bluuebunny/crossref_metadata_2025 huggingface dataset:
Mixed Layering of Illite-Smectite: Results from High-Resolution Transmission Electron Microscopy and Lattice-Energy Calculations
Authors: Olives Juan , Amouric Marc , Perbost Régis
Published: August 2006

Mixed layering of illite-smectite was studied both experimentally, by using high-resolution transmission electron microscopy (HRTEM) and analytical electron microscopy (AEM), and theoretically, by using lattice-energy calculations.

Samples from a hydrothermal origin show the transformation of smectite to illite with different ordering types in the illite-smectite layer sequences. Ordering ranges from complete disordered (Reichweite, R = 0 type) in the less transformed samples to increased local order, with IS and IIS sequences (R = 1 and R = 2, respectively; I = illite, S = smectite) in more illitized samples.

Lattice-energy calculations are used to determine the structure of the illite-smectite sequence, which corresponds to the minimum energy. The unit layers are: O0.5TI′TO0.5 (O, T, and I′, respectively, denote the octahedral and tetrahedral sheets, and the interlayer. The 0.5 signifies half of the octahedral cations.) For example, the arrangements of the perfectly ordered … ISIS … and … IISIIS … sequences are respectively … OM(TI′T)IOM(TI′T)S … and … OM(TI′T)IOI(TI′T)1OM(TI′T)S … (the subscripts I, S, and M, respectively, refer to compositions of illite, smectite, and midway between at 0.5). Such arrangements produce a polar model for TOT layers, which display a TIOMTS structure in the case of IS adjacent layers. Furthermore, the lattice energies of … ISIS … and … IISIIS … are found to be nearly equal to the corresponding sums of the lattice energies of illite and smectite. This result indicates that interstratified illite-smectite and the two-phase assemblage of illite + smectite have similar stabilities.

On the basis of the above model, the solid-state transformation of one smectite layer to one illite layer, which produces mixed-layer sequences, involves the transformation of an O0.5TI′TO0.5 unit of smectite into the same corresponding unit of illite.
Authigenic Illite and Organic Matter: The Principal Hosts of Vanadium in the Mecca Quarry Shale at Velpen, Indiana
Authors: Peacor Donald R. , Coveney Raymond M. , Zhao Gengmei
Published: August 2006

The Mecca Quarry Shale Member from Velpen, Indiana contains abundant vanadium which occurs in solid solution within illite-rich illite-smectite (I-S) having an average content of 1.65 wt. % V, and an overall composition of K0.8(Al2.8Mg0.5Fe0.4V0.3)(Si7.2Al0.8 g)O20(OH)4, analogous to the V-rich dioctahedral mica, roscoelite. The illite contains more than twice as much V as the associated kerogen. Detrital mica has a composition typical of 2M1, muscovite and contains no vanadium. The V-rich illite has a structure and composition typical of formation during normal prograde diagenesis and probably is widespread in the Mecca Quarry Shale because the bed is enriched in V throughout the Midwest. The smectite-to-illite reaction can not be a result of passive burial metamorphism because the host strata were buried no deeper than ~0.5 km at Velpen. The formation of illite occurred in unlithified sediments at shallow depths under the influence of pervasive 80–110°C basinal brines, possibly the same fluids that were responsible for the Mississippi Valley-type lead-zinc mineralization common in the Midwest. The presence of two types of K-rich phyllosilicates may be part of the reason for the lack of correlation between bulk V concentrations and the intensities of X-ray diffraction peaks of illite reported by others.
Authigenesis of Trioctahedral Smectite in Magnesium-Rich Carbonate Speleothems in Carlsbad Cavern and other Caves of the Guadalupe Mountains, New Mexico
Authors: Polyak Victor James , Güven Necip
Published: August 2006

Trioctahedral smectite is a constituent of Mg-rich carbonate crusts and moonmilks (pasty deposits) in caves of the Guadalupe Mountains of southeastern New Mexico. Energy dispersive X-ray microanalysis of individual crystallites and their aggregates along with the X-ray diffraction analysis indicates that the smectite is probably stevensite. Saponite is likely present in some samples also. The smectite is intimately associated with dolomite crusts and huntite moonmilks in Carlsbad Cavern, Lechu-guilla Cave, and other dolostone caves. Clay particles appear as fibers and films, with aggregates comprising decimicron-sized filamentous masses that envelop crystals of dolomite, huntite, and magnesite. The occurrence of smectite is related to the genesis of the Mg-rich carbonate minerals. In water films, progressive evaporation and carbon dioxide loss results in the sequential precipitation of Mg-rich calcite, aragonite, dolomite, huntite, and magnesite. This sequence of carbonate precipitation removes Ca and greatly increases the Mg/Ca ratio in the solutions. Silica is commonly available probably because of high pH conditions, and consequently, smectite forms in the Mg-rich alkaline environment. Along with the Mg-rich carbonate minerals, opal, quartz, and uranyl vanadates may precipitate with the smectite.
Iron-Oxide Mineralogy of a Mollisol from Argentina: A Study By Selective-Dissolution Techniques, X-Ray Diffraction, and Mössbauer Spectroscopy
Authors: Acebal Silvia G. , Mijovilovich Ana , Rueda Elsa H. , Aguirre María E. , Saragovi Celia
Published: August 2006

