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

A new, well-ordered, thermally robust ethylene glycol intercalate of kaolinite was formed by refluxing the dimethyl sulfoxide intercalate of kaolinite (Kao-DMSO) with dry ethylene glycol (EG). This new phase (Kao-EG 9.4 Å) which is characterized by a d001 of 9.4 Å is distinct from a previously reported ethylene glycol intercalated phase of kaolinite (Kao-EG 10.8 Å) which has a d001 of 10.8 Å. The characterization of these two phases was studied by XRD, NMR, FTIR, and TGA/DSC. It was found that the concentration of water in the ethylene glycol reaction media played a crucial role in governing which of the phases predominated. Water favored Kao-EG 10.8 Å formation, while anhydrous conditions favored the formation of Kao-EG 9.4 Å. It is hypothesized that Kao-EG 9.4 Å is a grafted phase resulting from the product of the condensation reaction between an aluminol group on the interlamenar surface of kaolinite and the alcohol group of ethylene glycol. Ethylene glycol units would be attached to the interlamellar surface of kaolinite via Al-O-C bonds. The Kao-EG 9.4 Å phase was found to be resistant to both thermal decomposition up to 330°C and also, once formed, in the absence of interlamellar water molecules, to decomposition by hydrolysis in refluxing water.

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.

Despite substantial scientific research efforts, accurate determination of the petrophysical effects of clay minerals on reservoir sands remains problematic. Diagenetic clays such as smectite and illite are of particular interest because of the pronounced effects these clays can have on reservoir quality. Here, results are reported from an experimental study based on the hydrothermal growth of smectite in synthetic sands. The sands contained quartz, dolomite and kaolinite, and were reacted at 175–200°C, for 19–45 d. The hydrothermal reaction can be written as follows:

$$dolomite + kaolinite + quartz \to smectite + calcite + CO<Subscript>2</Subscript>$$

Formation of kaolinite-smectite (K-S) mixed layers in a soil toposequence developed from basaltic parent material was examined. The soil formed in a temperate climate with alternating dry and wet seasons in Sardinia (Italy). Chemical composition and charge characteristics of the smectite component in the K-S mixed layers were analyzed to help determine a mechanism for formation. Soils were sampled at the top, intermediate, and base of a steep (35%) slope. As indicated by X-ray diffraction data, the fine clay fraction (>0.1 μm) in the soils is dominated by K-S with a decreasing proportion of kaolinite from the top (70%) to the base (30%). Rapid internal drainage induced by the slope is probably the major factor responsible for the formation of K-S. Chemical composition and charge characteristics of the smectite component in the K-S were analyzed by X-ray diffraction (intercalation with alkylammonium ions), cation exchanged capacity (CEC) and surface area measurements, and infrared spectroscopy. Results indicate that the smectite component is nearly identical over the soil toposequence. The smectite component is the same with respect to charge magnitude and chemical composition, independent of the proportion of kaolinite and smectite components. This suggests the pedogenic formation of K-S by transformation of smectite through dissolution of some smectite layers and subsequent crystallization of kaolinite between the layers of the remaining smectite crystallites.

The sorption of the uranyl oxo-cation (UO22+)at different types of binding sites on layer silicate mineral surfaces was investigated. Well-characterized samples of vermiculite and hydrobiotite were exposed to aqueous uranyl under conditions designed to promote surface sorption either at fixed charge ionexchange sites or at amphoteric surface hydroxyl sites. The local structure of uranium in the sorption samples was directly measured using uranium L3-edge extended X-ray absorption fine structure (EXAFS). Polarized L1- and L3-edge X-ray absorption near-edge structure (XANES) measurements were used to characterize the orientation of uranyl groups in layered samples. X-ray diffraction (XRD) measurements of interlayer spacings were used to assess the effects of ion-exchange and dehydration upon the mineral structure. The most significant findings are: (1) Under conditions which greatly favor ion-exchange sorption mechanisms, uranyl retains a symmetric local structure suggestive of an outer-sphere complex, with a preferred orientation of the uranyl axis parallel to the mineral layers; (2) Upon dehydration, the ionexchange complexes adopt a less symmetric structure, consistent with an inner-sphere complex, with less pronounced orientation of the uranyl axis; and (3) For conditions which favor sorption at surface hydroxyl sites, uranyl has a highly distorted equatorial shell, indicative of stronger equatorial ligation, and the detection of a neighboring U atom suggests the formation of surface precipitates and/or oligomeric complexes.

