bluuebunny/crossref_metadata_2025 huggingface dataset:
Solid-State Nuclear Magnetic Resonance Spectroscopy on Synthetic Ammonium/Aluminum-Saponites
Authors: Kloprogge J. T. , Breukelaar J. , Wilson A. E. , Geus J. W. , Jansen J. B. H.
Published: August 2006

Ammonium-saponite is hydrothermally grown at temperatures below 300°C from a gel with an overall composition corresponding to (NH4)0.6Mg3Al0.6Si3.4O10(OH)2. Using 27Al and 29Si solid-state Magic Angle Spinning NMR techniques it is demonstrated that synthetic ammonium-saponites have a rather constant Si/AlIV ratio (≈ 5.5) and an AlIV/AlVI ratio that varies between 1.5 and 3.8. The above ratios are independent of the synthesis temperature, although an increasing amount of Si, N, and, to a lesser extent, Al are incorporated in an amorphous phase with increasing temperature. 27Al MAS-NMR is unable to differentiate between Al at octahedral and Al3+ at interlayer sites. CEC, XRD, and the inability to swell prove the AlVI to be mainly on the interlayer sites. Based on the NH4- exchange capacity, X-ray fluorescence, 27Al and 29Si MAS-NMR, it is possible to calculate a relatively accurate structural formula.
Cation Exchange Capacity and Condition of Zero Charge of Hydroxy-Al Montmorillonite
Authors: Helmy A. K. , Ferreiro E. A. , de Bussetti S. G.
Published: August 2006

The effect of interlayering montmorillonite with different amounts of hydroxy aluminum cation on the cation exchange capacity (CEC) and the point of zero charge (PZC) of the clay was studied. The CEC decreased as the Al content of the clay increased. Both the CEC and the loss in the CEC were linearly dependent on the Al content, thus indicating the predominance of a single polynuclear interlayered species. Its composition is [Al6(OH)16.5]1.5+. Acid base titration of the interlayered montmorillonites produced values for the PZC in the range 4.5-5.9, increasing with the Al content of the materials. The values, however, did not represent real conditions of zero charge and some samples were still negatively charged at the determined PZC. The PZC values obtained by acid-base titration are thought to be adversely affected by secondary reactions involving the interlayered material with a concomitant release of soluble Al in amounts dependent on the pH and ionic strength.
Mobility of Small Molecules in Interlayers of Hectorite Gels: ESR Study with an Uncharged Spin Probe
Authors: McBride M. B.
Published: August 2006

Electron spin resonance (ESR) spectroscopy was used to measure the rotational mobility of an uncharged nitroxide spin probe (4-hydroxy-2,2,6,6-tetramethyl-piperidinyloxy) in hectorite gels of variable water content. Physical adsorption segregated the probe molecules into two populations: probes in the solution or a solution-like phase, and motionally restricted probes in the adsorbed phase. Although the spectra of these two populations were discrete, indicating that exchange between them was slow on the time scale relevant to ESR, their overlap prevented a straightforward determination of mobility of the adsorbed probes. Even though adsorption was weak, effects of the adsorbed population on the spectral lineshape were detectable for suspensions containing as little as 20 grams clay per liter of water. Orientation of the adsorbed probes on the fully hydrated hectorite surfaces was similar to that of a positively charged nitroxide probe, suggesting that steric factors rather than electrostatic forces control short-range organic molecule interaction with the silicate. The possibility of reaching false conclusions about probe mobility and interlamellar water viscosity when using a weakly adsorbing probe is discussed.
A Nexafs Study of the Orientation of Benzoate Intercalated into a Layer Double Hydroxide
Authors: Moggridge G. D. , Parent P. , Tourillon G.
Published: August 2006

NEXAFS is shown to be an excellent technique, of potentially widespread application, for the determination of the orientation of organic molecules intercalated in preferentially oriented thin films of polycrystalline, layered minerals. A NEXAFS study of [Mg2Al(OH)6]+C7H5O2 · nH2O, a layered anionic clay, is described. This material shows a transition from a layer spacing of 15.4 Å to only 9 Å at a remarkably low temperature (below 100°C). This is shown to be accompanied by a change in the angle of the plane of the benzoate molecule to the 00ℓ planes from 35° ± 10° to 0° ± 10°. The tilt of the benzoate anion in the room temperature structure demonstrates the presence of an interaction between the phenyl ring and the positively charged, brucite-like layers. Furthermore it is suggestive of the importance of hydrogen bonding in determining the interlayer spacing and stability.
Ba-Bearing Clinoptilolite from ODP Leg 127, Site 795, Japan Sea
Authors: Ogihara Sigenori
Published: August 2006

Ba-bearing clinoptilolite (with >2 wt. % BaO) occurs in Neogene marine siliceous sediments from ODP Leg 127 Site 795 in the Japan Sea. Ba-bearing clinoptilolite is formed by reaction of volcanic glass and Ba-rich pore water during burial diagenesis.
Refinement of the Crystal Structure of Cronstedtite-3T
Authors: Smrčok Ľubomír , Ďurovič Slavomil , Petříček Václav , Weiss Zdeněk
Published: August 2006