Selective-dissolution techniques by ammonium oxalate (OX), dithionite-citrate-bicarbonate (DCB), and dithionite-ethylenediaminetetraacetic acid (D-EDTA), and X-ray diffraction and Mössbauer spectroscopy were used to identify and characterize iron oxides and oxyhydroxides in the <2-mm, <50-μm, and <2-μm size fractions of a Mollisol from Bahia Bianca, Argentina. Iron compounds are present at low concentrations in mixtures with quartz, Na-rich feldspar, illite, interstratified illite-montmorillonite, and traces of kaolinite. Total Fe and Al content increases as soil particle size decreases, from 4.3 and 13.3 wt. % in the <2-mm size fraction to 8.5 and 22.8 wt. % in the clay fraction (<2 μm), respectively. No more than 25–30% of the total Fe is associated with the crystalline and the amorphous Fe oxides. Weakly ferromagnetic hematite and goethite were identified in the different fractions. These phases have small particle sizes and/or low crystallinity. They may also have Al for Fe substitutions. Crystalline magnetite or maghemite is rare. These Fe-rich phases are probably coating coarser particles.

The efficiency of Fe removal is highest for the D-EDTA treatment and least efficient for the OX method, for all fractions. The opposite is true for Al removal. Poorly crystalline hematite and goethite, which are soluble in oxalate, are only present in the coarser fractions. Poorly crystalline and crystalline hematite and goethite, which are soluble in DCB and EDTA, are present in coarser fractions, but do not occur in the clay fraction. DCB treatment probably dissolves Al in the 2:1 type phyllosilicates occurring in this soil, whereas D-EDTA dissolves Fe in the hydroxy interlayers of the smectite minerals or in the silicate phases.
Refinement of the Crystal Structure of Cronstedtite-1T
Authors: Hybler Jiří , Petříček Václav , Ďurovič Slavomil , Smrčok Ĺubomír
Published: August 2006

The crystal structure of cronstedfite-1T was refined in space group P31m, using two crystals: a triangular tabular crystal from Herja, Romania and a conical crystal from Lostwithiel, Cornwall, England. The Herja sample has the composition of (Fe2+2.20Fe3+0.80)(Si1.20Fe3+0.78Al0.02)O5(OH)4 and the Lostwithiel sample has the composition of (Fe2+2.32Fe3+0.68)(Si1.32Fe3+0.66Al0.02)O5(OH)4. The results of refinements are as follows: a = 5.512(1) Å, c = 7.106(1) A, R = 3.07%, and 342 independent reflections; and a = 5.503(1), c = 7.104(1) Å, R = 2.24%, and 335 independent reflections for the Herja and Lostwithiel samples, respectively. The structure consists of one tetrahedral and one octahedral sheet. There is one octahedral site, M1, occupied by Fe only, and one tetrahedral site, T1, occupied by Si and Fe in the ratio of 0.617(8):0.383 (Herja) and 0.699(6):0.301 (Lostwithiel). Positions of two hydrogen atoms were determined from a difference map for the Lostwithiel data. The ditrigonalization angle of the tetrahedral sheet is α = −11.5° (Herja) and α = −11.1° (Lostwithiel), and the structures have a Franzini-layer type of B. The crystals studied are affected by ± b/3 stacking faults which produced slight streaking of h - k ≠ 3n reflections.
Electron Microscopy Study of Volcanic Tuff Alteration to Illite-Smectite Under Hydrothermal Conditions
Authors: de la Fuente S. , Cuadros J. , Fiore S. , Linares J.
Published: August 2006

Experimental alteration of volcanic tuff from Almeria, southeastern Spain, was performed in solutions with different Na/K ratios (0.01, 1, 10, and 100), different total salt concentrations (0.01, 0.1, 0.2, 0.33, and 1 M), and in deionized water, at 60, 80, 120, and 160°C, for periods of 60, 90, 180, and 360 d. Two particle size fractions of volcanic tuff were used: 10–200 and 20–60 μm. Alteration products were examined by X-ray diffraction (XRD), Fourier-transform infrared spectroscopy (FTIR), laser-particle size analysis, scanning electron microscopy equipped with an energy dispersive X-ray spectrometer (SEM-EDS), image computer analysis, and transmission electron microscopy with microanalysis (TEM-AEM). XRD detected neoformed phases only in the products from experiments of 180–360 d at high temperatures (120–160°C), and with Na/K ratios above unity and in deionized water. The synthesized phase is a random mixed-layer illite-smectite (I-S) with 75% smectite. The quantity of newly formed I-S, determined by FTIR, ranged between 3–30%. There was no apparent change in grain size and shape of the grains after the experiments as compared to before.

SEM-EDS and TEM-AEM revealed the following alteration sequence: 1) intense etching on glass-grain surfaces; 2) formation of hemispherical morphologies on grain surfaces; 3) precipitation of very thin, individual flakes of illite-smectite on glass-grain surfaces; 4) development of I-S at the edges of glass grains; and 5) development of I-S honeycomb structures either covering large areas of the glass grains or resulting from the complete alteration of glass grains. A direct transformation of glass to I-S seems to be the major reaction mechanism, although there also is evidence of glass dissolution and subsequent I-S precipitation.
Clay-Mineral Authigenesis in the Late Permian Coal Measures, Bowen Basin, Queensland, Australia
Authors: Uysal I. Tonguç , Golding Suzanne D. , Audsley Frank
Published: August 2006

Mineralogical studies were performed on authigenic clay minerals of mudrocks, sandstones, and bentonites from 38 boreholes in the Late Permian coal measures of the Bowen Basin. Clay-mineral separations of samples from the northern Bowen Basin consist mainly of (Reichweite, R) R = 1 and R ≥ 3 interstratified illite-smectite (I-S), chlorite, and kaolinite. In the southern Bowen Basin, samples from higher stratigraphie sections are characterized by randomly ordered (R = 0) I-S mixed layers, and kaolinite and chlorite in smaller amounts. Samples from the lower sections consist of (R ≥ 3) I-S, chlorite, chlorite-rich chlorite-smectite (C-S), and laumontite.

