Garnierites represent significant Ni ore minerals in the many Ni-laterite deposits worldwide. The occurrence of a variety of garnierite minerals with variable Ni content poses questions about the conditions of their formation. From an aqueous-solution equilibrium thermodynamic point of view, the present study examines the conditions that favor the precipitation of a particular garnierite phase and the mechanism of Ni-enrichment, and gives an explanation to the temporal and spatial succession of different garnierite minerals in Ni-laterite deposits. The chemical and structural characterization of garnierite minerals from many nickel laterite deposits around the world show that this group of minerals is formed essentially by an intimate intermixing of three Mg-Ni phyllosilicate solid solutions: serpentine-népouite, kerolite-pimelite, and sepiolite-falcondoite, without or with very small amounts of Al in their composition. The present study deals with garnierites which are essentially Al-free. The published experimental dissolution constants for Mg end-members of the above solid solutions and the calculated constants for pure Ni end-members were used to calculate Lippmann diagrams for the three solid solutions, on the assumption that they are ideal. With the help of these diagrams, congruent dissolution of Ni-poor primary minerals, followed by equilibrium precipitation of Ni-rich secondary phyllosilicates, is proposed as an efficient mechanism for Ni supergene enrichment in the laterite profile. The stability fields of the solid solutions were constructed using [log aSiO2(aq), log ((aMg2+ aNi2+)/(aH+)2)] (predominance) diagrams. These, combined with Lippmann diagrams, give an almost complete chemical characterization of the solution and the precipitating phase(s) in equilibrium. The temporal and spatial succession of hydrous Mg- Ni phyllosilicates encountered in Ni-laterite deposits is explained by the small mobility of silica and the increase in its activity.

To test the ability of illitic clay minerals to retain argon, K/Ar ages were measured on grain-size separates from the Cretaceous Mancos Shale and associated bentonites that have been transformed into K-bentonite near the contact with a large Tertiary igneous stock. The ages of size separates of illite/ smectite from the K-bentonite nearest the contact were internally concordant and matched the hornblende K/Ar age of the stock. In contrast, K/Ar data from clay size fractions from shales adjacent to each K-bentonite were internally discordant with measured ages that were much greater than the age of the intrusion. Thus, significant radiogenic argon was retained by fine-grained detrital illite, even in shale samples very near the igneous contact. These results are convincing evidence that illitic clay minerals are excellent K/Ar clocks under conditions prevailing in sedimentary and diagenetic environments.

The transformation of clay minerals into organo-clays by surfactant intercalation is of great environmental and industrial importance because it causes the clay to attract hydrophobic contaminants and other non-polar organic compounds, but a better understanding is needed of the mechanisms by which different classes of surfactants are intercalated. The purpose of this study was to synthesize and characterize an organo-clay comprising triethylene glycol monodecyl ether (C10E3) non-ionic surfactant, which has a lamellar phase at room temperature, intercalated into Ca-montmorillonite from Wyoming (SWy-2). The C10E3 non-ionic surfactant differed from previous non-ionic surfactants used in the formation of a lamellar phase in that it consisted of the stacking of molecules by hydrophobic interaction. C10E3-clay composites were characterized by complementary techniques (adsorption isotherms, X-ray diffraction, and infrared spectroscopy) and were compared to benzyldimethyltetradecyl ammonium chloride (BDTAC) cationic surfactant-clay composites for different loadings of the surfactant. For large loadings, the amount of C10E3 adsorbed, which can be described by the Langmuir equation, seemed to reach a steady state close to that of the cationic surfactant. The adsorption processes of the two surfactants were different. For the cationic surfactant, the adsorption, as described in the literature, was due to ion exchange between organic cations and Ca2+ counterions. The adsorption of C10E3 did not depend on electrostatic interaction but rather was due to several interaction mechanisms (H-bonding, ion-dipole, and hydrophobic interaction). For both surfactants, the expansion was limited to two adsorbed monolayers parallel to the clay surface. The expansion of the basal spacing to 17 Å suggested a complete dissociation of the C10E3 lamellar phase when adsorbed on the Ca-smectite. Organo-clays made using the non-ionic surfactant were stable, changing the chemical nature of clay to hydrophobic, and allowing for other cations to be exchanged, which has importance in the manufacture of new nanocomposites or geochemical barriers.

Changes in hydraulic conductivity (HC) and clay dispersion of smectite-sand mixtures as a function of exchangeable Na in Na-Ca and Na-Mg systems were measured. The charge density on the smectites had no effect on Na-Ca and Na-Mg equilibrium, and the affinity of the clays for Na was similar in both systems. A decrease in HC at 0.01 M concentration was found to be due to clay swelling. Mg was found to be less effective than Ca in preventing the breakdown of the packets by low concentrations of exchangeable Na, and Na-Mg-smectite swelled more than Na-Ca-smectites.