The crystal structure of cronstedtite-3T from Kutná Hora (Bohemia, Czechoslovakia), space group P31, was refined to Rw(all) = 3.1% for 1336 independent diffractions. There are two and three independent tetrahedral and octahedral positions, respectively, in this structure. The tetrahedra are occupied by 0.75 Si and 0.25 Fe while the octahedra are uniformly occupied by Fe. The refinement process was hindered by two problems: a “strong” superposition structure (all atoms of the octahedral sheets, i.e., ÷ 70% of the total diffraction power contribute almost solely to the family diffractions with mod(h–k, 3) = 0), and a slight disorder of the investigated crystal. The first problem was resolved by a preliminary block-diagonal refinement procedure where the atoms coinciding in the superposition structure were separated into individual blocks. The second problem was resolved by including two scale factors into the final full-matrix refinement: one for family diffractions, the other for the remaining ones which are characteristic for this polytype.
Nacritic Clay Associated with the Jiangshan-Shaoxing Deep Fault in Zhejiang Province, China
Authors: Shen Z. Y. , Wilson M. J. , Fraser A. R. , Pearson M. J.
Published: August 2006

A kaolin clay occurring in Carboniferous mudstone near the Jiangshan-Shaoxing deep fault in Zhejiang Province, eastern China was characterized by XRD and IR. Although the dominant mineral appeared to be kaolinite, IR also suggested the possible occurrence of nacrite. This was confirmed by forming intercalation complexes with potassium acetate and with hydrazine hydrate, both water complexes having the same characteristic spacing at 8.35 Â. Different particle size fractions of the kaolin clay were studied and the results indicated that nacrite content increased with increasing particle size. This occurrence of nacrite is consistent with previous findings of the polytype in high temperature and pressure environments.
Redox Treatment of an Fe/Al Pillared Montmorillonite. A Mössbauer Study
Authors: Bakas T. , Moukarika A. , Papaefthymiou V. , Ladavos A.
Published: August 2006

Pillared structures with an interlayer opening of ∼0.3 nm were obtained after successive heat treatments of the PILC precursor in reducing and oxidizing conditions. This precursor was prepared by reacting a Na+-montmorillonite with an intercalant containing Al and Fe oxo-hydroxides (Al/Fe = 1). Powder X-ray diffraction, elemental analysis, 57Fe Mössbauer spectroscopy, catalytic activity measurements and surface area data were used to characterize the samples. On the basis of Mössbauer spectra taken at temperatures between 4.2 and 300 K, it is deduced that oxidizing steps produce Al substituted maghemite which converts into Al substituted magnetite upon reducing heat treatment. Firing the precursor in oxidizing atmosphere forms pillars of few nm in diameter. However, heating under reducing conditions yields pillars of smaller diameter. This later behaviour is maintained even after reheating the material in oxidizing atmosphere. From the temperature dependence of Mössbauer spectra it is deduced that the diameter of the Fe oxide particles in the pillars is smaller than 10 nm.
Electrochemical Coagulation of Clay Suspensions
Authors: Szynkarczuk J. , Kan J. , Hassan T. A. T. , Donini J. C.
Published: August 2006

In the electrocoagulation process a suspension of kaolinite and bentonite is coagulated by electrochemical treatment where aluminum anodes are dissolved and aluminum ions react with clay particles, forming flocs which precipitate. Several factors affecting the efficiency of electrocoagulation are investigated. They include NaCl concentration, voltage, and flow conditions within the cell. Increased NaCl concentration led to lower electric resistance and cleaner running electrodes. Enhanced shear associated with recirculation resulted in clear supernatant and more compact floes. While increasing the feed rate, which was equivalent to decreasing aluminum concentration through the system, reduced cake height but increased turbidity.
Formation of Smectite Crystals at High Pressures and Temperatures
Authors: Yamada Hirohisa , Nakazawa Hiromoto , Hashizume Hideo
Published: August 2006

Smectite single crystals of superior quality were synthesized at high pressures and temperatures using a modified belt type high pressure apparatus. Pressure-temperature conditions were established for smectite formation by quenching experiments in the pressure range from 2–5.5 GPa and temperatures of 700°–1000°C. Smectite crystals with extraordinary quality were formed beyond 3 GPa and 1000°C with coexisting phases of coesite, kyanite, jadeite, and in some cases with mica and glass. Smectite was confirmed from the XRD taken after intercalation of ethylene glycol. The smectite crystals were considered to be quenched crystals metastably from the hydrous silicate melts formed at high pressures and temperatures.
Sorption of Cesium on Compacted Bentonite
Authors: Oscarson Dennis W. , Hume Harold B. , King Fraser
Published: August 2006

Sorption parameters are important components of models used to predict mass transport through dense or compacted earthen materials. These parameters are, however, generally determined in batch tests with loose, unconsolidated materials. Here we directly measure, using a specially designed cell, the extent of Cs+ sorption on bentonite compacted to a series of densities ranging from 0.50 to 1.50 Mg/m3, and compare the results with those obtained from batch tests with loose bentonite. The clay was saturated with a Na-Ca-Cl-dominated solution with an effective ionic strength of 220 mol/m3. The sorption data were expressed as distribution coefficients, Kd. Over the clay density range examined, Kd values for Cs+ with compacted clay are about one-half to one-third the value of those with loose clay. The lower sorption on compacted clay is attributed to small and occluded pores that Cs+ cannot enter; thus it cannot access the entire volume, or all the sorption sites, of compacted clay. The data suggest that reasonable estimates of Kd with compacted clay can be obtained by scaling down the Kd values measured on loose clay by a factor na/n, where na is the accessible porosity and n the total porosity of compacted clay.
Particle Morphological Evolution During the Conversion of I/S to Illite in Lower Cretaceous Shales from Sergipe-Alagoas Basin, Brazil
Authors: Varajão Angélica , Meunier Alain
Published: August 2006

