Chromate (CrO42−) adsorption was investigated on kaolinite (0.2–2 μm) saturated with NaClO4 over a range of pH. Adsorption increased with decreasing pH because of protonation of chromate and/or variable charge sites on kaolinite. Chemical pretreatment to remove noncrystalline and crystalline oxide contaminants affected the magnitude of CrO42− adsorption, but not the pH range over which CrO42− adsorbed. Chromate adsorption at different sorbate and sorbent concentrations increased below the pHzpc for the kaolinite edge, suggesting the formation of weak surface complexes. If CrO42− and SO42− were present at equal concentration (5.0 × 10−7 M), the two solutes sorbed independently, suggesting binding to separate sites. The presence of excess SO42− (5.0 × 10−4 M), however, unexplainably enhanced CrO42− adsorption. The adsorption of both Chromate and sulfate can be described in terms of a site-binding model of the kaolinite edge, in which the edge is viewed as composite layers of Al and Si oxide. Surface complexation constants for CrO42− on kaolinite were similar to those for alumina, pointing to the importance of Al-OH edge sites in Chromate adsorption.

Clay samples from shales and bentonites in the Mancos Shale (Cretaceous) and its stratigraphic equivalents in the southern Rocky Mountain and Colorado Plateau have been analyzed by X-ray powder diffraction methods. The major clay in the shales is mixed layered illite/smectite, with 20–60% illite layers. The regional distribution of ordered vs. random interstratification in the illite/smectite is consistent with the concept of burial metamorphism in which smectite interlayers are converted to illite, resulting finally in ordered interstratification. The interstratification data correlate with other geologic information, including rank of coal and Laramide tectonic activity. In addition, contact metamorphism of the shale by Tertiary igneous intrusions produced a similar clay suite. Chemical variation within these shales (particularly the presence or absence of carbonate) affected the clay conversion reactions in the interbedded bentonites and the shale itself during the early stages of transformation. In extreme cases, shales and bentonites from a single outcrop may contain clays that range from pure smectite (calcareous shales) to ordered illite/smectite containing ⩾50% illite layers (noncalcareous shales). The use of mixed-layered illite/smectite compositions to infer thermal regimes, therefore, may be misleading unless allowance is made for local chemical controls.

The micropore volumes of 2 montmorillonites (SAz-1 and SWy-1), each exchanged with Ca, Na, K, Cs and tetramethylammonium (TMA) ions, were calculated from the measured vapor adsorption data of N2 and neo-hexane by use of t- and αs-plots. The corresponding surface areas of the exchanged clays were determined from Brunauer-Emmett-Teller (BET) plots of N2 adsorption data. Micropore volumes and surface areas of the samples increased with the size of exchanged cation: TMA > Cs > K > Ca > Na. The SAz-1 exchanged clays showed generally greater micropore volumes and surface areas than the corresponding SWy-1 clays. The vapor adsorption data and d(001) measurements for dry clay samples were used together to evaluate the likely locations and accessibility of clay micropores, especially the relative accessibility of their interlayer spacing. For both source clays exchanged with Na, Ca and K ions, the interlayer spacing appeared to be too small to admit nonpolar gases and the accessible micropores appeared to have dimensions greater than 5.0 Å, the limiting molecular dimension of neo-hexane. In these systems, there was a good consistency of micropore volumes detected by N2 and neo-hexane. When the clays were intercalated with relatively large cations (TMA and possibly Cs), the large layer expansion created additional microporosity, which was more readily accessible to small N2 than to relatively large neo-hexane. Hence, the micropore volume as detected by N2 was greater than that detected by neo-hexane. The micropore volumes with pore dimensions greater than 5 Å determined for clays exchanged with Na, Ca and K likely resulted from the pores on particle edges and void created by overlap regions of layers. The increase in micropore volumes with pore dimensions less than 5 Å determined for clays exchanged with TMA and possibly Cs could be caused by opening of the interlayer region by the intercalation of these large cations.