Examination of the mineralogy and distribution of authigenic clay minerals from the Late Permian coal measures in the northern part of the Bowen Basin indicated that the presence of clay minerals is not systematically related to depth and clay occurrences do not occur regularly. These mineralogical variations of clay in volcaniclastic sediments are incompatible with thermal control. Variations in the rate of fluid flow and potassium supply owing to permeability exert major influences on clay-mineral paragenesis and the reaction of illitization. In more permeable zones (possibly faults or fracture zones), highly illitic clays with lath-shaped morphologies may have precipitated directly from potassium-rich fluids migrating from deeper parts of the basin. In addition, abundant chlorite precipitated contemporaneously with illitic clays, which may have resulted from sufficient magnesium and iron occurring in the fluids as a result of dissolution of intermediate or mafic-rock fragments. At the same time, clay paragenesis with less illitic I-S, kaolinite, and minor chlorite occurs outside the channelized zones of high fluid flow, where a diffusive-flow regime may have predominated with lower ratios of the activities of K+ and H+ (i.e., αK+/αH+) in the solutions.

In the southern Bowen Basin, depth-related changes in the distribution of clay minerals are evident and may be indicative of thermal control on clay-mineral reactions. Zeolites are present locally in the Late Permian volcaniclastic rocks in the southern Bowen Basin, but not in the north. This is attributed to a low ratio of αCO2/αH2O (where α = activity) and/or more saline and alkaline solutions.
Mg-Rich Smectite “precursor” Phase in the Tagus Basin, Spain
Authors: de Santiago Buey Cristina , Suárez Barrios Mercedes , García Romero Emilia , Doval Montoya Mercedes
Published: August 2006

The pink clays from the Tagus basin, Spain, were characterized by X-ray difraction (XRD), infrared spectroscopy (IR), scanning electron microscopy (SEM), and transmission electron microscopy (TEM). Chemical data were obtained by plasma emission spectroscopy and analytical electron microscopy (AEM), and specific surface and cation-exchange capacity were measured also. The data indicate that these pink clays are primarily stevensite. This Mg-rich smectite is characterized by poor crystallinity, a high degree of structural disorder, trioctahedral character (pure magnesian), a very low cation-exchange capacity, a very small crystal size (which generates an abnormally high specific surface area), and a deficiency of octahedral cations. On the basis of the very small crystal size, a large number of edge dislocations, the lack of periodicity (turbostratic) in the structure, and a cellular (spherical) texture observed by TEM, we consider this occurrence to be an early stage of crystallization. Unlike other precursor clay materials described in the literature, this clay is not an alteration of volcanic ash, but it was generated by precipitation from a Si- and Mg-saturated medium.
Heats of Adsorption of N-Hexane by Thermal Gravimetry with Differential Scanning Calorimetry (Tg-DSC): A Tool for Textural Characterization of Pillared Clays
Authors: Pires J. , de Cavalho M. Brotas , Carvalho A. P. , Guil J. M. , Perdigón-Melón J. A.
Published: August 2006

Microporous materials, (materials with pore sizes with widths <2 nm) were prepared by pillaring of smectites obtained from different soil deposits. The materials were prepared by intercalation with oligomeric cations of aluminum, which were transformed to aluminum-oxide pillars by calcination. The adsorption of n-hexane in the pillared clays was studied by the determination of heats of adsorption. Heats of adsorption were measured using either a static microcalorimeter or differential scanning calorim-etry coupled with thermogravimetry (TG-DSC). In this latter case, two different procedures were used that differ on the introduction of the (n-hexane) molecules that are to be adsorbed. The results obtained by the (standard) static microcalorimeter method and the TG-DSC method were compared. This comparison showed the heats of adsorption obtained by TG-DSC are differential heats of adsorption, and it showed the range of adsorption. Characterizing the texture of pillared clays, especially microporosity, is important for monitoring the intercalation process and for determining potential applications of these materials. Correlations between the obtained heats of adsorption and the dimensions of micropores suggest that TG-DSC is a semi-quantitative method for characterizing micropores in aluminum-pillared clays.
Intercalation Characteristics of 1,1′-Diethyl-2,2′-Cyanine and other Cationic Dyes in Synthetic Saponite: Orientation in the Interlayer
Authors: Iwasaki Masashi , Kita Masaki , Ito Kengo , Kohno Atsuya , Fukunishi Koushi
Published: August 2006

The basal spacings of complexes of saponite with five cationic dyes, 1,1′-diethyl-2,2′-cyanine, crystal violet, methylene blue, 1,1′-diethyl-2,2′-carbocyanine, and 1,1′-diethyl-2,2′-dicarbocyanine, varied with degree of saturation of each dye. At low loading of dye to saponite, each cationic dye showed nearly the same absorption spectrum in the UV-visible region as that of its dilute aqueous solution, whereas the spectrum changed distinctly at high loading. With increasing degree of dye loading, the absorption band shifted to longer wavelength for 1,1′-diethyl-2,2′-cyanine (J band) and to shorter wavelength for the others (D, H bands). On the basis of the basal spacing of each respective dye-clay complex, the orientation of the intercalated dye molecules is proposed as follows: the major plane of the cationic dye lies horizontal to the 2:1 layer surface at low loading. With increasing loading, the dye molecules interact with adjacent dye molecules and orient vertically to the 2:1 layer at high loading near the cation-exchange capacity.
Stepwise Hydration of High-Quality Synthetic Smectite with Various Cations
Authors: Tamura Kenji , Yamada Hirohisa , Nakazawa Hiromoto
Published: August 2006

