bluuebunny/crossref_metadata_2025 huggingface dataset:
Hydrolysis of Aluminum-Tri-(Sec-Butoxide) in Ionic and Nonionic Media
Authors: Serna Carlos J. , White Joe L. , Hem Stanley L.
Published: August 2006

The hydrolysis of aluminum-tri-(sec-butoxide), ASB, in ionic and nonionic media is shown to be a useful method for the synthesis of aluminum minerals. Infrared and X-ray analysis were used to identify the reaction products. Pseudoboehmite is formed at low water to aluminum ratios. At higher water content, transformation of pseudoboehmite occurs with bayerite as the final phase. Dawsonite-type minerals are produced when ASB is hydrolyzed in the presence of sodium, potassium, or ammonium bicarbonate. Infrared evidence suggests that the carbonate group is more perturbed than indicated by the proposed crystal structure. A compound with a structure like the pyoaurite-sjögrenite group was obtained when ASB reacted with a lithium carbonate solution. The infrared spectrum indicates the possible existence of bicarbonate and carbonate ions between the brucite-like layers.
Trimethylsilylation of Biotite
Authors: Kuroda Kazuyuki , Kato Chuzo
Published: August 2006

Organic solvent soluble organosilicate compounds retaining silicate backbone were obtained by the reaction between biotite and trimethylsilylating reagent. The soluble product which was formed at room temperature or at reflux temperature was a viscous liquid and was soluble in a wide range of organic solvents, but insoluble in water. Molecular weights of the soluble products and their thinlayer chromatograms made it clear that the soluble products consisted of several trimethylsilylated derivatives of silicic acids which were mainly the derivatives of mono- and disilicic acid. The influence of reaction temperature for the trimethylsilylation reaction also was discussed.
Determination of Structural Defects in Phyllosilicates by X-Ray Powder Diffraction—I. Principle of Calculation of the Diffraction Phenomenon
Authors: Plançon A. , Tchoubar C.
Published: August 2006

This paper describes the calculation of the diffracted intensity for models of powdered minerals with lamellar structure, in order to compare experimental and theoretical X-ray diagrams. The calculation takes into account at the same time (i) the possibility of coexistence of different kinds of layers in the stackings, (ii) the possibility of stacking faults between the layers (translative or rotative ones) and (iii) the unavoidable orientation of particles in the powder sample (the method of determination of the orientation is described).
Characterization of the Particle Size and the Crystallinity of Certain Minerals by Infrared Spectrophotometry and other Instrumental Methods—I. Investigations on Clay Minerals
Authors: Hlavay J. , Jonas K. , Elek S. , Inczedy J.
Published: August 2006

Effects of particle size, crystallinity and the amount of the structural water in kaolinites on their infrared spectra, were studied. The samples were ground in a vibrating ball-mill, and infrared and X-ray spectra, as well as thermal and specific surface area measurements, were taken on the initial and ground samples. Changes of the 3705-cm−1 infrared band intensity and of the absorbance ratio of the A 3630/A 3705-cm−1 bands were determined as a function of the grinding time. Correlation functions between the absorption ratio, calculated from the infrared spectra, and the average particle size, as well as between the amorphism, calculated from the X-ray spectra, and the average particle size, were obtained.
The Decomposition of Organic Amines on Montmorillonites under Ambient Conditions
Authors: Frenkel M. , Solomon D. H.
Published: August 2006

The physical and chemical interactions between organic amines and mineral surfaces are of considerable importance in many industrial applications. For example, the preparation of organophilic minerals often involves the adsorption of organic amines, or the ion exchange of the minerals with quaternary ammonium salts (Jordon, 1951; Miller and Faust, 1972). Chemical interactions occurring in these systems have been studied because of their relevance to an understanding of the chemical nature of the clay surface. A number of these studies have reported on the decomposition of adsorbed amines and alkylammonium-mineral complexes at elevated temperatures, usually in excess of 100°C (Chaussidon and Calvet, 1965; Weiss and Roloff, 1963; Durand, Pellet and Fripiat, 1972; Chou and McAtee, 1969). It is now well established that under these conditions the mineral may have potential strong-acidity, and these reactions have been explained in terms of acid-induced decomposition or rearrangement of the adsorbed amines or their derivatives. However, there have been few studies of the reactions of organo-mineral complexes at temperatures below 100°C, under conditions where retention of adsorbed water could be expected to moderate the mineral surface acidity.
Hydroxy-Nickel Interlayering in Montmorillonite by Titration Method
Authors: Yamanaka S. , Brindley G. W.
Published: August 2006

Nickel nitrate solution is potentiometrically titrated (a) with montmorillonite, (b) without montmorillonite, in the nitrate solution. X-ray powder diffraction and chemical analyses are made of the products formed by the clay at various stages of titration. The pH values of the titration curve (a) are lower than those of curve (b) until the brucite-like hydroxynickel interlayer is more or less complete. The resulting product then closely resembles a chlorite. The preferential precipitation of hydroxide in the interlayer region is explained in terms of the acidic character of montmorillonite interlayers.
Observation of the Hydrated form of Tubular Halloysite by An Electron Microscope Equipped with An Environmental Cell
Authors: Kohyama Norihiko , Fukushima Kurio , Fukami Akira
Published: August 2006

