bluuebunny/crossref_metadata_2025 huggingface dataset:
Clay Minerals in Mixtures: Sample Preparation, Analysis, and Statistical Interpretation
Authors: Gold C. M. , Cavell P. A. , Smith D. G. W.
Published: September 2006

A method of clay mineral sample preparation for electron microprobe analysis has been developed in which a film of clay plus 10–12 wt. % colloidal graphite is deposited on a porous ceramic disc using a specially designed suction device. Correction procedures are used to obtain quantitative elemental analyses representing the average chemical composition of the prepared sample. A statistical technique is employed to estimate the most likely proportions of clay minerals representing the known composition. Chemical compositions of clay minerals are presented in terms of five coordinates (“Si,” “Al,” “Mg,” “K,” and “Fe”). Using literature data, the chemical compositions of 13 different clay mineral groupings were defined statistically by their multivariate means and variance-covariance matrices. A correlation parameter, χ2, was calculated to compare the chemical composition of a sample with that of any mixture of the defined clay mineral groupings, the minimum χ2 indicating the best-fit mixture.

From chemical analyses of artificial mixtures only approximate clay mineral proportions could be determined when the various clay mineral groupings had been defined statistically from literature analyses. The best results were obtained when the actual compositions of the end-members forming the artificial mixtures replaced the statistical definitions. Tests of the estimation procedure on clay mineral mixtures for which chemical compositions and corresponding clay mineral proportions were found in the literature, indicate that the technique has appreciable merit.
Structure of a Vermiculite-Aniline Intercalate
Authors: Slade P. G. , Stone P. A.
Published: September 2006

A vermiculite-aniline intercalate with a basal spacing of 14.78 Å was investigated by one- and two-dimensional X-ray diffraction methods. The intercalate, prepared by ion exchange between Na-saturated vermiculite from Llano, Texas, and a 1% aniline hydrochloride solution, contains only one aniline cation per single layer cell. A reduced effective cell-charge is believed to be responsible for this. Structure factor calculations were made in space group C2/c and with unit cell dimensions of a = 5.33, b = 9.18, c = 29.78 Å, and β = 97.0°. However, extra reflections in the a*b* plane, which are similar to those in a vermiculite-benzidine intercalate, showed that after aniline intercalation the true unit cell became primitive. The aniline cations are distributed statistically over equivalent crystallographic sites in the interlayer space. The organic molecules are orientated with their planes vertical and their nitrogen atoms over the projected centers of the ditrigonal cavities into which they key. The aniline cations form ordered arrays upon the silicate layers by packing into rows. Perpendicular to [010], populated and vacant rows alternate. Along populated rows aromatic ring planes are alternately parallel and perpendicular to [010]. With small adjustments this model is similar to that of benzidine-vermiculite.
Activity/Composition Relations among Silicates and Aqueous Solutions: II. Chemical and Thermodynamic Consequences of Ideal Mixing of Atoms on Homological Sites in Montmorillonites, Illites, and Mixed-Layer Clays
Authors: Aagaard Per , Helgeson Harold C.
Published: September 2006

The activities of thermodynamic components of clay minerals corresponding in composition to pyrophyllite, muscovite, paragonite, and margarite were computed from chemical analyses reported in the literature assuming ideal mixing of atoms on homological sites in the minerals. These activities were then used to generate stability fields for smectites, illites, and mixed-layer clays on logarithmic activity diagrams representing equilibrium among minerals and aqueous solutions at 25°C and 1 bar. Comparative analysis indicates that the approach affords close approximation of both mineral and water compositions in geologic systems.
Hydration State of Cu2+ in Mixed Cu2+-Hexadecylpyridinium montmorillonit by Electron Spin Resonance
Authors: Dyrek K. , Kłapyta Z. , Sojka Z.
Published: September 2006

Electron spin resonance (ESR) spectra of Cu2+-hexadecylpyridinium (HDP) montmorillonites were investigated as a function of HDP+ content and the hydration state of Cu2+ at relative humidities of p/p0 = 0.52-8 × 10-7 at 298°K. The symmetry of the Cu2+ ESR spectra and the intensity of the ESR signal increased upon dehydration of the complex. The HDP+ cation caused an increase in the hydration state of Cu2+ at a given p/p0 and an increase in the covalency of the Cu-O bond.
Rubification of Terrae Rossae in Slovakia: A Mössbauer Effect Study
Authors: Bronger A. , Ensling J. , Gütlich P. , Spiering H.
Published: September 2006

Mineralogical and 57Fe Mössbauer spectroscopic analyses were made on seven terrae rossae and two terrae fuscae samples of Pliocene to Early Pleistocene age from Slovakia and limestone residues from their parent materials. In most of the samples, no mineral weathering or clay mineral formation could be detected by optical or X-ray powder diffraction investigation, compared with their parent limestone residues; only one terra rossa showed a strong weathering of primary feldspar and phyllosilicates and a high rate of clay formation, especially kaolinite. Mössbauer measurements between 5° and 300°K showed that hematite and goethite are the dominant color pigments in the rubified terrae rossae and their corresponding limestone residues. The mean particle size of hematite and goethite was estimated from Mössbauer effects and X-ray powder diffraction data to be 95 and 250 Å, respectively. Reduced values of the hyperfine fields at 5°K of the soil iron oxides, as compared with those of the pure oxides, indicate a partial substitution of Fe(III) by Al. The hematite content correlates with the Munsell color notation of 5 of the 7 terrae rossae samples and their corresponding limestone residues. All terrae rossae samples showed higher hematite contents than their corresponding limestone residues, indicating that the rubification of such materials is independent of the degree of weathering.
Goyazite in Kaolinitic Altered Tuff Beds of Cretaceous Age Near Denver, Colorado
Authors: Triplehorn Don M. , Bohor Bruce F.
Published: September 2006