The illitic end of mixed-layer illite-smectite series (I/S) in shales from Lower Cretaceous Barra de Itiúba Formation, Sergipe-Alagoas basin, was examined with X-ray powder diffraction (XRD) and transmission electron microscopy (TEM). A mathematical decomposition of XRD patterns shows different I/S and illite populations. All the samples contain ordered (R = 1) I/S, poorly crystallized illite (PCI) and well crystallized illite (WCI). A randomly interstratified (R = 0) I/S was also identified in a fractured zone at 1020 m. The percentage of expandable layers in ordered I/S decrease progressively from 20% to 10%. TEM observations show a continuous change in morphology between two basic particle shapes: elongated (lath) and isometric. The size and morphology of particles change with increasing depth. The proportion of laths decreases while isometric particles become predominant. However, both particle types continuously grow and enrich the larger size fraction. The growth process is driven by a mass transfer from the dissolving small particles of predominantly I/S (R = 1) composition to the larger (more illitic) lath and isometric ones. The proportion of lath-shaped particles decreases with depth indicating that the more stable population upon increased burial is the isometric well crystallized illite (WCI) particles. Very large laths are observed in the fault zone where conditions may favor faster growth processes.
A Technique for Maintaining Texture and Permanent Expansion of Smectite Interlayers for TEM Observations
Authors: Kim Jin-Wook , Peacor Donald R. , Tessier Daniel , Elsass Francoise
Published: August 2006

A process for treating smectite-bearing rock samples that utilizes LR White resin; allows TEM observation of expanded smectite interlayers and therefore preservation of original rock textures. Examples of several lattice fringe images are shown, including: (1) Dioctahedral smectite layers from a shale (1388.9 meter depth, Texas Gulf Coast) give fringes that consistently have spacings of 1.2–1.3 nm, yet duplicate other features previously observed in collapsed samples. (2) Packets of illite layers give fringes with 1.0-nm spacings coexisting with packets of (dominantly) R1 I/S having 2.1-nm lattice fringe spacings in a Gulf Coast shale from 4742.1 m. (3) Rectorite from Garland Co., Arkansas gives 2.3-nm lattice fringes. Samples with wide ranges of I/S ratios and lithologies have been found to be permanently expanded with retention of original textures, commonly leading to unambiguous identification of illite and smectite interlayers in lattice fringe images.
Layer Charge Characteristics of Smectites in Salt-Affected Soils in Alberta, Canada
Authors: Kohut Connie K. , Dudas M. J.
Published: August 2006

The layer charge characteristics of expanding phyllosilicates in four salt-affected soils in Alberta, Canada were investigated using X-ray diffraction analysis of alkylammonium saturated samples. The layer charge was found to be lower and more heterogeneous than previously reported for non-saline Alberta soils, with the mean layer charge ranging between 0.261 to 0.339 tool (—)/O10(OH)2. Layer charge characteristics varied inconsistently with location, depth and particle size, likely the result of both different origins and weathering processes. Different degrees of K depletion from the micaceous component after equilibration with alkylammonium compounds may also account for some variability between samples. Extreme broadening and essential disappearance of smectite diffraction maxima was noted for some samples after intercalation with alkylammonium cations of all carbon chain lengths, indicating unusual alteration of the layer charge characteristics in some salt-affected soils.
Separation of Sub-Micron Particles from Soils and Sediments without Mechanical Disturbance
Authors: Churchman G. J. , Weissmann D. A.
Published: August 2006

A method is described for the separation of the finest particles from soils and sediments without mechanical disturbance. Particles are separated through the induction of osmotic stress. Generally, samples are treated with a concentrated sodium salt solution and then exposed to water by diffusion. Naturally sodic samples are simply exposed to water. Solid samples and the swollen and dispersed material they produce are confined by dialysis tubing. Examples show that the method gives a size gradient of particles in a vertical column of suspension. The compositions of particles can vary with size. The method can be used to show the effects on separated particles of ions other than Na+ and also of other physicochemical treatments of soils and sediments. It is inexpensive and requires little labor.
Layer Charge of the Expandable Component of Illite/Smectite in K-Bentonite as Determined by Alkylammonium Ion Exchange
Authors: Cetin Kenan , Huff Warren D.
Published: August 2006

—The charge of the expandable interlayers in a series of fourteen diagenetic illite/smectites (I/S) from lower Paleozoic K-bentonites was determined by the alkylammonium ion exchange method. The magnitude (<0.50 equivalents per half formula unit) and characteristic heterogeneous distribution of interlayer charges in eight samples with expandabilities from 70% to about 15% confirm the smectitic character of the expandable interlayers in this range. This result coupled with the lack of a correlation between expandability and interlayer charge is consistent with the hypothesis of a layer-by-layer transformation from a precursor smectite to highly illitic I/S clays during K-bentonite diagenesis. The charge of the expandable interlayers in I/S samples with about 10% or less expandabilities have been inferred to be vermiculitic rather than smectitic. The K-fixed interlayers and expandable interlayers in these samples appear to be similar in charge. The significantly higher charges inferred for the highly illitic samples can be consistent both with a layer-by-layer transformation and the neoformation mechanisms proposed in the literature for the formation of illite.
Dehydroxylation of Aluminous Goethite: Unit Cell Dimensions, Crystal Size and Surface Area
Authors: Ruan H. D. , Gilkes R. J.
Published: August 2006