Smectites synthesized from experiments at 5.5 GPa and 1500°C are of high quality, crystals are large at >10 μm, and the 2:1 layers may have a homogeneous charge distribution. Smectite was exchanged with various cations (Na+, Li+, K+, Ca2+, and Mg2+) and the hydration behavior of each sample was observed by an in situ powder X-ray diffraction method under precisely controlled relative humidity (RH). The smectite showed distinct stepwise (discontinuous) hydration versus RH. During the transition between two hydration states, the coexistence of the two states was observed. Randomly interstratified structures with one and two planes of H2O are time-dependent phenomena and relate to hydration and dehydration processes.
Saponite from the Emet Colemanite Mines, Kütahya, Turkey
Authors: Çolak Mümtaz , Helvaci Cahit , Maggetti Marino
Published: August 2006

Clay mineralogy and whole-rock chemistry of the borate-bearing layers of the Hisarcik and Esbey mines were examined. The Hisarcik clays occur as laminated or unlaminated clay layers with sharp contacts. Unlaminated layers contain quartz derived from metamorphic rocks and carbonate fragments in a clay matrix, and are interpreted as reworked tuffs deposited in playa-lake environments. An important feature is that the unlaminated clays contain little MgO (3–15 wt. %) as compared with the laminated clays (15–30 wt. %). As previous studies have shown, the clay fraction of the studied profile contains predominantly Li-bearing saponite, and accounts for 60–90 wt. % of the clay fraction (<2 μm). Illite in the clay fraction varies from 0 to 67 wt. % and the average illite percentage never exceeds 40 wt. %. Chlorite is scarce (2–5 wt. %). Illite-smectite interstratified clays (illite at 70%, smectite at 30%) were only found in low concentrations in the laminated clay layers of the upper limestone unit (above the borate zone), where illite-2M of detrital origin is also present. The Esbey clays occur interstratified with colemanite layers and envelope colemanite nodules. Calcite is the major mineral of the clays whereas quartz, plagioclase, feldspar, colemanite, and cahnite are minor components. The MgO contents vary between 4.70–13.95 wt. % in the clays interstratified with colemanite layers, between 7.24–11.89 wt. % in the enveloping clays, and between 10.27–21.25 wt. % in clays located above the colemanite zone. The composition of the clay fraction (<2 μm) in all samples is similar. Smectite represents between 40–90 wt. % of the clay fraction in the upper portion of the stratigraphic profile and decreases towards the lower part of the stratigraphic profile. Smectite always occurs with illite which may vary from 20 to 90 wt. % of the clay fraction, and a small amount of kaolinite and chlorite. Illite-2M polytype is abundant. The d(060)-reflection position suggests that the smectite minerals from the Hisarcik and Esbey colemanite mines contain both dioctahedral and trioctahedral smectites to form a transitional zone. These smectites are a product of a magnesium-rich alkaline playa-lake environment.
Characterization and Assignment of Far Infrared Absorption Bands of K+ in Muscovite
Authors: Diaz M. , Farmer V. C. , Prost R.
Published: August 2006

To assign far infrared (FIR) absorption bands of K+ in muscovite, dichroic experiments were performed. For a muscovite crystal rotated about a crystallographic axis, c*, a, or b, two bands corresponding to vibration modes of K+ appear, respectively, at 107 and 110 cm−1 (rotation about c*), 107 and 143 cm−1 (rotation about a), and 110 and 143 cm−1 (rotation about b). Two in-plane modes at 107 and 110 cm−1 and one out-of-plane mode at 143 cm−1 are identified for the vibrations of K+ in muscovite. Each of these transition moments are near the crystallographic axes b, a, and c, respectively. These observations match well predictions based on the approximate C3i symmetric environment of K+, although the site symmetry in the space group of muscovite is only C2.
Quantitative Measurement of Paramagnetic Fe3+ in Kaolinite
Authors: Balan Etienne , Allard Thierry , Boizot Bruno , Morin Guillaume , Muller Jean-Pierre
Published: August 2006

A method is proposed to measure the absolute concentration of paramagnetic Fe3+ ions in kaolinite from various geochemical environments using powder X-band electron paramagnetic resonance (EPR) data. An Fe3+-doped corundum sample is used as a concentration standard. The Fe3+ signal is calibrated by calculating the powder EPR spectra of Fe3+ ions in corundum and low-defect kaolinite. The paramagnetic Fe3+ concentration in other samples is obtained by an extrapolation procedure. This study provides a direct assessment of the iron distribution between isolated structural Fe3+ ions and other iron species, such as Fe3+ concentrated phases and Fe2+ ions. The concentration of isolated structural Fe3+ ranges between 200–3000 ppm and represents less than half of the total iron within kaolinite crystals.
Evolution of Fundamental-Particle Size during Illitization of Smectite and Implications for Reaction Mechanism
Authors: Środoń J. , Eberl D. D. , Drits V. A.
Published: August 2006