A hydrated alumino-phosphate mineral was identified in thin, kaolinitic clay beds of the Cretaceous Dakota Group and the overlying Mowry Shale in the Dakota hogback west of Denver, Colorado. It occurs as 1–3-μm size euhedral crystals and makes up as much as 15% of the rock. Sr is by far the dominent divalent cation present, ranging from 9.4 to 13.1%, confirming the X-ray powder diffraction identification of this mineral as goyazite, the Sr member of the plumbogummite group. The characteristic pseudo-cubic, rhombohedral morphology of this mineral is plainly visible in scanning electron micrographs. On the basis of its euhedral morphology and its occurrence in volcanic ash-derived kaolin beds, the goyazite probably formed during early diagenesis, before or during the alteration of the ash, and before much compaction of the beds.
Sorption of Trace Constituents from Aqueous Solutions Onto Secondary Minerals. II. Radium
Authors: Ames L. L. , McGarrah J. E. , Walker B. A.
Published: September 2006

Radium sorption efficiencies as a function of temperature, Ra concentration, and secondary mineral sorbate were determined in a 0.01 M NaCl solution. Radium sorption on a characterized clinoptilolite, montmorillonite, nontronite, opal, silica gel, illite, kaolinite, and glauconite under comparable experimental conditions allowed determination of Ra sorption efficiency curves for each, through use of Freundlich constants, over the same temperature and initial Ra solution concentration range. Similar sorption data for U on the same secondary minerals over the same temperatures allowed comparison of sorption efficiencies for Ra and U. Clinoptilolite, illite, and nontronite were the most efficient Ra sorbents, while opal and silica gel were the poorest Ra sorbents. Generally, Ra sorption on secondary minerals was much greater than U sorption under the same experimental conditions.
Sorption of Uranium And Radium By Biotite, Muscovite, and Phlogopite
Authors: Ames Lloyd L. , McGarrah Jeffery E. , Walker Becky A.
Published: September 2006

The sorption of U and Ra on finely ground biotite, muscovite, and phlogopite was adequately described by the Freundlich adsorption equation, (x/m) = KCn, at low U and Ra concentrations despite Ra precipitation at the higher temperature. Radium and U sorption-efficiency curves derived from the Freundlich constants generally showed decreased distribution coefficients in response to increasing temperature and increasing Ra or U concentrations. Temperatures investigated were 5°C, 25°C, and 65°C. Solution compositions used were 0.1 M NaCl and 0.01 M NaHCO, for U, and 0.01 M NaCl for Ra. Uranium initial solution concentrations ranged from 1.00 × 10−4 M to 4.00 × 10−7 M; the Ra initial solution concentration range was 6.80 × 10−7 M to 8.60 × 10−9 M.

In 0.01 M NaHCO3 solutions, anionic uranyl carbonate complexes were prevalent, and because they are weakly sorbed relative to free uranyl ion and uranyl hydroxy complexes, the result was a relatively low U sorption efficiency on biotite and phlogopite and excellent sorption efficiency on muscovite. Uranyl carbonate complexes decreased in solubility with increasing temperature, so that U sorption efficiency on biotite increased with increasing temperature. Sorption of uranyl ion and uranyl hydroxy cations on biotite decreased with incresaing temperature.
Atom Positions in Highly Ordered Kaolinite
Authors: Suitch P. R. , Young R. A.
Published: September 2006

The crystal structure of kaolinite(Pl, a = 5.153(1), b = 8.941 (1), c = 7.403 (1)Å, α = 91.692(3)°, β = 104.860(3)°, γ = 89.822(3)°, specimens from Keokuk geodes) has been refined in detail and that of dickite (Cc, a = 5.1460(3), b = 8.9376(5), c = 14.4244(6) Å, β = 96.761(5)°) has been re-refined, both from powder diffraction data with the Rietveld method. Except for the hydrogen atoms, the layer structures in both clays are very similar and are much as inferred or determined previously by others. The rotation in the tetrahedral sheet is 7(1)°. The two inner hydroxyl O-H bonds in kaolinite are differently oriented; one points into an octahedral vacancy and the other somewhat away from the octahedral sheet and toward the unoccupied center of an oxygen triangle formed by the two apical oxygens and shared basal oxygen of two adjacent SiO4 tetrahedra. All six of the inner surface hydrogen atoms appear to be nearly equally involved in the hydrogen bonding between kaolinite layers in kaolinite.
Fourier Transform Infrared Studies of Aluminous Goethites and Hematites
Authors: Fysh Stuart A. , Fredericks Peter M.
Published: September 2006

Synthetic aluminous hematites and goethites have been examined by Fourier-transform infrared spectroscopy. For aluminous hematites prepared at 950°C a linear relationship exists between Al content and the location of the band near 470 cm−1, up to 10 mole % Al substitution which is shown to be the solubility limit. The spectra of aluminous goethites prepared in two different ways are qualitatively similar to each other, but differ as to the relationship between the position of the band near 900 cm−1 and the Al content. The spectra of the two series of hematites produced by calcining the goethites at 590°C also show a strong dependence of band position and intensity on the goethite preparative method.
Alteration of Clay Minerals and Zeolites in Hydrothermal Brines
Authors: Komarneni Sridhar , Roy Della M.
Published: September 2006

