bluuebunny/crossref_metadata_2025 huggingface dataset:
Authigenic Chrysotile Formation in the Matrix of Quaternary Debris Flows, Northern Southland, New Zealand
Authors: Craw D. , Landis C. A. , Kelsey P. I.
Published: August 2006

Quaternary debris flows derived from ophiolite melange in northern Southland, New Zealand, are locally cemented and veined by cross-fiber and fine-grained chrysotile. Chrysotile was identified by optical, X-ray powder diffraction, electron microprobe, differential thermal (DTA), and infrared analysis methods. Microprobe and DTA also suggested the presence of as much as 6% of sub-microscopic, noncrystalline alumina, probably in the form of pseudoboehmite. Cavity fillings and irregular veins containing chrysotile are as thick as 40 cm and commonly contain lizardite clasts. Calcite commonly accompanies chrysotile as a vein mineral. Magnetite and pyrite are found near and adjacent to chrysotile veins. These accessory minerals imply that the chrysotile formed under alkaline, reducing conditions. Surface water seepages have pH = 9. Remnant debris-flow topography, Holocene radiocarbon dates, and the absence of hot spring activity confirms that chrysotile can form under near-surface, low-temperature conditions. Growth of chrysotile fibers on a lizardite substrate suggests that the chrysotile formed by solution of detrital lizardite and subsequent precipitation in cavities within the debris flow.
Reactions of Thiophene and Methylthiophenes in the Interlayer of Transition-Metal Ion-Exchanged Montmorillonite Studied by Resonance Raman Spectroscopy
Authors: Soma Yuko , Soma Mitsuyuki , Furukawa Yukio , Harada Issei
Published: August 2006

The adsorption and reaction of thiophene and methylthiophenes in the interlayer of Cu2+- and Fe3+-montmorillonites were investigated by resonance Raman spectroscopy. Thiophene and 3-methylthiophene polymerized to form cations of polythiophene and polymethylthiophene respectively, which were characterized by absorption bands in the near-infrared region. These polymer cations formed in the interlayer were reduced to their neutral polymers if the clay-polymer complexes were in contact with water, and the formation of their neutral polymers was clearly demonstrated by their resonance Raman spectra. 2,5-Dimethylthiophene in which polymerization was hindered by methyl substitution at the 2 and 5 positions, was oxidized to 2,5-dimethylthiophene cation in the interlayer.
Fourier-Transform Infrared Study of Ethylene Glycol Monoethyl Ether Adsorbed on Montmorillonite: Implications for Surface Area Measurements of Clays
Authors: Nguyen T. T. , Raupach M. , Janik L. J.
Published: August 2006

Infrared spectra of 2-ethoxyethanol (ethylene glycol monoethyl ether, EGME) adsorbed on Camontmorillonite were obtained using diffuse-reflectance infrared-Fourier-transform (DRIFT) and attenuated total-reflectance (ATR) spectroscopy. The molecular conformation of adsorbed EGME shows predominantly a gauche configuration for the CH2-CH2 linkage as originally present in the liquid. The orientation of the adsorbed EGME molecule in the interlamellar region of the clay was deduced from measurements of the polarized ATR spectra. The planar zig-zag skeleton of the molecule appears to have its long axis tilted at an angle of 44° to the clay surface; the molecule is in van der Waals contact with both adjacent surfaces. Further, the plane of the skeleton of the molecule is tilted at an angle of 69° to the clay surface. This orientation leads to estimates of the d-value of the clay-EGME complex and of the surface area occupied by each molecule. These values are in excellent agreement with independent measurements of both parameters. The full surface coverage on montmorillonite is represented by a single layer of tilted EGME molecules shared by two adjacent clay sheets; each molecule occupies a total surface area consisting of one portion (25.4 Å2) on the lower surface of the interlayer plus another portion (14.8 Å2) on the upper surface. The implication of this model for materials such as kaolinite, where adsorption takes place on the external surface only, is that on these materials each EGME molecule occupies 20 Å2 at full surface coverage.
Quinoline Sorption on Na-Montmorillonite: Contributions of the Protonated and Neutral Species
Authors: Ainsworth Calvin C. , Zachara John M. , Schmidt Ron L.
Published: August 2006

Dilute aqueous solutions of quinoline were contacted with Na-montmorillonite to elucidate the sorption process of the neutral and protonated species. Sorption occurs via a combination of ion exchange and molecular adsorption and yields S-type isotherms. Exchange between the quinolinium ion (QH+) and Na can be described by means of Vanselow selectivity coefficients and a thermodynamic exchange constant (Kex). Due to the apparent adsorption of the neutral species at high mole fractions (x) of the solid phase, the thermodynamic standard state was defined as 0.5 mole fraction. The selectivity at pH ~4.95 of the QH+ species over Na (at XQH+ = 0.5) was determined to be Kv = 340. At pH ≥ 5.5 surface mole fractions of 0.5 could not be obtained without adsorption of the neutral species. This study suggests that at dilute solution concentrations quinoline is sorbed preferentially as the cation even at pHs ≫ pKa. A critical surface-solution concentration is apparently necessary for adsorption of the neutral species.
Weathering of Basalt: Changes in Rock Chemistry and Mineralogy
Authors: Eggleton Richard A. , Foudoulis Chris , Varkevisser Dane
Published: August 2006

