Hydrothermal alteration has caused illitization along a 40m vertical profile in the Tsantilis bentonite deposit, Eastern Milos, Greece which consists principally of a Wyoming-type montmorillonite and authigenic K-feldspar. The product K-bentonite which contains illite/smectite, kaolinite, K-feldspar, quartz, sulphates and sulphides exhibits an unusual tendency for increase of expandability with depth.

Mineralogy and I/S textures were determined with X-ray diffraction and SEM and TEM methods respectively and chemistry using X-ray fluorescence. Illitization is characterized by a 5- to 6-fold increase of K and release of Si, Fe, Mg Na, and Ca from the parent rock, indicating a K-influx (K-metasomatism) in the system.

The I/S particle morphology is characterized by both flaky and lath-like particles, the former dominating in the range 100-50% expandable layers (R0 ordering) and the latter in the range 50-10% expandable layers (R1 and R > 1 ordering). Flaky particles are also abundant in samples with R1 ordering and abundant kaolinite, indicating that the latter might affect illitization. The I/S particles are classified in populations with thickness multiples of 10 A, their thickness being probably smaller than the coherent XRD domain. As the reaction proceeds, particles grow thicker and more equant. The distribution of I/S particle dimensions forms steady state profiles showing log-normal distribution; however, sensu stricto Ostwald ripening is unlikely. It seems that the reaction proceeds toward minimization of the surface free energy of I/S, being affected principally by temperature and K-availability. The spatial distribution of expandability implies that the heating source was probably a mineralized vein with T < 200°C, directed away from the bentonite, suggesting that illitization might be used as an exploration guide for mineral deposits.

This work investigates unit cell dimensions, crystal size and specific surface area of aluminous goethite that was progressively dehydroxylated to form hematite. Goethite synthesized from the ferrous system altered to hematite with DTGA maximum increasing from 236° to 273°C for 0 to 30.1 mole % Al-substitution. Unit cell dimensions of goethite and hematite decreased as Al-substitution increased and increased as excess OH increased. The crystallographically equivalent a axis of goethite and c axis of hematite were more sensitive than other axes to the presence of excess structural OH associated with Al-substitution. Specific surface area increased from 147 to 288 m2/g for goethite and from 171 to 230 m2/g for hematite as Al-substitution increased. An increase in specific surface area on heating goethite at temperatures between 200° and 240°C is related to a decrease in the size of coherently diffracting domains of goethite crystals and to the development of pore and structural defects associated with the formation of hematite. The decrease in specific surface area for heating temperatures above 240°C is attributed to the growth of hematite crystals by diffusion.

Adsorption of uranyl to SWy-1 montmorillonite was evaluated experimentally and results were modeled to identify likely surface complexation reactions responsible for removal of uranyl from solution. Uranyl was contacted with SWy-1 montmorillonite in a NaCIO4 electrolyte solution at three ionic strengths (I = 0.001, 0.01, 0.1), at pH 4 to 8.5, in a N2(g) atmosphere. At low ionic strength, adsorption decreased from 95% at pH 4 to 75% at pH 6.8. At higher ionic strength, adsorption increased with pH from initial values less than 75%; adsorption edges for all ionic strengths coalesced above a pH of 7. A site-binding model was applied that treated SWy-1 as an aggregate of fixed-charge sites and edge sites analogous to gibbsite and silica. The concentration of fixed-charge sites was estimated as the cation exchange capacity, and non-preference exchange was assumed in calculating the contribution of fixed-charge sites to total uranyl adsorption. The concentration of edge sites was estimated by image analysis of transmission electron photomicrographs. Adsorption constants for uranyl binding to gibbsite and silica were determined by fitting to experimental data, and these adsorption constants were then used to simulate SWy-1 adsorption results. The best simulations were obtained with an ionization model in which AlOH2+ was the dominant aluminol surface species throughout the experimental range in pH. The pH-dependent aqueous speciation of uranyl was an important factor determining the magnitude of uranyl adsorption. At low ionic strength and low pH, adsorption by fixed-charge sites was predominant. The decrease in adsorption with increasing pH was caused by the formation of monovalent aqueous uranyl species, which were weakly bound to fixed-charge sites. At higher ionic strengths, competition with Na+ decreased the adsorption of UO22+ to fixed-charge sites. At higher pH, the most significant adsorption reactions were the binding of UO22+ to AlOH and of (UO2)3(OH)5+ to SiOH edge sites. Near-saturation of AlOH sites by UO22+ allowed significant contributions of SiOH sites to uranyl adsorption.