Clay minerals and zeolites, candidate backfill minerals for nuclear waste repositories, were treated with saturated NaCl brine and Mg-rich (Mg-Ca-Na-K) brine at 200°C and 300°C for 4 weeks under a confining pressure of 30 MPa. The Al concentrations released in NaCl brine were lower than those in Mg-rich brine at both temperatures indicating that the Mg-rich brine is more acidic than the NaCl brine under these hydrothermal conditions. The Si concentrations in both brines were low because of the relatively acidic conditions developed during the hydrothermal treatment. As determined by X-ray powder diffraction or by specific Cs and Sr sorption measurements, no alteration could be detected in clay minerals treated with NaCl brine at 200°C. Among the zeolites tested, only phillipsite and erionite altered to analcime in NaCl brine at 200°C. Zeolites and most of the clay minerals tested did not alter in the Mg-rich brine treated at 200°C. Vermiculite altered to randomly interstratified vermiculite/K-vermiculite (mica-like) by selective K uptake from the Mg-rich brine.

At 300°C, the clay minerals did not greatly alter, whereas the zeolites altered to analcime and/or albite in the presence of the NaCl brine. In the Mg-rich brine, Al-rich montmorillonite from Wyoming did not alter, whereas Al-poor montmorillonite from Texas altered to randomly interstratified montmorillonite/ illite at 300°C. Vermiculite collapsed to form K-vermiculite (~ 10.2 Å) by the selective uptake of K from the Mg-rich brine at 300°C. Most of the zeolites altered to smectites in the Mg-rich brine at 300°C because of the acidic conditions generated by the hydrolysis of Mg. The selective Cs-sorption Kd decreased from 11,700 for untreated phillipsite to 240 and 15 for the hydrothermally produced analcime/albite mixtures from the phillipsite at 200° and 300°C, respectively, in NaCl brine. These results suggest that montmorillonites and mordenites are relatively more resistant than vermiculite or other zeolites at elevated temperatures and pressures in concentrated hydrothermal brines expected in a salt repository.
Physical Arrangement of High-Alumina Clay Types in a Missouri Clay Deposit and Implications for Their Genesis
Authors: Keller W. D. , Stevens R. P.
Published: September 2006

Sedimentologic zones that are differentiated by changes in lithology, mineralogy, chemical composition, and crystal morphology observable in scanning electron micrographs occur in Missouri high-alumina clay deposits. These properties and changes suggest that the high-alumina materials originated from Pennsylvanian-age, paludal sediments deposited in depressions underlying Paleozoic carbonate rocks. Alumina was relatively enriched in zones of the deposits by leaching of silica and of alkali and alkaline earth metals from the sediments. The most intense leaching occurred on the highest parts of the Ozark Dome.

Diaspore is the predominant high-alumina mineral. Boehmite, although far less abundant than diapsore, may have paragenetically preceded diaspore in some deposits. Chlorite, presumably an Al-rich variety because the content of MgO is typically <0.5%, is also present. Li, which is sporadically present, is inferred to have accumulated in the chlorite which may be a proto-variety of cookeite. Because Li+ and Al3+ are similar in size, Li is inferred to have accompanied Al as a resistate element in contrast to K and Na which were leached from parent phyllosilicates.
Smectite Interactions with Riboflavin
Authors: Mortland M. M. , Lawless J. G.
Published: September 2006

Smectite with polyvalent cations on the exchange complex readily absorbed riboflavin from aqueous solution to a limit of about 0.5 mmole/g. The shape of the adsorption isotherms was of the Langmuir type. An exception was Na+-smectite which provided an S-shaped isotherm and smaller amounts of adsorption. Ca2+-vermiculite had no interlamellar adsorption of riboflavin, suggesting that this mineral does not swell sufficiently to permit such adsorption. Adsorption isotherms, X-ray powder diffraction data, and UV-visible spectroscopic data suggest that the mechanisms of interaction between smectite and riboflavin may involve a combination of ion-dipole, charge transfer, hydrogen bonding, and physical effects.
Comparison of Rapid Methods for Chemical Analysis of Milligram Samples of Ultrafine Clays
Authors: Rettig S. L. , Marinenko J. W. , Khoury H. N. , Jones B. F.
Published: September 2006

Two rapid methods for the decomposition and chemical analysis of clays were adapted for use with 20–40-mg size samples, typical amounts of ultrafine products (<0.5-μm diameter) obtained by modern separation methods for clay minerals. The results of these methods were compared with those of “classical” rock analyses. The two methods consisted of mixed lithium metaborate fusion and heated decomposition with HF in a closed vessel. The latter technique was modified to include subsequent evaporation with concentrated H2SO4 and re-solution in HCl, which reduced the interference of the fluoride ion in the determination of Al, Fe, Ca, Mg, Na, and K. Results from the two methods agree sufficiently well with those of the “classical” techniques to minimize error in the calculation of clay mineral structural formulae. Representative maximum variations, in atoms per unit formula of the smectite type based on 22 negative charges, are 0.09 for Si, 0.03 for Al, 0.015 for Fe, 0.07 for Mg, 0.03 for Na, and 0.01 for K.
Infrared Studies of 1-Hexene Adsorbed onto Cr3+-Exchanged Montmorillonite
Authors: Adams John M. , Clapp Terry V.
Published: September 2006