The hydrated form of tubular halloysite [halloysite (10 Å)] was observed by a conventional electron microscope equipped with an environmental cell (E.C.), by which the “natural” form was revealed without dehydration of the interlayer water. This study mainly reports the selected area electron diffraction (SAED) analysis of the halloysite (10 Å) and its morphological changes by dehydration. The SAED pattern showed halloysite (10 Å) has two-layer periodicity in a monoclinic structure with the unit cell parameters of a = 5.14 Å, b = 8.90 Å, c = 20.7 Å, β = 99.7°, in space group Cc, and almost the same structure as the dehydrated form of halloysite [halloysite (7 Å)]. This means that the dehydration of the interlayer water did not greatly change or affect the structure of halloysite (10 Å). Accompanying the dehydration of the interlayer water, there appeared along the halloysite tube axis clear stripes that were about 50–100 Å in width. The diameters of the tubular particles also increased about 10%. From the results of various experiments, such as a focussing series, observation of the surface structure by the replica method, observation of end-views of the tubular particles, and others, these two phenomena were explained as follows: Halloysite crystals have “domains” along the c-axis direction, the thicknesses of the “domains” vary ca. 50–100 Å. They are tightly connected with each other when the halloysite is hydrated, but are separated from each other by the dehydration of the interlayer water, whereupon the stripes come into existence along the tube axis. Taking these considerations into account, a model of dehydration is proposed. Moreover, a new method of calculating the β-angle is proposed in the Appendix.
An Experimental Study of Cadmium Ion Exchangeability
Authors: Ferrell R. E. , Price C. A.
Published: August 2006

A laboratory study of cadmium exchangeability revealed large differences in extractable cadmium which are dependent on the exchange solution being utilized. The standard exchange solutions employed in this study were: N NaNO3, N NaOAc, N NH4OAc, NCaCl2, and 2N CaCl2, in order of increasing Cd removal. An interpretation of the chemical behavior of Cd and an experiment with mixed sodium nitrate and acetate solutions suggest that cadmium carbonate, octavite, was precipitated when the sediments were saturated with Cd prior to the exchange experiments and that the quantities of Cd recovered in the acetate solutions were erroneously high because of the dissolution of the carbonate material. Dissolution of solid phases, the lack of pH buffering, and the possible formation of a complex hydroxyl chloride salt also made the Cd values obtained with the chloride solutions too high. Sodium nitrate exchange solutions minimize these problems and are thought to best represent the exchangeable cadmium in the sediment.
The Electrostatic Interlayer Forces of Layer Structure Minerals
Authors: Giese Rossman F.
Published: August 2006

Using a simple ionic model, the energy necessary to expand a layer structure by a certain distance can be calculated. This has been done for a series of 15 structures including hydroxides, 2:1 and 1:1 structures of various types. Plots of energy versus separation distance show three major groups which have common bonding properties. For large separations, the group with the strongest interlayer bonds contains the brittle micas, the hydroxides, and the 1:1 structures. Intermediate bonding structures are the normal micas and the weakest bonds occur in the zero layer charge 2:1 structures. The relative energies needed for a given separation are not constant so that for small separations the zero layer charge structures such as talc and pyrophyllite are more strongly bonded than the normal micas. These groupings correlate very well with the expandability of the structures by water and other substances. It is proposed that this approach to the study of the layer structures will provide a simple theory explaining the expansion properties of layer silicates.
Sepiolite Deposits of the Las Vegas, Nevada Area
Authors: Post J. L.
Published: August 2006

Four sepiolite deposits of different origin, which occur near Las Vegas, Nevada, are compared and described. They include a playa deposit, a valley terrace deposit, and two types of vein deposits. The physical and chemical characteristics of the four materials are described, the engineering and commercial features are considered, and the varied origins of the sepiolite are discussed. X-ray powder diffraction data, infrared spectra, thermal characteristics, and chemical analyses are given for the Two Crows sepiolite. The vein deposit is proposed for use as a clay mineral reference standard because of its purity and availability. The apparent diverse morphology of the sepiolite deposits is shown with its common, lathlike basic structure.
Kaolinite Intercalation Procedure for all Sizes and Types with X-Ray Diffraction Spacing Distinctive from other Phyllosilicates
Authors: Jackson M. L. , Abdel-Kader F. H.
Published: August 2006

Kaolinites of all kinds (fine, ‘fireclay,’ ‘type IV,’ etc.), some of which do not expand or expand incompletely with the usual intercalation methods used for comparison, are expanded completely by treatment of dry (110°C) clay with dry CsCl salt, followed by contact with hydrazine for 1 day at 65°C and then with DMSO overnight at 90°C. Comparison treatments were grinding in KOAc, soaking in hydrazine, and Li-DMSO, as well as combination of these. Following the Cs-hydrazine-DMSO treatment, the 7.2 Å spacing of 1:1 dioctahedral layer silicates shifts to 11.2 Å and the 11.2 Å/(7.2 + 11.2 Å) ratio ≃1.0. The trioctahedral 1:1 layer silicates and chlorite are not expanded by the Cs-hydrazine-DMSO procedure.
Reduction and Oxidation of Fe3+ in Dioctahedral Smectites—III. Oxidation of Octahedral Iron in Montmorillonite
Authors: Rozenson I. , Heller-Kallai L.
Published: August 2006

Structural Fe2+ in montmorillonite is readily oxidized by contact with water, salt solutions or on mild heating. This is shown clearly by the Mössbauer spectra and is associated with a sharpening of the infrared absorption near 880 cm−1. It was inferred that this band comprises the Fe2+—OH—Al and Fe3+—OH—Al deformations. The rate at which oxidation occurs depends on the exchangeable cations. High acidity of the interlayers is conducive to oxidation, as is contact with Cu2+-containing solutions or concentrated H2O2 solutions.