An improved model for the interpretation of thermal effects during dehydroxylation in aluminous dioctahedral 2:1 layer phyllosilicates considers trans-vacant (tv) and cis-vacant (cv) 2:1 layers and leads to very different temperatures of dehydroxylation for these tv and cv vacant modifications. In particular, smectites and illites consisting of cv 2:1 layers are characterized by dehydroxylated temperatures which are higher by 150°C to 200°C than those for the same minerals consisting of the tv 2:1 layers. A considerable lengthening of the OH-OH edges in cv 2:1 layers in comparison with the OH-OH edges in the tv 2:1 layers is postulated as the reason for the higher dehydroxylation.

Dehydroxylation in aluminous cv 2:1 layer silicates should occur in two stages. Initially, each two adjacent OH groups are replaced by a residual oxygen atom and the Al cations, which originally occupied cis -and trans-sites, become 5- and 6-coordinated, respectively. The structure of 2:1 layers corresponding to this stage of the dehydroxylation is unstable. Thus the Al cations migrate from the former trans-sites to vacant pentagonal prisms. The resulting dehydroxylated structure of the original cv 2:1 layers is similar to that of the former tv 2:1 layers.

Diffraction and structural features of the cv dehydroxylates predicted by the model are in agreement with X-ray diffraction effects observed for cv illite, illite-smectite and montmorillonite samples heated to different temperatures. In particular, the diffusion of Al cations to empty five-fold prisms during dehydroxylation of the tv 2:1 layers explains why dehydroxylation of reheated cv montmorillonites occurs at temperatures lower by 150°C to 200°C than samples that were not recycled.

The Lower Pleistocene bentonite deposits of Eastern Milos, Greece have been formed at the expense of volcaniclastic rocks under submarine conditions. Systematic variation of the major chemical elements reveals that the deposits were formed from different precursors which were erupted from different volcanic centers belonging to at least two separate volcanic provinces. The volcanic eruptions were probably subaqueous. The major authigenic phases are smectite, K-feldspar, opal-CT and the zeolites mordenite and clinoptilolite. The deposits have a complex history and have been affected by hydrothermal alteration.

The geological features of bentonites coupled by the presence of abundant authigenic K-feldspar indicate that alteration of the parent volcanoclastic rocks took place under low temperatures and is probably not related to hydrothermal alteration, which is a separate event. Hydrothermal alteration has modified both the mineralogical characteristics and the properties of bentonites. Alteration of the parent rocks to bentonites was favoured by high water: wall rock ratios and fluid flow and is associated with leaching and subsequent removal of Na, K and Ca. The source of Mg was the parent rocks and only small scale Mg-uptake from the sea water has probably taken place. The formation of authigenic K-feldspar has probably been favoured by a high K+/H+ activity ratio and high Si activity of the pore fluid. Such conditions might have been favoured by the pH conditions and the cooling history of the parent rocks.