The weathering of eastern Australian basalts, sampled from the rounded, hard, core-stone to the rind of softer weathered material, has been examined by bulk chemical analyses, thin section petrography, electron microprobe, and X-ray powder diffraction analyses. Using density as a measure of weathering intensity, data from four core-stones show that at a stage of weathering in which the total loss due to dissolution is – (i.e., at the core-stone rim), the percentages lost of the following major elements are: Ca, 85; Mg, 80; Na, 70; K, 50–80; P, 55; Si, 45; Mn, 40; Al, 5; Fe, 0; and Ti, 0. With more intense weathering, deposition of some elements, particularly rare earths and Ba, and mobilization and deposition of Al and Fe make quantification impossible. The rate of weathering of individual minerals is consistent with the well-known susceptibility series: glass ∼ olivine > plagioclase > pyroxene > opaque minerals. Clay minerals in the core-stones are dominated by smectites, whereas those in the surrounding more intensely weathered rinds are dominated by halloysite and goethite.
Crystal Structure of a Vermiculite-Anilinium Intercalate
Authors: Slade P. G. , Dean C. , Schultz P. K. , Self P. G.
Published: August 2006

If anilinium ions are intercalated into Llano vermiculite, the stacking order of adjacent silicate layers is increased, resulting in a relatively sharp single crystal X-ray diffraction (XRD) pattern. The packing of intercalated organic members forms a superstructure and produces bonding from layer to layer which favors the stacking order. Superlattice reflections occur which, although sharp in the a*b* plane, are streaked along c*. Apparently there is little coherence between adjacent layers of ordered organic units.

A three-dimensional set of XRD reflections for a triclinic sub-cell having the following lattice parameters was measured: a = 5.326(3), b = 9.264(4), c = 14.82(5) Å, α = 90.31(7), β = 96.70(6), and γ = 89.55(5)°. In this unit cell (symmetry Cl), ditrigonal cavities in adjacent silicate layers are approximately opposite. Differential Fourier analyses and least-squares refinements showed that the principal axes of the anilinium ions, i.e., N-C(1)-C(4), are nearly perpendicular to the silicate layers. The planes of the aromatic rings, however, are about ±30° to X, neither parallel nor perpendicular to that direction, as indicated by earlier studies.

Inorganic cations and water molecules are also present in the interlayer; the former and some of the latter occupy sites near the middle of the layer. Anilinium-rich and anilinium-poor domains coexist. In the latter, the cation-water system predominates and apparently conforms to the superstructure. Although the cation-water structure could not be uniquely established from the reflections produced by the sub-cell, possible positional coordinates were obtained. From structural data for the silicate layers, no evidence was found for long-range Si/Al ordering in the tetrahedral sites.
Characterization of Overgrowth Structures Formed Around Individual Clay Particles During Early Diagenesis
Authors: Steinberg Michel , Holtzapffel Thierry , Rautureau Michel
Published: August 2006

The coarse (0.4–2 µm) clay fraction of an Albian black shale collected in the Atlantic Ocean (Deep Sea Drilling Project leg 11) consists chiefly (90–95%) of smectite and 5–10% illite. Both minerals are locally surrounded by overgrowth structures, such as fine laths about 0.05–0.4 µm long and 0.02–0.1 µm wide. Individual laths or assemblages of laths protrude from the center of smectite flakes at angles of about 60° to each other. Laths occur around illite crystals in a similar manner or coalesce into a rim that consists of 0.05–0.1-µm-size particles. On the basis of scanning transmission electron microscopy: (1) the center of individual illite crystals consists of a dioctahedral mineral, but the overgrowth structures are Al-Fe beidellites; and (2) the smectite flakes have highly variable compositions, but correspond chiefly to Fe-Al-beidellite, whereas the overgrowths are compositionally close to montmorillonite.

The overgrowth structures seem to have formed during early diagenesis. The chemical composition of overgrowths around illite and smectite tend to be similar in response to the new environment, implying an addition of silica to both materials.
Hydrothermal Treatment of Smectite, Illite, and Basalt to 460°C: Comparison of Natural with Hydrothermally Formed Clay Minerals
Authors: Yau Yu-Chyi , Peacor Donald R. , Essene Eric J. , Lee Jung H. , Kuo Lung-Chuan , Cosca Michael A.
Published: August 2006

Wyoming bentonite, Fithian illite, and basalt from the Umtanum Formation, Washington, were treated hydrothermally at 200° to 460°C and 260 to 500 bars for 71 to 584 days. No change was detected for the bentonite and basalt, except for the loss of calcite and exchange of Ca for K in the smectite and the growth of a small amount of smectite (presumably from a glass phase) in the basalt. Calcite in the initial bentonite may have stabilized the smectite by Ca/K exchange; thus, if the latter is used as a packing material in a nuclear waste repository, limestone should be added. No change was detected in the illite samples treated <300°C; however, at 360°C, euhedral crystals of berthierine and illite grew at the expense of original illite/smectite, apparently by a solution-crystallization process. Significant changes involving the dissolution of starting phases and the formation of illite and chlorite were also detected in mixtures of basalt and bentonite at 400°C; at temperatures <400°C, no changes were observed.