The results show clearly that any chemical treatment of montmorillonite causes changes in the oxidation state of structural iron.
Vanadium-Titanium-Bearing Mixed-Layered Clay from Potash Sulphur Springs, Arkansas
Authors: McCormick George R.
Published: August 2006

A unique vanadium-titanium-bearing mixed-layered clay is currently being mined as an ore of vanadium at Potash Sulphur Springs, AR. The clay contains 80% expandable portion and has both a 14.22 and 18.24 Å hydration state in addition to the 9.49 Å dehydrated state; ethylene glycol expands this material to 16.69 Å. The 060 reflection for all hydration states is between 1.50 and 1.51 Å indicating the material is dioctahedral. The “mean chemical formula” calculates as
(Ca0.08 K0.02 Na0.03)0.13 (Al0.11 V0.90 Ti0.19 Fe0.64 Mg0.14)1.98 (Si3.79 Al0.21)4 O10 (OH)2·nH2O.
Copper(II) Interactions with Kaolinite: Factors Controlling Adsorption
Authors: McBride M. B.
Published: August 2006

The adsorption of Cu2+ on kaolinite was studied at different ionic strengths following various treatments of the mineral surface in order to evaluate the conditions influencing adsorption. The data indicate a strong preference of the Na+ exchange form of kaolinite for Cu2+ but a weak affinity of the natural kaolinite for Cu2+. Protons are generated by Cu2+ adsorption, a result of the exchange of surface protons, and possibly the enhancement of Cu2+ hydrolysis at the kaolinite surfaces. The exchange of Na+ by Cu2+ on the kaolinite is not described by the mass-action equation, but can be interpreted in terms of permanent charge sites on the surfaces when the additional factors of Na+-H3O+ exchange and blockage of sites by Al ions are considered.
Differential Scanning Calorimetric study of the Kaolinite: N-Methylformamide Intercalate
Authors: Adams J. M.
Published: August 2006

The thermal decomposition of the kaolinite: N-methylformamide intercalate [Al2Si2O5(OH)4·HCONHCH3] has been studied by differential scanning calorimetry (DSC). The decomposition starts at 355 K, finishes at 450 K and follows Avrami-Erofeev kinetics for α = 0.04–0.96. ΔH for the loss of organic is 19 ± 2 kJ mol−1; the activation energy for the reaction is 30 ± 3 kJ mol−1.
Extrapolation of Aqueous Dissolution Data to Determine Comparative Free Energies of Formation (CΔGf0), and Relative Mineral Stabilities
Authors: Reesman A. L.
Published: August 2006

Analytical data from aqueous dissolution studies of minerals, mineral systems, and naturally equilibrated solutions such as surface waters and groundwaters provide the basic ingredients necessary to calculate comparative solubility (or activity) products (CKs) and comparative free energies of formation (CΔGf0) of possible minerals or hypothetical minerals. Using a thermodynamic approach, quasi-thermodynamic values are obtained which can help in understanding the relative stabilities of different but similar materials and changes in reacting systems. Illite equilibrated solutions demonstrated that: 1) there is a 5 kcal spread in comparative free energies of formation of the five illites used, 2) the comparative stabilities remain about the same when highly simplified but similar hypothetical mineral formulas are considered, and 3) some of these illites are probably not the most stable phase in a closed chemical system at standard temperature and pressure.

A “mineral index system” composed of common rock-forming minerals, products of chemical weathering and perhaps hypothetical minerals is proposed, which offers a means of studying naturally equilibrated solutions. Such a system can show changes with respect to CΔGf0 of these minerals at a particular site through time or in relationship to spatial distribution and geologic changes through synchronous sampling at different sites.
Unifying Features Relating to the 3D Structures of some Intercalates of Kaolinite
Authors: Adams J. M.
Published: August 2006

The recent determination of the three-dimensional crystal structure of a dickite:formamide intercalate allows insight into the clay:organic bonding schemes of amides and other small organic molecule intercalates of the kaolin minerals. It is demonstrated that the observed basal spacings of intercalates with these molecules are consistent with hydrogen bonding schemes in which, if possible, triple hydrogen bonds from the clay hydroxyls to 0=C< are formed. Variations in basal spacing within a series of amides can be explained by considering the maximization of hydrogen bonding while avoiding close van der Waals contacts.
The Effect of Grinding on the Structure and Behavior of Bentonites
Authors: Mingelgrin U. , Kliger L. , Gal M. , Saltzman S.
Published: August 2006

The structure and behavior of homoionic bentonites was markedly affected by a grinding procedure often applied to clays. The main changes observed on clay powders were the breakage of weakly bound large aggregates, the reduction in the tactoids’ thickness by delamination, the reduction in the plates’ area, and the formation of colloidal matter. The tendency of clays to form secondary aggregates in aqueous suspensions is probably due to the exposure of active broken edges following grinding.

The mild mechanical stress applied increased both the rate and the amounts of parathion sorbed by clays from an apolar solvent. The effect of grinding on parathion adsorption in aqueous clay suspensions seems to be a rate effect.
Ion Exchange and Intersalation Reactions of Hectorite with Tris-Bipyridyl Metal Complexes
Authors: Traynor Mary Frances , Mortland M. M. , Pinnavaia T. J.
Published: August 2006

The binding of tris-bipyridyl metal complexes of the type M(bp)32+ (M = Fe2+, Cu2+, Ru2+) to hectorite surfaces is shown to occur by two mechanisms. (1) replacement of Na+ ions in the native mineral by cation exchange up to its cation exchange capacity and (2) intersalation of excess salt beyond the exchange capacity. In the cation exchange mechanism, the binding of metal complex is strongly favored over Na+. The intersalation reactions are dependent on the nature of the counter-anion: SO42-, Br- > CIO4−, Cl−. The homoionic M(bp)32+-hectorites, which exhibit rational 18 Å X-ray reflections, have been characterized with regard to their BET surface areas, water adsorption isotherms, types of water present, selected reactions in the intercalated state, and orientation of the complex ions in the interlayer regions. Mixed Fe(bp)32+, Na+-hectorites have also been examined and the results suggest segregation of the two ions between interlayers or within interlayers. Solid state intersalated phases have been isolated with 18 Å and 29.5 Å spacings. In general, surface areas of the intersalated phases are low, but the 18 Å phase derived from [Fe(bp)3]SO4 adsorption shows a high surface area, which even exceeds the surface area of homoionic Fe(bp)32+-hectorite.
The Influence of Aluminum on Iron Oxides. Part I. The Influence of Al on Fe Oxide Formation from the Fe(II) System
Authors: Taylor R. M. , Schwertmann U.
Published: August 2006