Pillaring of montmorillonite and beidellite with aluminum polyhydroxypolymer takes place first by the saturation of the cation-exchange capacity by monomeric and/or dimeric aluminum hydroxide species and then the intercalation of the so-called Al13-polyhydroxypolymer. The clay slurry must have a solid concentration greater than 0.01% (w/w) to produce a basal spacing of about 18 Å. Sizeable clay tactoids must therefore exist in the slurry in order to produce a turbostratic structure ordered along the c axis. The main difference between pillared montmorillonite and pillared beidellite seems to be a more ordered distribution of pillars within the interlamellar space of the clays that are rich in tetrahedral substitutions. Recent 27Al and 21Si high-resolution nuclear magnetic resonance data suggest that this higher degree of ordering results from the reaction of the aluminic pillars and the clay sheet near the sites of the tetrahedral substitutions.

The crystal structure of the kaolinite: dimethylsulfoxide (DMSO) intercalate (P1, a = 5.187(2), b = 8.964(3), c = 11.838(4) Å, α = 91.53(1)°, β = 108.59(2), γ = 89.92(1)°) has been determined using spectroscopic and X-ray and neutron powder diffraction data. Both the X-ray and neutron powder diffraction patterns were refined. Solid-state 13C, 29Si, and 27Al nuclear magnetic resonance data and previously collected infrared spectroscopic data provided a useful starting model for structural refinement. Due to the extreme overlap of reflections of this low-symmetry unit cell, the Rietveld method proved inadequate, and quasi-single crystal methods were employed. Each DMSO molecule was found to be triply hydrogen bonded above the octahedral vacancy in the gibbsitic sheet of the kaolinite layer. One methyl group is keyed into the ditrigonal hole in the tetrahedral sheet with the other S-C bond parallel to the sheet. The DMSO molecules are accommodated by significant horizontal displacement of individual kaolinite layers to achieve almost perfect overlap of the octahedral vacancy by the adjacent ditrigonal hole.

We studied a set of 15 reference clays from The Clay Minerals Society (CMS) Source Clays repository. Our aim was to use them as reference materials in our version of the QUAX mineral database. The QUAX software (Quantitative Phase-Analysis with X-ray Powder Diffraction) has been used successfully at the KTB site (German Continental Deep Drillling) to determine mineral assemblages quickly, in an automatic fashion, on a large number of samples (∼40,000). It was also applied to Quaternary marine sediments of the Japan Sea. Our current research focuses on marine and lacrustrine sediments from the Arctic Ocean and Siberia.

QUAX is a full-pattern method using a reference materials database. The quality of a particular quantification depends on the availability of the relevant mineral phases in the database. Our aim is to extend and improve the database continuously with new data from our current projects, particularly from clay and feldspar minerals.

A reference material in the QUAX software must be monomineralic. Before X-ray diffraction (XRD) patterns of CMS clays could be added to the database, quantification of any impurities was necessary. After measuring the bulk material by XRD, the <2 µm fraction was separated because we assumed it would contain the smallest amount of impurities. Here we present grain-size data, XRD data and X-ray fluorescence (XRF) data for this clay-sized fraction. The results of chemical and mineralogical preparation techniques and (elemental) analysis methods were combined. For XRD, random and oriented clay-aggregate samples as well as pressed pellets for QUAX analysis were prepared. Semi-quantitative clay mineral determinations were run for comparison.

Allophane samples from soils, pumice, and stream beds have been studied by electron optical, infrared absorption, X-ray fluorescence, gas chromatography, and phosphate adsorption methods. The allophane particles were hollow spherules or polyhedra 35 and 50 Å in diameter with molar Al/Si ratios close to 2.0. The thickness of the wall of the spherules was estimated to be 7 Å. For the pumice allophanes, the wall was largely composed of imogolite structural units (OH)3Al2O3SiOH. Defects or pores were present in the wall and probably were the sites where phosphate was adsorbed. It is suggested that these allophanes with molar Al/Si ratios close to 2.0 should be called “proto-imogolite” allophane.

Two soil allophanes had a similar structure to the allophane from Stratford pumice, but small amounts of layer silicates, including halloysite, were also present in the soil samples, as indicated by infrared bands at 470, 1030, and 1100 cm−1. The allophane from the stream bed at Silica Springs had an infrared spectrum similar to feldspathoids, and it did not have the imogolite structure.

Sepiolite from Mara (Zaragoza, Spain) and palygorskite from Attapulgus (Georgia, USA) were activated by treatment at different concentrations with solutions of boiling HCl under reflux conditions. The natural and treated solids were characterized by mineralogical, chemical and textural analyses.

Acid attack resulted in a progressive dissolution of the octahedral layer of these silicates. Silica contents increased and octahedral cations (Al, Mg and Fe) decreased with the intensity of the acid attack. In both cases, fibrous free silica was obtained.