When 1-hexene was adsorbed by Cr3+-montmorillonite at room temperature, all evidence of C=C(str) vibrations was lost. Protonation of the alkene occurred, and the secondary carbocation formed was bound at a site on the primary coordination sphere of the interlayer cation. Some of the hydrogen atoms of these primary-sphere water molecules were involved in strong hydrogen bonds to the silicate sheets, whereas others did not form such bonds, but were free and directed into the interlayer space. These latter hydrogen atoms were labile and protonated the alkene molecules.
Interlayer Structures of The Two-Layer Hydrates of Na- and Ca-Vermiculites
Authors: Slade P. G. , Stone P. A. , Radoslovich E. W.
Published: September 2006

The three-dimensional order shown by the two-layer hydrates of Na- and Ca-vermiculite, prepared from Mg-vermiculite from Llano, Texas, has enabled clear, two-dimensional Fourier projections of their interlayer structures to be obtained. Structure factor calculations were made in space group C2 and with unit-cell dimensions of a = 5.358 Å, b = 9.232 Å, and ß = 96.82°; for Na-vermiculite C = 14.96 Å and for Ca-vermiculite c = 15.00 Å. In Na-vermiculite the interlayer cations are octahedrally coordinated to water molecules with the sodium-water polyhedra only located between the triads of oxygen atoms forming bases to tetrahedra in adjacent silicate layers. In Ca-vermiculite the interlayer cations are in both octahedral and 8-fold (distorted cubic) coordination with water molecules. The octahedrally coordinated Ca ions are between the bases of tetrahedra in adjacent silicate layers, but the 8-fold coordinated Ca ions are between the ditrigonal cavities. In both Na- and Ca-vermiculite some water molecules are drawn from planar networks appreciably towards the ditrigonal cavities. The three-dimensional order observed for these vermiculites contrasts with the stacking disorder reported for Mg-vermiculite from Llano. The distinct crystallographic behavior of Na+, Ca2+, and Mg2+ in the hydration layers of Llano vermiculite probably depends on cation sizes and field strengths, together with the need to achieve local charge balance near the sites of tetrahedral Al-for-Si substitution.
Surface Condensation of Organophosphate Esters on Smectites
Authors: Mingelgrin U. , Tsvetkov F.
Published: September 2006

Parathion and methyl parathion adsorbed at high loads on clays and similar surfaces exhibited properties of a bulk phase, such as a well-defined solubility and a characteristic X-ray powder diffraction (XRD) pattern, different from those of the free substances. The aqueous solubility of parathion condensed at these surfaces was as low as 1.2 μg/ml as compared to 14 μg/ml for free parathion. The BET isotherm described the behavior of the investigated surface condensates even though these condensates were different from the multilayer adsorption for which the BET isotherm was originally developed. The XRD patterns of parathion and methyl parathion adsorbed on Na-bentonite exhibited reflections which were shifted towards higher angles as compared with the XRD patterns of the free compounds. This is in agreement with the lower solubility of the surface condensates. The properties of these condensates were easily controlled by the choice of adsorbent as well as by the choice of conditions under whch they were prepared. The existence of such surface-condensed phases and the manipulation of their properties can be utilized for the slow-release formulation of organophosphate esters which is important, for example, in pesticides application.
Structure Refinement of Deuterated Boehmite
Authors: Corbató Charles E. , Tettenhorst Rodney T. , Christoph Gary G.
Published: September 2006

The crystal structure of a deuterated synthetic boehmite powder, γ-AIOOD, has been determined by time-of-flight neutron diffraction and Rietveld profile refinement in space group Cmcm to a weighted profile R of 3.71%. Cell dimensions are a = 2.868(1), b = 12.2336(4), and C = 3.6923(1) Å. Alternate space groups for the boehmite structure suggested in the recent literature were found to be unacceptable. Atom positions, bond distances, and angles, with the exception of those involving hydrogen, were nearly identical to those determined by R. J. Hill in 1981 who studied a single crystal of boehmite by X-ray diffraction. All atoms were refined with anisotropic thermal parameters. The b value is 0.013 Å larger, and the thermal ellipsoids of oxygen are slightly more anisotropic than those reported by Hill and may reflect the different samples studied.
Development of Layer Charge and Kinetics of Experimental Smectite Alteration
Authors: Howard James J. , Roy Della M.
Published: September 2006