The influence of Al on the products formed by aerial oxidation at pH 5.5-7 and 20°C of Fe(II) chloride, sulfate and carbonate solutions, was examined. In all cases Al at levels Al/Al + Fe = 0.09−0.30 inhibited the formation of y phases (lepidocrocite and maghemite) in favor of goethite under conditions where, in the absence of Al, these y phases formed. The influence of Al in these laboratory studies was supported by field observations.

At higher levels of Al, ferrihydrite formation was favored. This effect of Al was seen to be the result of a slowing down in the hydrolysis/oxidation rate of the Fe(II) system.

The presence of Al not only changed the direction of mineral formation, but also caused the formation of Al substitued goethites which resembled in particle size and morphology the natural aluminiferous goethite extracted from a soil.
Effects of Micro-Sized Mixtures of Kaolin Minerals on Properties of Kaolinites
Authors: Keller W. D. , Haenni R. P.
Published: August 2006

“Kaolinites” from classic, large deposits of kaolin are shown commonly in scanning electron micrographs to be mixtures, at least in part, in microdimensions, of kaolin-mineral polymorphs.

Artificial mixtures of selected kaolin polymorphs simulating the natural mixtures, also micrographed, show crystallinities intermediate between the crystallinities of the end members in X-ray powder diffractograms. Thus, apparent crystallinity interpreted from diffractograms of a kaolin specimen may be a product of kaolin-mineral mixture in microdimensions as well as from ordering in the crystals. Evaluation of the crystallinity of a kaolin from powder diffraction may be suspect if independent means, such as SEM, are not used to assess the monomineralic character of that kaolin specimen.

Analogous to the apparent crystallinity of a “kaolinite” being the product of a mixture, so may other widely ranging properties of “kaolinite” be products of kaolin-mineral mixtures in microdimensions. These properties include DTA, IR, chemical composition, free energies of formation, and industrial applications.

Specifications for a monomineralic, nearly ideal kaolinite are considered—the Keokuk geode variety possesses desired crystallographic and chemical properties.
The Release of Aluminum from Aluminosilicate Minerals. I. Kinetics
Authors: Cabrera F. , Talibudeen O.
Published: August 2006

The rates of release of Al by M NH4NO3 (pH 3) from minerals saturated with Al ions at pH 3 suggest that Al ions migrated from the surface layers and the matrix cores of kaolinite, montmorillonite, illite, and biotite, but only from the matrix core of muscovite mica. From the 0.25–0.5 μm kaolinite and montmorillonite, part of the ‘surface’ Al is released ‘instantaneously’ and the rest by first order kinetics, but the coarse 1.5–2.5 μm kaolinite has only the former component. From illite and biotite, ‘surface’ Al is released by ‘bulk diffusion’ kinetics suggesting the existence of disturbed peripheral layers of finite thickness. The diffusion coefficients, Dm, for the matrix core follow the trend: mica ≃ biotite > illite > montmorillonite > kaolinite.

Based on models proposed in previous work, the ionic composition of the ‘surface’ Al is calculated. This shows that (1) this composition varies according to the mineral from 3 to 100% Al3+, the remainder being in the hydrolyzed form, and (2) the apparent hydrolysis constants are different for each mineral and significantly different from those of Al ions in solution.
Adsorption of Uranium from Solutions by Montmorillonite; Compositions and Properties of Uranyl Montmorillonites
Authors: Tsunashima A. , Brindley G. W. , Bastovanov Marija
Published: August 2006

Wyoming montmorillonite, <2-µm particle size, saturated with Na, K, Mg, Ca, and Ba ions, was reacted with uranyl nitrate solutions in the concentration range 1–300 ppm uranium. With constant amounts of clay and solution volume, the adsorption isotherms of uranyl ions on the clay followed Langmuir-type curves with increasing concentration of uranium. The maximum adsorption derived from linear Langmuir plots corresponds to the exchange capacity of the clay. Experiments with solutions of constant volume and constant ionicity, but with variable proportions of uranyl and other cations, showed that uranyl ions were strongly preferred by the clay to Na+ and K+, but less strongly than Mg2+, Ca2+, and Ba2+.

Chemical analyses of uranyl montmorillonites prepared with nitrate solutions, 0.05 M and pH ≃ 2.0, gave interlayer cations (UO2)0,094H0,12. Addition of NaOH to the uranyl nitrate solution to increase the pH to 4.0 gave a montmorillonite with interlayer cations (UO2)0,083Na0,12H0,04. A fully exchanged uranyl montmorillonite was prepared with 0.05 M uranyl acetate solution, pH ∼ 4.0, followed by further treatment with 1.25 × 10−5 M solution, pH ∼ 4.5. The resulting interlayer composition was (UO2)0,19(H2O)1.15 which corresponds with the hexahydrate ion, [(UO2)−6H2O]. X-ray powder diffraction and thermal data are recorded for the fully exchanged uranyl montmorillonite.
Potassium- and Ammonium-Treated Montmorillonites. II. Calculation of Characteristic Layer Charges
Authors: Machajdík Daniel , Číčel Blahoslav
Published: August 2006