The newly formed mineral phases (berthierine, illite, and chlorite) observed by transmission electron microscopy showed euhedral to subhedral shapes. These shapes are the same as those observed in hydrothermally altered sediments from the Salton Sea field and different from those from burial metamorphic environments, such as Gulf Coast sediments. The reaction mechanism is apparently the dissolution of reactants followed by the crystallization of products from solution, without conservation of structural elements of the reactants. Reactions apparently required temperatures greater than those for analogous changes in nature, suggesting that the degree of reaction was controlled by kinetics. The lack of dissolution in experimental runs at low temperatures, however, does not necessarily imply long-term stabilities of these clay minerals.
Authigenesis of Kaolinite and Chlorite in Texas Gulf Coast Sediments
Authors: Burton J. H. , Krinsley D. H. , Pye K.
Published: August 2006

Core cuttings from numerous wells traversing Oligocene through Recent sediments of the Texas Gulf Coast were examined with a scanning electron microscope using the back-scattered electron imaging mode (BSE) to ascertain diagenetic changes in clays and associated minerals of mudrocks and of adjacent sandstones. Several occurrences of authigenic kaolinite and chlorite were noted, each characterized by a specific texture and a specific diagenetic microenvironment. In all occurrences kaolinite appears to have formed before chlorite, and in some the kaolinite appears to have precipitated directly from solution. Chlorite, ubiquitously an iron-rich variety, appears to have precipitated in some places directly from solution. It has also been noted pseudomorphous after kaolinite. A progressive decrease in the iron content of mixed-layer illite/smectite with increasing depth is believed to have released the necessary iron and to have driven the kaolinite-to-chlorite reaction.
Effect of Exchangeable Potassium on the Hydraulic Conductivity of Smectite-Sand Mixtures
Authors: Shainberg I. , Keren R. , Alperovitch N. , Goldstein D.
Published: August 2006

Changes in hydraulic conductivity of smectite-sand mixtures (using four reference smectites) as a function of the concentration (0.01, 0.003, 0.002, 0.001 M Cl- and distilled water) and potassium adsorption ratio (of 2, 4, and 6) of the percolating solution were measured. Swelling and dispersion of the clays were evaluated from the changes in hydraulic conductivity of the mixture and from the clay concentration in the effluent.

The effect of exchangeable potassium percentage (EPP) on the hydraulic conductivity of the smectites depended on the charge density of the clays. The effect of potassium at EPPs <20 on the hydraulic conductivity of smectites having high charge density was negligible. Conversely, the hydraulic conductivity of smectites having low charge density (smectites from Wyoming and Belle Fourche, South Dakota), changed markedly when leached with dilute solutions as the EPP of the clay increased. The dispersive effect of exchangeable potassium on low-charge smectites was similar to that of exchangeable sodium. The low hydration energy of the K+ cations, coupled with the strong electrostatic attraction forces between platelets of smectites with high charge density account for the “inefficiency” of K+ in dispersing these smectites.
Optical Density of Vertisol Clay Suspensions in Relation to Sediment Volumes and Dithionite-Citrate-Bicarbonate-Extractable Iron
Authors: Ben-Dor Eyal , Singer Arieh
Published: August 2006

Clay fractions of eight vertisols and vertisolic soils from Israel were found to consist principally of a Fe-rich beidellite. Sediment volumes of Na-clay suspensions, obtained in measuring cylinders and read every 24 hr for as long as 720 hr, ranged from 3.8 to 8.4 cm/l00 mg clay and were as much as 19 times larger than corresponding suspensions of Ca-clays. Optical density data for all clay suspensions showed absorption curves typical of smectite. The relative number of platelets per tactoid, calculated from optical density measurements, ranged between 1.4 and 5.4 for the Na-clays and between 7.4 and 14.1 for the Ca-clays. In the Ca-clays, the sediment volume decreased with an increase in the relative number of platelets per tactoid. With increase in the major dimension of particles (calculated also from optical density curves), sediment volume tended to increase for the Na-clays and decrease for the Ca-clays. These relationships can be explained on the basis of particle arrangement patterns: face-to-face arrangements dominated the Ca-clays and edge-to-edge and edge-to-face arrangements dominated the Na-clays. The amount of iron extractable in dithionite-citrate-bicarbonate (DCB) correlated positively with the relative number of plates per tactoid and with the major dimensions of the particles in the Ca-clay suspensions. This correlation suggests that DCB-extractable iron affects the tactoid dimensions of Ca-clays from vertisols and, therefore, may also affect structural properties of vertisols.
Vapor-Phase Sorption Kinetics for Tetrahydrofuran, Tetrahydropyran, and 1,4-Dioxan by Al3+- and Cr3+-Exchanged Montmorillonite
Authors: Breen C. , Deane A. T. , Flynn J. J.
Published: August 2006

The rate of vapor-phase sorption of tetrahydrofuran (THF), tetrahydropyran (THP), and 1,4-dioxan (DIOX) onto a Wyoming montmorillonite saturated with Al3+ or Cr3+ has been studied by isothermal gravimetry in the temperature range 18° to 105°C using samples of different weights and grain-size distributions. The rate of sorption for all the cyclic ethers increased with decreasing sample and grain size, demonstrating that inter-, rather than intraparticle mass transfer was rate-determining. Optimization of the sample parameters (2 mg sample of <45-μm grain size, pretreated at 120°C yielded integral diffusion coefficients at 18°C of 0.5 × 10−14 m2/s for DIOX for the Cr3+-clay to 3.5 × 10−4 m2/s for THF for the Al3+-clay; however, no temperature or cationic dependence of the cyclic ether uptake was observed. In general, the rate of sorption of the cyclic ethers increased as THF ≥ THP > DIOX indicating that the sorption rate of THF and THP was dependent on concentration or that DIOX sorption was retarded by bidentate coordination to aluminum ions at the edges of the clay platelets.
Interpretation of Mössbauer Spectra of Nontronite, Celadonite, and Glauconite
Authors: Daynyak Lydia G. , Drits V. A.
Published: August 2006

