bluuebunny/crossref_metadata_2025 huggingface dataset:
Regular Solution Site-Mixing Model for Chlorites
Authors: Stoessell R. K.
Published: August 2006

Activity expressions are presented for a six end-member, regular solution, site-mixing model for chlorites. The end members are ideal 14-Å chlorites for which experimental stability data are lacking. Estimates were made of the standard state 25°C and 1 bar molar 3rd law entropies, volumes, and the Maier-Kelley heat capacity coefficients. Experimental stability data from the literature for 14-Å chlorites were used with different sets of exchange energies, for cations on adjacent sites, to compute estimates of the standard state chemical potentials of the end members at 25°C and 1 bar. More experimental data are needed for an adequate definition of the exchange energies and the standard state chemical potentials. The model was applied to diagenesis in clastic reservoirs. Aqueous activity ratios of Mg2+:Fe2+ were computed as an equilibrium function of the corresponding molar ratios in authigenic chlorites. The aqueous activity ratio was independent of the chlorite Al content at a constant molar ratio of Mg2+:Fe2+ in the chlorite. The model predicts a wide range of molar Mg2+:Fe2+ ratios in authigenic chlorites in equilibrium with reservoir fluids. Trends in these molar ratios should be independent of the Al content in the chlorites. The model can be applied directly to 7-Å chlorites when experimental data become available to estimate the various thermodynamic parameters of the 7-Å end members.
Mineralogy and Genetic Relationships of Tonstein, Bentonite, and Lignitic Strata in the Eocene Yegua Formation of East-Central Texas
Authors: Senkayi A. L. , Dixon J. B. , Hossner L. R. , Abder-Ruhman M. , Fanning D. S.
Published: August 2006

A kaolinite-rich bed (tonstein) and an associated bentonite in the upper part of Yegua Formation at College Station, east-central Texas, were formed by in situ weathering processes in a late Eocene swamp. X-ray powder diffraction, infrared spectroscopy, petrographic studies, and scanning and transmission electron microscopy not only show that dioctahedral smectite and coarsely crystalline kaolinite are the dominant minerals in the bentonite and tonstein, respectively, but that cryptocrystalline halloysite and kaolinite are localized along the weathering front (transitional zone) between the tonstein and the bentonite. As weathering progressed, the cryptocrystalline minerals gradually recrystallized to yield the coarse books and vermicular growths of kaolinite characteristic of the tonstein.

Small amounts of cristobalite, sanidine, and euhedral zircon crystals with liquid or gaseous inclusions accord with the formation of the bentonite by alteration of volcanic ash. Clinoptilolite in the lignitic layer and sandstone below the bentonite probably formed from ions that were released during alteration of the volcanic materials to smectite, but clinoptilolite in the tonstein and overlying strata appear to have formed after kaolinization of the bentonite.
Chemisorption of Cu(II) and Co(II) on Allophane and Imogolite
Authors: Clark C. J. , McBride M. B.
Published: August 2006

Adsorption of Cu2+ and Co2+ by synthetic imogolite, synthetic allophanes with a range of SiO2/ Al2O3 ratios, and allophanic clay fractions from volcanic ash soils was measured in an ionic medium of 0.05 M Ca(NO3)2. The effect of pH (and metal concentration) on adsorption was qualitatively similar for the synthetic and natural allophanes with relatively minor changes in behavior caused by variable SiO2/Al2O3 ratios. Cu and Co were chemisorbed by allophane at pH 5.0–5.5 and 6.9–7.2 (pH values for 50% adsorption level), respectively, with concomitant release of 1.6–1.9 protons/metal ion adsorbed. Quantitatively, adsorption by imogolite was less than that by the allophanes, presumably because of fewer sites available for chemisorption on the tubular structure of imogolite. Electron spin resonance studies of the imogolite and allophanes revealed that Cu2+ was adsorbed as a monomer on two types of surface sites. The preferred sites were likely adjacent AlOH groups binding Cu2+ by a binuclear mechanism; weaker bonding occurred at isolated AlOH or SiOH groups. These chemisorbed forms of Cu2+ were readily extracted by EDTA, CH3COOH, and metals capable of specific adsorption, but were not exchangeable. In addition, the H2O and/or OH− ligands of chemisorbed Cu2+ were readily displaced by NH3, with the formation of ternary Cu-ammonia-surface complexes.
Effects of Reduction and Reoxidation of Structural Iron on the Surface Charge and Dissolution of Dioctahedral Smectites
Authors: Stucki Joseph W. , Golden D. C. , Roth Charles B.
Published: August 2006

The effect of Fe oxidation state on the surface charge (CEC) and solubility of smectites were studied using the <2-μm, Na+-saturated fraction of an Upton, Wyoming; a Czechoslovakian; and a New Zealand montmorillonite; and a Garfield, Washington, nontronite. The reduction of structural Fe3+ in the octahedral sheet of each clay produced a net increase in the negative surface charge of the clay. The observed cation-exchange capacities deviated from the linear relationship predicted by charge-deficit calculations, assuming changes only in the Fe2+/Fe3+ ratio, and reversibly followed Fe reduction according to a 2nd-degree polynomial function. The deviations suggest reversible changes in mineral structure and composition during Fe reduction.