Na-Mg-clay particles dispersed more readily than Na-Ca-clay particles when the mixtures were leached with distilled water; however, if the electrolyte concentration in the clay-sand mixture was controlled by the leaching solutions, no difference between the Na-Mg- and Na-Ca-clays was noted. Thus, the effect of Mg on clay mixtures leached with distilled water was apparently due to the effect of Mg on the hydrolysis of the clays. Increase in charge density increased the stability of the R2+ clay packets, and higher concentrations of Na were needed to break the packets. Mg was less effective than Ca in stabilizing the packets, and lower concentrations of Na were needed to break the Mg-packets.

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 dielectric properties of saturated kaolinite clay-water-electrolyte systems were determined over the frequency range of 30–105c/s. Very large dielectric constants are observed at low frequencies. Since the experimental data approach constant values at each end of this frequency spectrum, they can be described by a fairly well defined spectrum of relaxation times. The particle size and orientation, the type and amount of electrolyte, and temperature affect the low frequency dielectric increment and the average relaxtion time. Several physical processes, such as relaxtion due to dipolar rotational polarization, interfacial polarization, free space charge and bound ion polarization, are examined in an attempt to explain the observed data. It is concluded that there exists at present no theory to explain all the data, but the bound ion polarization mechanism appears to explain some of the results.

The treatment of smectites with a hydroxy-Al polymer produced chemically modified clays that had much greater affinities for chlorinated dioxins and biphenyls than untreated clays. For hydroxy-Al-treated kaolinite, the high affinity for chlorinated dioxins is thought to have arisen from an interaction between the hydroxy-Al polymer bound to the clay and the chlorinated dioxin in solution. Thus, the adsorption of dioxins from aqueous solution by hydroxy-Al-treated clays is similar to the adsorption of reactants from the gas phase by metals supported on mineral oxides during catalysis. In both systems, the essentially inert mineral oxide support effectively disperses the active adsorptive agent. At the concentrations of octachlorodioxin used in this study (≤5 ppb), hydroxy-Al-montmorillonite had a distribution coefficient of 90,000 (ml/g), corresponding to about 95% removal efficiency of the dioxin from solution per batch. For hexachlorohiphenyl, the distribution coefficient was 30,000 (ml/g), and the removal efficiency was 85%.

A set of 99 samples covering the whole range of low- and very low-grade metamorphic conditions has been used to compare Kübler index (KI) values measured on the illite 10 Å reflection (KI10 Å) with those obtained from the 5 Å reflection (KI5 Å). Evaluation of peak widths have been carried out both graphically on the recorded peak profiles from chart-strip X-ray diffraction (XRD) patterns and with the WINFIT computer program (Krumm, 1996) on fitted and decomposed profiles. All the measurements were performed both on air-dried and glycolated preparations. The data collected show that in the rock samples where illite is associated with significant amounts of I-S interstratified minerals, and/or K/Na intermediate micas, paragonite and other interfering phases, full width at half-maximum (FWHM) measurements on the 5 Å peak in fitted and decomposed XRD profiles from glycolated mounts give more reliable KI values than those obtained from the 10 Å peak. This is because of the easier and more complete de-summation of the illite second reflection from the contributions of all the interfering phases. In each sample population in which the rocks have the same metamorphic grade, KI5 Å values from fitted and decomposed profiles show much lower scattering in comparison with KI10 Å values and appear consistent with the values measured in lithologies without interfering phases.

The relationship between KI10 Å and KI5 Å appears very close to a 1:1 linear relationship; nevertheless, the conversion from KI5 Å to KI10 Å through the appropriate equation (KI10 Å = KI5 Å × 0.965 + 0.023°2θ) is recommended in order to avoid a small, but systematic, error.

In the range from late diagenesis to middle anchizone, where several phases may give diffraction effects interfering with illite peaks, the proposed procedure (i.e. FWHM measurements on the 5 Å peak in fitted and decomposed XRD profiles from glycolated mounts) seems to allow better estimates of the metamorphic grade than those obtained through traditional KI measurements.

Previous studies of the line profiles of the basal reflections of microcrystalline muscovites were refined by an adaptation of the method developed by Maire and Méring. In order to evaluate the variation of interlayer spacings, the method required only relative values of Fourier coefficients, without the correction for instrumental broadening, which was the source of one of the most critical problems previously. Instead of Kα radiation, Kβ radiation was used to record line profiles since difficulties associated with the separation of Kα1 and Kα2 radiations could not be overcome satisfactorily.

The data reconfirmed that the line broadening of 00l reflections was due not only to a small particle-size effect, but also to structural disorders involving the variation of the interlayer spacings. For the four specimens investigated here, the mean squares of the variation of interlayer spacings ranged from 0 to 0·0358, the square roots of which were inversely proportional to the total number of interlayer cations. It is considered that the observed distortions were mainly attributed to non-uniform interlayer spaces between silicate layers arising from an irregular distribution of interlayer cations. The data also indicated that the crystallites of all four specimens consisted of a similar number of layers. The method showed promise for the study of the nature and extent of structural disorders in micas or other silicate minerals.