A new approach to the interpretation of Mössbauer spectra of Fe3+-phyllosilicates having vacant trans-octahedra is based on (1) crystal structure simulation methods that allow for the size and the shape of a Fe3+-octahedron as a function of the nearest surrounding cations; and (2) calculations of electric field gradients (EFG) on Fe3+ in terms of the ionic point-charge model. Calculations were performed by direct summation within the region of radius ≤50 Å. Coordinates for the anions in the coordination octahedra have been assigned to take into account the nearest cationic environment. Atomic coordinates for the rest of the summation volume are those for the average unit cell. EFG calculations for cation combinations responsible for the visible quadrupole splitting Δvis in the spectra of nontronite, “red” muscovite, and celadonite have led to good agreement between Δvis and Δcalc. Computer fitting of the nontronite and celadonite spectra based on EFG calculations for the rest of the possible cation combinations suggests that the distribution of tetrahedral cations in nontronite obeys the Loewenstein rule, and in celadonite, the distribution of R3+ and R2+ over cis-octahedra is predominantly ordered, in agreement with electron diffraction and infrared spectroscopy data. The Mössbauer spectrum of one of the glauconites suggested the presence of celadonite-like and muscovite-like domains in its 2:1 layers.
Intervalence Electron Transfer and Magnetic Exchange in Reduced Nontronite
Authors: Lear Paul R. , Stucki Joseph W.
Published: August 2006

The effects of chemical reduction of structural Fe3+ in nontronite SWa-1 (ferruginous smectite) on intervalence electron transfer (IT) and magnetic exchange were investigated. Visible absorption spectra in the region 800-400 nm of a chemical reduction series of the SWa-1 nontronite revealed an IT band near 730 nm (13,700 cm−1). Both the intensity and position of this band were affected by the extent of Fe reduction. The intensity increased until the Fe2+ content approached 40% of the total Fe, then decreased slightly with more Fe2+. The position of the band also shifted to lower energy as the extent of reduction increased.

Variable-temperature magnetic susceptibility measurements showed that the magnetic exchange in unaltered nontronite is frustrated antiferromagnetic, but ferromagnetic in reduced samples. Magnetic ordering temperatures are in the range 10–50 K, depending on the extent of reduction. The ferromagnetic component in the magnetization curve increased with increasing Fe2+ in the crystal structure. The positive paramagnetic interaction likely is due to electron charge transfer from Fe2+ to Fe3+ through such structural linkages as Fe2+-O-Fe3+ (perhaps following a double exchange mechanism), which is consistent with the visible absorption spectra.
Cation-Exchange Properties of (Al + Na)-Substituted Synthetic Tobermorites
Authors: Komarneni Sridhar , Breval Else , Miyake Michihiro , Roy Rustum
Published: August 2006

Tobermorite, Ca5Si6O16(OH)2·4H2O, is a hydrous calcium silicate that has a layer-type of structure similar to that of the 2:1 clay minerals. In its natural form, tobermorite exhibits little or no exchange for alkali cations; synthetic tobermorites, however, exhibit reversible alkali cation exchange and selective cesium uptake upon a coupled substitution of (Al3+ + Na+) for Si4+. Substituted tobermorites were synthesized using aluminosilicate gels, NaOH, and CaO, in Parr bombs at 175°C for 4 days. Unsubstituted tobermorite was synthesized using quartz and CaO in a Parr bomb at 175°C for 20 hr. Two (Al + Na)-substituted tobermorites showed cation-exchange capacities (CEC) of 77 and 71 meq/100 g, whereas an unsubstituted tobermorite showed a CEC of 12 meq/100 g. The substituted tobermorites exhibited selective Cs exchange from either NaCl or CaCl2 solutions. For example, one substituted tobermorite showed a Cs-exchange coefficient (Kd) of 15,100, whereas unsubstituted tobermorite showed a Kd of only 90 from a 0.02 N CaCl2 solution containing 0.0002 moles/liter CsCl. Exchange isotherms for Na+ ⇋ Cs+ showed that Cs+ is preferred over Na+ throughout the exchange in the (Al + Na)-substituted tobermorites. This group of cation exchangers is expected to find applications in radioactive waste disposal.
Optically Selective Adsorption of α-Amino Acids on Montmorillonite-Cu-1-Lysine Complexes in High-Pressure Liquid Chromatography
Authors: Tsvetkov Faina , Mingelgrin U.
Published: August 2006

Optically active cationic complexes adsorbed on montmorillonite can be used for the resolution of racemic mixtures. Montmorillonite-Cu-lysine systems were used as a solid phase in high-pressure liquid chromatography for the resolution of the optical isomers of α-amino acids. Selectivity constants > 1.5 were measured for phenylalanine and tryptophan. The selectivity constants for the amino acids containing saturated-hydrocarbon side chains were in the range of 1.25–1.44. The montmorillonite-Cu-l-lysine complex displayed a stronger affinity for the l-isomers of α-amino acids than for the d-isomers at pHs near neutrality. Inasmuch as surface-catalyzed peptide formation on clays has been proposed as a step in chemical evolution, this stronger affinity between the clay-Cu-l-amino acid complex and l-amino acids might have been significant in prebiotic evolution. The mechanism of optical resolution probably involved ligand exchange. Optimizing the choice of the optically active ligands and of the chelating cation in the chiral agent may improve the resolution of the optical isomers.
Diagenetic Alteration of Silicic Ash in Searles Lake, California
Authors: Hay Richard L. , Guldman Sandra G.
Published: August 2006