These clays were susceptible to partial dissolution in citrate bicarbonate (CB) and citrate-bicarbonate-dithionite (CBD) solutions. Small amounts of Fe and Si dissolved as a result of Fe reduction in CBD, but affected <1% of the total clay mass except for the Czechoslovakian clay in which 2% of the clay dissolved. Although slightly more Fe dissolved than Si, no change in surface charge was noted. Almost no dissolution of these elements was detected in CB solution. In contrast, significant Al was detected in the CB solution, suggesting a heterogeneous dissolution mechanism. The CEC, however, was unchanged by the CB treatment. These results may be explained by the adsorption of hydrogen ions into the vacated Al3+ sites in the mineral structure. Dissolution seems to have been independent of the effects of Fe oxidation state on surface charge.
Nontronite in a Deep-Sea Core from the South Pacific
Authors: Singer A. , Stoffers P. , Heller-Kallai L. , Szafranek D.
Published: August 2006

Smectite close to the pure Fe end member of the nontronite-beidellite series was found in the fine clay separated from a 354-cm deep sediment core in the southwestern Pacific Basin. The mineral has a b-axis of 9.09 Å and an unusually low dehydroxylation temperature of 454°C and is composed of sheaves of fibers less than 50 Å wide. Its charge density is 5.09 × 10~4 esu/cm2. The charge originates mainly from the presence of 18% of the total Fe in tetrahedral positions, as determined by Mössbauer analysis. Slight deviations of the infrared spectra from those reported for nontronites are probably due to the presence of more octahedral Mg. The presence of authigenic quartz in the same sample permits some speculation on the concentration of dissolved silicon during nontronite genesis. A δ18O value of 26 ± 0.3‰ indicates a temperature of formation of about 22°C. The Sr isotope ratio suggests that the nontronite formed at least 12 million years ago.
Static and Dynamic Structure of Water in Hydrated Kaolinites. I. The Static Structure
Authors: Costanzo P. M. , Giese R. F. , Lipsicas M.
Published: August 2006

Four hydrates with d(001) = 8.4, 8.6, and 10 Å (two types) were synthesized by intercalating kaolinite with dimethylsulfoxide and treating the intercalated clay with fluoride ions. X-ray powder diffraction, infrared spectroscopy, differential scanning calorimetry, thermal gravimetric analysis, and kinetics of dehydration experiments have led to the identification of two types of interlayer water. One type of water (hole water) is situated in the ditrigonal holes of the silica tetrahedral surface; the second type (associated water) forms a discontinuous layer of mobile water. The 8.4-Å and 8.6-Å hydrates have only hole water, whereas the two synthetic 10-Å hydrates and halloysite(10Å) contain both hole and associated water. The hole water is probably hydrogen bonded to the basal oxygens of the silica tetrahedra or, in the 8-Å hydrates when fluorine exchanges for inner-surface hydroxyls, the water molecules may reorient and form stronger hydrogen bonds to the fluorine. Associated water forms water-water hydrogen bonds approximately equal in strength to liquid water but is less strongly bonded to the clay surfaces than hole water. At room temperature the hole and associated water in the 10-Å hydrates do not form an ice-like structure.
Polytypism of Micas. II. Classification and Abundance of MDO Polytypes
Authors: Ďurovič S. , Weiss Z. , Backhaus K.-O.
Published: August 2006

The maximum-degree-of-order (MDO) polytypes in all three mica families have been classified into two subfamilies and five homomorphous MDO groups according to their superposition structure and the YZ projection of their structure, respectively. This classification, which is closely related to the diffraction pattern of micas, can be derived directly from the fully descriptive polytype symbols and facilitates the calculation of the identification diagrams as well as the recognition of the relations of homomorphy between the three mica families. All mica structures refined so far by the least-squares method according to the present standards, are those of MDO polytypes.
Relation of Infrared, Crystallochemical, and Morphological Properties of Al-Substituted Hematites
Authors: Barron V. , Rendon J. L. , Torrent J. , Serna C. J.
Published: August 2006

Synthetic Al-hematites prepared from ferrihydrites, at low (∼ 100°C) and high (400° and 800°C) temperatures were studied for their morphological, crystallochemical, and infrared (IR) characteristics. Low-temperature Al-hematites had a platy morphology (the plate thickness was inversely related to amount of Al substitution), and the high temperature Al-hematites showed a poorly defined morphology due to interparticle sintering. In the low-temperature Al-hematites shifts in the IR mode frequencies were noted and could be partly explained by a shape factor that was deduced from particle morphology. The intrinsic effect of Al substitution, however, was to produce shifts of as much as 10–15 cm−1 for the highest Al substitution (∼ 16%). Similar shifts were observed for the high-temperature hematites in which morphology was not appreciably affected by Al substitution.
Pillaring Processes of Smectites with and Without Tetrahedral Substitution
Authors: Plee D. , Gatineau L. , Fripiat J. J.
Published: August 2006

