Raman and Fourier-transform-infrared (FTIR) spectroscopic methods and X-ray powder diffraction (XRD) techniques have been used to study the influence of hydrazine on the vibrational modes of kaolinite. Strong vibrational perturbations of the OH-stretching and -deformation bands were observed in the Raman and FTIR spectra on intercalation. The intensities of the Raman- and IR-active OH-stretching bands decreased significantly upon intercalation; the intensities of the Raman bands were reduced to a greater extent than the IR bands. The deformation bands were also strongly perturbed by the presence of hydrazine in the interlamellar region. Upon evacuation of the intercalate, two new bands at 3628 and 912 cm−1 were noted, indicating the presence of a different structural conformation of the complex under vacuum. Similar results were obtained using XRD, on evacuation of the kaolinite-hy-drazine (KH) complex the d(001) value decreased from 10.4 to 9.6 Å. Partial collapse of the intercalate from 10.4 to 9.6 Å was probably due to keying of the -NH2 moiety of hydrazine into the siloxane ditrigonal cavity, as indicated by a blue-shift of the inner-OH band from 3620 to 3628 cm-1. Structural OH vibrational modes may therefore be useful probes of amine interactions with clay mineral surfaces.

Stability determinations were made by solubility methods on two trioctahedral mica-derived vermiculites. The phlogopite-derived vermiculite was found to be unstable under acid solution conditions, where stabilities of montmorillonite, kaolinite and gibbsite had previously been determined. An attempt was next made to locate a possible montmorillonite-vermiculite-amorphous silica triple point. This triple point involved conditions of alkaline pH, high pH4SiO4 and high Mg2+. These are conditions where phlogopite and biotite-derived vermiculites are most likely to control equilibria if they are stable minerals. The montmorillonite-vermiculite-amorphous silica samples went to the montmorillonite-magnesite-amorphous silica triple point, leaving no stability area whatsoever for the vermiculites. These large particle-size, trioctahedral, mica-derived vermiculites appear to be unstable under all conditions of room T and P.

Arguments are presented indicating that micas are unstable in almost all weathering environments. A hypothesis is proposed that mica-derived vermiculites result from the unique way in which unstable micas degrade in these environments. It is proposed that vermiculite derives from a series of reactions whose relative rates often result in an abundance of vermiculite. These relative reaction rates are slow for mica dissolution, rapid for K removal and other reactions pursuant to vermiculite formation, and slow for vermiculite dissolution. In chemical terms, mica-derived vermiculites may be considered fast-forming unstable intermediates.

Samples of nacrite, dickite, kaolinite, and halloysite were investigated using X-band electron paramagnetic resonance (EPR) and Mössbauer spectroscopy. Fe3+ gave rise to EPR signals at g ≃ 4 which differed with the individual polytype. Only nacrite had no resonance in this region of the spectrum, but it had one at g ≃ 2. Dickite had a quadruple line, kaolinite a triple line, and halloysite a single line in this region. The EPR spectra of these minerals are apparently dependent also on the orientation of adjacent layers in the structures. Other resonances were attributed to (1) clusters of ferric ions giving rise to broad resonance near g ≃ 2, (2) trapped holes, and (3) free radicals linked with organic matter. The Mössbauer spectroscopic results suggest that iron occurs in the ferric state (except in nacrite where Fe2+ is present also) as an ionic substitution (IS) in octahedral layers. This suggestion follows from the difference is the IS values between octahedral and tetrahedral symmetry sites occupied by Fe3+ equal to ∼0.4 mm/sec. Linewidths depend mainly on the way the layers stack; for monoclinic modifications represented by nacrite and dickite, the linewidths are narrow (Γ = 0.45 mm/sec and 0.56 mm/sec, respectively); pseudomonoclinic halloysites also gave narrow linewidths (Γ = 0.39 mm/sec and 0.48 mm/sec). The widest line was observed for triclinic kaolinite (Γ = 0.62 mm/sec and 0.71 mm/sec).