Ash layers from Searles Lake, California, were sampled in core of drill hole KM-3, which penetrated 693 m of lacustrine sediment deposited in a playa-lake complex over the past 3.2 my. Lake water changed from moderately saline and slightly alkaline (pH ~7.5) to highly saline 2.04 my ago and to highly saline and alkaline (pH ~9.5) 1.28 my ago. As a result of brines flushing downward, the upper 291 m of sediment, spanning the past 1.28 my, contain highly saline, alkaline pore fluid. Silicic ash layers in contact with highly saline, alkaline pore fluid were first altered to phillipsite and meriinoite and then to K-feldspar and searlesite. The transformation of phillipsite and/or meriinoite to K-feldspar required more than 45,000 years and was largely completed in 140,000 years. Tephra layers in contact with moderately saline, slightly alkaline pore fluid vary from uncemented vitric ash containing minor smectite to bentonites in which glass is wholly altered to smectite, clinoptilolite, analcime, and opal. Layers with much fine tephra are more altered than the coarser, better-sorted layers. Alteration is attributed to hydrolysis in essentially a closed hydrologic system, in which the alteration of glass to smectite raised the pH, aSiO2, and (Na+ + K+)/H+ activity ratio to the level where clinoptilolite formed. Some diffusion and/ or fluid flow is, however, indicated by the loss of SiO2 during the alteration of ash layers to smectite and by anhydrite deposited during and after clinoptilolite in some tuffaceous sandstones.
Sodium, Calcium, and Ammonium Exchange on Clinoptilolite from the Fort Laclede Deposit, Sweetwater County, Wyoming
Authors: Hulbert Matthew H.
Published: August 2006

Clinoptilolite from the Fort LaClede deposit in Sweetwater County, Wyoming, shows a moderate selectivity for NH4− over Na+ in aqueous solution. At 30°C, the standard free energy of this replacement reaction is −0.7 kcal/mole at an ionic strength of 0.05 M and −0.8 kcal/mole at 0.5 M. The Na+-NH4+ exchange is complete within 3 days in agitated solution and proceeds to the same extent from the clinoptilolite saturated with either cation.

The Ca2+-Na+ exchange also is complete within 3 days in agitated aqueous solution and proceeds to the same extent from either the calcium or the sodium form of the zeolite. Using test methods which take into account the slower equilibration of Ca2+-loaded clinoptilolite, the cation-exchange capacity is substantially the same over the full range of loading by Ca2+ and Na+. Ca2+ replaces Na+ with decreasing selectivity as Ca2+ loading increases to about 80% at 30°C (95% at 63°C), above which the selectivity reverses. The standard free energy of replacement of two Na+ ions by one Ca2+ ion in 0.05 M solution is −1.2 ± 0.2 kcal/mole at 63°C and −0.3 to −0.8 kcal/mole at 30°C.
Transmission Electron Microscope Study of Biotite Weathering
Authors: Banfield Jillian F. , Eggleton Richard A.
Published: August 2006

Transmission electron microscopy suggests that biotite transforms to vermiculite primarily by direct structural modification, involving the replacement of K+ by hydrated interlayer cations, and only minor reorganization of the 2:1 layer. A second relatively uncommon mechanism appears to involve redistribution of components from two biotite sheets to form a single vermiculite layer. Distortion of the surrounding structure initially inhibits growth of vermiculite in the surrounding biotite, and promotes the propagation of vermiculite layers in opposite directions. This phenomenon may contribute to the development of relatively regular, widely spaced interstratifications of biotite and vermiculite. Additional components and space are provided by the dissolution of biotite where access of solutions is greater.

During weathering, biotite and vermiculite become increasingly replaced by kaolinite, which crystallizes epitactically onto existing layers, and goethite, which develops from a poorly crystalline iron oxyhydroxide precursor to form oriented laths. In areas parts of strongly weathered samples kaolinite and goethite appear to develop in proportions consistent with a reaction that conserves both Al and Fe.
Investigation of a K-Bentonite by X-Ray Powder Diffraction and Analytical Transmission Electron Microscopy
Authors: Huff W. D. , Whiteman J. A. , Curtis C. D.
Published: August 2006

The <0.1-μm size fraction of an Ordovician K-bentonite from northern Kentucky was characterized by X-ray powder diffraction (XRD). Using A.I.P.E. A. criteria for interstratification nomenclature and Reynolds’ computer algorithm the dominant clay mineral proved to be an R2 ordered illite/smectite. The best fit of observed and calculated XRD tracings was obtained using 12 > N > 5, where N is the number of layers within a diffracting domain.

Sections of the K-bentonite were prepared by ion-beam milling and examined in an analytical transmission electron microscope (ATEM). One-dimensional lattice images observed parallel to the a-b plane showed subparallel packets, about 50–100 Å thick, each of which consisted of about 10-Â thick unit layers. Somewhat thicker unit layers (as much as 14.5 Å) were also seen. The former are presumed to be illite, whereas the latter may be partially collapsed smectite. Selected-area electron diffraction patterns suggested simultaneous diffraction from several packets, each containing at least five layers. Both h0l and 0kl spacings were usually present, indicating that the stacking of the subparallel packets was random. Quantitative analysis by AEM and electron microprobe show the clay to be low in tetrahedral Al but high in octahedral Mg, the latter presumably contributing largely to the interlayer charge responsible for K fixation. The TEM data are broadly reconcilable with the accepted XRD interpretation of a two-component, mixed-layer clay. Alternatively, the TEM images may be interpreted as a single phase having numerous packet boundaries, the latter being responsible for swelling behavior. These two interpretations will not be fully reconciled until greater analytical precision and resolution permit individual packets to be studied. This work suggests that mineral definitions based purely on XRD interpretations may have to be reconsidered as more electron microscope data become available.
New Data and a Revised Structural Model for Ferrihydrite
Authors: Eggleton Richard A. , Fitzpatrick Robert W.
Published: August 2006