Area-weighted thickness distributions of fundamental illite particles for samples of illite and illite-smectite from seven locations (including bentonites and hydrothermally altered pyroclastics) were measured by Pt-shadowing technique, by transmission electron microscopy. Most thickness distributions are described by lognormal distributions, which suggest a unique crystallization process. The shapes of lognormal distributions of fundamental illite particles can be calculated from the distribution mean because the shape parameters α and β2 are interrelated: β2= 0.107α − 0.03. This growth process was simulated by the mathematical Law of Proportionate Effect that generates lognormal distributions. Simulations indicated that illite particles grow from 2-nm thick illite nuclei by surface-controlled growth, i.e., the rate of growth is restricted by how rapid crystallization proceeds given a near infinite supply of reactants, and not by the rate of supply of reactants to the crystal surface. Initially formed, 2-nm thick crystals may nucleate and grow within smectite interlayers from material produced by dissolution of single smectite 2:1 layers, thereby transforming the clay from randomly interstratified (Reichweite, R = 0) to ordered (R = 1) illite-smectite after the smectite single layers dissolve. In this initial period of illite nucleation and growth, during which expandable layers range from 100 to 20%, illite crystals grow parallel to [001]* direction, and the dimensions of the (001) plane are confined to the size of the original smectite 2:1 layers. After nucleation ceases, illite crystals may continue to grow by surface-controlled growth, and the expandable-layer content ranges from 20 to 0%. This latter period of illitization is characterized by three-dimensional growth. Other crystal-growth mechanisms, such as Ostwald ripening, supply-controlled growth, and the coalescence of smectite layers, do not produce the observed evolution of α and β2and the observed shapes of crystal thickness distributions.
A New Method for the Prediction of Gibbs Free Energies of Formation of Hydrated Clay Minerals Based on the Electronegativity Scale
Authors: Vieillard Philippe
Published: August 2006

A new method for the prediction of Gibbs free energies of formation for hydrated clay minerals is proposed based on the parameter ΔGO= Mz+(clay) characterizing the oxygen affinity of the cation Mz+. The Gibbs free energy of formation from constituent oxides is considered as the sum of the products of the molar fraction of an oxygen atom bound to any two cations multiplied by the electronegativity difference defined by the ΔGO= Mz+(clay) between any two consecutive cations. The ΔGO= Mz+(clay) value, using a weighting scheme involving the electronegativity of a cation in a specific site (interlayer, octahedral, or tetrahedral) is assumed to be constant and can be calculated by minimization of the difference between experimental Gibbs free energies (determined from solubility measurements) and calculated Gibbs free energies of formation from constituent oxides. Results indicate that this prediction method compared to other determinations, gives values within 0.5% of the experimentally estimated values. The relationships between ΔGO= Mz+(clay) corresponding to the electronegativity of a cation in either interlayer or octahedral sites and known ΔGO= Mz+(aq) were determined, thereby allowing the prediction of the electronegativity of transition metal ions and trivalent ions in hydrated interlayer sites and octahedral sites. Prediction of Gibbs free energies of formation of any clay mineral with various ions located in the interlayer and with different cations in octahedral sites is possible. Examples are given for Al-rich montmorillonite from Aberdeen, transition element-exchanged montmorillonite, and Ni-rich stevensite, and the results appear excellent when compared to experimental values.
A Nuclear Magnetic Resonance (NMR) and Fourier-Transform Infrared (FTIR) Study of Glycine Speciation on a Cd-Rich Montmorillonite
Authors: Di Leo Paola
Published: August 2006

As a consequence of treatments with glycine solutions, glycine molecules enter the interlayer of both Ca- and Cd-rich montmorillonite. Measurements of d value suggest that at low glycine concentration (0.01 and 0.1 M glycine solutions) a “flat” arrangement of the glycine molecules occurs in the interlayer. In contrast, intercalation of more than one monolayer of glycine molecules occurs for the montmorillonite treated with a higher concentration of glycine (1 M glycine solution).

Interlayer complexation of glycine occurs only for the Cd-rich form of montmorillonite, whereas no complexation is observed for Ca-rich montmorillonite. Both nuclear magnetic resonance (NMR) and Fourier-transform infrared (FTIR) results suggest that the adsorbed glycine, which fully protonates in the interlayer of montmorillonite to give the GlyH2− species, interacts with the interlayer Cd2+ to form the CdGlyx complex mainly through the carboxylate group. The interlayer cadmium, present as both Cd2+ and CdCl−, is complexed by the ligand glycine. In contrast, the cadmium adsorbed on the external surfaces of montmorillonite does not interact with the ligand. Complexation of CdCl+ only occurs for large amounts of adsorption of glycine (e.g., for samples treated with 1 M glycine solution).
Effect of Phosphate on the Formation of Nanophase Lepidocrocite from Fe(II) Sulfate
Authors: Cumplido Jesús , Barrón Vidal , Torrent José
Published: August 2006

The effect of phosphate on the formation of Fe oxides from Fe(II) salts is important because phosphate is a ubiquitous anion in natural environments. For this reason, the products formed by oxidation of phosphate-containing Fe(II)SO4solutions neutralized with bicarbonate were characterized. The rate of oxidation of Fe(II) increased with increasing P/Fe atomic ratio to 0.2 in the initial solution. Goethite (α-FeOOH) or lepidocrocite (γ-FeOOH) or both were produced and identified by powder X-ray diffraction (XRD). The ratio between lepidocrocite and goethite increased with increasing P/Fe. In the 5–8.5 pH range, the formation of goethite predominated at P/Fe < 0.005, but only lepidocrocite was detected by XRD for P/Fe > 0.02. Thus, phosphate favors lepidocrocite formation because lepidocrocite has (1) a layered structure (like its precursor green rust), and (2) a structure less dense than that of goethite, thereby requiring less complete removal of the green-rust interlayer phosphate to form. The lepidocrocite crystals were platy, with prominent {010} faces and the thickness of the plates decreased with increasing P/Fe from >25 nm for P/Fe < 0.005 to <5 nm for P/Fe > 0.1. The solubility of lepidocrocite in acid oxalate was nearly complete for P/Fe > 0.03. The lepidocrocite contained occluded phosphate,i.e., phosphate that could not be desorbed by alkali treatment. The decrease in thebunit-cell length with increasing P/Fe suggests that lepidocrocite may contain structural P.
Formation of Banded Iron-Manganese Structures by Natural Microbial Communities
Authors: Tazaki Kazue
Published: August 2006