The formation of an interstratified structure in dioctahedral smectite was assumed to be influenced by (1) the overall layer charge density and its distribution in the structure, (2) the solvation energy of the cation, and (3) the nature of the solvation agent. By holding factors (2) and (3) constant it was possible to calculate the average local charge densities $\overline {{\rm{QA}}}$, $\overline {{\rm{QC}}} $, and $\overline {{\rm{QE}}} $ which are necessary for formation of 10-, 14-, and 16.8-Å mixed-layer phases in potassium-treated and ethylene glycol (EG) saturated smectites. The values of $\overline {{\rm{QA}}} $, $\overline {{\rm{QC}}} $, and $\overline {{\rm{QE}}} $ were 1.99, 1.2, and 0.56 esu/unit cell, respectively. Ammonium-treated smectites saturated with EG gave corresponding mean local charge densities of 2.7, 1.6, and 0.72 esu/unit cell. Calculations were made under the limiting condition QA > QC > QE > 0.

For K-smectites saturated with EG, Qtot = 1.99pA + 1.2pC + 0.56pE, where Qtot is the total charge (esu/unit cell), and pA, pC, and pE are probability coefficients for 10-, 14-, and 16.8-Å phases in the interstratified structure. The above equation calculated with the aid of least squares and without the limiting condition yields
$${{\rm{Q}}_{{\rm{tot}}}} = {\rm{2}}{\rm{.05pA + 1}}{\rm{.29pC + 0}}{\rm{.33pE}}{\rm{.}}$$
There is a good agreement between values obtained for K-smectites and those for mica, vermiculite, and montmorillonite layer charges for which the above unit-structure distances are typical.
Adsorption of Ethylene Glycol on Amine-Substituted Montmorillonites
Authors: Burba John L. , McAtee James L.
Published: August 2006

To determine the reason why the adsorption of ethylene glycol on organo-smectites does not result in an expansion along the c-axis of the clays, smectites containing relatively small organo-ammonium ions (lauryl-, benzyl-, dibenzyl-, and dicyclohexylammonium), larger organic cations (dimethylbenzyloctadeyl- and methylbenzyldioctadecylammonium), and the heterocyclic organo-ammonium ion 1,4a-dimethyl-7-isopropyl-1,2,3,4,4a,9,10,10a-octahydro-1-phenanthrenemethylammonium and the corresponding ethoxylated compound were exposed to ethylene glycol vapor for up to several months and examined by X-ray powder diffraction (XRD), surface area, and thermogravimetric methods. Weight loss data showed that all samples adsorbed ethylene glycol. XRD data for oriented samples indicated that lauryl-, benzyl-, dicyclohexyl-, and ethoxylated heterocyclic ammonium clays expanded by one layer of ethylene glycol and that methylbenzyldioctadecylammonium smectite expanded by two layers. Dibenzyl-, dimethylbenzyloctadecyl-, and heterocyclic smectites did not expand because the clay oriented in such a manner as to leave free clay surface between the organo-ammonium cations.
Redetermination of the Lepidolite-2M1 Structure
Authors: Swanson Teresa H. , Bailey S. W.
Published: August 2006

The structure of a lepidolite-2M1 from Biskupice, Czechoslovakia, has been redetermined. Violations of systematic extinctions and of monoclinic equivalences plus the results of a second harmonic generation test indicate that the true symmetry most likely is C1̄. The deviation of the data set from C2/c symmetry, however, proved to be too small to permit a statistically significant refinement in C1̄. Refinement in C2/c symmetry indicated no ordering of tetrahedral cations but ordering of octahedral cations so that M(1) = Li0.93R2+0.06Fe3+0.01 and M(2) = Al0.58Li0.35□0.07. The tetrahedra are elongated to form trigonal pyramids with a rotation angle of 6.2°. The anomalous orientation of the thermal ellipsoid for the F,OH anion plus the large equivalent isotropic B value of 2.58 for F,OH and of 1.74 for the interlayer K cation, whose position is partly restricted in C2/c symmetry, suggest a lower symmetry than C2/c.

The compositions of this sample and of a second lepidolite-2M1 from Western Australia fall outside the stability field of lepidolite-2M1 in the synthetic system. Structural control of the stacking sequence is discounted on the basis of the structural similarity of the lepidolite unit layers. Crystallization parameters are considered more important than composition or the structure of the unit layer in determining the stability and occurrence of different layer-stacking sequences in lepidolite.
Dissolution Kinetics of Phlogopite. I. Closed System
Authors: Lin Feng-Chih , Clemency Charles V.
Published: August 2006

Dry ground phlogopite was placed in deionized water saturated with CO2 at room temperature and pressure. The bulk solution was buffered between a pH of 5 and 6 which is close to the pH of natural weathering systems. The conditions simulated a closed system. After 1010 hr, 2.0% of the total K, 0.95% of the Mg, 0.54% of the Si, and 0.74% of the F had been released, indicating that the dissolution was incongruent. Most of the K was released within 3 min, apparently by a rapid surface exchange with hydrogen ion. One-third of the cation-exchange capacity of this phlogopite arises from cations released from the outer surfaces, while two-thirds arises from the release of more deeply seated cations. All cations exhibited decreasing release with time, the slowest being Si. The rate-controlling “factor” in the later stages is related to the release of Si. It is difficult to distinguish linear from parabolic kinetics in the later stages because of the slow rate of dissolution; however, linear kinetics is most likely. If linear kinetics is applicable, the dissolution rate of Si was 3.8 × 10−17 mole/cm2/sec. Conclusions may be affected by the length of the experimental run.
Chemical Characteristics and Origin of Ordovician K-Bentonites along the Cincinnati Arch
Authors: Huff Warren D. , Türkmenoglu Asuman Günal
Published: August 2006

K-bentonites of the Middle Ordovician High Bridge Group along the Cincinnati arch are characterized by interstratified illite/smectite (I/S) clays with rectorite-type ordering. Approximately 20% of the layers are expandable. They are structurally similar to I/S formed at temperatures exceeding 100°C during burial diagenesis, however stratigraphic evidence and a color alteration index of < 1.5 for conodonts in associated carbonates reveals they have never been deeply buried or subjected to temperatures greater than 80°C.