Sodium-saturated Wyoming bentonite was hydrothermally reacted at 150° and 250°C for 30 to 180 days to determine smectite alteration rates that might be applied to nuclear-waste repository design. Na-Ca solutions deficient in K were used to determine the role of interlayer cations in the creation of high layer-charge in the smectites. The results provide insight into the mechanism and timing of various steps in the diagenetic alteration of smectite to illite. X-ray powder diffraction (XRD) analyses of the reacted clay showed little effect on the character of the 17-Å reflection even after 180 days at 250°C. Potassium saturation of these reacted clays and re-examination by XRD indicated collapse of some smectite layers, leaving at most only 60% expandable layers. The development of layer charge sufficient to cause collapse on saturation with a low hydration energy exchange-cation does not require K in the reacting fluid. Rate constants for the illitization reactions as determined by K-saturated collapse are between 1.0 × 10−3 and 2.8 × 10−3/day with activation energies <3.5 kcal/mole. Ca in a Na-silicate-bicarbonate solution slightly reduced the illitization rate constants. These rate constants are higher than expected from extrapolation of studies of beidellite-composition glasses at higher temperatures, but lower than values obtained in studies of natural clays in artificial sea water. The release of Si, Al, and Mg in the 150°C experiments suggests congruent dissolution of the smectite. In contrast, at 250°C the release of Al was not stoichiometric with Si; as little as one half of the relative available Si was released. Rather than different mechanisms for dissolution at the two temperatures, the conclusion is that noncrystalline Al-rich phases formed at greater rates at higher temperatures. The cation-exchange capacities for several of these reacted smectites were significantly less than expected, suggesting a clogging of interlayer sites, perhaps by Al-complexes.
Cross-linked Smectites. IV. Preparation and Properties of Hydroxyaluminum-Pillared Ce- and La-Montmorillonites and Fluorinated NH4+-Montmorillonites
Authors: Tokarz M. , Shabtai J.
Published: September 2006

Reaction of hydroxy-Al oligocations with Ce3+- and La3+-exchanged montmorillonites, using 1.25, 1.60, or 2.0 mmole Al/g smectite, yielded partially pillared hydroxy-Al montmorillonite products containing a significant concentration of residual Ce3+ or La3+. After heat treatment at 250°C these products showed high surface areas (∼340–500 m2/g) and high basal X-ray powder diffraction spacings (18.0–18.6 Å). Calcination at 400°–700°C resulted in lower surface areas of ∼200–450 m2/g and basal spacings of 16.3–18.3 Å, the values showing a gradual decrease with a decrease in the Al/smectite weight ratio and/or increase in the heat-treatment temperature. A major modification and improvement in the cross-linking procedure was achieved by fast aging (6–48 hr) of the hydroxy-Al oligomeric solution at 95°–100°C, instead of conventional aging for 2–3 weeks at 25°C.

Fluorinated NH4+-montmorillonites, containing 0.4 to 2.1 wt. % F, were prepared by reaction of NH4+-montmorillonite at 60°C with 1.0 to 3.0 N aqueous solutions of NH4F. Interaction of the fluorinated montmorillonites with hydroxy-Al oligocations, using a ratio of 2.0 mmole Al/g smectite, yielded a series of cross-linked fluorinated montmorillonites with basal spacings of 17.9–18.0 Å and surface areas of 180–325 m2/g after heat treatment at 250°C. Calcination at 400°–500°C resulted in lower d(001) (16.6–17.7 Å) and surface-area values (140–300 m2/g). Increase in the fluorine content caused gradual decrease in both values. Transmission electron microscopy of pillared Ce-montmorillonite showed a highly oriented network of well-separated, parallel unit layers with an interlayer distance, Δd(001), of 9–10 Å. Calculated lateral (interpillar) distances were in good agreement with the pore-size distributions determined in independent adsorption studies.
Mineralogy, Crystallinity, O18/O16, and D/H of Georgia Kaolins
Authors: Hassanipak Ali Asghar , Eslinger Eric
Published: September 2006

Mineralogy, kaolin crystallinity, Fe content, δO18, and δD were determined for late Cretaceous “soft” and early Tertiary “hard” Georgia kaolins. The crystallinity of the <0.5-, 0.5–1.0-, and 1.0–2.0- μm size fractions of soft kaolins was higher than that of equivalent size fractions of hard kaolins. δO18 and δD of the soft and hard kaolins ranged between 18.5 to 23.1‰, and −64 to −41‰, respectively, and could not be used to discriminate soft from hard kaolins. The trends of crystallinity vs. δO18 were different for kaolins collected at different localities, and, for a given sample, δO18 generally decreased with increasing crystallinity and with increasing crystallite size. These data indicate that the Tertiary kaolins could not have been simply derived from the Cretaceous kaolins by winnowing unless post-sedimentation recrystallization of one or both occurred. δD vs. δO18 systematics indicate that the late Cretaceous to early Tertiary Georgia kaolins crystallized over a temperature range of about 15°C in the presence of waters that varied little in isotopic composition.
Quantitative Clay Mineral Analysis Using Simultaneous Linear Equations
Authors: Johnson L. J. , Chu C. H. , Hussey G. A.
Published: September 2006

A program of simultaneous linear equations has been developed to calculate component proportions and/or component property values for mineral mixtures in soil clays and sediments. The analysis is based on quantitatively measured chemical and physical properties of samples and involves (1) qualitative identification of the mineral components in the mixture by any appropriate means; (2) quantitative measure of the sample property values selected for use in the program; (3) estimation of the proportion of each component in the mixture by a technique such as X-ray powder diffraction; (4) assignment of limits to component property ranges; (5) selection of one of four available calculation options and application of the simultaneous linear-equations program; (6) examination of the residuals of the analysis and, if appropriate, adjustment of the initial estimates for component proportions or property ranges and then repeating step 5; and (7) verification of the final component proportions by comparison with information from step 1. Completeness and/or accuracy of the final results for component proportions may be checked by the closeness of approach to 1.0 for the sum of the component proportions. The method requires that, at minimum, the number of properties measured must equal the number of components in the samples being analyzed and that the minimum number of samples must equal the number of properties measured.