Microbial structures in the form of banded zebra patterns have been found as periodic iron-manganese layers in living biomats on the coast of Satsuma-Iwo Jima, a small volcanic island near southern Kyushu, Japan. Electron microscopic observation shows that coccus, fibrous, and bacillus-type bacterial communities construct zebra architecture Fe-Mn layers through biomineralization on and within cells. A living microbial fumarolic ferro-manganese precipitation growing in seawater around an active volcanic island explains one mechanism of banded formation. Biological processes form the elemental zebra pattern, with periodic distribution of bacterial cells with Fe-Mn in each layer of the architecture. Fibrous bacteria are sometimes mineralized with goethite, ferrihydrite, and buserite microcrystals, coated with granular mucoid substances. The biomineralization may then mature to form a recent stratified banded-iron formation. The Satsuma-Iwo Jima zebra architecture is unusual in that it forms under aerobic conditions in a warm shallow-water environment, in contrast to the intermittent oxidizing and reducing conditions in which deep-sea analogues develop.
Structural Chemistry of Fe, Mn, and Ni in Synthetic Hematites as Determined by Extended X-Ray Absorption Fine Structure Spectroscopy
Authors: Singh Balwant , Sherman D. M. , Gilkes R. J. , Wells M. , Mosselmans J. F. W.
Published: August 2006

The incorporation of transition metals into hematite may limit the aqueous concentration and bioavailabity of several important nutrients and toxic heavy metals. Before predicting how hematite controls metal-cation solubility, we must understand the mechanisms by which metal cations are incorporated into hematite. Thus, we have studied the mechanism for Ni2+ and Mn3+ uptake into hematite using extended X-ray absorption fine structures (EXAFS) spectroscopy. EXAFS measurements show that the coordination environment of Ni2+ in hematite corresponds to that resulting from Ni2+ replacing Fe3+. No evidence for NiO or Ni(OH)2 was found. The infrared spectrum of Ni-substituted hematite shows an OH-stretch band at 3168 cm−1 and Fe-OH bending modes at 892 and 796 cm−1. These vibrational bands are similar to those found in goethite. The results suggest that the substitution of Ni2+ for Fe3+ is coupled with the protonation of one of the hematite oxygen atoms to maintain charge balance.

The solubility of Mn3+ in hematite is much less extensive than that of Ni2+ because of the strong Jahn-Teller distortion of Mn3+ in six-fold coordination. Structural evidence of Mn3+ substituting for Fe3+ in hematite was found for a composition of 3.3 mole % Mn2O3. However a sample with nominally 6.6 mole % Mn2O3 was found to consist of two phases: hematite and ramsdellite (MnO2). The results indicate that for cations, such as Mn3+ showing a strong Jahn-Teller effect, there is limited substitution in hematite.
Evaluation of the Acidity of Pillared Montmorillonites by Pyridine Adsorption
Authors: Sun Kou M. R. , Mendioroz S. , Muñoz V.
Published: August 2006

Two series of pillared clays were prepared from a purified montmorillonite (95%) from La Serrata of Nijar, Spain, and polycations of Al and Zr using various methods. The effect of both the pillaring cation and the procedure of preparation on the physicochemical characteristics of the resulting materials was studied. Changes in texture were determined by X-ray diffraction (XRD) and N2 adsorption at 76 K and changes in acidity were determined by thermogravimetry following pyridine adsorption at room temperature and further desorption at a constant heating rate of 10 K min−1 in the range of 298–623 K. The relation between the size and charge (n/q) of the pillaring cation, which is dependent on the degree of cation hydrolysis, is the main factor affecting pore size and acidity of the synthesized materials. The pH of the pillaring solution affects the stability of the parent clay and the properties of the pillared clay. Below a pH of 3 and depending on contact time, the montmorillonite may delaminate and partially dissolve to produce products that affect the properties of the resulting materials. Microporosity increases for both Al or Zr-pillared clays. For Zr-pillared clays, microporosity is accompanied by changes in the mesoporosity and macroporosity as a result of clay delamination. Acidity dramatically increases by pillaring, especially strong acidity, and the acid strength distribution depends on starting salt concentration, aging time, and temperature.
Geology and Characterization of Two Hydrothermal Nontronites from Weathered Metamorphic Rocks at the Uley Graphite Mine, South Australia
Authors: Keeling John L. , Raven Mark D. , Gates Will P.
Published: August 2006