Whole-rock samples of K-bentonites contain ∼8% K2O and ∼4% MgO, whereas the <0.1-µm size fraction contains 6–7% K2O and 5% MgO. By comparison with a hypothetical parent ash, these values represent a net gain of K and Mg and a net loss of Si, Fe, Ca, and Na during post-depositional alteration. K-fixation is accounted for by a layer charge imbalance arising primarily out of octahedral substitution of Mg+2 for Al+3, indicating that the interstratification evolved from a montmorillonite precursor. The chemical characteristics of I/S layers in K-bentonites developed early during the alteration of volcanic ash to montmorillonite. Relatively high contents of K and Mg probably reflect both seawater and parent material composition at the time of formation. The composition and ordered stacking in K-bentonites was determined by the composition of the original smectite rather than by the pressure-temperature conditions of burial diagenesis.
Experiments on the Hydrothermal Formation of Calcium Zeolites
Authors: Wirsching Ulrike
Published: August 2006

The crystallization of calcium zeolites was carried out in an open hydrothermal system at 100°–250°C, using reactants that in nature are known to alter to calcium zeolites and 0.1 N CaCl2, 0.01 N CaCl2, and 0.01 N CaCl2 + 0.01 N NaOH (1:1) solutions. The following calcium zeolites were identified by X-ray powder diffraction:

Rhyolitic glass: heulandite, phillipsite, epistilbite, wairakite;

Basaltic glass: phillipsite, scolecite, wairakite, levynite;

Nepheline: thomsonite, wairakite, gismondine;

Oligoclase: heulandite, phillipsite, wairakite.

Factors that influenced the type of zeolite formed were: Si/Al ratio of the starting material, calcium/alkali ratio of the starting material, calcium activity of the reacting solution, presence of an open alteration system, and temperature. The Si/Al ratio of the starting material was of special importance in that zeolites formed with Si/Al ratios similar to or smaller than that of the parent material. The calcium/alkali ratio of the starting material also influenced the kind of the early alteration products in the open system. As alteration progressed, the importance of the starting material decreased. The importance of the calcium activity of the reacting solution and the influence of the open system increased as alteration proceeded. Because of mass transfer during alteration in the open system, the calcium content of the minerals formed increased, while their Si/Al ratio decreased. Temperature was especially effective during prolonged alteration, in that the higher the alteration temperature the smaller was the H2O content of the alteration product. Initially, H2O-rich zeolites formed transitorily at higher temperatures.
Geochemistry and Mineralogy of an Unusual Diabase Saprolite Near Columbia, South Carolina
Authors: Gardner L. R. , Kheoruenromne I. , Chen H. S.
Published: August 2006

Empirical reaction progress diagrams showing the trends of major element oxide concentrations (in g/cm3) as functions of bulk density for a diabase saprolite reveal discontinuities in the trends of Al2O3, MgO, H2O+, and nonextractable Fe2O3. The discontinuities coincide with discontinuities in the trends of (1) the kaolinite-smectite 001 peak-intensity ratio, (2) the smectite 002-001 peak intensity ratio, and (3) the smectite basal spacing as functions of bulk density. The discontinuities are apparently related to redox conditions in the weathering profile because they occur at a depth where siderite veins first appear in the saprolite. Oxidizing conditions in the upper part of the profile appear to have favored the formation of Ferich smectite over kaolinite, whereas reducing conditions deeper in the profile favored the formation of kaolinite over Al-rich smectite. These results indicate that where geochemical conditions favor retention of Fe over Al, smectites can form in preference to kaolinite or gibbsite even under conditions of strong leaching.
Boron Adsorption by Clay Minerals Using a Phenomenological Equation
Authors: Keren R. , Mezuman U.
Published: August 2006

Boron adsorption by Ca forms of montmorillonite, illite, and kaolinite was determined as a function of pH and boron concentration in solution. Data from batch experiments were compared with results computed for each clay according to fitted adsorption coefficients (maximum boron adsorption and affinity constants related to the binding energy). The agreement between calculated values and experimental results indicates that a phenomenological equation can be used to predict boron adsorption on clays as a function of both of these variables. For the solution-to-clay ratios examined, the water content does not affect the boron-surface interaction as expressed by the above adsorption parameters. Because the affinity of clays for B(OH)4− is much stronger than for B(OH)3 , the adsorption maximum was obtained only under alkaline conditions at approximately pH 9.0 to 9.7. It is suggested that the pH of maximum adsorption is a function of the ratios of affinity coefficients of the three species B(OH)3, B(OH)4−, and OH− competing for the same adsorption sites. The adsorption coefficients indicate that in some cases the difference in the amount of adsorbed boron between montmorillonite and kaolinite could be either small or large, depending on the circumstances. The main factor that would affect this difference is the total amount of boron in the suspension. Estimated value of the adsorption maximum was 2.94, 11.8 and 15.1 µmole/g for Ca-kaolinite, Ca-montmorillonite, and Ca-illite, respectively.
Mössbauer Studies of Palygorskite and Some Aspects of Palygorskite Mineralogy
Authors: Heller-Kallai L. , Rozenson I.
Published: August 2006