Synthetic 2-line and 6-line ferrihydrite samples prepared from ferric nitrate solutions have the bulk compositions Fe4(O,OH,H2O)12 and Fe4,6(O,OH,H2O)12, respectively. The composition depends on crystal size, which averages 20 Å for 2-line and 35 Å for 6-line ferrihydrite. X-ray absorption edge spectra indicate the presence of tetrahedral Fe3+, a conclusion supported by heating experiments which show the development of maghemite after heating to 300°C in the presence of N2, followed by the formation of hematite at higher temperatures. These two reactions are recorded on differential thermal analysis traces by exotherms at 350° and 450°C. Transmission electron microscopy shows that 2-line ferrihydrite has no Z-axis regularity but does show hexagonal 2.54-Å lattice fringes. Six-line ferrihydrite forms faceted crystals having 9.4-Å c-parameter only detectable in dark field. In bright field, 2.54-Å lattice fringes indicate greater atomic regularity than in 2-line ferrihydrite. Analysis of the X-ray powder diffraction pattern of 6-line ferrihydrite suggests a structure based on double-hexagonal close-packed oxygens, containing 36% Fe in tetrahedral sites. Selective chemical dissolution, surface area measurements, and magnetic susceptibility are consistent with the recorded properties of ferrihydrite.
An Occurrence of Authigenic Nacrite
Authors: Bühmann D.
Published: August 2006

Euhedral, pseudohexagonal nacrite was discovered as a thin layer coating a carbonaceous shale in the Sherwood Tunnel in Durban, Republic of South Africa. The nacrite apparently formed authigenically within a few weeks at ambient temperature by precipitation from pore solutions, probably as a result of evaporation. This observation suggests that nacrite can no longer be considered to indicate a high-temperature genetic environment. Precipitation from saturated pore solution may have been the mechanism of formation for this kaolin-mineral polymorph.
Analysis and Implications of the Edge Structure of Dioctahedral Phyllosilicates
Authors: White G. Norman , Zelazny L. W.
Published: August 2006

Crystal growth theory was applied to describe edge sites of phyllosilicates. Three face configurations were found to exist. One face has one tetrahedral site per tetrahedral sheet and two octahedral one-coordinated sites per crystallographic area ac sin β, where a and c are layer dimensions and β is the angle between them. The other two faces are similar except that they have one less octahedral site which is replaced by one SiIV-O-AlVI site in this same ac sin β area. A transfer of bonding energy from the remaining octahedral site to the SiIV-O-AlVI site is believed to neutralize all edge charge on faces containing these latter sites at normally encountered pHs (pH 3–9). A similar charge rearrangement along the edges results in an apparent decrease in the permanent charge of the mineral with an increase in edge area.

On the basis of such an analysis, lath-shaped illite can be described as a very fine grained dioctahedral mica in which the apparent deficient occupancy of the octahedral sheet, presence of excess water, and measurable cation-exchange capacity may in part be the result of a large ratio of edge area to total volume, with no other chemical or structural change in the mica layers. The increasing importance of edge charge relative to layer charge produces erroneous formulae for 2:1 phyllosilicates in very fine grained samples containing fewer than 2 of 3 octahedral sites occupied by cations, on the basis of a 22-charge half cell.
Preparation of Delaminated Clay Having a Narrow Micropore Distribution in the Presence of Hydroxyaluminum Cations and Polyvinyl Alcohol
Authors: Suzuki Kenzi , Mori Toshiaki , Kawase Kaoru , Sakami Hiroshi , Iida Shozo
Published: August 2006

The pillaring of Na-montmorillonite with cationic oligomers of hydroxyaluminum (COHA) in the presence of an aqueous solution of polyvinyl alcohol resulted in the formation of a clay having a large surface area and pore volume. The pore-size distribution determined from a N2 adsorption/desorption hysteresis was narrow and centered at about 25 Å. The peak width at half height in the distribution curve was < 5 Å. As a result of delamination, the layer structure of the prepared clay was found from X-ray powder diffraction measurements to be lost. Short-range ordering, however, still existed in this delaminated clay, because exchangeable cations in the montmorillonite completely exchanged with Al3+, a requisite step for pillaring.

The order of adding the starting materials (Na-montmorillonite, polyvinyl alcohol, and COHA) greatly affected the surface area and the pore volume of the delaminated clay. Two orders of addition (Namontmorillonite, then COHA, then polyvinyl alcohol; and COHA, then Na-montmorillonite, then polyvinyl alcohol) gave no measurable surface area and pore volume. Two other orders of addition (polyvinyl alcohol, then COHA, then Na-montmorillonite; and polyvinyl alcohol, then Na-montmorillonite, then COHA) gave surface areas of 107 and 160 m2/g and pore volumes of 0.13 and 0.29 cm3/g, respectively. The amounts of the COHA solution and polyvinyl alcohol added greatly influenced the surface area and pore volume of the delaminated clay. Both properties increased monotonically with increasing amount of added polyvinyl alcohol, and increased to a maximum and then decreased with increasing amount of added COHA solution. The maximum surface area of the prepared delaminated clay was 330 m2/g.
Photostabilization of a Nitromethylene Heterocycle Insecticide on the Surface of Montmorillonite
Authors: Margulies L. , Rozen H. , Cohen E.
Published: August 2006

