublime, with or without vacuum, to a dry specimen, probably without introducing surface tension. Wyoming montmorillonite saturated in 10−3 M NaCl and 1 M CaCl2 solutions has been examined to compare preservation of its initial structure after Peldri II, critical point, and freeze drying techniques. Transmission electron microscopy of ultrathin sections, scanning electron microscopy, and mercury intrusion porosimetry techniques were used. No differences were detected between Peldri II and critical point drying methods. Peldri II appears to be a significant improvement as an alternative drying agent for clay materials in studies of their structural properties. It is also very convenient for drying large numbers of samples.

The sedimentation behavior of a fine kaolinite, comprising a substantial proportion of colloidal particles as well as non-colloidal ones, has been studied when fresh FeCl3 or F2(SO4)3 electrolytes are added. The sedimentation behavior depends on the pH and the nature of electrolytes and can be explained qualitatively, in our study, by the theory of Derjaguin, Landau, Verwey, and Overbeek (DLVO theory). Fe helps also to aggregate the kaolinite particles in flocs. Two extreme kinds of qualitative sedimentation have been observed: flocculation-sedimentation and accumulation-sedimentation. However, the transition between the two kinds of sedimentation is quite progressive. The present results are discussed in reference to the DLVO theory and the hydrolysis behavior of Fe electrolytes.

High-resolution transmission electron microscopy has revealed spherical and hemispherical structures on the surface of partly hydrated volcanic and synthetic glasses. These structures contrast with the bulk of the glass in showing lattice-fringe images indicative of the early stages of crystallization. Heavy-ion Rutherford scattering analysis of the noncrystalline volcanic glass indicates a structural water with hydrogen and deuterium. Depth profiles show that the glass grains contain structural water without adsorbed water on the surface. The presence of structural water in volcanic glass must be of interest to the formation of primitive clays. The spherical and hemispherical structures favor production of clay precursors in the presence of water.

The surface thermodynamic properties of a series of n-alkylammonium and quaternary ammonium treated clay films were determined by contact angle measurement of drops of test liquids using the Young equation for polar materials. The two clays were a Wyoming montmorillonite (SWy-1) and Laponite RD. For a series of primary n-alkyl (6 ≤ n ≤ 15) and several quaternary organic cations, the organo-clay (both SWy-1 and Laponite RD) showed very little change in the value of γLW compared to the equivalent ammonium-saturated clay. Also, γ⊕ remained small or increased slightly compared to the ammonium-saturated clay. For SWy-1 exchanged by both quaternary ammonium and primary n-alkylammonium cations, the value of γ⊖ was smaller (0.1 ≤ γ⊖ ≤ 15.8 mJ/m2) than for the ammonium-saturated clay (γ⊖ = 36.2 mJ/m2) and decreased linearly with the number of carbon atoms. The γ⊖ values for the organic cation-exchanged Laponite RD samples (24.2 ≤ γ⊖ ≤ 31.2 mJ/m2) were smaller than or comparable to the ammonium saturated clay (γ⊖ = 30.7 mJ/m2), and were relatively insensitive to the number of carbon atoms in the organic cation. Thus, for both clays the increased adsorption of organic molecules resulting from replacement of inorganic cations by organic cations is due primarily to the decrease in the value of the Lewis base parameter, γ⊖.

X-ray photoelectron spectroscopy (XPS) has been used to characterize the bonding state of Cu2+, Si4+, Al3+, and O2− ions in structural (octahedral and interlamellar) or adsorbed position in phyllosilicates. Five smectites, 5 kaolinites, and 1 chrysocolla with Cu(II) in known positions (octahedral, interlamellar, or surface adsorbed) have been investigated. Their spectra were compared with those of pure Cu metal and of pure Cu(I) and Cu(II) oxides.

The line for Cu 2p3/2 (binding energy of 935.4 eV) and well-defined shake-up lines (binding energy of about 943 eV) observed after 1 hr of X-ray irradiation are characteristic of Cu(II) in phyllosilicate octahedral sites. But due to the photoreduction effect, they show Cu(I) oxidation states (Cu 2p3/2, binding energy of 933.2 eV and near absence of shake-up lines) for the phyllosilicates with adsorbed Cu or in interlamellar positions. The kinetics of photoreduction distinguishes octahedral from interlamellar positions, and the latter from a surface adsorbed position. The enlargement of the FWHM (full width at half maximum) of XPS lines has been used to describe crystallochemical parameters linked to local ordering around the probe cations. Crystallization produces decreasing O 1 s and Cu 2p (octahedral cation) line widths but has no effect on the Si 2p (tetrahedral cation) line width. The enlargement of FWHM for all ion lines of the lattice is linked to the nature (Cu > Mg > Al) and the number and amount of structural cations in the phyllosilicates.