Mining operations during the early 1990s at Uley Graphite Mine near Port Lincoln on southern Eyre Peninsula, South Australia, uncovered abundant nontronite veins in deeply weathered granulite facies schist, gneiss, and amphibolite of Palaeoproterozoic age. Two types of nontronite are present: a bright yellowish-green clay (NAu-1) distributed as veinlets and diffuse alteration zones within kaolinized schist and gneiss, and a massive to earthy, dark-brown clay (NAu-2) infilling fracture networks mainly in amphibolite or basic granulite. The nontronites are the product of low-temperature hydrothermal alteration of primary minerals, biotite, and amphibole. The principal chemical difference between NAu-1 and NAu-2 is a higher alumina content in NAu-1, which was either inherited during hydrothermal alteration of biotite in the host rock or acquired through recrystallization of nontronite during subsequent weathering and associated kaolinization. Sufficient bulk samples of both NAu-1 and NAu-2 were collected to supplement reference nontronite of the Source Clay Repository of The Clay Minerals Society. The clay fraction of the bulk samples is typically >85%. NAu-1 contains minor kaolin and quartz which are easily removed to give a high purity nontronite of composition M+1.05[Si6.98Al1.02][Al0.29Fe3.68Mg0.04]O20(OH)4, similar to that of nontronite from Garfield, Washington. NAu-2 contains fewer total impurities but the presence of trace amounts of submicron carbonate and iron oxyhydroxide requires additional chemical treatment to produce a nontronite of purity comparable to NAu-1. Composition of NAu-2 was calculated as M+0.72[Si7.55Al0.45][Fe3.83Mg0.05]O20(OH)4, although infrared data indicate that at least some Fe is in tetrahedral coordination.
Bleaching Properties of Alumina-Pillared Acid-Activated Montmorillonite
Authors: Falaras Polycarpos , Lezou Fani , Seiragakis Georgios , Petrakis Dimitrios
Published: August 2006

The bleaching of cottonseed oil by alumina-pillared (Al-pillared) acid-activated clays was investigated. Acid activation of a Ca-rich montmorillonite (CMS STx-1) following treatment with 1, 4, and 8 eq/L sulfuric-acid solutions, as well as subsequent pillaring with alumina, produces new materials. These materials have bleaching properties dependent upon the extent of activation of the clay prior to pillaring. The pillared acid-activated montmorillonites possessed higher bleaching efficiency compared to pillared products of the untreated clay. Mild activation of the montmorillonite matrix, pillaring with the Keggin ion [Al13O4(OH)24(H2O)12]7+, and calcination temperatures to 500°C produced materials with the best fractional degree of bleaching. Direct comparison to the performance of a commercial bleaching earth (Tonsil Optimum 214, Sud-Chemie AG. Moosburg, Germany) shows that the efficiency of the Al-pillared acid-activated montmorillonite may be improved. The optimization of the bleaching process is achieved via a judicious utilization of intermediate surface area, relatively high acidity, and enhanced pore volume.
The Effect of Thermal Treatment on Some of the Physicochemical Properties of a Bentonite
Authors: Sarikaya Yüksel , Önal Müşerref , Baran Bülent , Alemdaroğlu Tülay
Published: August 2006

A white calcium bentonite (CaB) from the Kütahya region, Turkey, contains 35 wt. % opal-CT and 65 wt. 9c Ca-rich montmorillonite (CaM). Samples were heated at various temperatures between 100–1300°C for 2 h. Thermal gravimetric (TG), derivative thermal gravimetric (DTG), and differential thermal analysis (DTA) curves were determined. Adsorption and desorption of N2 at liquid N2 temperature for each heat-treated sample was determined. X-ray diffraction (XRD) and cation-exchange capacity (CEC) data were obtained. The change in the <d(001) value and the deformation of the crystal structure of CaM depend on temperature. Deformation is defined here as changes of the clay by dehydration, dehydroxylation, recrystallization, shrinkage, fracture, etc. The activation energies related to the dehydration and dehydroxylation of CaB calculated from the thermogravimetric data are 33 and 59 kJ mol−1, respectively. The average deformation enthalpies, in the respective temperature intervals between 200–700°C and 700–900°C, were estimated to be 25 and 205 kJ mol−1 using CEC data and an approach developed in this study. The specific surface area (S) and the specific micropore-mesopore volume (V) calculated from the adsorption and desorption data, respectively, show a “zig zag” variation with increasing temperature to 700°C, but decrease rapidly above this temperature. The S and V values were 43 m2 g−1 and 0.107 cm3 g−1, respectively, for untreated bentonite. They reach a maximum at 500°C and are 89 m2 g−1 and 0.149 cm3 g−1 respectively. The XRD data clearly show that, at 500°C, where the irreversible dehydration is completed without any change in the crystal structure, the porosity of CaM reaches its maximum.
Ion Exchange of Zeolite Na-Pc with Pb2+, Zn2+, and Ni2+ Ions
Authors: Moirou Aggeliki , Vaxevanidou Aikaterini , Christidis Georgios E. , Paspaliaris Ioannis
Published: August 2006

This paper examines the ion-exchange properties of synthetic zeolite Na-Pc, which was produced from perlite-waste fines and has a SiO2:Al2O3 ratio of 4.45:1 and a cation-exchange capacity (CEC) of 3.95 meq g−1. Although equilibrium is attained rapidly for all three metals, exchange is incomplete, with Ac(max) (maximum equilibrium fraction of the metal in the zeolite) being 0.95 for Pb, 0.76 for Zn, and 0.27 for Ni. In both Na → ½Pb and Na → ½Zn exchange, the normalized selectivity coefficient is virtually constant for NAC (normalized equilibrium fraction of the metal in the zeolite) values of ≤0.6, suggesting a pronounced homogeneity of the available exchange sites. The Gibbs standard free energy, ΔG°, of the Na → ½Pb exchange calculated from the normalized selectivity coefficient is −3.11 kJ eq−1 and, for the Na → ½Zn exchange, it is 2.75 kJ eq−1.