Nanomorphological structure of well-crystallized Georgia and poorly crystallized North Queensland kaolinite particles have been compared using field emission scanning electron microscopy (SEM) and atomic force microscopy (AFM). In general, there is good agreement in information from the 2 very different imaging techniques. AFM gives more detailed information on step and ledge dimensions, microvalleys and crystallographic orientation of irregularities on basal planes and edges of the crystallites. There are major differences in nanomorphology and surface structure between the 2 kaolin samples with the Georgia kaolin showing 200–500-nm, relatively flat basal planes with some cascade-like step growth 50–100 nm wide. The edges, apparently flat and right-angled in SEM images, appear beveled in AFM images due to artifacts from the aspect ratio of the AFM tip. The North Queensland kaolinite has much more complex surface structure with anhedral crystallites attached to larger particles, high density of steps and nm-scale irregularities (often crystallographically directed). The additional step edge site contribution from the attached crystallites is estimated as a minimum of 6%, giving a total edge contribution above 30% of the kaolinite total surface area. These structures will generate a substantial pH-dependent charge across the surfaces of the North Queensland kaolinite platelets. An idealized, uniform, pH-independent, negatively charged basal plane cannot be assumed from these structures. There is also some evidence, from both SEM and AFM images, of curvature in the thinner, poorly ordered structures of the North Queensland kaolinite particles.

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.

The cation exchange capacities (CEC) and extractable cations in smectite, corrensite and palagonitized glass from hydrothermally-altered pillow lavas and hyaloclastite breccias were measured by both bulk wet chemical and in situ microanalytical techniques. Smectite has CEC's between 60 and 120 meq/100 g, palagonitized glass between 30 and 60 meq/100 g, and corrensite approximately 35 meq/100 g as determined by the in situ CsCl-exchange method. These experiments generally verify that Cs exchanges for those cations that are presumed (from the stoichiometry implied by microprobe analyses) to occupy interlayer sites in sheet silicates. Results of conventional CEC determinations are consistent with those determined by the in situ experiments: the individual microanalytical values for smectite and palagonitized glass bracket the bulk CEC values. The in situ experiments imply that Mg is the major extractable cation in smectite, Ca in corrensite, and both Mg and Ca in the palagonitized glass. We speculate that discrepancies between the equivalents of extractable cations predicted from elemental analysis and the equivalents of Cs sorbed may be due to the presence of charge-balancing protons that are not detected by the microprobe analyses. The sum of equivalents of cations extracted by NH4-acetate is about the same as the CEC determined by both the in situ and the bulk methods. Cation proportions indicated by NH4-acetate extractions from bulk samples are also generally consistent with the in situ results for all elements except Mg, which is a minor leachate of the NH4-acetate extractions in all the samples. To explain this discrepancy, we propose that 1) Mg may occupy structural sites within palagonitized glass, which inhibit its extraction by NH4 or Cs, and/or 2) there is a significant quantity of smectite, unsampled by the electron microprobe analyses, which contains insignificant interlayer Mg.

The Middle Proterozoic (1.1 Ga) Nonesuch Formation, host of the stratiform copper deposit at White Pine, Michigan, consists of 200 m of principally dark grey clastic sediments which contain detritus obtained dominantly from underlying mafic to intermediate volcanic rocks. Clay minerals from samples collected from the mine area and drill holes up to 100 km away have been studied using SEM, EMPA, TEM and AEM. Two morphologies of phyllosilicates, both including white mica and chlorite, occur in the ‘lower’ Nonesuch Formation: (1) detrital-shaped and (2) matrix. Detrital-shaped phyllosilicate grains are up to 450 microns long with long axes parallel to bedding. Matrix phyllosilicates occur as packets typically <200 Å thick and as pore-filling cement.

TEM images of detrital-shaped chlorite generally display 14-Å periodicity, although 24-Å corrensite- like units occur locally. Most detrital-shaped chlorite from the mine area samples have a relatively restricted range of Fe/(Mg+Fe) ratios from 0.52 to 0.58, but the Fe/(Fe+Mg) ratios of detrital-shaped chlorite outside the mine area range from 0.27 to 0.64. TiO2 crystals occur within and surrounding the detrital-shaped chlorite. Matrix chlorite has Fe/(Fe+Mg) ratios of 0.47 to 0.63, indicating that it is relatively homogeneous and enriched in Fe compared to detrital-shaped chlorite.