The intercalation of formamide, potassium acetate, and hydrazine by halloysite and/or ka-olinite-rich samples, with and without subsequent displacement of the interlayer species by water or glycerol/water, has been investigated. Halloysite, as such, or in mixtures with kaolinite is completely expanded by all the treatments used, thereby enabling halloysite concentrations to be determined from the basal X-ray powder diffraction (XRD) peak ratios of the appropriate complexes. The values so obtained are usually proportional to the abundance of tubes, laths, and spherules in the transmission electron micrographs of the samples. The analysis of kaolin samples (halloysite plus kaolinite) by intercalation methods is less straight forward because a proportion of the kaolinite component in the system may not expand, even after lengthy (≥ 18 days) contact of the sample with the intercalating agent. Only prolonged immersion in hydrazine produces complete or nearly complete expansion of this component. When allowance is made for the presence of non-clay mineral components, kaolin-mineral percentages estimated from XRD peak intensity ratios of the hydrazine complexes generally agree with values derived from differential thermal analysis to within ±10%. Kaolinite in mixtures with halloysite cannot be directly determined by intercalation procedures inasmuch as treatments which result in complex formation with kaolinite also expand halloysite. In such systems, kaolinite can be estimated by difference between the concentration of kaolin minerals and halloysite.

Most detrital ilmenite grains in sandstones of the Chaswood Formation are completely altered to pseudorutile, leucoxene and rutile. The textural, chemical and mineralogical changes involved in alteration were tracked using electron microprobe analyses, backscattered electron images, and elemental maps. Ilmenite grains (Ti/(Ti+Fe) ≈ 0.48) alter patchily to pseudorutile (Ti/(Ti+Fe) 0.5–0.7) with volume loss, forming a porous structure and this process continues with the development of leucoxene (Ti/(Ti+Fe) 0.7–0.9). Within the pseudorutile and leucoxene, stubby prismatic rutile crystals have been precipitated. Si and A1 occur in the altered ilmenite, either (1) inherited from original quartz and muscovite inclusions in the parent crystal or (2) as kaolinite altered from muscovite inclusions or precipitated in the pore space, under pedogenic or early diagenetic conditions. Distribution of alteration phases has been related to facies and diagenetic variations. With increasing amounts of leaching in different types of paleosols, there was increasing alteration of pseudorutile to leucoxene. In light gray mudstones and interbedded sandstones with diagenetic kaolinite that formed beneath the water table from percolating meteoric water, most leucoxene was converted to rutile. Burial diagenesis (to vitrinite reflectance values >0.4%) also promoted the change from leucoxene to rutile. The alteration of ilmenite is an important source of Fe for diagenetic minerals in the Chaswood Formation and correlative offshore deltaic and marine facies of the Scotian basin.

In the absence of oxygen, Fe(II) chloride, sulfate, and carbonate solutions react at pH 6.5 to 7 with aluminum hydroxide suspensions to form new Fe(II)-Al(III) hydroxy anion compounds of the pyroaurite group. The Fe(II)-Al(III) hydroxy-chloride and -sulfate compounds are isostructural with Fe(II)- Fe(III) “green rust” compounds with A1 essentially substituting for Fe(III). Where CO32- is the only anion in the system, an Fe(II)-Al(III) compound isostructural with hydrotalcite is formed. Either in the dried or wet state, these compounds are unstable in air due to oxidation of Fe(II). Oxidation of the dried sample in air yields akaganeite or aluminous ferrihydrite, whereas, if the sample is maintained in a moist condition and oxidized by air under water, lepidocrocite or aluminous goethite is produced along with small amounts of ferrihydrite. On X-ray powder diffraction, the lepidocrocite so formed commonly shows no diagnostic (020) basal reflection, or one with a markedly reduced intensity. The products of oxidation, and the rapidity of their formation, appear to be dependent on the composition of the initial double hydroxy compound and the conditions under which the oxidation is carried out.