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 Clay Minerals Society Source Clay kaolinites, Georgia KGa-1 and KGa-2, have been subjected to particle size determinations by 1) conventional sedimentation methods, 2) electron microscopy and image analysis, and 3) laser scattering using improved algorithms for the interaction of light with small particles. Particle shape, size distribution, and crystallinity vary considerably for each kaolinite. Replicate analyses of separated size fractions showed that in the <2 µm range, the sedimentation/centrifugation method of Tanner and Jackson (1947) is reproducible for different kaolinite types and that the calculated size ranges are in reasonable agreement with the size bins estimated from laser scattering. Particle sizes determined by laser scattering must be calculated using Mie theory when the dominant particle size is less than ∼5 µm. Based on this study of two well-known and structurally different kaolinites, laser scattering, with improved data reduction algorithms that include Mie theory, should be considered an internally consistent and rapid technique for clay particle sizing.

Volcanic tuff from the Cabo de Gata region in Almería, southeastern Spain, was altered under hydrothermal conditions at different temperatures (60 to 180°C), reaction times (60 to 360 days), and reacting solutions (deionized water and NaCl and KCl solutions with Na/K ratios from 0.01 to 100, and a total salt concentration of 0.1 to 1 M).

X-ray diffraction (XRD) patterns of the reacted samples revealed a very weak, broad peak at ∼13 Å that migrated to 17 Å upon glycolation. Comparison between simulated (NEWMOD) and experimental XRD patterns indicated that the neoformed phase is a random mixed-layer illite-smectite (I-S) with 75% expandable layers. Fourier transform infrared (FTIR) spectroscopy showed that I-S formation was most extensive for high pH (8–9) solutions, corresponding to dilute solutions and, especially, to deionized water. Analytical electron microscopy (AEM) analyses of isolated I-S particles showed that most of them are smectite-rich I-S regardless of the experimental conditions, in agreement with XRD results. The I-S particles had a wide range of octahedral Mg contents. The pH and Na, K, Ca and Mg concentrations in the final solutions suggested cation (including H+) exchange as a major process in the alteration experiments. Analysis of aqueous activity diagrams (log aK/aHvs. log $a_{{\text{SiO}}_{\text{2}}}$) showed that some solution compositions are consistent and some are inconsistent with I-S formation. These results, combined with complementary electron microscopy analyses (de la Fuente et al., 2000a), are interpreted to be due to direct transformation of the glass into I-S in a process controlled by glass composition.

Hydroxy-chromium solutions were prepared from chromium nitrate solutions by adding NaOH with OH/Cr = 2.

The solutions were treated at 20°C and 60°C. The hydrolysis times were from 1 to 100 days. Polymeric species in hydrolyzed chromium solutions were followed by visible absorption spectra within the range 325–800 nm and by pH measurement. OH-Cr-smectite with high d(001) spacing (2.07 nm) was obtained when hydroxy-chromium solution was prepared at 60°C and with 1-day hydrolysis. When this sample was heated up to 350°C the basal spacing collapsed at 1.8 nm.

The samples were characterized by X-ray diffraction and N2 adsorption-desorption isotherms.

Intercalation of amino acids into 10.0-Å hydrated kaolinite was studied by powder X-ray diffraction (XRD), differential thermal analysis-thermal gravimetry (DTA-TG), and infrared (IR) spectroscopy. Intercalation was found to be dependent on the chain-length, pH, and the concentration of the amino acid zwitterion. Near the isoelectric point, fully intercalated phases were obtained in solutions of concentration >0.5–1 M for glycine (Gly), 2–3 M for β-alanine (β-Ala), and 12 M for both γ-aminobutyric acid (γ-Aba) and δ-aminovaleric acid (δ-Ava). ∊-aminocaproic acid (∊-Aca) with a long chain (C = 6) was only partially intercalated. Intercalated amino acid formed a mono-molecular arrangement with the alkyl chain tilting toward the layer at an angle related to H2O content. The compositions of the intercalates of the Gly and β-Ala are Al2Si2O5(OH)4·(Gly)0.67·0.24H2O and Al2Si2O5(OH)4·(β-Ala)0.63·0.25H2O, respectively, based on TG data. From IR data, Gly and β-Ala molecules are found intercalated as zwitterions and these molecules form hydrogen bonds with both the Al-OH and Si-O surfaces of kaolinite. Washing the intercalate with water produced a hydrated kaolinite, which may form a second amino-acid intercalate of high order. Thus, hydrated kaolinite intercalates or deintercalates amino acids depending on concentration and conditions.

A method is described for quantitatively expressing orientation of kaolinite particles in a wet clay mass. Wet clay is impregnated with a polyalcohol which permits grinding of a very flat surface (without disrupting the original fabric) for quantitative X-ray measurement. In the specific procedure discussed, a Norelco diffractometer equipped with a pole figure device and a Geiger detector was employed to measure by reflection the diffracted intensity of the 002 and 020 kaolinite reflections. The amplitude of the 002 peak to the amplitude of the 020 peak is called the peak ratio, PK, which quantitatively expresses particle orientation at any chosen angle to the specimen surface. Limits of orientation are random and maximum orientation. For the kaolinite tested, truly random orientation was achieved which gave a PR = 2.0. Maximum orientation found experimentally was PR = 200 for thoroughly dispersed slurry slowly dried on a glass slide. Vertical and lateral variations can be measured either continuously or in steps of any chosen size.

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.