Detrital-shaped white mica occurs as a 2Mi polytype and generally has a phengitic composition. Matrix illite-rich I/S occurs as a 1Md polytype, is K and Al deficient relative to end-member muscovite and contains significant Fe and Mg.

The data are consistent with homogenization of detrital-shaped chlorite in the White Pine mine area by hydrothermal fluids during copper mineralization. The TiO2 crystals and corrensite-like units in detrital- shaped chlorite imply that it is at least in part derived from alteration of biotite. The presence of immature 1Md illite-rich I/S and a one layer chlorite polytype with stacking disorder suggests that the matrix clays are in their original, post-smectite state of formation as consistent with an authigenic origin during early burial diagenesis; i.e., they have not undergone subsequent transformation even though sedimentation and ore deposition occurred prior to 1 Ga.

A nickel hydroxide-vermiculite complex (NHVC) with csinβ = 1.41 nm and particle sizes from 0.075 to 0.15 mm was obtained hydrothermally by adding nickel nitrate solution to vermiculite from Transvaal, South Africa. The quantity of nickel hydroxide included in NHVC was controlled by adjusting the concentration of the nickel nitrate solution. The thermal behavior of NHVC at 450°C or above was independent of the Ni content. However, small differences exist in the dehydration behavior of NHVC below 450°C. One-dimensional Fourier electron density analysis of the NHVC structure containing 2.43 mol of Ni per half unit cell showed that Ni cations occupy the interlayer of NHVC, and 10% of the total Ni cations is in the ditrigonal cavity of the basal-oxygen plane of the tetrahedral sheet.

Structural transformations of illite-smectite samples of hydrothermal genesis with increasing contents of illite layers were studied by X-ray powder diffraction. The samples were K-saturated and subjected to wetting and drying cycles to increase three-dimensional structural ordering. Diffraction profiles were analyzed with the help of a specially devised computer program based on the approximation of individual diffraction reflections by “bell-shaped” functions, with minimization of the differences between experimental and simulated profiles. The data indicate that the transformations of these illite-smectite samples were accompanied not only by variations in the proportion of illite and smectite layers and in the pattern of their alternation, but also by a change in structure within 2:1 layers.

Experimental data on structure formation in highly concentrated aqueous dispersions of kaolinite were analyzed using rheological models. The physicochemical properties of the clay mineral surface were studied during heating at a range of temperatures, and correlation of acid-base properties with physicomechanical characteristics of the spatial structures formed during heating was obtained. It was shown that interparticle interactions and plastic yield mechanisms under load are dependent upon interfacial phenomena. A method for estimating optimal structural parameters was developed for semidry dispersions, enabling regulation of physicochemical and mechanical properties of ceramic mixtures during processing.

The evolution of texture, structure and chemical composition of chloritic clays in coeval pairs of metabasites and metapelites of a prograde sequence from the Bükk Mountains has been investigated using electron microscopy techniques. Samples are from the Bükkium (innermost Western Carpathians, Hungary) that underwent Alpine metamorphism, ranging from late diagenesis to epizone for pelites and from prehnite-pumpellyite to greenschist facies for the metabasites.

Although bulk-rock compositions, textures and primary minerals are different, chlorite evolved at similar rates in coeval metabasites and metasediments, but along different paths. The principal similarities in the prograde sequence are a decrease in the percentage of interstratified material in both dioctahedral and trioctahedral phyllosilicates and increase in thicknesses of chlorite and illite crystallites. The principal difference is in the type of interstratification in chlorite, with berthierine in metapelites, and smectite (saponite) in metabasites, although smectitic mixed layers also occur in the former. The evolution of trioctahedral phyllosilicates is marked by a decrease in the number of mineral species with increasing grade, chlorite, sensu stricto, being the only trioctahedral mineral at higher grades. This is consistent with the trend in reaction progress where both metastable systems (metabasites and metapelites) tend toward the same end-member, thermodynamically stable chlorite, as well as texture (crystal size), and where all intermediate states are metastable, and determined by the Ostwald step rule.