The photochemical stability of the insecticidal compound tetrahydro-2-(nitromethylene)-2H-1,3-thiazine (NMH) adsorbed on montmorillonite (Mont), in the presence or in the absence of a second organic chromophore was studied. Two different organic dyes were investigated as possible stabilizers of NMH: the divalent cation methyl green (MG) and the monovalent cation thioflavin T (TFT). Samples of free NMH and of the adsorption complexes Mont-NMH, Mont-MG-NMH, and Mont-TFT-NMH were exposed to direct sunlight, and the residual insecticidal activity was estimated. Some photostabilization of the pesticide adsorbed to the clay was observed. The highest degree of photoprotection was achieved in samples containing 0.5 mmole of TFT and 0.2 mmole of NMH/g clay. Increasing the load of TFT to 0.8 mmole/g clay resulted in a complete loss of photostabilization. The interactions of the organic molecules at the clay surface were studied by UV-VIS absorption and Fourier-transform infrared spectroscopy. For the Mont-NMH and Mont-MG-NMH complexes, the observed photostabilization is probably due to clay-NMH interactions. In the Mont-TFT-NMH complex specific interactions between the cationic dye and the pesticide molecules probably occurred as well.
Quantitative Determination of Hematite and Goethite in Lateritic Bauxites By Thermodifferential X-Ray Powder Diffraction
Authors: Boski T. , Herbillon A. J.
Published: August 2006

An X-ray thermodifferential powder diffraction method for the quantitative determination of goethite and hematite in lateritic bauxites has been developed and consists of measuring the integrated intensities of the 012 line of hematite before and after heating the sample at 900°C and of correcting the obtained values by the X-ray mass absorption coefficient of either the untreated or heated matrix. From the corrected line intensities and the chemical analyses, the amounts of iron to be allocated to goethite and hematite in the untreated samples can be estimated. The actual content of goethite and hematite in a sample is calculated by taking into account the degree of Al substitution in each of these minerals. The method was tested on artificial mixtures of goethite and hematite and subsequently used to analyze 98 auger drill samples from lateritic bauxites of Guinea Bissau. The estimated precision of the determination of goethite and hematite content was ±2% (absolute). The method can not be applied to samples containing < 10% Fe2O3 (on a whole weight basis) unless preconcentration is carried out.
X-Ray Diffraction Identification of the Polytypes of Mica, Serpentine, and Chlorite
Authors: Bailey S. W.
Published: August 2006

Six standard polytypes of micas exist that have c-periodicities between 1 and 6 layers; these can be subdivided into groups A and B according to whether the octahedral cations are in the same set of positions in every layer or alternate regularly between I and II possible sets of positions (alternate slant directions), respectively. Correspondingly, 12 standard polytypes exist for 1:1 layers of the serpentine-type structures, which are divisible into four groups A-D. Groups A and B differ as in the micas, as do groups C and D. Groups A and B have ±a/3 interlayer shifts, whereas groups C and D have zero or ±b/3 interlayer shifts. Six structural types of semi-randomly or regularly stacked 1-layer chlorites exist that differ in the slant of the interlayer sheet (I or II) and its position (a or b) relative to 6-member rings in adjacent 2:1 layers.

Criteria have been established that permit the X-ray diffraction identification of the above-mentioned groups as well as the individual polytypes within each group. These criteria involve inspection of the strong X-ray diffraction reflections of index k = 3n for identification of the groups and of the generally weaker k ≠ 3n reflections for identification of the polytypes (assuming indexing on orthohexagonal axes throughout for convenience). In all hydrous phyllosilicates the octahedral cations and anions repeat at intervals of b/3 and thus contribute strongly to X-ray diffraction reflections of index k = 3n. The intensities of these reflections identify the two mica groups, the four serpentine-type groups, and the six chlorite groups. The periodicities of these reflections along Z* is that between identical octahedral sheets. The basal oxygen atoms do not repeat at intervals of b/3 and are a primary contributor to the intensities of k ≠ 3n reflections. The period along Z* for these reflections is that between identical basal oxygen planes, and the periodicity plus the symmetry identify the individual trioctahedral polytypes. For dioctahedral polytypes of the kaolin-group minerals and chlorites, the position of the vacant octahedral site must be considered also.

These general principles can be illustrated especially well by single-crystal precession photographs and extrapolated to powder photographs.
Modification of the Porous Structure and Surface Area of Sepiolite under Vacuum Thermal Treatment
Authors: Grillet Y. , Cases J. M. , Francois M. , Rouquerol J. , Poirier J. E.
Published: August 2006

Modifications of the external surface area and the two types of microporosity of sepiolite (structural microporosity and inter-fiber porosity) were examined as a function of the temperature of a vacuum thermal treatment to 500°C. The methods used included: reciprocal thermal analysis, N2 and Ar low-temperature adsorption microcalorimetry, gas adsorption volumetry (for N2, Ar, and Kr at 77 K and CO2 at 273 and 293 K), water-vapor adsorption gravimetry, and immersion microcalorimetry into liquid water at 303 K. If the sample was not heated >100°C, only 20% of the structural microporosity was available to N2, whereas 52% was available to CO2 at 293 K. In both experiments, the channels filled at very low relative pressures. At >350°C, the structure transformed to anhydrous sepiolite, which showed no structural microporosity. The inter-fiber microporosity decreased from 0.031 to 0.025 cm3g (as seen with N2), and the external specific surface area decreased from 120 to 48 m2/g. The water adsorption isotherms showed a lower and lower affinity of the external surface of fibers for water as the temperature of thermal treatment increased. The thickness of the bound water on the external surface was estimated to be ≤ 3.5 monolayers, i.e., less than 10 Å.
Quantification Curves for Mica/Smectite Interstratifications by X-Ray Powder Diffraction
Authors: Tomita Katsutoshi , Takahashi Hidewo , Watanabe Takashi
Published: August 2006