Pillaring of montmorillonite and beidellite with aluminum polyhydroxypolymer takes place first by the saturation of the cation-exchange capacity by monomeric and/or dimeric aluminum hydroxide species and then the intercalation of the so-called Al13-polyhydroxypolymer. The clay slurry must have a solid concentration greater than 0.01% (w/w) to produce a basal spacing of about 18 Å. Sizeable clay tactoids must therefore exist in the slurry in order to produce a turbostratic structure ordered along the c axis. The main difference between pillared montmorillonite and pillared beidellite seems to be a more ordered distribution of pillars within the interlamellar space of the clays that are rich in tetrahedral substitutions. Recent 27Al and 21Si high-resolution nuclear magnetic resonance data suggest that this higher degree of ordering results from the reaction of the aluminic pillars and the clay sheet near the sites of the tetrahedral substitutions.
Chemical and Morphological Evidence for the Conversion of Smectite to Illite
Authors: Inoue Atsuyuki , Kohyama Norihiko , Kitagawa Ryuji , Watanabe Takashi
Published: August 2006

The continuous conversion of smectite to illite in samples from the Shinzan hydrothermal alteration area of Japan has been examined by X-ray powder diffraction (XRD) and transmission (TEM) and analytical transmission electron microscopy (AEM). TEM shows that randomly interstratified illite/ smectite (I/S) containing 100-50% expandable layers exhibits a flakey shape, whereas regularly and partially ordered interstratified I/S having 50-0% expandable layers exhibits a lath-like habit. An early- formed lath of regularly interstratified I/S is typically <35 Å in thickness and 300–500 Å in width; these dimensions gradually increase with decreasing percentage of expandable layers. XRD shows that the lathshaped I/S has a 1M polytype mica structure. AEM shows that the interlayer K content of flakey I/S increases monotonously with decreasing percentage of expandable layers in the range 100-50% expandable layers, whereas the interlayer K content of lath-shaped I/S increases along a different trend from that for the flakey I/S in the range 50-0% expandable layers. These observations suggest that randomly interstratified I/S is fundamentally smectite that is undergoing K-fixation and dissolution and that regularly and partially ordered interstratified I/S are immature illite which is still growing. Consequently, they suggest a mechanism for the hydrothermal smectite-to-illite conversion that is based on the K-fixation in and dissolution of smectite and the precipitation and growth of thin illite particles. Furthermore, these data suggest that the kinetics of smectite dissolution and illite growth are the most important factors controlling the smectite-to-illite conversion.
Alteration of Phlogopite to Corrensite at Sharbot Lake, Ontario
Authors: De Kimpe C. R. , Miles N. , Kodama H. , Dejou J.
Published: August 2006

A low-charge corrensite, i.e., a regular 1:1 interstratified smectite/chlorite was found in veins and fissures of an extensively fractured dolomite south of Perth, Ontario, Canada. Total chemical analysis indicated that the mineral was trioctahedral, having a structural formula corresponding to:
<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">(Ca0.17)(Mg7.36Al0.90Fe3+ 0.45Fe2+ 0.42)VI(Si6.06Al1.94)IVO20(OH)10.

The coefficient of variation (CV) of the d(00l) spacings calculated for the mineral from X-ray powder diffraction data was 0.42, well below the maximum recommended value for corrensite, 0.75. The corrensite coexists with phlogopite, which is present as small (~0.5 mm) crystals throughout the rock and locally as large (~5 cm) crystals in pegmatitic veins. Microscopic observatiofls of large phlogopite crystals partially altered to corrensite suggest that corrensite formed at the expense of phlogopite by hydrothermal alteration.
Preparation and Characterization of Bidimensional Zeolitic Structures Obtained from Synthetic Beidellite and Hydroxy-Aluminum Solutions
Authors: Schutz A. , Stone W. E. E. , Poncelet G. , Fripiat J. J.
Published: August 2006

Beidellite was synthesized hydrothermally from a noncrystalline gel at 320°C and 130 bar pressure. The beidellitic character of the product was verified by infrared spectroscopy on the NH4+-exchanged form. Intercalation was achieved with hydroxy-aluminum solutions having different OH/Al molar ratios. The solutions were investigated by several methods, including 27Al nuclear magnetic resonance. Essentially, two Al species were detected: monomelic Al and a polymerized form containing Al in four-fold coordination. This latter species was found to be selectively fixed in the interlamellar region, which resulted in a stable spacing of 18 Å at 110°C and 16.2 Å at 700°C. The pillared beidellites had specific surface areas of > 300 m2/g, mainly due to micropores. Both Brönsted and Lewis acid sites were evidenced by infrared spectroscopy using pyridine as a probe molecule.
New Members of the Hydrotalcite-Manasseite Group
Authors: Drits V. A. , Sokolova T. N. , Sokolova G. V. , Cherkashin V. I.
Published: August 2006