The sepiolite was destroyed more rapidly than palygorskite under the conditions used because of its magnesic composition and the larger size of its structural microchannels. The maximum increase in specific surface area was obtained for sepiolite at 3 N and for palygorskite at 9 N. Cleaning and disaggregation of the particles and the increase in the number of micropores were responsible for this increase in specific surface area.

When kaolinite undergoes percussive grinding, pronounced changes take place in its i.r. absorption spectrum even in the earliest stages of the grinding when the lattice is not yet destroyed. In this report, attention is directed to the change in the stretching bands of the hydroxyl ions. A remarkably rapid effect on the band of the intralayer hydroxyl ions has been observed and is attributed to a permanent removal of the protons from these ions. Auxiliary measurements of X-ray diffraction, thermal water loss, and DTA were used to corroborate the spectroscopic evidence for this ready prototropy.

Fe(II) and Fe(III) in various proportions were coprecipitated by NH3 at pH ≈ 11. The Fe(II)/Fe(III) ratio (x) was varied from 0.10 to 0.50. After stabilization by aging at pH ≃ 8 in anaerobic conditions, hydrous precipitates were characterized by electron microscopy, Mössbauer spectroscopy, and kinetics of dissolution in acidic medium. At any x value, all stable products exhibited the structure of (oxidized) magnetite. For x ≤ 0.30, two distinct species were coexisting: the one (“m”) was made up of ca. 4nm-sized particles with a low Fe(II) content (Fe(II)/Fe(III) ≈ 0.07), and the other (“M”) consisted of particles of larger, more or less distributed sizes, and composition Fe(II)/Fe(III) ≈ 0.33; “M” increased relative amount with increasing x. For x ≥ 0.35, “M” was the only constituent and its Fe(II)/Fe(III) ratio was equal to x. “M” is identified with (nonstoichiometric) magnetite, whereas “m” is likely to be an oxyhydroxide. Mechanisms of formation are discussed, and a phase diagram is proposed which schematizes the evolution of the coprecipitation products with x and with time. Addition of Fe(II) after the precipitation of Fe(III), instead of coprecipitation, yielded very similar results.

Contaminant-transport modeling requires information about the charge of subsurface particle surfaces. Because values are commonly reused many times in a single simulation, small errors can be magnified greatly. Goethite (α-FeOOH) and pyrolusite (β-MnO2) are ubiquitous mineral phases that are especially contaminant reactive. The objective of the present study was to measure and compare the point of zero charge (PZC) using different methods. The pyrolusite PZC was measured with three methods: mass titration (MT) (PZC = 5.9±0.1), powder addition (PA) (PZC = 5.98±0.08), and isoelectric point, IEP (PZC = 4.4±0.1). The IEP measurement was in agreement with literature values. However, MT and PA resulted in a statistically larger PZC than the IEP measurement. The surface area of pyrolusite, 2.2 m2g−1, was too small to permit PZC determination by the potentiometric titration (PT) method. Goethite PZC values were measured using MT (7.5±0.1), PT (7.46±0.09), and PA (7.20±0.08). The present work presents the first reported instance where MT and PA have been applied to measure the point of zero charge of either pyrolusite or goethite. The results illustrate the importance of using multiple, complementary techniques to measure PZC values accurately.

The formation of siderite and magnetite by Fe(III)-reducing bacteria may play an important role in C and Fe geochemistry in subsurface and ocean sediments. The objective of this study was to identify environmental factors that control the formation of siderite (FeCO3) and magnetite (Fe3O4) by Fe(III)-reducing bacteria. Psychrotolerant (<20°C), mesophilic (20–35°C) and thermophilic (>45°C) Fe(III)-reducing bacteria were used to examine the reduction of a poorly crystalline iron oxide, akaganeite (β-FeOOH), without a soluble electron shuttle, anthraquinone disulfuonate (AQDS), in the presence of N2, N2-CO2(80:20, V:V), H2 and H2-CO2 (80:20, V:V) headspace gases as well as in -buffered medium (30–210 mM) under a N2 atmosphere. Iron biomineralization was also examined under different growth conditions such as salinity, pH, incubation time, incubation temperature and electron donors. Magnetite formation was dominant under a N2 and a H2 atmosphere. Siderite formation was dominant under a H2-CO2 atmosphere. A mixture of magnetite and siderite was formed in the presence of a N2-CO2 headspace. Akaganeite was reduced and transformed to siderite and magnetite in a -buffered medium (>120 mM) with lactate as an electron donor in the presence of a N2 atmosphere. Biogeochemical and environmental factors controlling the phases of the secondary mineral suite include medium pH, salinity, electron donors, atmospheric composition and incubation time. These results indicate that microbial Fe(III) reduction may play an important role in Fe and C biogeochemistry as well as C sequestration in natural environments.