The green colored compounds commonly observed in gleyed soils also rapidly become yellow brown on exposure to air, and difficulty arises in the identification of the Fe oxide phases assumed to be present. Similar conditions and reactants to those involved in the formation of the compounds described above are expected in these soils, and it is suggested that Fe(II)-Al(III) members of the pyroaurite group may form in such an environment.

Diffuse Reflectance Fourier Transform Infrared spectroscopy was used to monitor both molecular interactions and concentrations of volatile organic chemicals adsorbed on a commercial montmorillonite. Chemicals tested included propanoic acid, hexanal, heptanal, trimethylamine, dimethylsulfide and dimethyldisulfide. Diffuse Reflectance Fourier Transform Infrared spectroscopy had several advantages over other infrared techniques including ease of sample preparation, greater numbers of useful bands and the ability to detect both major and minor components from the same spectra. Evidence for the formation of organo-clay complexes was found for all chemicals except dimethylsulfide. Spectra of mixed chemicals on the clay showed numerous overlapping bands. Organic concentrations were determined by multicomponent analysis using a least squares curve fitting technique. Significant correlation (P < 0.01) between actual and determined concentrations of added organics was obtained for all except dimethylsulfide. Here the weak spectral contribution appeared to be overshadowed by the strongly adsorbing montmorillonite with consequent decrease in sensitivity. Diffuse Reflectance Fourier Transform Infrared spectroscopy of organo-montmorillonite complexes could be used both as a means of studying molecular interactions and for the determination of adsorbed organic concentrations.

A study of the mineralogy, chemical composition and structure of poorly-crystalline saponite precipitated from a submarine hot spring in Eyjafjordur, northern Iceland is reported. Special emphasis was placed on the microstructures of the minerals and a possible connection with biological activity during their precipitation. The microstructures of the minerals were found to be very similar to specific clay minerals precipitated from geothermal vents in oceanic rift zones. The composition of the minerals was, however, found to be similar to magnesium silicate scales formed in geothermal installations in Iceland where geothermal waters were mixed with cold fresh waters. High contents of organic substances were found in the clay mineral samples as compared to geothermal precipitates from other localities. Microstructural features of the layer silicates in one of the samples suggest that a gelatinous substance was a precursor of the saponite clay. The organic matter content appears to be greater when the precipitates are more crystalline.

The Al-clay-rich rock units at Mawrth Vallis, Mars, have been identified as mixtures of multiple components based on their spectral reflectance properties and the known spectral character of pure clay minerals. In particular, the spectral characteristics associated with the ~2.2 μm feature in Martian reflectance spectra indicate that mixtures of AlOH- and SiOH-bearing minerals are present. The present study investigated the spectral reflectance properties of the following binary mixtures to aid in the interpretation of remotely acquired reflectance spectra of rocks at Mawrth Vallis: kaolinite-opal-A, kaolinite-montmorillonite, montmorillonite-obsidian, montmorillonite-hydrated silica (opal), and glass-illite-smectite (where glass was hydrothermally altered to mixed-layer illite-smectite). The best spectral matches with Martian data from the present study’s laboratory experiments are mixtures of montmorillonite and obsidian having ~50% montmorillonite or mixtures of kaolinite and montmorillonite with ~30% kaolinite. For both of these mixtures the maximum inflection point on the long wavelength side of the 2.21 μm absorption feature is shifted to longer wavelengths, and in the case of the kaolinite-montmorillonite mixtures the 2.17 μm absorption found in kaolinite is of similar relative magnitude to that feature as observed in CRISM (Compact Reconnaissance Imaging Spectrometer for Mars) data. The reflectance spectra of clay mixed with opal and of hydrothermally altered glass-illite-smectite did not represent the Martian spectra observed in this region as well. A spectral comparison of linear vs. intimate mixtures of kaolinite and montmorillonite indicated that for these sieved samples, the intimate mixtures are very similar to the linear mixtures with the exception of the altered glass-illite-smectite samples. However, the 2.17 μm kaolinite absorption is stronger in the intimate mixtures than in the equivalent linear mixture. Modified Gaussian Modeling of absorption features observed in reflectance spectra of the kaolinite-montmorillonite mixtures indicated a strong correlation between percent kaolinite in the mixture and the ratio of the area of the 2.16 μm band found in kaolinite to the area of the 2.20 μm band found in montmorillonite.