This work investigates unit cell dimensions, crystal size and specific surface area of aluminous goethite that was progressively dehydroxylated to form hematite. Goethite synthesized from the ferrous system altered to hematite with DTGA maximum increasing from 236° to 273°C for 0 to 30.1 mole % Al-substitution. Unit cell dimensions of goethite and hematite decreased as Al-substitution increased and increased as excess OH increased. The crystallographically equivalent a axis of goethite and c axis of hematite were more sensitive than other axes to the presence of excess structural OH associated with Al-substitution. Specific surface area increased from 147 to 288 m2/g for goethite and from 171 to 230 m2/g for hematite as Al-substitution increased. An increase in specific surface area on heating goethite at temperatures between 200° and 240°C is related to a decrease in the size of coherently diffracting domains of goethite crystals and to the development of pore and structural defects associated with the formation of hematite. The decrease in specific surface area for heating temperatures above 240°C is attributed to the growth of hematite crystals by diffusion.
Quantification Curves for XRD Analysis of Mixed-Layer 14Å/10Å Clay Minerals
Authors: Pons C. H. , de la Calle C. , Martin de Vidales J. L.
Published: August 2006

Using theoretical profiles of diffracted X-ray intensity for interstratification between layers having d-spacings around 14.3 Å and 10.1 Å, a series of diagrams was derived from which the proportion of 14.3 Å layers (W14) and the probability of passing from a 14.3 Å layer to a 10.1 Å layer (P14/10) can be derived. W14 can be derived independently of P14/10 using the angular distance between reflections situated at 18.2° and 25.4° 2θ (CuKα). Once W14 is determined, P14/10 may be obtained using the angular width of the diffuse reflections between 27° and 34° 2θ. In this case, two different diagrams are proposed for P14/10 determination because experimental X-ray patterns show either one or two diffuse reflections. Comparison of five experimental patterns with theoretical patterns calculated using W14 and P14/10 obtained using these diagrams indicates that the method can be useful for determining W14 and P14/10 in unknown samples. Moreover, the method described is independent of the Lorentz polarization factor and the layer type. The d-spacings associated with the two kinds of layers, however, should be similar (± 1%) to those for which the determinative diagrams were calculated.
Monte Carlo Simulation of Interlayer Molecular Structure in Swelling Clay Minerals. 1. Methodology
Authors: Skipper N. T. , Chang Fang-Ru Chou , Sposito Garrison
Published: August 2006

Monte Carlo (MC) simulations of molecular structure in the interlayers of 2:1 Na-saturated clay minerals were performed to address several important simulation methodological issues. Investigation was focused on monolayer hydrates of the clay minerals because these systems provide a severe test of the quality and sensitivity of MC interlayer simulations. Comparisons were made between two leading models of the water-water interaction in condensed phases, and the sensitivity of the simulations to the size or shape of the periodically-repeated simulation cell was determined. The results indicated that model potential functions permitting significant deviations from the molecular environment in bulk liquid water are superior to those calibrated to mimic the bulk water structure closely. Increasing the simulation cell size or altering its shape from a rectangular 21.12 Å × 18.28 Å × 6.54 Å cell (about eight clay mineral unit cells) had no significant effect on the calculated interlayer properties.
Model Calculation of Sepiolite Surface Areas
Authors: Hibino Toshiyuki , Tsunashima Atsumu , Yamazaki Atsushi , Otsuka Ryohei
Published: August 2006

In general, the N2-BET surface areas of sepiolite samples range from 95 to 400 m2/g depending on deposits.

The surface areas of five sepiolites, all varying in crystallite size, were measured on heating, and were compared with a model calculation. A sharp decrease in the surface area, due to crystal folding, was observed between 200° and 400°C. Both before and after the folding, each sepiolite sample had peculiar values. Our model sufficiently explains this difference in surface areas among the samples. In the model, which is based on the Brauner-Preisinger structural model, surface area is a function of the crystallite size and the ratios of the coverage for nitrogen adsorption on both the internal and external surfaces. These ratios of the coverage can be inversely estimated from the model. The ratios of the coverage on the internal surface are less than 0.19, and that on the external surface between 0.7 and 1.0.
Low-Charge to High-Charge Beidellite Conversion in a Vertisol from South Italy
Authors: Righi Dominique , Terribile Fabio , Petit Sabine
Published: August 2006

The fine silt (2–5 μm) coarse clay (0.1–2 μm) and fine clay (<0.1 μm) fractions of a Vertisol from South Italy were studied with X-ray diffraction. The most reactive fine clay (<0.1 μm) fraction was investigated in detail using a curve decomposition method analysis of X-ray diffraction diagrams, FTIR spectroscopy and chemical analysis. In the soil parent material, the fine clay fraction was dominated by low-charge smectites (beidellite and montmorillonite) whereas, high-charge beidellite was the dominant clay mineral in the fine clay from the upper soil horizons. This suggested that high-charge beidellite was produced through alteration of the preexisting low-charge smectites and was the stable clay phase in this soil environment, characterized by high pH (>8.0). After K-saturation and 25 wetting and drying cycles, the high-charge beidellite from the soil horizons lost expandability far more than the original low-charge smectites.
Synthesis and Catalytic Properties of Silicate-Intercalated Layered Double Hydroxides Formed by Intragallery Hydrolysis of Tetraethylorthosilicate
Authors: Yun Sang Kyeong , Constantino Vera R. L. , Pinnavaia Thomas J.
Published: August 2006