The ammonium acetate saturation (AMAS) method was used to study the cation-exchange capacity (CEC) of zeolitic volcaniclastic materials from Santorini and Polyegos Islands, Greece. The AMAS method was tested with respect to the time required to saturate the samples of zeolites with ammonium (NH4+) ions, the efficient liberation of NH4+ ions, and the suitability of two widely used techniques to measure ammonia (NH3) (Kjeldahl ammonia distillation technique and the ammonia electrode technique). By using the inductively coupled plasma-mass spectrometry (ICP-MS) technique and measuring the number of cations exchanged during ammonium acetate (NH4OAc) saturation, it was found that the saturation period for zeolitic materials must be increased to 12-day cycles to ensure effective saturation. Following NH4OAc saturation, the AMAS method produces NH4+ solutions, after the NH4+-saturated samples of zeolites are washed with 10% NaCl. The amount of the NH4+ ions in solution (i.e., exchangeable cations) is a measure of the CEC. The NH4+ ions can not be directly measured and must be converted to NH3. The Kjeldahl ammonia distillation technique and the ammonia electrode technique for measuring NH3 give identical CEC results. However, the ammonia electrode technique, when used directly with the NH4+ samples of zeolite without 10% NaCl treatment, generally gives higher CEC values. The amount of NH4+ treated (converted to NH3), when the NH4+-saturated zeolitized samples were used directly, was higher than the amount of the NH4+ treated when the NH4+ solutions were obtained after washing the NH4+-saturated zeolitized samples with 10% NaCl. Therefore, washing with 10% NaCl does not facilitate the release of all NH4+ initially within the zeolite structure. A modified AMAS technique is proposed for measuring the CEC of zeolitic material.

Three samples of volcanic tuff were hydrothermally altered at ∼82°C in a soxhlet apparatus for periods from 745 to 2706 h. The samples correspond to partially altered specimens of volcanic tuff with 6 wt. % (T3a) and 9 wt. % (T3b) smectite and to the calcination product of the latter (T3c). The calcination treatment melted the smectite in the sample. Untreated samples and alteration products were studied by X-ray diffraction (XRD), differential thermal analysis (DTA) and thermogravimetry (TG), scanning electron microscopy (SEM) with energy dispersive X-ray (EDX) analysis, and oxygen isotope analysis. DTA-TG of the <2-µm size fractions showed that there was a small increase of smectite relative to glass after alteration for samples T3a and T3b, with the amount of smectite increasing exponentially with time. No smectite formed in sample T3c. These results suggest that smectite acts as a nucleation site for the precipitation of new smectite. The amount of glass in the <2-µm size fraction increased, although slightly decreased relative to smectite. SEM-EDX analysis showed smectite with the approximate structural formula of Na0.22K0.08Mg0.12Ca0.03VI(Al1.47Fe0.05Mg0.48)IV(Si3.97Al0.03)O10(OH)2.

Oxygen isotope composition of the <2-µm size fraction became enriched in 18O by alteration, the >2-µm size fraction of T3b did not vary, and that of T3c was depleted in 18O. Our results are consistent with three processes during alteration: 1) oxygen isotope exchange between volcanic glass and water, 2) neoformation of smectite, and 3) hydration and consequent hydroxylation of the calcined glass.

Magnesite pebbles in Miocene lacustrine conglomerates in northwest Turkey have been partially to totally replaced by sepiolite. Only 5% of the magnesite pebbles have been converted to essentially pure sepiolite; the rest represent mixtures of magnesite and sepiolite. This process of sepiolitization is documented by X-ray diffraction (XRD), chemical, scanning electron microscopy (SEM) and Brunauer-Emmett-Teller (BET) techniques. These techniques show that the sepiolitization proceeds from the rim towards the core of the pebbles. The conglomerates, with pebbles of magnesite and ultramafic rocks, were deposited in a near-shore environment on the margin of a large Miocene lake with an ophiolitic substratum. The diagenetic transformation of magnesite to sepiolite is believed to have been caused by the interaction of mixed meteoric and lacustrine waters, which were undersaturated with respect to magnesite. The sepiolitization occurred during the highstands of the lake, when the near-shore conglomerates were flooded by the silica-rich lake waters. The pH of the water during the sepiolitization was probably on the order of 10.5–11.5. The sedimentary magnesite beds in the center of the Miocene basin show no sepiolitization, which is explained by the presence of pore water saturated with respect to magnesite.

The magnesite-sepiolite replacement process is chemically modeled as a 4-stage process from dimerization to polymerization.