Experimental alteration of obsidian with HCl solution was performed to elucidate dissolution mechanism and formation process of clay minerals in acid solution. Reactions were carried out using 0.1, 0.5, and 4.0 g of obsidian to 100 ml of 0.01 N HCl solution at 150° and 200°C for 1 to 60 days. The reaction products were examined by X-ray powder diffraction, scanning electron microscopy, transmission electron microscopy (TEM), and energy dispersive X-ray analysis. The surface composition of obsidian before and after alteration was investigated by X-ray photoelectron spectroscopy (XPS). TEM showed that boehmite precipitated at early stage and spherical kaolinite appeared subsequently by 200°C reactions. However, spherical halloysite occurred predominantly with small amounts of allophane, boehmite, and kaolinite by 150°C reaction in which formation process of the halloysite from allophane passing through an intermediate phase of small size rounded aggregate that consists of fine particles of allophane was observed. A boehmite exhibiting hexagonal platy habit with higher degree of crystallinity was formed by 200°C reaction as a stable phase in solution containing lower Si concentration at which the solution composition coincides with the stability field of boehmite on activity diagram for the system Na2O-Al2O3-SiO2-H2O. The fibrous boehmite having lower crystallinity appeared with increasing Si concentration, considered as a metastable phase in the stability field of kaolinite. XPS indicated that dissolution of obsidian in acid solution proceeded initially by cation exchange between Na ions and hydronium ions in solution and subsequently by preferential release of Al ions relative to Si from the Na depleted surface.

High resolution transmission electron microscopy (HRTEM) have been performed on dispersed portions of one R > 1 and two R3 illite/smectite (I/S) samples from Silurian K-bentonites. R > 1 sample was studied by HRTEM before and after alkylammonium ion treatment and R3 samples were studied only after alkylammonium ion treatment. The HRTEM images of the chemically untreated R > 1 sample were predominated by lattice fringe contrast with 20–40 Å periods, interpreted to represent various ordered I/S units. HRTEM images of the three alkylammonium-treated samples displayed very small, dispersed particles composed of illite packets separated by alkylammonium expanded interlayers. In the R > 1 sample, illite packets were mostly 20 Å to 40 Å thick whereas in R3 samples they were predominantly over 40 Å. Although a good degree of dispersion of the bulk samples was achieved, dispersed particles recorded on images were thicker than the fundamental particles postulated by Nadeau and coworkers. Alkylammonium ion-expanded interlayer thicknesses point out a trend toward a higher charge in the expandable interlayers (i.e., illite particle surfaces) with increasing illite content from the R > 1 sample to the R3 samples. In the R3 samples, the interlayer charge is sufficiently high to be vermiculitic.

Young marine green grains, from Fe-rich sediments, were studied by using HRTEM systematically combined with punctual microchemical EDX analyses. Experimental results demonstrated these grains were made of a mixture of very small phases (mainly 1:1 and 2:1 silicates layer phases) with a dominant 7-Å Fe specie. All the main crystallochemically characterized phases appeared intimately related in the same evolutionary process. Each of them experienced different and well described conversion mechanisms. So first, a starting original Fe-rich kaolinite recrystallized via solution into another particular 7-Å Fe-rich phase, the composition of which varies from a di-tri to a pure trioctahedral (Mg + Fe) end member.

This Fe-rich 1:1 mineral is effectively not a classical one. Then crystallization of a 10Å, rather dioctahedral K-rich phase occurs at the expense of it, through 1:½:1 interstratified structures. Such an evolution takes place through a solid state mechanism in which one 10-Å layer replaces one 7-Å layer. Another part of mica-like structures may also directly develop after dissolution of original kaolinites. The development of 10-Å K-rich phases could be significative of the beginning of the glauconitization process in these grains.

The layer charge characteristics of expanding phyllosilicates in four salt-affected soils in Alberta, Canada were investigated using X-ray diffraction analysis of alkylammonium saturated samples. The layer charge was found to be lower and more heterogeneous than previously reported for non-saline Alberta soils, with the mean layer charge ranging between 0.261 to 0.339 tool (—)/O10(OH)2. Layer charge characteristics varied inconsistently with location, depth and particle size, likely the result of both different origins and weathering processes. Different degrees of K depletion from the micaceous component after equilibration with alkylammonium compounds may also account for some variability between samples. Extreme broadening and essential disappearance of smectite diffraction maxima was noted for some samples after intercalation with alkylammonium cations of all carbon chain lengths, indicating unusual alteration of the layer charge characteristics in some salt-affected soils.