The adsorption behavior of quaternary ammonium cationic surfactants with different hydrocarbon chain lengths, i.e. HDTMA (hexadecyltrimethylammonium), TDTMA (tetradecyltrimethylammonium) and DDTMA (dodecyltrimethylammonium), onto clinoptilolite has been investigated. The adsorption isotherms of these surfactants are correlated with the ζ potential curves of clinoptilolite. Accordingly, the applicability of the hemimicelle hypothesis to the adsorption of cationic surfactants at the clinoptilolite/water interface considering in the electrical double layer (EDL) of clinoptilolite is discussed. Even though the adsorption occurs in the EDL of clinoptilolite, the adsorption of HDTMA, TDTMA and DDTMA onto clinoptilolite is not conveniently described by the hemimicelle hypothesis. The absence of all expected marked increase in the ζ potential curves at the hemimicelle concentration is ascribed to the large external cation exchange capacity of clinoptilolite. The hydrocarbon chain length of surfactant molecules is found to have a significant effect on the ion exchange as well as hydrophobic interaction mechanisms. The effectiveness of both ion exchange and hydrophobic interactions increases with increasing chain length, and so the greatest surfactant adsorption onto clinoptilolite was obtained by HDTMA.

A new method has been developed for quantifying smectite abundance by sorbing polyvinylpyrrolidone (PVP) on smectite particles dispersed in aqueous solution. The sorption density of PVP-55K on a wide range of smectites, illites and kaolinites is ∼0.99 mg/m2, which corresponds to ∼0.72 g of PVP-55K per gram of montmorillonite. Polyvinylpyrrolidone sorption on smectites is independent of layer charge and solution pH. PVP sorption on SiO2, Fe2O3 and ZnO normalized to the BET surface area is similar to the sorption densities on smectites. γ-Al2O3, amorphous Al(OH)3 and gibbsite have no PVP sorption over a wide range of pH, and sorption of PVP by organics is minimal. The insensitivity of PVP sorption densities to mineral layer charge, solution pH and mineral surface charge indicates that PVP sorption is not localized at charged sites, but is controlled by more broadly distributed sorption mechanisms such as Van der Waals’ interactions and/or hydrogen bonding. Smectites have very large surface areas when dispersed as single unit-cell-thick particles (∼725 m2/g) and usually dominate the total surface areas of natural samples in which smectites are present. In this case, smectite abundance is directly proportional to PVP sorption. In some cases, however, the accurate quantification of smectite abundance by PVP sorption may require minor corrections for PVP uptake by other phases, principally illite and kaolinite. Quantitative XRD can be combined with PVP uptake measurements to uniquely determine the smectite concentration in such samples.