Fe3+ ions in palygorskite occupy sites at the edges and in the interior of the alumino-silicate chains. The Mössbauer parameters of the doublets associated with Fe3+ ions in edge sites indicate that the sites have a regular 6 coordination. Fe3+ ions in the interior of the chains occupy M(1) sites in three of the samples examined and M(2) sites in the fourth. Fe3+ ions in edge positions of palygorskite become 5-coordinated when water is lost on heating. They maintain this coordination on dehydroxylation, probably by cross-linking of the chains. The temperatures at which changes occur in the X-ray powder diffraction patterns and the Mössbauer and infrared (IR) spectra differ from sample to sample. The intermediate stages observed also vary, either due to different reaction paths or to different stabilities of the intermediate phases. The deduced distribution of cations in the octahedral sheets is in good qualitative agreement with the observed IR hydroxyl absorptions.
Adsorption of Alkylphosphoric Acid on Kaolinite and Smectite in an Organic Medium (Decane)
Authors: Siffert B. , Trescol J. J.
Published: August 2006

Di-ethyl 2-hexylphosphoric acid (di-2 EHPA) was chemisorbed on kaolinite and smectite in decane solution. The resultant isotherms were of the Langmuir type and made possible the determination of limiting adsorption values of 12 mg/g and 23.8 mg/g on H+-kaolinite and H+-montmorillonite, respectively. The acidic phosphoric group of the di-2 EHPA molecule reacted in the anionic form (RO)2PO2− with the surface cations of the clay structures. Theoretical calculations, based on structural considerations, are in agreement with the experimental data and show that adsorption took place at the rate of one alkylphosphate anion per surface cation if the phyllosilicate was dioctahedral (e.g., montmorillonite and kaolinite). If the phyllosilicate was trioctahedral (e.g., hectorite), adsorption took place at the rate of two di-2 EHPA molecules for three surface cations. Spectroscopic investigations performed with visible, ultraviolet, and infrared radiation confirmed the formation of salts or surface complexes.
Kinetic Model of Zeolite Paragenesis in Tuffaceous Sediments
Authors: Dibble W. E. , Tiller W. A.
Published: August 2006

The sequence of mineral reactions involving zeolites and other authigenic phases in tuffaceous sedimentary rocks can be explained by growth- and dissolution-reaction kinetics. Kinetic factors may determine the specific authigenic phases which form and the temporal and spatial constraints on the solution composition during irreversible dissolution and growth reactions in glass-bearing rocks. The glass phase generates a high level of supersaturation with respect to a variety of aluminosilicates in the pore fluid. The sequence of assemblages formed during a series of metastable reactions resembles an Ostwald step sequence. Metastable reactions occur because formation of less stable phases such as gels, clays, and disordered zeolites may lower the total free energy of the glass-bearing system faster than the growth of the stable assemblage including ordered feldspars, quartz, and micas. Eventually, after a series of steps, the most stable silicate assemblage for the bulk composition, temperature, and pressure may form. However, the formation of intermediate metastable phases can delay the attainment of equilibrium by as much as tens of millions of years.
Zeolite Mineral Reactions in a Tuff in the Laney Member of the Green River Formation, Wyoming
Authors: Ratterman Nancy G. , Surdam Ronald C.
Published: August 2006

Two diagenetic stages of zeolitic alteration were recognized in a study of a thin bed of rhyolitic ash that was deposited in Eocene Lake Gosiute (Laney Member of the Green River Formation). The ash bed can be traced for 30 km along strike and represents a single volcanic event. The bed was not buried deeply (<100°C), and originally it was compositionally homogeneous. Initially, the bed altered to clino-ptilolite, heulandite, an intermediate phase between these two zeolites, and mordenite. These early reactions involved the hydration and solution of glass by saline, alkaline solutions and the subsequent precipitation of zeolites. The variation in zeolite mineralogy is due to differences in interstitial fluid chemistry that resulted from either fluctuations in lake-water chemistry or the proximity of spring discharge. These reactions, exclusive of the addition of H2O, involved only minor amounts of mass transfer over very small distances. Later, after burial, the early-formed zeolites reacted with upward moving sodium carbonate brines that were produced by dewatering of underlying evaporite deposits. The sodium carbonate brines, in equilibrium with trona and nahcolite, elevated the activity of Na+ and produced analcime. These later dehydration reactions involved significant mass transfer.
Synthesis of a 10-Å Hydrated Kaolinite
Authors: Costanzo P. M. , Giese R. F. , Clemency C. V.
Published: August 2006

Hydrated kaolinite (d(001) = 10 Å) can be synthesized by mild heating of a kaolinite-organic suspension, allowing time for the clay to be intercalated by the organic solvent, and then dissolving a fluoride salt in the liquid. After mild heating of the suspension, the salt and organic solvent are removed by repeated water washings. The kaolinite retains interlayer water in the form of a 10-Å kaolinite hydrate. The influence of the intercalating agent, type of salt, concentration of salt, and the time of treatment on the synthesis of 10-Å hydrate was examined for several kaolinites. The most effective salt is NH4F; much smaller yields were obtained using KF and RbF. Not all organic molecules gave high yields of the hydrate; dimethyl sulfoxide, formamide, and hydrazine worked well but N-methyl formamide did not. The reaction between clay and salt resulted in the replacement of some hydroxyls by fluoride. This replacement was rapid; after 1 min of fluoride treatment a substantial yield of hydrate was obtained. The intercalation step separated the layers and also disordered the kaolinite, facilitating the F for OH replacement at or near crystallite edges. This replacement weakens the interlayer bonding at the edges and thereby reduces the possibility of layer collapse and attendant dehydration.
Adsorption of Molybdate Anion (MoO42−) by Sodium-Saturated Kaolinite
Authors: Phelan Patrick J. , Mattigod Shas V.
Published: August 2006