The Sinya Beds of the Amboseli Basin in Tanzania and Kenya consist largely of carbonate rocks and Mg-rich clays that are intensely deformed where exposed in and near former meerschaum mines. The carbonate rocks consist of limestone and dolomite in Tanzania, but only dolomite has been identified in Kenya. Sepiolite and mixed-layered kerolite/stevensite (Ke/St) are subordinate constituents of the carbonate rocks. The carbonate rocks and overlying bedded sepiolite were deposited in a semiarid lake basin at the foot of the large volcano Kilimanjaro. Calcite and dolomite of the carbonate rocks have δ18O values 4–6‰ lower than calcite and dolomite of the late Pleistocene Amboseli Clays, suggesting that the Sinya Beds were deposited in the middle or early Pleistocene under a different climatic regime when meteoric water had lower δ18O values than at present.

Mg-rich clay minerals form veins and fill cavities in the Sinya Beds. The principal clay minerals are sepiolite and Ke/St, some of which contains substantial Al and Fe (Al-Ke/St). NEWMOD® modeling and other X-ray diffraction (XRD) data suggest that most of the Ke/St contains 25–50 percent kerolite layers, but minor amounts of kerolite-rich Ke/St are present in some samples. Illite with an inferred high content of Fe or Mg is a minor constituent of the samples with Al-Ke/St. The cavity-filling clays were chemically precipitated, as shown by field relationships and SEM study. The early-deposited clays of veins and cavities are principally Ke/St with minor sepiolite, and the latest clay is sepiolite (meerschaum), generally with minor Ke/St.

The δ18O values of cavity-filling Ke/St range from 22.5–25.6‰ and correlate with mineral composition, with the highest values associated with the highest content of stevensite and the lowest values with the highest content of kerolite. This relation suggests that high salinities favored stevensite and low salinities favored kerolite. δ18O values of sepiolite (meerschaum) fall in the middle of the range for Ke/St, suggesting that salinity was not the main control on sepiolite precipitation. High values of $a_{Si{O}_2}/a_{M{g}^{2+}}$ may have been a major factor in sepiolite precipitation.

Different mixtures of dilute ground water and saline, alkaline lake water in pore fluids may largely account for the differences in clay mineralogy of cavity-filling clays. Sepiolite is the dominant clay mineral in lacustrine sediments of the Amboseli Basin, and the cavity-filling sepiolite may reflect a high proportion of lake water. The low-Al Ke/St may have formed from fluids with a higher proportion of ground water. Detrital clay was very likely a factor in forming the Al-Ke/St, for which δ18O values suggest a saline environment.

IronIII for TiIV substitution in the structure of pedogenic and synthetic anatase of up to Fe/ (Ti+Fe) 0.1 mol/mol was indicated by an increase in unit cell size as measured by XRD line shifts. Mössbauer- and electron paramagnetic resonance spectra at both, 298 K and 4.2 K supported this by the presence of signals typical for octahedrally coordinated FeIII in a diamagnetic matrix. Charge compensation was achieved by structural OH, as indicated by FTIR bands at 3360 and 960 cm−1, which were absent in pure anatase and which disappeared on heating. The weight loss on heating amounted to ca. 0.5 mol H2O/mol Fe. At 600°C structural Fe was ejected, the unit cell size decreased to that of pure anatase, and pseudobrookite, Fe2TiO5, was formed.

The adsorption of the herbicide imazamethabenz-methyl, a mixture of the two isomers methyl (±)-2-[4,5-dihydro-4-methyl-4-(1-methylethyl)-5-oxo-1 H-imidazol-2-yl]-4-methylbenzoate para isomer) and methyl (±)-2-[4,5-dihydro-4-methyl-4-(l-methylethyl)-5-oxo-1 H-imidazol-2-yl]-5-methyl-benzoate (meta isomer), from water onto Al3+, Fe3+-, Ca2+-, K+- and Na+-montmorillonite was studied by analytical (HPLQ methods. The adsorption from an organic solvent was also investigated by spectroscopic (IR) and X-ray diffraction measurements. It was observed that, depending on the acidic properties of the exchangeable cations, two different mechanisms may take place. The first one, acting on Fe3+- and Al3+-clays, involves the protonation of the more basic nitrogen atom of imidazolinone ring of the herbicide because of a proton transfer from the acidic metal-bound water, followed by adsorption on the clay surfaces. In this case, the clay surfaces have greater affinity for the meta than the para isomer, due to the extra-stabilization of the meta protonated form by resonance. The second mechanism, taking place on Ca2+-, K+- and Na+-clays, is hydrogen-bond formation between the ester carbonyl group of the herbicide and hydration water metal ions and is not affected by the structure of the isomers.