Several new minerals, structurally and chemically similar to the hydrotalcite-manasseite group, have been found in the saline deposits of the central pre-Caspian depression and in those of Middle Asia. Their structures consist of layers of (Mg1-xAlx)(OH)2 plus interlayers of anions and molecular water. In addition to manasseite itself, [(Mg4Al2)(OH)12][(CO3)-3H2O], having unit-cell parameters of a = 3.042, c = 2 × 7.56= 15.12 Å and a calculated density of Dc = 2.15 g/cm3, other varieties were identified whose interlayers contain alternately SO42− or SO42− and CO32− anions. The following new phases were recognized: (1) an 8.85-Å phase having the composition [(Mg4Al2)(OH)12][(SO4)·3H2O], subcell dimensions of a' = 3.04, c' = 8.85 Å, and Dc = 1.96 g/cm3; (2) an 11-Å phase having the composition [(Mg3.96Fe0.06Al1.98)(OH)12][Na0.56(SO4)1.30·7.3H2O], hexagonal unit-cell parameters of a = √3 · 3.042 = 5.28 Å, c = 11.16 Å, and Dc = 1.90 g/cm3; (3) a 16.5-Å mixed-layer phase having the composition [(Mg4Al2)(OH)12][(SO4)0.5(CO3)0.5·3H2O] and an ordered ABAB... alternation of 7.56-Å layers (i.e., a brucite-like layer + a CO32−-containing interlayer) and 8.94-Å layers containing SO42− anions in interlayers; this phase has unit-cell dimensions of a' = 3.05, c' = 16.5 Å and Dc = 2.06 g/cm3; and (4) an 18.5-Å ordered mixed-layer phase having the ideal composition [(Mg8Al4)(OH)24][M+0.5(SO4)1.25(CO3)1.0·9H2O] and an alternation of 7.56-Å, CO3-containing layers and 11-Å layers having SO42− anions and Na and Mg cations in interlayers (M+0.5 corresponds to interlayer cations). This last phase has unit-cell dimensions of a = 3.046, c = 3 × 18.54 = 55.62 Å and Dc = 1.99 g/cm3. Some of the varieties containing SO42− in the interlayers swelled with ethylene glycol or glycerol.

For this diverse family of minerals whose structures are based on brucite-like layers of the composition (R2+1-xR3+x)(OH)2, a unifying system of nomenclature is offered for consideration. In describing these brucite-like structures intercalated with anion- and cation-containing interlayers, the composition of the hydroxide sheet and the interlayers, the periodicity of the layers, and the mixed-layer nature of the material should be described. By means of symbols, a single term might be used to describe the crystal chemistry of any member of the group having a given cation composition for the brucite-like layers, for example, manasseite, a 2H polytype of hydrotalcite that has a repeat distance of 7.56 Å and CO3-containing interlayers, might be designated as 7.56-Å CO3-hydrotalcite-2H.
Cross-Linked Smectites. V. Synthesis and Properties of Hydroxy-Silicoaluminum Montmorillonites and Fluorhectorites
Authors: Sterte Johan , Shabtai Joseph
Published: August 2006

Solutions containing hydroxy-SiAl (HSA) oligocations were prepared by two procedures: (1) treatment of a mixture of orthosilicic acid and AlCl3 with aqueous NaOH, followed by aging of the product; and (2) preliminary preparation and aging of hydroxy-Al13 oligocations followed by reaction of the latter with orthosilicic acid. Ion exchange of Na,Ca-montmorillonite with HSA oligocations yielded pillared, cross-linked montmorillonites (designated as HSA-CLM) showing a maximum d(001) value of 19.5 Å for air-dried samples, and maximum surface areas of ~500 m2/g after outgassing at 250°C/10−3 torr. Corresponding ion exchange of Li-fluorhectorite yielded HSA fluorhectorites (HSA-CLFH) showing a maximum d(001) value of 19.0 Å and a surface area of 355 m2/g. Calculated structural formulae for the HSA-CLM and HSA-CLFH products, based on elemental analysis, showed a gradual increase in the Si/Al ratio in the intercalated HSA oligocations with increasing Si/Al ratio in the pillaring solution. Optimum d(001) values and surface areas of HSA-CLM and HSA-CLFH products were obtained using method 2 and applying a ratio of 1.6–2.5 mmole (Si)Al/g smectite.