Rehydration is shown to be straightforward for the reconstruction of polyoxometallate-pillared layered double hydroxides. Zn-Al hydrotalcite-like minerals were prepared with Zn/Al ratios of 1 to 5 by coprecipitation at pH 7. Good crystallinity was obtained for samples with Zn/Al ratios above 2. Thermal decomposition was achieved by calcining the samples at 300 to 900 °C. The calcined samples were exposed to decarbonated water, with or without hydrothermal treatment to evaluate reconstruction of the hydrotalcite-like minerals by rehydration. Restoration of the hydrotalcite-like structure was found to be independent of the Zn/Al ratios for samples calcined between 300 and 400 °C; however, asecond phase, aluminum hydroxide or zinc oxide, was generally detected. A spinel phase, formed during the calcination of samples at temperatures above 600 °C, inhibited reconstruction of the hydrotalcite-like phase. The rehydrated hydrotalcite-like minerals had Zn/Al ratios close to 2, irrespective of the chemistry of the starting material.

Adsorption of neutral organic molecules and the monovalent organic cations methylene blue (MB) and crystal violet (CV) to sepiolite was determined experimentally and investigated by an adsorption model. The largest amounts of MB and CV adsorbed were about 4-fold of the cation exchange capacity (CEC) of sepiolite. Consequently, it was proposed that most of the above described adsorption was to neutral sites of the clay. The adsorption model considered combines the Gouy-Chapman solution and specific binding in a closed system. The model was extended by allowing cation adsorption to neutral sites of the clay, in addition to adsorption to negatively charged sites and adsorption to neutral complexes formed from 1 cation adsorbed to a negative surface site. The amount of available neutral sites was determined from the adsorption of the neutral molecule Triton-X 100 (TX100). The model could adequately simulate the adsorption of the neutral molecules TX100 and crown ether 15-crown-5 (15C5) as well as the organic cations. Due to aggregation of MB molecules in solution, their adsorption was somewhat less than that of CV at the larger added concentrations. A consideration of the molecular dimensions of TX100, MB and CV suggested that their adsorption was mostly to external sites of the clay and that their entry to the sepiolite channels was largely excluded. This interpretation is supported by infrared spectroscopy (IR) measurements, which show large perturbations of the peak corresponding to vibrations of external Si-OH groups of the clay and confirm complete occupancy of external sites by MB and CV.

The effects of exchanged cation and layer charge on the sorption of water and ethylene glycol monoethyl ether (EGME) vapors on montmorillonite have been studied on SAz-1 and SWy-1 source clays, each exchanged respectively with Ca, Na, K, Cs and tetramethylammonium (TMA) cations. The corresponding lattice expansions were also determined, and the corresponding N2 adsorption data were provided for comparison. For clays exchanged with cations of low hydrating powers (such as K, Cs and TMA), water shows a notably lower uptake than does N2 at low relative pressures (P/P0). By contrast, EGME shows higher uptakes than N2 on all exchanged clays at all P/P0. The anomaly for water is attributed to its relatively low attraction for siloxane surfaces of montmorillonite because of its high cohesive energy density. In addition to solvating cations and expanding interlayers, water and EGME vapors condense into small clay pores and interlayer voids created by interlayer expansion. The initial (dry) interlayer separation varies more significantly with cation type than with layer charge; the water-saturated interlayer separation varies more with cation type than the EGME-saturated interlayer separation. Because of the differences in surface adsorption and interlayer expansion for water and EGME, no general correspondence is found between the isotherms of water and EGME on exchanged clays, nor is a simple relation observed between the overall uptake of either vapor and the cation solvating power. The excess interlayer capacities of water and of EGME that result from lattice expansion of the exchanged clays are estimated by correcting for amounts of vapor adsorption on planar clay surfaces and of vapor condensation into intrinsic clay pores. The resulting data follow more closely the relative solvating powers of the exchanged cations.