Examination of the solid exchange products with X-ray diffraction (XRD) revealed a possible decrease in crystallinity of zeolite Pb-Pc as suggested by the significant broadening and disappearance of diffraction lines. This decrease is associated with a reduction of pore opening, as indicated from Fourier-transform infrared analysis (FTIR), which in turn results in a decrease of the amount of zeolitic water. Thermogra-vimetric-differential thermogravimetric (TG-DTG) analysis showed that water loss occurs in three steps, the relative significance of which depends on the type of exchangeable cation and subsequently on the type of complex formed with the cation and/or the zeolite channels. Zeolite Na-Pc might be utilized in environmental applications, such as the treatment of acid-mine drainage and electroplating effluents.
Thermal Decomposition of a Dickite-Hydrazine Intercalation Complex
Authors: Ruiz Cruz María Dolores , Franco Francisco
Published: August 2006

The intercalation complex of a low-defect dickite from Tarifa, Spain, with hydrazine was studied by high-temperature X-ray diffraction (HTXRD) differential thermal analysis (DTA), and ther-mogravimetry (TG). The X-ray diffraction (XRD) pattern obtained at room temperature indicated that the intercalation of hydrazine and H2O into dickite caused an increase of the basal spacing from 7.08 to 10.24 Å, which is slightly lower than the 10.4-Å spacing commonly observed after intercalation into kaolinite. Heating between 25–50°C produced a structural rearrangement of the complex, which decreased the basal spacing from 10.24 to 9.4 Å, and the resulting 9.4-Å complex was stable between 50–90°C. Heating between 90–300°C caused a gradual reduction in spacing, which occurred through a set of intermediate phases. These phases were interpreted to be interstratifications of intercalated and non-intercalated layers. These changes were also observed by DTA and TG. Two main endothermic reactions and two main stages of mass loss, respectively, were indicated in the DTA and the TG curves in the temperature range 25–200°C. This behavior suggests that intercalated molecules, hydrazine and H2O, occupied well-defined sites in the interlayer of the dickite. The intercalated molecules were lost in an ordered fashion as confirmed by the infrared analysis of the decomposition products; H2O was lost in the first stage and ammonia was identified in the second stage. Above 300°C, complete removal of the intercalated molecules restored the basal spacing of the dickite. However, the basal reflections were broadened, the relative intensities were changed, and changes in the dehydroxylation temperature indicated that the intercalation-desorption process induced some stacking disorder in the dickite structure.
Sorption of Organic Compounds by Al and Zr-Hydroxy-Intercalated and Pillared Bentonite
Authors: Matthes Winnie , Kahr Guenther
Published: August 2006

Owing to their large and chemically active surface, hydroxy-intercalated and pillared clays can be potent sorbents for organic compounds. The sorption behavior of Al and Zr-hydroxy-intercalated bentonite (HAl-, HZr-MX80), Al and Zr-pillared bentonite (Al-MX80, Zr-MX80), and a commercial Al-pillared bentonite (EXM 534) for 3-chloroaniline (3-CA), atrazine (AT), and 3-chlorophenol (3-CP) was investigated. The results were compared with the sorption behavior of the untreated Na-rich bentonite (MX80) and granulated activated carbon (GAC). Also the influence of the salinity of the sorbate and the age of the sorbents was studied.

Al and Zr-hydroxy-intercalated and pillared bentonites sorbed higher amounts of 3-CA, AT, and 3-CP than the untreated bentonite. The quantities sorbed related to the electron-donating properties of the sorbate and the acidity of the sorbents. Sorbed quantities increased from the hydroxy-intercalated to the pillared species, and from the Al to the Zr forms. The organic bases, 3-CA and AT, were sorbed in higher quantities than the organic acid 3-CP. For AT, the sorbents exhibited a high affinity. Aging of the samples and a high ionic strength of the sorbate reduced the sorption of 3-CA, whereas the sorption of AT was not affected greatly. The sorption capacity of GAC for organic bases was generally higher than that of the hydroxy-intercalated and pillared bentonites.

The data suggest that at initial concentrations at a ppm level, 3-CA and AT can be entirely removed from aqueous solutions by Al and Zr-hydroxy-intercalated and pillared bentonites. These materials, especially Zr-pillared bentonites, represent potent alternative sorbents for atrazine, chloroanilines, and probably a wide range of other organic bases.
Effects of Clay Fraction and Temperature on the H2O Self-Diffusivity in Hectorite Gel: A Pulsed-Field-Gradient Spin-Echo Nuclear Magnetic Resonance Study
Authors: Nakashima Yoshito
Published: August 2006

Self-diffusion coefficients of H2O molecules in Na-rich hectorite gel were measured by 'H nuclear magnetic resonance (NMR), Spin-echo pulse sequences with magnetic field gradient pulses for the translational diffusion measurement were applied to the hectorite gel at the Larmor frequency of 20 MHz. Effects of clay fraction (0-51.2 wt. %) and temperature (20.0-60.3°C) were studied. The results show: (1) Phenomenologically, the self-diffusion coefficient, D, of 1H2O in the clay gel is expressed by the normalized diffusivity, D/D0 = exp(−0.0257w), where D0 is the water self-diffusivity in bulk water at temperature and w is the weight fraction of the hectorite (wt. %). (2) The activation energy of H2O diffusivity in the hectorite gel is nearly equal to that in bulk water. Hence, the normalized diffusivity, D/D0, obeys a temperature-independent curve. (3) The exponential dependence of D/D0 on w for w <30 wt. % is explained by a random-walk model, in which free or unbound H2O molecules migrate in the geometrically complex and tortuous pore structure of randomly scattered clay-mineral grains.