The thermal stabilities of HSA-CLM and HSA-CLFH products were determined by heat treatment between 250° and 700°C and subsequent measurement of the d(001) values and surface areas. HSA-CLFH products showed the unusual behavior of increase of d(001) with increase in temperature from 400° to 500°C, and essential constancy of d(001) from 500° to 600°C. The HSA-CLM products showed a gradual decrease in surface area, whereas the HSA-CLFH products prepared with a Si/Al ratio of 1.04–2.18 in the pillaring solution showed constant surface areas with increasing temperature from 250° to 600°C. HSA-CLM and HSA-CLFH show sharply higher acidities compared with those of reference Al-CLM and Al-CLFH samples obtained by pillaring with hydroxy-Al13 oligocations. This increased acidity is probably due to the presence of acidic, surface silanol groups in the HSA oligocations.
Visible Spectroscopy of Methylene Blue on Hectorite, Laponite B, and Barasym in Aqueous Suspension
Authors: Cenens J. , Schoonheydt R. A.
Published: August 2006

The absorption spectra of methylene blue ion exchanged on hectorite, Laponite B, Barasym, or sepiolite in dilute aqueous suspensions show the presence of the monomer, the protonated monomer, the dimer, and the trimer. Due to conformational differences, the absorption band maximum of the monomer with respect to its maximum in aqueous solution is red shifted when it is adsorbed on the external surface and blue shifted when it is adsorbed on the interlamellar surface. The availability of the interlamellar surface for methylene blue as a function of the type of clay and/or the counterion present thereby can be probed. The results indicate that 0.6–0.7% of the cation-exchange capacity of Barasym consists of acid sites capable of protonating methylene blue. Counterions of low hydration energy were found to induce a small number of similar sites in hectorite and Laponite B; hence, these sites must be situated on the external surface. Dimers formed on external surfaces show one absorption band. Dimers formed on the interlamellar surface of hectorite yield spectra having two absorption bands. The trimer was formed only at the external surface. With increasing loading of the clays, the spectra of methylene blue showed metachromasy. The metachromatic behavior can be fully explained by dye aggregation, which is the result of its concentration on the surface. No π-electron interaction with the surface oxygens need be invoked.
Transformation of Hausmannite into Birnessite in Alkaline Media
Authors: Cornell R. M. , Giovanoli R.
Published: August 2006

The transformation of hausmannite (Mn3O4) into a K-bearing, 7-Å phyllomanganate (K-birnessite) in KOH was followed using X-ray powder diffraction and transmission electron microscopy. The transformation involved dissolution of Mn3O4 followed by reprecipitation of the 7-Å phase. The rate-determining step was the dissolution of Mn3O4. The reaction was accelerated by increasing the pH and/or the temperature of the system.

K-birnessite precipitated initially as thin, irregular plates and films that gradually recrystallized to thicker, more structured plates and laths. A pseudohexagonal unit cell with a0 = 2.87 Å and c0 = 7.09 Å was found for this phase. Synthetic K-birnessite was stable in KOH at 70°C for many months. In neutral to slightly acidic media it converted rapidly to Mn7O13•5H2O, and in more acid media, it dissolved and reprecipitated as γ-MnO2. The replacement of K+ by Na+ was not achieved. Jacobsite and magnetite also underwent a dissolution/reprecipitation transformation in KOH.
Estimation of Heavy Atom Content and Distribution in Chlorite Using Corrected X-Ray Powder Diffraction Intensities
Authors: Walker Jeffrey R. , Hluchy Michele M. , Reynolds Robert C.
Published: August 2006

The heavy atom content and distribution in chlorite were estimated using the relative intensities of basal X-ray powder diffraction (XRD) peaks. For these peaks to be meaningful, however, corrections had to be made for the effects of sample thickness, sample length, and preferred orientation of the mineral grains, all of which are 2θ dependent. The effects of sample thickness were corrected for by a simple formula. The effects of sample length were accounted for by using rectangular samples and by ensuring that the sample intersected the X-ray beam through the range of diffraction angles of interest. Preferred orientation of mineral grains were either measured directly or estimated. Estimated values were quicker and easier to obtain and were within 5% of measured values. A comparison of the compositional parameters of chlorite estimated before correcting for these sample effects with those estimated after the corrections had been applied indicate that the uncorrected values differed from the corrected values by as much as 55% of the latter values. Mounts of a single sample prepared by different filter-membrane peel and porous-plate techniques yielded widely different compositions until the measurements were corrected for sample effects. Analyses in triplicate indicated that the XRD intensity ratio 003/001 is preferred for calculating heavy atom distributions and abundances in chlorite because of the relative strength of the 001 peak.
Kaolinization of Bauxite: A Study of the Vlasenica Bauxite Area, Yugoslavia. II. Alteration of Oolites
Authors: Dangić Adam
Published: August 2006

During the epigenetic alteration of boehmitic karstic bauxite in the Vlasenica region of Yugoslavia, which was caused by siliceous water descending through the deposit by means of cracks, fissures, etc., oolites were less altered compared with the coexisting matrix material, which was intensely kaolinized. The following zonal alteration pattern of the oolites was identified: a diaspore enrichment zone, followed by a diaspore-boehmite enrichment zone, and then the original bauxite. Considering this alteration pattern and that determined previously for the matrix material, the following overall pattern of alteration was established: a kaolinite-diaspore zone, followed by a boehmite-diaspore zone, and then the original bauxite. The alteration solutions reacted with the bauxite to form solution-matrix and solution-oolite subsystems, which were characterized by different types of diffusion and geochemistry.