Surface acidity of almost homoionic montmorillonites was measured by titrating selected Hammett indicators adsorbed on the clay with n-butylamine.

As expected, the acidity is strongly affected by the exchangeable cations and the degree of hydration of the clay. Greater polarizing ability of the interlayer cations increases both the strength and number of acid sites per H0 value. The acidity of ‘activated’ or heated H-montmorillonite does not exceed that of untreated H-montmorillonite. The origin of the negative charge in the montmorillonite appears to affect the acidity of the clay.

It is concluded that the very high acidities reported in the literature (H0 < −5·6) are apparent only and are due to physisorption of the indicator.

We investigated the crystallization of ferrihydrite prepared by hydrolysis of Fe(NO3)3 solutions containing phosphate. Crystallization was studied at different pH (3–9), temperatures (298, 323, and 373 K), and initial P/Fe atomic ratios for periods to 730 d. Generally, crystallization was inhibited or only poorly crystallized lepidocrocite was formed at P/Fe > 2.5%. Phosphate favored the formation of hematite over goethite at all temperatures for most of the pH and P/Fe ranges investigated. This result is consistent with a model in which phosphate acts as a template for hematite formation, in analogy with other anions, such as oxalate. However, goethite was preferentially formed at alkaline pH and P/Fe > 1%, probably because high phosphate concentration resulted in a large increase in the negative charge of the ferrihydrite particles. This resulted in turn in less aggregation, a process that is known to precede dehydration to hematite. Phosphate greatly influenced the morphology of hematite and goethite. Hematite was often ellipsoidal or spindle-shaped. Twinned goethite crystals with a hematite core were formed at alkaline pH at P/Fe > 1%. Both hematite and goethite particles incorporated phosphate in an occluded form not desorbable by repeated alkali treatments.

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

A macroscopic energy balance model for crystalline swelling of 2:1 phyllosilicates is presented. Crystalline swelling for a static system is modeled by a balance among the potential energies of attraction, repulsion and resistance. The potential energy of attraction is due to both the electrostatic interaction between the interlayer cations and the negative surface charge sites and to van der Waals attraction between layers. The potential energy of repulsion is due to the net hydration energy for the interlayer cations, the net hydration energy for the negative surface charge sites and Born repulsion. The potential energy of resistance represents irreversible work needed to overcome the mechanical resistance of the clay water system to both expansion and collapse. The potential energy of resistance is responsible for both hysteresis and the stepwise nature of crystalline swelling.

A numerical solution of the crystalline swelling model is presented and shown to yield reasonable estimates of basal spacings for octahedrally charged clays. Measured and predicted basal spacings are directly compared and are in general agreement (r2 = 0.39). Most of the scatter for the measured vs. predicted basal spacing relationship is attributed to inaccuracies of the assumptions used for the numerical solution. The crystalline swelling model readily accounts for the effects of layer charge and nature of the interlayer cations upon crystalline swelling, but does not account for the effect of charge site location upon crystalline swelling.

A structural model for the geometry of Fe(III) octahedra near the surface of finely divided ferrihydrite was elaborated based on the bond-valence theory and by considering the interaction of water molecules in the 2 nearest hydration spheres. In contrast to bulk Fe atoms, which are bonded to bridging oxo (O) and hydroxo (OH) ligands, surface Fe atoms are also octahedrally coordinated to H2O ligands forming the 1st hydration shell ((H2O)I). In the wet state, external water molecules of the 2nd hydration shell ((H2O)II) are singly H-bonded to (H2O)I, while they are doubly coordinated in the dry state. Accordingly, wet ferrihydrite contains twice as many sorbed water molecules as dry ferrihydrite, and the structural difference due to the 2nd hydration shell accounts quantatively for the 15% increase of ferrihydrite weight experimentally measured in moist atmosphere. The interaction of surface Fe atoms with their 2 nearest hydration spheres modifies the geometry of surface Fe octahedra as compared to bulk octahedra, and idealized Fe-OH and Fe-H2O bond lengths in the wet and dry state were evaluated by the bond-valence theory. Our structural model provides a sound crystal-chemical basis to describe many apparent incongruities of Fe X-ray absorption near edge structure (K-XANES) and extended X-ray absorption fine structure (EXAFS) spectroscopic data that have led to differing interpretations of the coordination environment of Fe in ferrihydrite by various investigators.