Using the clay fractions of 15 Pennsylvania soils containing kaolinite, illite, smectite, vermiculite, chlorite, interstratified vermiculite/chlorite, quartz, and noncrystalline material, and measuring methylene blue cation-exchange capacity, the amount of Ca displaced by Mg from a Ca-saturated clay, the amount of K displaced by NH4from a K-saturated clay heated to 110°C, % K2O, % SiO2, % MgO, and weight loss at 110°–300°C and 300°–950°C, the adjustment of property values was found to have the lowest residual value and the most consistent results. The source of analytical errors was also located by examination of residual tables. Samples that were similar in composition gave more reliable component proportions.
Co, Cu, Ni, and Ca Sorption by a Mixed Suspension of Smectite and Hydrous Manganese Dioxide
Authors: Traina S. J. , Doner H. E.
Published: September 2006

The sorption properties of Co, Cu, Ni, and Ca were studied in a mixed mineral suspension of synthetic MnO2 and Wyoming montmorillonite. The distribution of the sorbed cations between the two solid phases was measured by indirect chemical fractionation with acidified NH2OH-HCl and by direct X-ray spectroscopic analysis of mineral particles using electron microscopy. Electron microscope and NH2OH-HCl measurements of the quantity of Co sorbed on MnO2 agreed within 6%. Seventy-seven, 67, and 69% of the total Co, Cu, and Ni sorbed by the mixed mineral suspension was found on the manganese oxide. The opposite distribution was found for sorbed Ca with 28% on the manganese oxide and 72% on the montmorillonite particles. The observed differences in metal sorption by these minerals are related to the cation-sorption mechanisms of manganese oxide and montmorillonite.
Vapor-Phase Sorption and Polymerization of Phenols by Smectite in Air and Nitrogen
Authors: Sawhney B. L.
Published: September 2006

Reactions of smectite with phenols were investigated to understand the role of clay minerals in abating transport of these organic pollutants to ground water. Sorption of o-methylphenol, o-chlorophenol, and m-methylphenol by the clay with different exchange cations was accomplished by passing phenol vapors in a slow stream of air or nitrogen through the samples. The resulting products, extracted with methanol and analyzed by using mass spectrometry, included monomers, dimers, trimers, and tetramers of the parent phenol and of the corresponding quinones, the oxidation product of the phenols. In extracts from the Fe-clay-phenol complexes formed in air, traces of the phenolic pentamers were also detected. Both sorption and polymerization were much higher in air than in nitrogen. The greatly reduced polymerization in nitrogen suggests that anaerobic environment of the landfill sites may facilitate phenol transport to ground water. The degree of polymerization and its magnitude was in the order Fe- > Al- > Ca- > Na-clay.
Interlayer Water and Swelling Properties of Natural and Homoionic Corrensite
Authors: Brigatti Maria Franca , Poppi Luciano
Published: September 2006

A corrensite-like mineral, from near Borgotaro, Parma (Taro Valley, Italy), was studied by X-ray powder diffraction (XRD) and thermal analysis at different temperatures and water vapor pressures in the natural state and after exchange with ten different cations. In the natural state the mineral is characterized by a basal reflection at ∼29 Å shifting to ∼24 Å on heating and to ∼32 Å by glycerol treatment. The dehydration features of the homoionic minerals show that the stability of the complex of water, compensating cation, and silicate framework depends on the electrostatic energy of the water dipole in the cation field, similarly to smectite.

XRD of the exchanged mineral shows a basal reflection of ∼58 Å particularly in the NH4-, Rb-, and Ba-exchanged states. This value suggests a structure characterized by a regular sequence of silicate layers with different layer charge, that generally results in a c periodicity of ∼29 Å, but which shifts to ∼58 Å, and perhaps higher values, because of small differences in the compensating cation layers.
Crystallization of Iron Oxides on Calcite Surfaces in Static Systems
Authors: Clarke E. T. , Loeppert R. H. , Ehrman J. M.
Published: September 2006

Iron salts react readily with calcite in oxidizing calcareous environments to produce solid phase Fe-oxides. These reactions represent important processes in aqueous, geologic, and pedogenic environments. In the present investigation, Fe-oxides were precipitated from Fe(ClO4)2 solutions on undisturbed calcite grains in aqueous suspension. In this way it was possible to investigate the sequence of events in the crystallization process. Following an initial precipitation on the calcite grains, a period of slow growth of lepidocrocite was noted wherein 4-μm euhedral platelets formed with uniform orientation perpendicular to the calcite surface. The slow growth and highly crystalline nature of the Fe-oxide product may be partially due to the diffusion barrier formed by the growing oxide crystal mass which influenced rate of movement of HCO3− to the dissolved Fe phase and Fe ions and H+ towards the calcite surface. Upon continued aging, the supernate became noticeably opaque. As the suspended nuclei settled, new surfaces for crystal growth were provided which resulted in somewhat less crystalline lepidocrocite and goethite.
Influence of Inorganic and Organic Ligands on the Formation of Aluminum Hydroxides and Oxyhydroxides
Authors: Violante A. , Huang P. M.
Published: September 2006

Hydroxide and oxyhydroxide products of aluminum were formed at room temperature at an initial Al concentration of 2 × 10-3 M, pH 8.2, and at varying concentrations of organic and inorganic ligands commonly found in nature. The effectiveness of the ligands in promoting the formation of noncrystalline products over crystalline Al(OH)3 polymorphs was found to be in the following order: phthalate ≅ succinate < glutamate < aspartate < oxalate < silicate ≅ fluoride < phosphate < salicylate ≅ malate < tannate < citrate < tartrate. The lowest ligand/Al molar ratio at which the production of Al hydroxides or oxyhydroxides was inhibited ranged from 0.02 to 15. Above critical ligand/Al ratios, crystalline products were inhibited and ligands coprecipitated with noncrystalline products which remained unchanged for at least 5 months. Polydentate and large ligands generally were more inhibitive than those with fewer functional groups or of smaller size.