In the kaolinite-diaspore zone Si-metasomatism kaolinized the matrix, and excess Al partly migrated into the oolites, forming diaspore, and outward into the bauxite. The latter Al-remobilization resulted in a transition zone, in which new boehmite was formed in both the matrix and the oolites, and diaspore only in the oolites. Thermodynamic models of oolites and whole bauxite alterations were established, on the basis of stability diagrams calculated for the mineral assemblages of both the oolites and the matrix, in the alteration zones and in the deposit as a whole. Based on these models, the genesis of the diaspore and the relationship of diaspore-boehmite-kaolinite assemblages in natural systems at low temperature and low pressure can be described.
Influence of Manganese Oxide Minerals on the Formation of Iron Oxides
Authors: Krishnamurti G. S. R. , Huang P. M.
Published: August 2006

The influence of manganese oxide minerals (cryptomelane, hausmannite, and pyrolusite) on the formation of iron oxides was studied in the FeCl2-NH4OH system at different Mn/Fe molar ratios (0, 0.01, 0.1, and 1.0) and pHs (3.0, 4.0, 5.0, and 6.0) by X-ray powder diffraction, infrared absorption, transmission electron microscopic, and chemical analyses. In the absence of Mn minerals, lepidocrocite (γ-FeOOH) precipitated at pHs 5.0 and 6.0; however, no precipitate formed at lower pHs. All the Mn minerals studied promoted the precipitation of iron oxides and oxyhydroxides. In the presence of Mn oxides, Fe2+ was oxidized to Fe3+, which hydrolyzed and precipitated as noncrystalline and/or different crystalline iron oxides and oxyhydroxides, depending on the nature of the Mn oxides present in the system. Simultaneously, Mn2+ was detected in solution after the reaction by electron spin resonance spectroscopy. The presence of cryptomelane and hausmannite resulted in the formation of åkaganeite (β-FeOOH) and magnetite (Fe3O4), respectively. Thus, the effect of Mn oxides on the formation of Fe oxide minerals in the weathering zone merits attention.
Adsorption Properties of Montmorillonite and Synthetic Saponite as Packing Materials in Liquid-Column Chromatography
Authors: Nakamura Yuji , Yamagishi Akihiko , Iwamoto Toschitake , Koga Makoto
Published: August 2006

The adsorption of tris(1,10-phenanthroline)-ruthenium(II) (Ru(phen)32+) by two kinds of colloidally dispersed clays, sodium montmorillonite and synthetic saponite, was studied by spectrophotometric and electron-optical methods. Montmorillonite adsorbed this complex stronger than saponite. The electronic spectrum measurements suggested that the electronic states of the complex were more perturbed on adsorption by montmorillonite than by saponite. High-performance liquid chromatography was attempted on an ion-exchanged adduct of optically active Ru(phen)32+ and these clays. 1,1′-Binaphthol was eluted with a 1:1 (v/v) water-methanol mixture as an eluent. The compound was resolved with a separation factor of 15 and 1.4 on the saponite and montmorillonite columns, respectively. If tris(acetylacetonato)-chromium(III) was eluted with water, the compound was resolved with separation factors of 1.9 and 11 on the saponite and montmorillonite columns, respectively. These separation tendencies were probably due to the difference in the external surface area and the density of the bound chelates.
High-Resolution Transmission Electron Microscopy of Mixed-Layer Illite/Smectite: Computer Simulations
Authors: Guthrie George D. , Veblen David R.
Published: August 2006

High-resolution transmission electron microscope images of dioctahedral mixed-layer clay structures (illite/smectite) having various substitutional and polytypic schemes were modeled using computer simulation methods. Both one- and two-dimensional calculations were performed using parameters characteristic of a typical range of imaging conditions. One-dimensional images formed by imaging only 00/ diffractions show three important results: (1) The 20-Å periodicity resulting from rigorously ordered R1 illite/smectite can be imaged, but unconventional focus conditions may be necessary. (2) For crystals oriented with the electron beam perfectly parallel to the layers, the brightest fringes in the image correspond to either the octahedral sheets or the interlayer sites, depending on focus conditions. Misorientation of the crystal, however, by only 1° or 2° shifts the positions of the fringes by 1 to 3 Å. Furthermore, in tilted specimens, some defocus values produce images suggesting that smectite layers have a 11–13-Å periodicity, despite the uniform 10-Å periodicity present in the model structure. Thus, direct correlations between image and structure generally should not be made. (3) Two-layer polytypes of pure illite or pure smectite can also produce images with a 20-Å periodicity.