Layered double hydroxides (LDH's) interlayered with silicate anions were prepared by reaction of tetraethylorthosilicate (TEOS) with synthetic meixnerite-like precursors of the type [Mg1−xAlx(OH)2][OH−]x·zH2O, where (1 − x)/x ≈ 2, 3, or 4. TEOS hydrolysis at ambient temperature occurred readily in the galleries of the hydroxide precursors with (1 − x)/x ≈ 3 or 4, but a temperature of ∼100°C was required to achieve silicate intercalation for the LDH composition with (1 − x)/x ≈ 2. On the basis of the observed gallery heights (∼7.0−∼7.2 Å) and 29Si MAS NMR spectra that indicated the presence of Q2, Q3, and Q4SiO4 sites, the intercalated silicate anions, which are formed by condensation reactions of silanol groups and partial neutralization of SiOH groups with gallery hydroxide ions, are assigned short chain structures. Also, some O3SiOH groups become grafted to the LDH layers by condensation with MOH groups on the gallery surfaces. The LDH-silicates exhibited comparable non-microporous N2 BET surface areas in the range 59–85 m2/g, but they differed substantially in acid/base reactivities, as judged by their relative activities for the catalytic dehydration/disproportionation of 2-methyl-3-butyn-2-ol (MBOH). Under reaction conditions where the LDH structure is retained (150°C), all the silicate intercalates showed mainly basic reactivities for the disproportionation of MBOH to acetone and acetylene. However, all the LDH silicates were less reactive than the corresponding LDH carbonates. Conversion of the LDH silicates to metal oxides at 450°C introduced acidic activity for MBOH dehydration, whereas the metal oxides formed by LDH carbonate decomposition were exclusivity basic under analogous conditions.
Variable-Temperature Mössbauer Spectroscopy of Nano-Sized Maghemite and Al-Substituted Maghemites
Authors: Da Costa G. M. , De Grave E. , Bowen L. H. , De Barker P. M. A. , Vandenberghe R. E.
Published: August 2006

Synthetic aluminum-substituted maghemite samples, γ-(Fe1-xAlx)2O3, have been prepared by thermal decomposition of Al-lepidocrocite (γ-Fe1-xAlxOOH), with × = 0, 0.04, 0.06, 0.14 and 0.18. The particles are needle-shaped and the mean crystallite diameter along the [311] crystallographic direction was found to be between 2.0 and 5.0 nm. Mössbauer spectra were collected at 6 K and from 80 K up to 475 K at steps of 25 K. In a wide range of temperatures the spectra of the non-substituted sample consist of a superposition of a broad sextet and a superparamagnetic doublet, whereas for the Al-maghemites this range is much smaller. From the temperature variation of the fractional doublet area two different parameters were defined: the temperature corresponding to a 50/50 doublet-sextet spectrum (T1/2), and the temperature below which the doublet ceases to exist (T0). These two parameters (T1/2 and T0) decrease from 390 K and 92 K (Al-free sample), to 118 K and 64 K (4 mole % Al) and to 100 K and 48 K (18 mole % Al), respectively. The average hyperfine fields at 6 K undergo a steep drop in going from the Al-free sample (Hhf = 506 kOe) to the sample with 4 mole % Al (Hhf = 498 kOe), but for higher substitutions the effect is much smaller. The A- and B-site quadrupole splittings, obtained from the data between 220 K and 475 K, were found as: ΔEQ,A = 0.86 ± 0.04 mm/s and ΔEQ,B = 0.65 ± 0.04 mm/s for the 4 mole % Al sample. The characteristic Mössbauer temperature, determined from the temperature dependence of the average isomer shift, was found to be in the range of 500–600 K.
Mechanism of Illitization of Bentonites in the Geothermal Field of Milos Island Greece: Evidence Based on Mineralogy, Chemistry, Particle Thickness and Morphology
Authors: Christidis George E.
Published: August 2006

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

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

The I/S particle morphology is characterized by both flaky and lath-like particles, the former dominating in the range 100-50% expandable layers (R0 ordering) and the latter in the range 50-10% expandable layers (R1 and R > 1 ordering). Flaky particles are also abundant in samples with R1 ordering and abundant kaolinite, indicating that the latter might affect illitization. The I/S particles are classified in populations with thickness multiples of 10 A, their thickness being probably smaller than the coherent XRD domain. As the reaction proceeds, particles grow thicker and more equant. The distribution of I/S particle dimensions forms steady state profiles showing log-normal distribution; however, sensu stricto Ostwald ripening is unlikely. It seems that the reaction proceeds toward minimization of the surface free energy of I/S, being affected principally by temperature and K-availability. The spatial distribution of expandability implies that the heating source was probably a mineralized vein with T < 200°C, directed away from the bentonite, suggesting that illitization might be used as an exploration guide for mineral deposits.
The Influence of Uranyl Hydrolysis and Multiple Site-Binding Reactions on Adsorption of U(VI) to Montmorillonite
Authors: McKinley James P. , Zachara John M. , Smith Steven C. , Turner Gary D.
Published: August 2006