The clay mineralogy of tuffs from Yucca Mountain, Nevada, the potential site of the nation's first high-level radioactive waste repository, has been studied in order to understand the alteration history of the rocks and to predict potential future alterations. Bulk-rock samples and clay-mineral separates from three drill holes at Yucca Mountain (USW G-1, USW G-2, and USW GU-3/G-3) were studied using X-ray powder diffraction, and supporting temperature information was obtained using fluid inclusion data from calcite. Twelve K/Ar dates were obtained on illite/smectite (I/S) separated from the tuffs from the two northernmost drill holes, USW G-1 and G-2. The predominant clay minerals in the Yucca Mountain tuffs are interstratified I/S, with minor amounts of chlorite and interstratified chlorite/smectite. The I/S reactions observed as a function of depth are similar to those observed for pelitic rocks; I/S transforms from R = 0 interstratifications through R = 1 and R ≥ 3 interstratifications to illite in USW G-2 and to R ≥ 3 I/S in USW G-1. The R = 0 I/S clays in USW GU-3/G-3 have not significantly transformed. K/Ar dates for the I/S samples average 10.4 my. These data suggest that the rocks at depth in the northern portion of Yucca Mountain were altered 10.0-11 my ago, soon after creation of the Timber Mountain caldera to the north. Both I/S geothermometry and fluid inclusion data suggest that the rocks at depth in USW G-2 were subjected to postdepositional temperatures of at least 275°C, those in USW G-1 reached 200°C, and rocks from USW GU-3/G-3 probably did not exceed 100°C. These data suggest that no significant hydrothermal alteration has occurred since Timber Mountain time, ~ 10.7 my ago.

Estimates of the temperature of formation of illite/smectites yield probable stability limits for several minerals at Yucca Mountain. Clinoptilolite apparently became unstable at about 100°C, mordenite was not a major phase above 130°C, and analcime transformed to albite above 175°-200°C. It appears that cristobalite transformed to quartz at 90°-100°C in USW G-2 but must have reacted at considerably lower temperatures (and for longer times) in USW GU-3/G-3. The reactions with increasing depth appear coupled, and clinoptilolite and cristobalite disappear approximately simultaneously, supporting aqueous silica activity as a controlling variable in the clinoptilolite-to-analcime reaction. The reaction of clinoptilolite to analcime also coincides with the appearance of calcite, chlorite, and interstratified chlorite/smectite. Although the hydrothermal fluids may have been a source for some cations, breakdown of clinoptilolite (and mordenite) probably provided the source of some of the Ca for calcite, Mg for chlorite, K for the I/S found deeper in the section, and Na for analcime and albite.

Using the rocks in USW G-1, G-2, and GU/G-3 as natural analogs to repository-induced thermal alteration suggests that the bulk of the clinoptilolite- and mordenite-bearing rocks in Yucca Mountain will not react to less sorptive phases such as analcime over the required lifetime of the potential repository. The zeolites in zeolite interval I, directly underlying the proposed repository horizon, may transform at the predicted repository temperatures. However, the reaction of clinoptilolite to analcime in interval I may require the transformation of all of the abundant opal-CT and glass to quartz, an unlikely scenario considering the unsaturated nature of these rocks and the predicted temperatures of <100°C.

Organic dyes such as methylene blue (MB) are often used in the characterization of clays and related minerals, but details of the adsorption mechanisms of such dyes are only partially understood from spectroscopic data, which indicate the presence of monomers, dimers, and higher aggregates for varying mineral surfaces. A combination of quantum (density functional theory) and classical molecular simulation methods was used to provide molecular detail of such adsorption processes, specifically the adsorption of MB onto kaolinite basal surfaces. Slab models with vacuum-terminated surfaces were used to obtain detailed structural properties and binding energies at both levels of theory, while classical molecular dynamics simulations of aqueous pores were used to characterize MB adsorption at infinite dilution and at higher concentration in which MB dimers and one-dimensional chains formed. Results for the neutral MB molecules are compared with those for the corresponding cation. Simulations of the aqueous pore indicate preferred adsorption on the hydrophobic siloxane surface, while charge-balancing chloride ions adsorb at the aluminol surface. At infinite dilution and in the gas-phase models, MB adsorbs with its primary molecular plane parallel to the siloxane surface to enhance hydrophobic interactions. Sandwiched dimers and chains are oriented perpendicular to the surface to facilitate the strong hydrophobic intermolecular interactions. Compared with quantum results, the hybrid force field predicts a weaker MB adsorption energy but a stronger dimerization energy. The structure and energetics of adsorbed MB at infinite dilution are consistent with the gas-phase binding results, which indicate that monomer adsorption is driven by strong interfacial forces rather than by the hydration properties of the dye. These results inform spectroscopic studies of MB adsorption on mineral surfaces while also revealing critical areas for development of improved hybrid force fields.