Two-dimensional images additionally showed that the cross fringes produced by some hkl diffractions can be imaged. The simulations showed that these cross fringes ideally might permit the determination of both layer stacking and compositional periodicity, but the fringes are lost by misorientations of a few degrees. These image simulations demonstrated, therefore, that mixed layering of illite and smectite theoretically can be directly imaged by transmission electron microscopy of chemically untreated specimens, but ambiguities may exist in the detailed intepretation of the images.
Shale Diagenesis in the Bergen High Area, North Sea
Authors: Glasmann J. Reed , Larter Steve , Briedis Nowell A. , Lundegard Paul D.
Published: August 2006

Illite diagenesis in Tertiary and Mesozoic shales in the Bergen High area, northern North Sea, was studied using mineralogic, isotopic, and computerized thermal modeling techniques. The Tertiary shales are dominated by smectite, with lesser amounts of illite, kaolinite, and chlorite. At present burial temperatures of >70°C smectite is absent, and the shales contain abundant lath-shaped illite which yields a mixed-layer illite/smectite (I/S) X-ray powder diffraction (XRD) pattern. Transmission electron microscopy (TEM) indicates that the illite laths increase in abundance and thickness with increasing depth; XRD patterns indicate a progressive increase in the illite component of the I/S. The deepest samples were found to contain long-range ordered (R=3) I/S, which showed platy particle morphology with the TEM. K-Ar ages of most of the <0.1-μm-size illite separates imply that illitization was a relatively brief event affecting a thick sequence of sediments during late Cretaceous to early Paleocene time (65–87 Ma); however, measured ages were affected by trace levels of detrital Ar contamination and do not represent the true age of diagenesis.

Several methods of quantifying Ar contamination were used to correct measured ages to obtain a reasonable estimate of the true age of diagenesis. The corrected ages are imprecise due to uncertainties in quantifying the levels of sample contamination, but generally suggest a Paleogene (38–66 Ma) period of illitization. In contrast, simple kinetic models of smectite-illitization suggest much younger ages of diagenesis (0–40 Ma at the Veslefrikk field; 0–60 Ma at the Huldra field). The timing of the diagenesis and the morphologic aspects of the authigenic illite suggest that illite precipitated before late Tertiary compaction and resulted in a decrease in fluid permeability. Low trapping efficiency of early Tertiary sediments, vertical escape of warm fluid from the Brent sandstone, and high heat flow may have promoted illite diagenesis in the shales prior to deep late-Tertiary burial.
Apatite Replacement and Rare Earth Mobilization, Fractionation, and Fixation During Weathering
Authors: Banfield Jillian F. , Eggleton Richard A.
Published: August 2006

During an electron microscope study of the weathering of granite from southern New South Wales, Australia, an assemblage of minerals including florencite and rhabdophane was discovered replacing apatite. Light rare earth elements released from allanite early in weathering apparently combined with P released by leaching of primary apatite to form secondary phases exhibiting a range of morphologies and compositions. Chondrite normalized fractionation patterns La > Nd > Sm > Ce; La > Ce > Nd ≥ Sm and La = Sm = Nd > Ce were identified. The rare earth elements were present in very small crystals and aggregates of secondary minerals (< 10 μm) and coexisted with clays and secondary Fe-Ti oxides. The weathered granite was enriched about 6 to 10 times in all rare earth elements except Ce relative to fresh granite if the abundances were corrected for apparent enrichment due to reduction in density. The rare earth elements were probably derived from higher in the weathering profile, possibly by destruction of florencite and rhabdophane in very intensively weathered rock. Ce remained relatively immobile during weathering, probably due to its oxidation to Ce4+.
Properties of Hexacyanocobaltate(III)-Exchanged Hydrotalcite-Like Minerals
Authors: Suzuki Eiichi , Idemura Satoshi , Ono Yoshio
Published: August 2006

Hydrotalcite-like minerals, containing Mg2+-Al3+-Xn− (Xn− = NO3−, Cl−, SO42−, or CrO42−), Zn2+-Al3+-NO3−, or Zn2+-Cr3+-NO3− ions, were intercalated with Co(CN)63− by an anion exchange method. For most of the minerals examined, the degree of anion exchange was 79–90%. X-ray powder diffraction patterns of the ion-exchanged samples revealed two peaks at about 8° and 11°2θ (CuKα radiation) attributable to reflections from expanded and non-expanded interlayers, respectively. The intensity of the peak at about 8°2θ was a linear function of the degree of anion exchange. The amount of hexane adsorbed onto the anion-exchanged sample increased linearly with the increase in degree of anion exchange. From these results, anions near the edge of the interlayers appear to have been preferentially replaced by Co(CN)63− at a low degree of anion exchange, whereas those at some distance from the edge were replaced only at a high degree of anion exchange. The adsorption capacity of the Co(CN)63−-exchanged sample for hydrocarbons was: hexane ≃ 2-methylpentane ≫ cyclohexane > methylcyclohexane. The adsorption of chain hydrocarbons and cyclic hydrocarbons was different.
Adsorption of Water by Homoionic Exchange Forms of Wyoming Montmorillonite (SWy-1)
Authors: Hall Peter L. , Astill Douglas M.
Published: August 2006