The perturbing ligands promoted and stabilized the formation of pseudoboehmite over crystalline Al(OH)3 polymorphs in the following sequence: chloride < sulfate < phthalate ≅ succinate < glutamate < silicate < aspartate < phosphate < salicylate ≅ malate < tannate < citrate < tartrate. The optimal range of the ligand/Al molar ratios for the formation of pseudoboehmite varied, for example, from 0.005–0.015 for tartrate to 600–1000 for chloride. Pseudoboehmite was not formed in the presence of fluoride.
Growth Conditions and Genesis of Spherical and Platy Kaolinite
Authors: Tomura Shinji , Shibasaki Yasuo , Mizuta Hiroyuki , Kitamura Masao
Published: September 2006

Spherical and platy kaolinite crystals were prepared under several hydrothermal conditions. Spherical kaolinite was produced mainly at high solid/water ratio (1/4) and at low temperatures (150°-200°C). Platy kaolinite predominated in products from experiments with intermediate solid/water ratios (1/256-1/16) and at high temperatures. Boehmite predominated at low solid/water ratios (1/4096) at all experimental temperatures (180°-220°C). The results indicate that the growth of the spherical kaolinite was favored at high degrees of supersaturation, whereas the growth of the platy kaolinite was favored at relatively low degrees of supersaturation.
Characterization of Dehydration-Induced Luminescence of Kaolinite
Authors: Lahav Noam , Coyne Lelia , Lawless James G.
Published: September 2006

Dehydration-induced luminescence (DIL), the emission of light from a clay paste upon dehydration, was characterized experimentally for a colloidal kaolinite. The relationship between total photon count of the emitted light and film thickness is linear up to a thickness of 30 μm. The photon emission was obtained over a critical range of water contents (25-60%) of the oven-dry clay, and the kinetics of photon emission was presumed to be closely associated with the kinetics of film dehydration. Whether drying proceeded throughout the bulk or via a moving front was undetermined, but in either mode it was preceded by the formation of a thin dry film at the interface with the atmosphere. Grinding of the kaolinite for several minutes by mortar and pestle before paste preparation resulted in an overall increase of photon emission compared to unground kaolinite and in the formation of more than one emission peak, as well as a prolongation of the light emission. This effect on the kinetics of light emittance was observed for about two months after the application of the mechanical stress and suggests a means of detecting the mechanical stress history of a clay.

An estimate was made of the spectral characteristics of the emitted light using optical filters and by incorporating tryptophan and salicylic acid into the kaolinite paste where they acted as fluorescent probes. The latter technique shifted the frequency of the light emitted by the kaolinite from the ultraviolet to the visible range where it was less effectively reabsorbed. The first method showed that the wavelengths of 97% of the emitted light was <460 nm and that 75% of the light had wavelengths <410 nm. The second method showed that the total intensity of DIL increased in the presence of fluorescence molecules, suggesting that the emittance was in the ultraviolet range.
Effect of Simple Sugars on the Alkaline Transformation of Ferrihydrite into Goethite and Hematite
Authors: Cornell R. M.
Published: September 2006

The transformation of ferrihydrite to goethite and hematite in the pH range 9–13 is retarded by the presence of simple sugars (>- 10-4 M concentration). The retarding effect is related to the extent of adsorption of the sugar on ferrihydrite. Maltose and glucose adsorb strongly and inhibit the transformation by preventing both aggregation and dissolution of the ferrihydrite. Sucrose adsorbs to a much lesser extent than the other sugars and appears to hinder the nucleation and growth of goethite in solution.

Hematite formation relative to that of goethite is favored by the sugars in the order: maltose >glucose ≫ sucrose. Maltose and glucose cause hematite to grow as prismatic crystals rather than as hexagonal plates and also lead to a new type of twinned goethite; one with epitaxial outgrowths of goethite on a prismatic crystal of hematite. In alkaline media glucose and maltose are partly transformed into a mixture of different sugars and hydroxycarboxylic acids, and it is probable that modification of the hematite crystal shape is due to the presence of the degradation products rather than to the nature of the original sugar.

The results of this work suggest that cyclic molecules influence the transformation of ferrihydrite to a lesser extent than do acyclic molecules.
Transmission Electron Microscopic Study of Diagenetic Chlorite in Gulf Coast Argillaceous Sediments
Authors: Ahn Jung Ho , Peacor Donald R.
Published: September 2006

Transmission and analytical electron microscopy have been used to study the diagenesis of the trioctahedral component of phyllosilicates (principally chlorite) in argillaceous core samples (depths of 1750, 2450, and 5500 m) from the Gulf Coast. Chlorite was observed as 100-150-Å thick packets intergrown within mixed-layer illite/smectite in the 2450-m sample and was more abundant and larger in packet thickness in the 5500-m sample. The chlorite is disordered in stacking sequence as characterized by diffuseness of reflections with k ≠ 3n in electron diffraction patterns. Berthierine (7-Å) was locally found to be intercalated within chlorite layers. Chlorite from the 5500-m sample is iron-rich and has an average chemical formula of Fe3.1Mg1.1Al2.7Si2.8O10(OH)8. This chemical composition and textural relations suggest that the chlorite formed within mixed-layer illite/smectite utilizing Fe and Mg released from the smectite during its conversion to illite. The berthierine is nearly identical in chemical composition with the coexisting chlorite although it may have a slightly higher Fe content. The 7-Å berthierine is probably a metastable precursor of the chlorite and may be diagnostic of the diagenetic environment.
Mineralogical and Morphological Evidence for the Formation of Illite at the Expense of Illite/Smectite
Authors: Pollastro Richard M.
Published: September 2006