Adsorption of Mo(VI) on 2-0.2-μm size fraction of sodium-saturated kaolinite at 25 ± 2°C and at a constant pH of 7.00 ± 0.05 was studied. The kaolinite sample was pretreated to remove any surface oxide and hydroxide coatings. The initial concentrations of Mo in solution ranged from 1 to 11 mg/liter in a NaClO4 background electrolyte at a constant ionic strength of 0.09 ± 0.01. Calculations of speciation using the GEOCHEM computer program indicated that under experimental conditions Mo(VI) was mainly in the MoO42− form. The experimental conditions were also shown to fulfill the requirements for applying the Langmuir equation in interpreting adsorption data. The Langmuir parameter for the adsorption maximum, n°, and the affinity parameter, <mml:math xmlns:mml="http://www.w3.org/1998/Math/MathML" xmlns:c="http://cambridge.org/core/content" xmlns:core="http://cambridge.org/core" xmlns:m="http://cambridge.org/core/metadata" xmlns:cup="http://contentservices.cambridge.org" xmlns:xlink="http://www.w3.org/1999/xlink" xmlns:mnf="http://cambridge.org/core/manifest">KMoO42−−ClO4− were computed to be 3.33 × 10−4 mole/ mole of adsorbent and 5.969 × 105, respectively. The large affinity parameter indicated that the Na-saturated kaolinite surface has a very high affinity for MoO42− ions relative to ClO4− ions.
Tris(Acetylacetonato)Silicon(IV) Binding to Montmorillonite and Hydrolysis to Interlayer Silicic Acid
Authors: Manos Charles G. , Mortland M. M. , Pinnavaia Thomas J.
Published: August 2006

The reactions of the tris(acetylacetonato)silicone(IV) cation (Si(acac)3+) with Na+-, Mg2+-, and Co2+-exchange forms of hectorite and montmorillonite have been investigated to understand better the formation process of clays pillared by silicic acid. In acetone as the solvating medium, Si(acac)3+ binds to the Na+- and Mg2+-clays with the desorption of only a small fraction (~5%) of the initial exchange cation, suggesting that the complex binds as the ion pair [Si(acac)3+][Cl−]. With the Co2+-clays, however, the exchange cation is desorbed quantitatively, and Si(acac)3+ binding is accompanied by the formation of an acetone-solvated CoCl2 solution complex which helps to drive the ion-exchange reaction. Thus, Co2+-smectites react with Si(acac)3+ in acetone to produce homoionic Si(acac)3+ intercalates, whereas Na+-and Mg2+-smectites produce mixed-ion intercalates. The interlayer hydrolysis of Si(acac)3+ to silicic acid in the homoionic Si(acac)3+- and mixed-ion Na+/Si(acac)3+- and Mg2+/Si(acac)3+-exchange forms of montmorillonite films is diffusion controlled. In water as the solvating medium, the reaction of Si(acac)3+ with Mg2+- or Co2+-montmorillonite results in the desorption of the exchange cations on a time scale which is comparable to that observed for the solution hydrolysis of Si(acac)3+. Thus, the precipitation of silicic acid from aqueous solution competes strongly with the formation of interlayer silicic acid. With aqueous Na+-montmorillonite dispersions, however, a significant fraction of the exchange cations desorbed rapidly upon Si(acac)3+ binding, and the formation of interlayer silicic acid is favored over the precipitation of Si(OH)4.
Saponite from Near Ballarat, California
Authors: Post J. L.
Published: August 2006

White saponite occurs in joints and open fracture zones in metamorphosed dolomitic limestone near Ballarat, California. The saponite appears to have formed by hydrothermal alteration, possibly during Pliocene times. The material shows a 06l X-ray powder diffraction peak at 1.529 Å, A12O3 and MgO contents of about 4.4 and 23.5%, respectively, and a half-cell octahedral atoms summation value of about 2.82. The saponite appears to consist of a single, uniform clay species; the main impurities are fine shards of diopside and tremolite. The infrared and thermal properties of the Ballarat saponite are similar to those of the Allt Ribhein saponite. It has a lower water-holding capacity than montmorillonite and is characterized by lower Atterberg limits and expansion pressures and higher compaction densities. The apparent density of the saponite, 2.865 g/cm3, is greater than that of montmorillonite. This saponite is available from the Source Clays Repository of The Clay Minerals Society.
Influence of Chloride on the Formation of Iron Oxides From Fe(II) Chloride. I. Effect of [Cl]/[Fe] on the Formation of Magnetite
Authors: Taylor R. M.
Published: August 2006

The formation of fine-grained magnetite (~0.1 μm) at pH 7 and 25°C from aeration of Fe(II) chloride solutions is presented. The magnetite converted at 105°C to maghemite with poorly developed superstructure lines. Under the experimental conditions employed, as the initial [Cl]/[Fe] ratio was increased from the stoichiometric value of 2, the final product contained increasing amounts of lepidocrocite. The degree of crystallinity of this phase, as measured by the width at half height of the 020 X-ray diffraction peak, also increased with this ratio. The hydrolysis rate (base consumption to maintain pH) showed a plateau whose position and extent changed with the initial [Cl]/[Fe] ratio. Through this plateau region the Eh decreased to a minimum value the position of which was directly related to the [Cl]/[Fe] value. The formation of lepidocrocite rather than magnetite is likely due to the high [Cl] where there would be increased difficulty for neighboring OH to condense and eliminate H2O. The formation of Fe-O-Fe bonds in this condensation would be impeded by Cl substitution for OH either in the first formed green rust stage or during its oxidation.