We investigated the sorption of Ni to gibbsite of two different surface areas at pH 7.5, in the presence and absence of citrate, over a time period of 180 days. Extended X-ray absorption fine-structure spectroscopy was employed to elucidate the sorption mechanisms at the molecular level. In agreement with former results, Ni-Al layered double hydroxide (LDH) formed in the presence of gibbsite of low surface area. However, gibbsite of high surface area suppressed the formation of the surface precipitate. Instead, two Al atoms neighboring Ni at distances of 2.95–2.98 Å indicated formation of an inner-sphere sorption complex, where each NiO6-octahedron shares edges with two AlO6-octahedra. Focused multiple scattering arising from Al atoms at a distance of 6 Å suggest that sorbed Ni(OH)2(OH2)4 monomers epitaxially extend the hexagonal arrangement of Al atoms in gibbsite. Only after 30 days or more was a small amount of LDH formed. The presence of citrate prevented the formation of LDH, while maintaining the formation of inner-sphere sorption complexes.

The internal fabric of glauconite pellets has been studied by high-resolution transmission electron microscopy (HRTEM) for a better understanding of the glauconitization process. Typical “lamellae” which make up the glauconite pellets showed a spindle-like arrangement of layered crystallite packets. Three main mineral phases were detected: (1) well-ordered glauconite sensu stricto (d(001) = 10 Å) generally in the middle of the spindles; (2) a poorly ordered and undetermined layered-phase “X” with d(001) ~ 12.5 Å, usually sandwiching glauconite such that the interface between the two materials is very sharp; and (3) a noncrystalline or gel-like phase located between the lamellae. A 14-Å smectite-like phase was rarely observed at the periphery of some grains. The glauconite crystallites clearly showed characteristic growth features (e.g., growth steps), whereas the unknown phase X exhibited destabilization characteristics. A structural analysis of the pure glauconite indicates that this dioctahedral mica was present in the IMd (disordered), 1M, and, to a much lesser extent, 2M1 polytypic forms. HRTEM revealed no interlayering of glauconite with the other layered phases. Rather, it appeared to have formed by a layer-growth mechanism at the expense of the unknown phase X which apparently converted into non-crystalline matter before converting to glauconite. The precursor function of the interlamellae “gel” phase during the evolutive process of glauconitization is not understood.

Helvetic sediments from the northern margin of the Alps in eastern Switzerland were studied by clay mineralogical methods. Based on illite “crystallinity” (Kübier index), the study area is divided into diagenetic zone, anchizone and epizone. Data on the regional distribution of the following index minerals are presented: smectite, kaolinite/smectite mixed-layer phase, kaolinite, pyrophyllite, paragonite, chloritoid, glauconite and stilpnomelane. Isograds for kaolinite/pyrophyllite and glauconite/stilpnomelane are consistent with illite “crystallinity” zones. Using the ordering of mixed-layer illite/smectite, the diagenetic zone is subdivided into three zones. The illite domain size distribution was analyzed using the Warren-Averbach technique. The average illite domain size does not change much within the diagenetic zone, but shows a large increase within the anchizone and epizone. The average illite b0 value indicates conditions of an intermediate-pressure facies series.

The Helvetic nappes show a general increase in diagenetic/metamorphic grade from north to south, and within the Helvetic nappe pile, grade increases from tectonically higher to lower units. However, a discontinuous inverse diagenetic/metamorphic zonation was observed along the Glarus thrust, indicating 5–10 km of offset after metamorphism. In the study area, incipient metamorphism was a late syn- to post-nappe-forming event.