Intercalation complexes of a Hungarian kaolinite were prepared with hydrazine and potassium acetate. The thermal behavior and decomposition of the kaolinite-potassium acetate complex was studied by simultaneous TA-EGA, XRD, and FTIR methods. The intercalation complex is stable up to 300°C, and decomposition takes place in two stages after melting of potassium acetate intercalated in the interlayer spaces. Dehydroxylation occurred, in the presence of a molten phase, at a lower temperature than for the pure kaolinite. FTIR studies revealed that there is a sequence of dehydroxylation for the various OH groups of intercalated kaolinite. The reaction mechanism was followed up to 1000°C via identification of the gaseous and solid decomposition products formed: H2O, CO2, CO, C3H6O, intercalated phases with basal spacings of 14.1 Å, 11.5 Å, and 8.5 Å as well as elemental carbon, K4H2(CO3)3 · 1.5H2O, K2CO3 · 1.5H2O, and KAlSiO4.

Cation exchange experiments were carried out on phlogopite, biotite, and muscovite using cryptand [222] as a complexing agent, dioxane as solvent, and Li as the exchanging cation. The results indicate greater than 90% exchange of the analyzed cations K+, Rb+, and Sr++ in phlogopite and biotite after two days. Similar results for the exchange in muscovite are observed but it is apparently slower. The amount of exchange observed for mica depends mainly on pH, time and the exchanging cation at a constant temperature. Residues of the mineral phase were also investigated by X-ray diffraction and a significant change of the interlayer spacing was detected. Some samples of the residue were analyzed for Li content. The compositions of the treated samples were in good agreement with the determined exchange of K+.

The fraction <20 μm of a bentonitic material was selected to study the transformation of smectite into illite under hydrothermal conditions. Powder XRD showed that the studied material was composed of 97% dioctahedral smectite and 3% of quartz, cristobalite and plagioclase. The XRD analysis of the oriented, glycolated sample showed that the smectitic phase was actually a randomly interstratified illite/smectite with 11% illite. The chemical analysis of the sample yielded the structural formula: K0.25Na0.25Ca0.12Mg0.13(Al2.76Fe0.33Mg1.03)(Si7.66Al0.34)O20(OH)4. The reaction conditions of the hydrothermal experiments were: KCl concentrations 0.025, 0.05, 0.1, 0.3, 0.5, 1 M; temperature 60, 120, 175, 200°C; run time 1, 5, 15, 30, 90, 180 days; solid: solution ratio 1:5. XRD of run products showed an important transformation of smectite into illite, in contrast with all other techniques (DTA, IR, NMR), which did not detect any transformation of the original material. This suggests that illite quantification in I/S by means of XRD patterns after hydrothermal experiences can be much affected by other variables. The original material and the run products were analysed by means of DTA. The starting material displayed two dehydroxylation peaks, one at 560°C corresponding to illite, and the other at 650°C corresponding to smectite. Quantification of the two dehydroxylation peaks also yielded a content of 11% illite. The run products displayed DTA diagrams in which the smectitic peak remained unaltered, but the illitic one was reduced or eliminated by the presence of exchangeable K in the interlayer. When exchangeable K was removed the illitic dehydroxylation peak appeared again. The coherence of XRD and DTA in quantifying the proportion of illite layers and the effect of exchangeable K on dehydroxylation of illite layers in mixed-layer illite/smectite seem to be positive proofs of the existence of polar layers.