The conversion of smectite to illite by way of a mixed-layer illite/smectite (I/S) series was found to be the major depth-related reaction in clay-mineral assemblages from two cored sedimentary sequences in the Rocky Mountains. The I/S reaction occurred in both interbedded sandstone and shale of Upper Cretaceous and lower Tertiary age in the Green River basin, Wyoming, and in chalk and chalky shale of the Upper Cretaceous Niobrara Formation, Denver basin, Colorado. As the proportion of illite layers in I/S increased with depth in these rocks, the amount of I/S in the clay fraction decreased, and the amount of discrete illite increased. Scanning electron microscopy revealed that the morphologies of highly expansible, randomly interstratified I/S clay (samples from shallow cores) exhibited no distinctive intergrowth or overgrowth textures. In deeply buried rocks containing highly illitic, ordered I/S and abundant discrete illite, however, fibers or laths of illite were formed on earlier I/S substrates. Less commonly, I/S of low expandability shows morphological features of both smectite and illite whereby rigid laths of illite appear to have formed diagenetically from the wall surfaces of I/S honeycombs. This combined morphology suggests some dissolution and reprecipitation (or some reorganization) of materials from the I/S substrate as the substrate was transformed into a more illitic mixed-layer clay.

These data suggest that some I/S clay was destroyed by the selective cannibalization of smectite layers in I/S to provide the components needed to make a more illitic I/S. Moreover, discrete illite and other minerals apparently were formed during the reaction. Also, coarser mineral phases, such as potassium feldspar and detrital micas, may not have been required to supply the chemical components in the reaction. The observations provide an explanation for late diagenetic I/S reactions that occurred in restricted or relatively closed geochemical systems, as in early cemented rocks having extremely low permeability and little or no potassium feldspar.
Review of the Diffusion of Water and Pyridinein the Interlayer Space of Montmorillonite: Relevance to Kinetics of Catalytic Reactions in Clays
Authors: Breen Christopher , Adams John M. , Riekel Christian
Published: September 2006

With the current interest in the use of transition metal-exchanged phyllosilicates as catalysts for novel organic syntheses, investigations into the factors which affect the movement of reactant, product, and solvent molecules into and out of their interlamellar region are of considerable importance. Mixed organic-water intercalates of a Wyoming montmorillonite, exemplified by the Na-montmorillonitepyridine-water system which can form four different intercalates exhibiting basal spacing of 29.3, 23.3, 19.4, and 14.8 Å depending on the pyridine: water ratio, have been used as a model system. X-ray and neutron diffraction and quasielastic neutron scattering data relating to the interconversion of interlayer species indicate that access to and exit from the interlayer space is hindered at high partial pressures of water by a water-film diffusion barrier in the interparticulate voids which exist between the aggregated silicate layers. At lower water vapor pressures the rate-limiting step for interconversion from one intercalate to another is the rate of transport of reagents and products to and from the clay particles. Under conditions where these rates are fixed, the rate-limiting step is the rate of diffusion of the pyridine molecule in the lower-spacing intercalate. Processes which involve a change in basal spacing do not necessarily proceed via a single discrete step, but are also affected by the amount of water made available to the system. In organic reactions catalyzed in the interlamellar space of various cation-exchanged montmorillonites (e.g., the conversion of alk-1-enes to di-2,2’-alkyl ethers and the reaction of alcohols to form ethers), rate-determining steps similar to those found above are likely to be operative. In particular, for reactions carried out in the liquid phase, where mass transport is facile and where phase-transfer problems are avoided, such reactions are likely to be diffusion controlled.
Adsorption of Dimethylanilines on Montmorillonite in High-Pressure Liquid Chromatography
Authors: Mingelgrin U. , Tsvetkov F.
Published: September 2006

High-pressure liquid chromatography columns were packed with quasi-spherical particles of bentonite (SP-bentonite) which were prepared from a predominantly Na-bentonite powder by spray drying. The strength of adsorption of ring-substituted dimethylanilines on bentonite was directly related to their basicity (pKa). The adsorption of the amino-substituted N, N-dimethylaniline was commonly much weaker than that predicted from its pKa, suggesting that the amino group was the dominant site of interaction between the substituted anilines and the clay.

A better separation between the dimethylaniline isomers was obtained on SP-bentonite than on a neutral silica under the same chromatographic conditions. A selectivity factor of 25 was achieved between the most strongly and the least strongly adsorbed ring substituted isomers (3, 5- and 2,6-dimethylaniline, respectively) on the SP-bentonite. The selectivity factor was 3.4 on the silica. This efficiency of separation demonstrated the potential advantage of the readily available bentonite in high-pressure liquid chromatography. The higher resolution achieved in column runs than in batch experiments may be utilized for the elucidation of mechanisms of interaction of organic molecules at clay surfaces by comparing the interaction of a number of closely related adsorbates.