The occurrences of sepiolite beds and nodules in alkaline and saline Miocene Eskisehir lake deposits provide unique examples of ancient lacustrine environments. Stockwork-type magnesite deposits, which were formed very close to the Miocene lake, served as parent rocks for sepiolite nodules (meerschaum). The Miocene succession consists of calcareous clay, clayey carbonate, dolomite, a gypsum-bearing calcareous clay series, siliceous tuffs, sepiolite beds, sepiolite-bearing dolomite, and basal conglomerates of ultramafic rocks. Sepiolite beds were deposited by direct precipitation from Si-supersaturated lake water under alkaline and saline conditions. They are underlain by a gypsum series. Organic matter-rich sepiolites suggest the presence of water stratification with anoxic bottom waters, which developed due to high sulphate input at the base from the ascending hydrothermal solutions along the fracture systems with extensive fresh water input near to the surface. Sepiolite nodules resulted from diagenetic replacement of magnesite pebbles at shallow burial under alkaline conditions in the vicinity of paleo-shorelines. Sepiolite beds were deposited in three ways: 1) black (up to 2.8 wt. % TOC) sepiolite beds rich in organic matter accumulated in an anaerobic paleoenvironment; 2) brown (about 0.5 wt. % TOC) sepiolite beds poor in organic matter, containing minor amounts of white, 2–6 mm long, discontinuous, and very soft dolomite laminae formed in a dysaerobic paleoenvironment; and 3) white dolomitic sepiolite beds in which dolomite content is about 20–40% in an aerobic paleoenvironment.

Cyclic dolomite and gypsum series indicate hypersaline-evaporative paleoenvironments with rapid changes in lake water chemistry. These cyclic evaporatic conditions are also related to cyclic changes in water depth. Based on X-ray powder diffraction data, except degree of crystallinity, no mineralogic difference was found between sepiolite in beds and nodules. SEM studies revealed fibers about 0.2 µm wide and up to 30 µm long in sepiolite beds; crystals less than 5 µm long with bent tips; and a more compacted appearance in sepiolite nodules.

The swelling of an n-butylammonium vermiculite in solutions of n-butylammonium chloride has been studied by neutron diffraction as a function of temperature and the concentration of the soaking solution. On heating a swollen sample a transition to the crystalline phase took place at a well-defined temperature, the c-axis spacing changing from 120 to 19.4 Å at 14°C in a 0.1 M solution and from 330 to 19.4 Å at 33°C in a 0.01 M solution. The phase transition was completely reversible, and a study of the temperature-concentration phase diagram was made as high as 50°C The swollen phase was studied in a range of concentrations of the external solution between 0.2 M and 5 × 10-4 M, for which the c-axis spacings were 85 and 910 Å, respectively. The reversibility, sharpness, and reproducibility of the phase change from crystalline to swollen gel suggest that the transition is truly thermodynamic, which is not in accord with DLVO theory. The concentration dependence of the observed d-values also could not be explained satisfactorily by DLVO theory.

Bentonite from the ‘Bogovina’ coal mine in Serbia, was characterized. The influence of acid treatment on its composition, as well as mathematical descriptions of this influence are reported. The purpose of this work was to correlate the concentration of the acid used for the treatment with the resulting bentonite composition. X-ray diffraction (XRD), infrared spectroscopy and quantitative chemical analysis were employed to define the changes caused by acid treatment.

The contents of all the cations, except Si, decreased exponentially with increasing concentration of the HCl used for the treatment of the bentonite. This approach was tested on previously published data and was shown to be valid.

The basal reflections of smectite decreased gradually and eventually disappeared after intense treatment, while the other reflections remained in the XRD patterns of all the samples, but decreased slightly with increasing acid strength. In addition, the amount of X-ray amorphous matter formed increased rapidly with increasing acid concentration up to 4.5 M. With further increase in the acid strength, the amount of X-ray amorphous matter remained virtually constant.