Cu montmorillonite heated with or without potassium halide was studied by IR and ESR spectroscopy, supplemented by XRD measurements, microprobe and chemical analyses. It appears that on heating Cu montmorillonite, most of the Cu ions migrate into hexagonal cavities and eventually, when dehydroxylation occurs, into octahedral vacancies. Some Cu ions may penetrate into octahedral vacancies before dehydroxylation. In the presence of potassium halide, deprotonation facilitates penetration of Cu into octahedral vacancies. The presence within the layers of non-exchangeable Cu ions that are inaccessible to water does not necessarily cause the perturbation of OH bending vibrations conventionally attributed to migration of small cations into the structure. Such perturbation was only observed when the basal spacing was reduced to ~9.5Å.

The uniformity of clay films affects the transport of an anionic electroactive probe through the film. When cations other than Na+ are present in the initial swelling of the film (such as native K+ and Ca2+), or when the native clay is highly charged, internal dislocations of the film, caused by variable stacking domains, enhance the diffusive transport of Fe(CN)63− across the film. This effect is investigated using clay-modified electrodes in which the clays are of variable exchange forms (Na+, Ca2+, or K+) and variable charge. The charge on the clay is determined both by the native form of the clay and by reduction of structural Fe3+. The results suggest that swelling of clays increases in a linear fashion with CEC, at least for minimally charged clays.

A method is described for the separation of the finest particles from soils and sediments without mechanical disturbance. Particles are separated through the induction of osmotic stress. Generally, samples are treated with a concentrated sodium salt solution and then exposed to water by diffusion. Naturally sodic samples are simply exposed to water. Solid samples and the swollen and dispersed material they produce are confined by dialysis tubing. Examples show that the method gives a size gradient of particles in a vertical column of suspension. The compositions of particles can vary with size. The method can be used to show the effects on separated particles of ions other than Na+ and also of other physicochemical treatments of soils and sediments. It is inexpensive and requires little labor.

The influence of surfactants on the flow behavior of sodium montmorillonite dispersions (2% w/w) was studied for a cationic (cetylpyridinium chloride, CPCl) and an anionic surfactant (sodium dodecylsulfate, SDS). When the dispersion pHs were >3.5 and <7, CPCl concentrations >10−4 M increased the shear stress but the Bingham yield value remained virtually unchanged (τo ≈ 100 mPa). At pH ≈ 7, the shear stress and yield point decreased with increasing CPCl concentration (τo from 430 to 100 mPa). The flow properties of sodium calcium bentonite dispersions were independent of pH and CPCl concentrations ≤ 10−4 M; they increased modestly at higher concentrations. At pH < 4, SDS addition to the sodium montmorillonite dispersions increased the shear stress and yield value to a maximum value (τo = 2100 mPa) at 10−3 M SDS; higher SDS concentrations reduced the shear stress and yield value. At pH > 4, the flow values decreased to a minimum value at 10−2 M SDS (τo from 430 to 50 mPa). The flow of the sodium calcium bentonite dispersions at pH > 4 was independent of SDS concentrations ≤ 10−3 mole/liter; at higher SDS concentrations, the flow values increased more strongly in sodium calcium bentonite than in sodium montmorillonite dispersions.

Surfactants influence the flow behavior of sodium montmorillonite dispersions by their action on the card-house networks in strongly acidic medium and, at higher pH, by the electroviscous effect. At the highest surfactant concentrations without flocculation, the shear stress and yield value are increased by interacting chains of opposed particles.

Addition of the surfactants increases the salt (NaCl) stability of the dispersions because the adsorbed surface active agents influence the counterion distribution between the Stern and the diffuse ionic layer.

Scanning electron microscopy has revealed the presence of spherical, lath and platy kaolinite in gels with Si/Al atomic ratio ranging from 1.84 to 0.76 that are hydrothermally treated under different temperature and time conditions. Hemispherical structures and excavated zones, at different stages of evolution, have been observed on the surface of the gel grains, indicating that spherical particles do not precipitate from the solution but are generated from the gels. The quantity of spherical particles depends on temperature, time and the chemical composition of the starting gel. Products from starting material with Si/Al ≈ 1 yield the highest quantity of these particles. Being metastable, sphere dissolution controls the chemistry of the solution and consequently the morphology of the precipitating crystals thus producing more elongated, curved and irregular outlines when gels with Si/Al ≈ 1 are hydrothermally treated.