X-ray powder diffraction (XRD) patterns for many interstratified mica/glycolated smectites were calculated by changing combinations of probabilities and transition probabilities of two-component layers. Three basal XRD reflections, 5. l°–7.6°2θ (p1), 8.9°–10.2°2θ (p2), and 16.1°–17.2°2θ (p3) were selected for the quantification curves. A distinct relationship exists between Δ2θ, (p2–p1) and Δ2θ2 (p3–p2) which shows systematic changes with expandability at constant Reichweite values. The calculated values were plotted with Δ2θ1 and Δ2θ2 as the axes of coordinates, and quantification curves were calculated. The components and stacking parameters of mica/smectites were estimated easily using this diagram. Probabilities of existence of component layers and their transition probabilities for Reichweite (R=0) and (R=l) structures, and special cases of R=2 and R=3 structures were obtained.
Model for Competitive Adsorption of Organic Cations on Clays
Authors: Margulies L. , Rozen H. , Nir S.
Published: August 2006

The adsorption on montmorillonite of two monovalent organic cations, methylene blue (MB) and thioflavin T (TFT), was studied in four different situations: (1) separate adsorption of MB or TFT; (2) competitive adsorption of TFT and Cs; (3) competitive adsorption of the two organic cations from their equimolar solutions; and (4) adsorption of TFT on a clay whose cation-exchange capacity (CEC) had been previously saturated with MB. MB and TFT adsorbed to as much as 120% and 140% of the CEC, respectively. Cs did not appear to compete with TFT for the adsorption sites of the clay. TFT molecules adsorbed more strongly than those of MB and displaced them from the clay surface. A model was developed to evaluate the strength of the clay-organic cation interactions. The specific binding of the cations to the negatively charged surface, determined by solving the electrostatic equations, appears to account for adsorption exceeding the CEC and formation of positively charged complexes, which are due to non-coulombic interactions between the organic ligands.

The charge reversal predicted by the model beyond the CEC of the clay was confirmed by microelec-trophoretic experiments. Particles in a sample of montmorillonite loaded with 50 meq TFT/100 g clay moved to the positive electrode, whereas in samples containing the two dyes, MB and TFT, coadsorbed at a total concentration of 100–120 meq/100 g clay, the particles moved to the negative electrode. Binding coefficients describing the formation of neutral and charged complexes of TFT and the clay were larger than those for MB and the clay, thereby explaining the preferential adsorption of TFT observed experimentally. The binding coefficients for the formation of neutral complexes of either MB and TFT and the clay were more than six orders of magnitude larger than those previously reported for inorganic monovalent cations.
Thermal Transformation of Talc as Studied by Electron-Optical Methods
Authors: de Souza Santos Helena , Yada Keiji
Published: August 2006

The thermal decomposition of a fibrous talc was studied by transmission electron microscopy (TEM) and selected-area electron diffraction (SAD). Small changes in the lengths of a and b unit-cell parameters were noticeable at 500°C, but the talc laths did not change morphologically until 800°C. At this temperature striations began to appear in the TEM image, and the talc SAD reflections began to develop faint satellite streaks. At 900°C the striations appeared to be crystallites, and reflections of orthorhombic enstatite were noted. Both TEM and SAD evidence showed that the enstatite crystallites were formed in three orientations corresponding to the three pseudohexagonal a axes of the talc. Thus, triple superposition of the electron diffraction pattern at the three equivalent angles explains the high symmetry star-shaped pattern. At 1000° to 1100°C the enstatite crystallites were shorter and thicker, and the streaks in the SAD pattern were nearly absent. Above 1200°C only one orientation of the enstatite crystallites was found. Noncrystalline regions were also detected at 900°C and became progressively scarce at 1000° and 1100°C. They were not detected at 1200°C. At 1300°C cristobalite was detected in some SAD patterns. The crystallographic axes and unit-cell parameters of the talc and enstatite were also topotactically related as follows: at (5.3 Å)//ce (5.2 Å); bt (9.16 Å)//be (8.8 Å); d(001)t (18.84 Å)//ae (18.2 Å). These results are compatible with an inhomogeneous decomposition mechanism as proposed by earlier workers.
Near-Infrared Reflectance Spectra of Mixtures of Kaolin-Group Minerals: Use in Clay Mineral Studies
Authors: Crowley James K. , Vergo Norma
Published: August 2006

Near-infrared (NIR) reflectance spectra for mixtures of ordered kaolinite and ordered dickite have been found to simulate the spectral response of disordered kaolinite. The amount of octahedral vacancy disorder in nine disordered kaolinite samples was estimated by comparing the sample spectra to the spectra of reference mixtures. The resulting estimates are consistent with previously published estimates of vacancy disorder for similar kaolin minerals that were modeled from calculated X-ray diffraction patterns. The ordered kaolinite and dickite samples used in the reference mixtures were carefully selected to avoid undesirable particle size effects that could bias the spectral results.

NIR spectra were also recorded for laboratory mixtures of ordered kaolinite and halloysite to assess whether the spectra could be potentially useful for determining mineral proportions in natural physical mixtures of these two clays. Although the kaolinite-halloysite proportions could only be roughly estimated from the mixture spectra, the halloysite component was evident even when halloysite was present in only minor amounts. A similar approach using NIR spectra for laboratory mixtures may have applications in other studies of natural clay mixtures.