Adsorption of uranyl to SWy-1 montmorillonite was evaluated experimentally and results were modeled to identify likely surface complexation reactions responsible for removal of uranyl from solution. Uranyl was contacted with SWy-1 montmorillonite in a NaCIO4 electrolyte solution at three ionic strengths (I = 0.001, 0.01, 0.1), at pH 4 to 8.5, in a N2(g) atmosphere. At low ionic strength, adsorption decreased from 95% at pH 4 to 75% at pH 6.8. At higher ionic strength, adsorption increased with pH from initial values less than 75%; adsorption edges for all ionic strengths coalesced above a pH of 7. A site-binding model was applied that treated SWy-1 as an aggregate of fixed-charge sites and edge sites analogous to gibbsite and silica. The concentration of fixed-charge sites was estimated as the cation exchange capacity, and non-preference exchange was assumed in calculating the contribution of fixed-charge sites to total uranyl adsorption. The concentration of edge sites was estimated by image analysis of transmission electron photomicrographs. Adsorption constants for uranyl binding to gibbsite and silica were determined by fitting to experimental data, and these adsorption constants were then used to simulate SWy-1 adsorption results. The best simulations were obtained with an ionization model in which AlOH2+ was the dominant aluminol surface species throughout the experimental range in pH. The pH-dependent aqueous speciation of uranyl was an important factor determining the magnitude of uranyl adsorption. At low ionic strength and low pH, adsorption by fixed-charge sites was predominant. The decrease in adsorption with increasing pH was caused by the formation of monovalent aqueous uranyl species, which were weakly bound to fixed-charge sites. At higher ionic strengths, competition with Na+ decreased the adsorption of UO22+ to fixed-charge sites. At higher pH, the most significant adsorption reactions were the binding of UO22+ to AlOH and of (UO2)3(OH)5+ to SiOH edge sites. Near-saturation of AlOH sites by UO22+ allowed significant contributions of SiOH sites to uranyl adsorption.
Iron Substitution in Soil and Synthetic Anatase
Authors: Schwertmann U. , Friedl J. , Pfab G. , Gehring A. U.
Published: August 2006

IronIII for TiIV substitution in the structure of pedogenic and synthetic anatase of up to Fe/ (Ti+Fe) 0.1 mol/mol was indicated by an increase in unit cell size as measured by XRD line shifts. Mössbauer- and electron paramagnetic resonance spectra at both, 298 K and 4.2 K supported this by the presence of signals typical for octahedrally coordinated FeIII in a diamagnetic matrix. Charge compensation was achieved by structural OH, as indicated by FTIR bands at 3360 and 960 cm−1, which were absent in pure anatase and which disappeared on heating. The weight loss on heating amounted to ca. 0.5 mol H2O/mol Fe. At 600°C structural Fe was ejected, the unit cell size decreased to that of pure anatase, and pseudobrookite, Fe2TiO5, was formed.
Migration of Cu Ions in Cu Montmorillonite Heated with and without Alkali Halides
Authors: Heller-Kallai L. , Mosser C.
Published: August 2006

Cu montmorillonite heated with or without potassium halide was studied by IR and ESR spectroscopy, supplemented by XRD measurements, microprobe and chemical analyses. It appears that on heating Cu montmorillonite, most of the Cu ions migrate into hexagonal cavities and eventually, when dehydroxylation occurs, into octahedral vacancies. Some Cu ions may penetrate into octahedral vacancies before dehydroxylation. In the presence of potassium halide, deprotonation facilitates penetration of Cu into octahedral vacancies. The presence within the layers of non-exchangeable Cu ions that are inaccessible to water does not necessarily cause the perturbation of OH bending vibrations conventionally attributed to migration of small cations into the structure. Such perturbation was only observed when the basal spacing was reduced to ~9.5Å.
Evolution of Benzylammonium-Vermiculite and Ornithine-Vermiculite Intercalates
Authors: de la Calle C. , Tejedor M. I. , Pons C. H.
Published: August 2006

This report consists of a study of l-ornithine hydrochloride-vermiculite and of benzylammonium hydrochloride-vermiculite complex. The evolution of these organo-vermiculite structures upon heating is studied by X-ray diffraction (XRD) as well as infrared spectroscopy.

After heating vermiculite saturated with 1-ornithine cations, it shows condensation of interlayer ornithine molecules (peptide complexes). The stacking mode, opposing ditrigonal cavities, is not modified between aminoacid complex and peptide complex.

For vermiculite saturated with benzylammonium cations, the stacking sequence changes through heating by changing benzylammonium to NH4+. This transformation implies a sliding of the layers over each other. The ditrigonal surface cavities become face to face, as in the original mica. There are no random translations as in the starting complex.
Evaluation of Kinetic Models for the Smectite to Illite Transformation
Authors: Elliott W. Crawford , Matisoff Gerald
Published: August 2006

Three different models have been reported previously to describe the kinetics of the transformation of smectite to illite (Pytte 1982; Velde and Vasseur 1992; Huang et al. 1993). In order to evaluate the general utility of these models to calculate the timing and extent of this transformation, each model was applied to four different geologic settings (Denver Basin, Gulf Coast, the Salton Sea Geothermal System, and Paris Basin) in which the ages, geothermal gradients and potassium ion activities vary markedly. The model results are compared to the measured percentages of illite in illite/smectite (I/S) and the K/Ar ages of I/S (if available) to test the utility of a given model to a particular basin.

Although individual models can be applied to study this transformation within a specific setting, none of these models was successful in simulating the transformation for all four basins. The Salton Sea was simulated best using the model by Huang et al. (1993), which incorporated an increased geothermal gradient during the last 20,000 years. These results indicate that a large fraction of illite formed due to this increased geothermal gradient, and underscores that temperature is a dominant kinetic factor in forming illite. The Denver Basin was simulated well by the models of Velde and Vasseur (1992) and Pytte (1982). The Gulf Coast was simulated very well by the model of Huang et al. (1993) using a term that terminates the transformation at 75% illite. For the Paris Basin, the results are mixed. The models can be refined by comparing the calculated and measured ages of illite such as the K/Ar ages of I/S to understand the thermal history of a particular basin. The calculated ages of illitization derived from these refined models can be used to indicate the time at which source rocks became thermally mature to form oil and gas.
Orientation of Trimethylphenylammonium (TMPA) on Wyoming Montmorillonite: Implications for Sorption of Aromatic Compounds
Authors: Stevens Jeffrey J. , Anderson Sharon J.
Published: August 2006

The orientation of TMPA cations on montmorillonite affects the adsorbate-accessible siloxane surface area and determines whether the TMPA phenyl ring can interact with other aromatic adsorbates by π-π interactions. The purpose of this study was to determine the orientation of TMPA ions in the interlayer of normal-charge and reduced-charge Wyoming montmorillonite. The orientation of TMPA's phenyl group was investigated using infrared dichroism of selected aromatic ring vibrations. X-ray diffraction (XRD) and MacEwan Fourier transforms were used to determine interlayer spacings and to ascertain whether reduced-charge Wyoming montmorillonite is a randomly interstratified mixture of layers with two different d-spacings. For normal-charge montmorillonite, the infrared results showed that the C-N bond axis is neither perpendicular nor parallel to the surface, yet X-ray data suggested that the TMPA phenyl ring is perpendicular or nearly perpendicular to the siloxane surface. In this orientation, the average adsorbate-accessible space between adjacent TMPA ions is 24 Å2, or about 1/3 of the total surface. When the phenyl ring of TMPA is perpendicular to the clay surface, aromatic compounds should be able to interact with TMPA's aromatic ring by π-π interactions, while polar compounds such as water can interact with positively charged nitrogen atom. The reduced-charge montmorillonite used in this study is a randomly interstratified mixture of about 25% collapsed layers with no adsorbed cations and 75% expanded layers that are propped open by TMPA's methyl groups, not by the aromatic ring. The adsorbate-accessible surface area on expanded layers of reduced-charge montmorillonite is 1.5 to 2 times that on normal-charge TMPA-clay, depending on the orientation of TMPA's aromatic ring.
Structural Transformations of Interstratified Illite-Smectites from Dolná Ves Hydrothermal Deposits: Dynamics and Mechanisms
Authors: Drits V. A. , Salyn A. L. , Šucha V.
Published: August 2006

Structural transformations of illite-smectite samples of hydrothermal genesis with increasing contents of illite layers were studied by X-ray powder diffraction. The samples were K-saturated and subjected to wetting and drying cycles to increase three-dimensional structural ordering. Diffraction profiles were analyzed with the help of a specially devised computer program based on the approximation of individual diffraction reflections by “bell-shaped” functions, with minimization of the differences between experimental and simulated profiles. The data indicate that the transformations of these illite-smectite samples were accompanied not only by variations in the proportion of illite and smectite layers and in the pattern of their alternation, but also by a change in structure within 2:1 layers.
Sorption Mechanisms of Lanthanum on Oxide Minerals
Authors: Fendorf Scott , Fendorf Mark
Published: August 2006

The retention of hazardous species, including many of the lanthanides, on soils and sediments is vital for maintaining environmental quality. In this study, high-resolution transmission electron microscopy (HRTEM) was used to identify surface precipitates of La and their degree of atomic ordering on oxides of Mn (birnessite), Fe (goethite) and Ti (rutile) over a pH range of 3 to 8. At pH >5.5, the aqueous concentration of La was fully depleted by all three metal-oxides. On birnessite, surface precipitation of La-hydroxide occurred at pH = 5 and appears to be the dominant sorption mechanism on this mineral. Surface precipitation was not observed on rutile or goethite until much higher pH values, 6.5 for rutile and 8.0 for goethite. Precipitation is thus correlated with the points of zero charge (PZC) of the minerals, 6.3 for rutile and 7.8 for goethite, and in each case was observed only at pH values above the PZC. Although La sorption was extensive on all of the minerals at the higher pHs, the depletion of La from solution by rutile and goethite at pH values well below the PZC indicates that the sorption mechanism differs from that on birnessite. While surface precipitation was found to be the dominant sorption mechanism of La on birnessite, surface complexation of monomelic or small multinuclear species appears to predominate in La retention on rutile and goethite at most commonly encountered pH values.
Dissolution of Hectorite in Inorganic Acids
Authors: Komadel P. , Madejová J. , Janek M. , Gates W. P. , Kirkpatrick R. J. , Stucki J. W.
Published: August 2006

The effect of acid type and concentration on the reaction rate and products of dissolution of hectorite in inorganic acids was investigated. The dissolution of hectorite in hydrochloric (HCl), nitric (HNO3) and sulphuric (H2SO4) acids was characterized using quantitative chemical analysis, infrared (IR) and multinuclear MAS NMR spectroscopies. The rate of dissolution increased with acid concentration and decreased in the order HCl ≥ HNO3 = H2SO4 at the same molar concentration. No differences were found in the reaction products of hectorite treated with the three acids. The rate of Li dissolution was slightly greater than that of Mg at lesser acid concentrations (0.25 M), indicating that protons preferentially attack Li octahedra. The gradual changes in the Si-O IR bands reflects the extent of hectorite dissolution. The analysis of 29Si MAS NMR spectra relative peak intensities with dissolution time and acid concentration provided direct dissolution rates for tetrahedral (Q3) Si. After acid dissolution, most Si was bound in a three dimensional framework site (Q4), but a substantial part also occurred in the Si(OSi)3OH (Q31OH) and Si(OSi)2(OH)2 (Q220H) environments. These three sites probably occur in a hydrous amorphous silica phase. Both AlJV and AlVt rapidly disappeared from 27Al MAS NMR spectra of the dissolution products with acid treatment. The changes in IR and MAS NMR spectra of hectorite due to acid dissolution are similar to those of montmorillonite.
Tem Observations of Coherent Stacking Relations in Smectite, I/S and Illite of Shales: Evidence for MacEwan Crystallites and Dominance of 2M1 Polytypism
Authors: Dong Hailiang , Peacor Donald R.
Published: August 2006

TEM characterization of stacking relations in I/S of expanded shale samples from the Gulf Coast and Michigan Basin was carried out to address the issues of the degree of coherency and the nature of layer stacking sequences in smectite, I/S and illite. The two-dimensional lattice fringe images obtained from this study show that cross fringes are commonly observed to be continuous over at least 3–4 layers for smectite, 6–7 layers for ordered I/S and 9–10 layers for illite-rich I/S. This demonstrates that such sequences are coherent, or at least semi-coherent (in smectite) units (MacEwan crystallites). The observations demonstrate that so-called fundamental particles are fragments of MacEwan crystallites formed primarily as a result of disaggregation along weakly-bonded smectite interlayers. However, both 0k1 and h01 reflections may coexist in selected area electron diffraction (SAED) patterns. The frequency of occurrence of the coexistence in SAED patterns decreases in the order smectite, I/S and illite for Gulf Coast samples. This is consistent with the presence of turbostratically-related interfaces in packets of all of these materials. Therefore, any given layer sequence in smectite, ordered I/S and illite may have both turbostratic and coherent interfaces. The proportion of coherently-related layers increases with increasing proportion of illite-like layers. The concept of fundamental or elementary particles is not related to layer sequences in non-disaggregated, original rocks. Indeed, it implies relations that are not valid.

The lattice fringe images, SAED and optical diffraction patterns demonstrate that where layers are coherently-related, 2M1 is the dominant polytypic sequence in all samples. However, this periodic 2M1 stacking is so frequently interrupted by stacking faults in smectite that it gives rise to apparent lMd polytypism. The degree to which the periodic 2M1 sequences are interrupted by stacking faults decreases with increasing proportion of illite-like layers. The SAED patterns of I/S and illite unmodified since its formation are diffuse parallel to c* and have poorly-defined, non-periodic reflections for indices k ≠ 3N as a measure of local ordering superimposed on poorly-ordered coherent sequences with a turbostratic component. X-ray diffraction (XRD) patterns, as integrated over domains with a range of heterogeneous stacking relations, do not represent simple mixtures of discrete IM and 2M1 polytypes.

The observations of this study imply that dissolution-crystallization is a dominant mechanism for the smectite-to-illite transition. The semi-coherent stacking of smectite-like layers in smectite-rich samples implies that either a dissolution-crystallization process took place subsequent to deposition of detrital smectite or that Gulf Coast smectite is an in-situ alteration product of volcanic ash.
Dickite, Nacrite and Possible Dickite/Nacrite Mixed-Layers from the Betic Cordilleras (Spain)
Authors: Ruiz Cruz M. D.
Published: August 2006

Nacrite, dickite and intermediate dickite-nacrite phases have been identified from the upper Paleozoic sequences of the Maláguide Complex (Betic Cordilleras, Spain). Nacrite developed as euhedral, pseudohexagonal or elongated crystals within sandstones and thin, irregular veins. Dickite developed preferently within extensive zones of fractures as very irregular, compact packets. Intermediate phases occurred in the sandstones and veins similar to the nacrite, or accompanying dickite. The mineral assemblage of the sandstones includes quartz-muscovite-kaolinite-type minerals, with or without albite, carbonates, chlorite and mixed-layers containing chlorite. The metamorphic conditions in which these minerals formed belong to anchizone, as can be deduced from the IC values. Dickite, nacrite and intermediate phases were studied by X-ray diffraction, infrared spectroscopy, differential thermal analysis and micros-copy. The results for dickite indicate a well-ordered mineral and agree with most of the published data. Conversely, IR spectra and DTA curves of nacrite show some differences in relation to the available data for this mineral. Based on the comparison with dickite and nacrite data, intermediate phases can be interpreted either as disordered varieties or as mixed-layered dickite/nacrite.