Adsorption isotherms for water on homoionic (Ca2+, Li+, Na+, and K+) exchanged forms of Crook County, Wyoming, montmorillonite (CMS Source Clay SWy-1) were measured between 25° and 70°C using a vacuum microbalance having automated control of water vapor pressure. From these adsorption data, integral enthalpies and entropies of adsorption were calculated. Both quantities were negative, but decreased in magnitude with increasing amounts of adsorbed water. For all four cationic forms of the clay, the amount of initial water adsorption at 25°C and at low relative humidities was sensitive to the sample temperature during prior evacuation of water, less water being adsorbed by samples evacuated at 100°C compared with samples evacuated at 25°. For Ca- and Na-montmorillonite, these changes were reversible after several subsequent desorption/adsorption cycles, but recovery was not observed for the Li-SWy-1 clay, probably because of migration of Li+ into the aluminosilicate structure.
A First-Order Markov-Chain Model of Zeolite Crystallization
Authors: Hawkins Daniel B.
Published: August 2006

A method using a finite, first-order Markov chain is presented to estimate rate constants for zeolite formation from experimental nuclear magnetic resonance (NMR) data on the abundance of different silica oligomers. An experimental design is suggested by which this method can be implemented. The method uses weighted least squares to estimate transition probabilities from aggregate NMR data. Rate constants, equilibrium constants, and free energies of elementary zeolite-forming reactions can be estimated. Hypothetical zeolite-forming reactions can also be modeled. An example of modeling, using hypothetical data, shows how zeolite formation can result from reactions involving mainly silica cyclic tetramers.
Oxidation of 1,2- and 1,4-Dihydroxybenzene by Birnessite in Acidic Aqueous Suspension
Authors: McBride M. B.
Published: August 2006

The rate and extent of oxidation of dihydroxybenzenes (DHB) to quinones in acetate-buffered suspensions of synthetic birnessite were studied using Mn dissolution to monitor reaction progress. Concentration of free Mn2+ in the aqueous phase was continuously monitored by electron spin resonance, and ultraviolet-visible (UV-VIS) spectroscopy was utilized to quantify dihydroxybenzene and quinone concentrations. Although dissolution of the oxide and release of Mn2+ to solution generally accompanied phenol oxidation, a threshold oxidation level had to be exceeded before Mn2+ appeared in solution. Once this threshold was surpassed, the mole quantity of Mn2+ dissolved equaled the mole quantity of organic oxidized for 1,4-DHB, but exceeded the quantity of organic oxidized for 1,2-DHB. Thus, the latter phenol was more efficient in dissolving the oxide. Soluble phosphate suppressed Mn2+ release without influencing the degree of organic oxidation, suggesting that phosphate chemically interacted with reduced Mn to hinder its dissolution. UV spectra provided tentative evidence for the transitory existence of Mn3+-1,4-DHB complexes in the solution phase.

Infrared spectra of the birnessite after reaction with 1,4-DHB indicated some new features, which may have been a result of the reduction of surface Mn atoms to the 3+ oxidation state. These features were not present after reaction with 1,2-DHB, confirming that the latter phenol efficiently dissolved the oxide to release Mn2+. Although the initial Mn dissolution was very rapid and was attributed to a surface reaction, further slow Mn release accompanied by more complete oxidation of the phenols suggests a process limited by the rate of dissolution of the solid.
Illite/Smectite from Gulf Coast Shales: A Reappraisal of Transmission Electron Microscope Images
Authors: Ahn Jung Ho , Peacor Donald R.
Published: August 2006

Transmission electron microscope (TEM) images of mixed-layer illite/smectite (I/S) from Gulf Coast shales obtained earlier by the authors have been reexamined by comparing them with the calculated images of G. D. Guthrie and D. R. Veblen. Ordered two-layer periodicity was not detected in the 1750- and 2450-m depth samples, for which X-ray powder diffraction (XRD) showed 20% and 40% illite randomly interstratified in I/S, respectively. Two-layer periodicities that occur in images of the 5500-m depth sample were inferred to reflect ordered I/S. XRD data for the same sample imply the presence of 80% illite in RI-ordered I/S. The two-layer periodicities were observed in slightly overfocused images, consistent with the image calculations of Guthrie and Veblen, with strong dark fringes inferred to correspond to smectite interlayers. Two-layer periodicities were observed only in small domains of a few of the images, consistent with the requirement of special orientation of layers, which varies continuously over a wide range. The lack of more frequent observations of ordered periodicities in TEM images may reflect the lack of the special observation conditions and chemical heterogeneity of illite and smectite layers. Ordered mixed-layering may exist in those specimens for which XRD indicates such ordering, in contrast to the previous interpretation of the authors.
Electronic State of Iron Complexes in the Interlayer of Hydrotalcite-Like Materials
Authors: Idemura Satoshi , Suzuki Eiichi , Ono Yoshio
Published: August 2006

Infrared and Mössbauer spectroscopic studies were made on hydrotalcite-like materials, Mg6Al2(OH)16(NO3)2·4H2O, anion exchanged in aqueous solution of K3Fe(CN)6, K4Fe(CN)6·3H2O, or Na2Fe(CN)5NO·2H2O. The material anion-exchanged in aqueous solution of K3Fe(CN)6 gave infrared (IR) absorption bands at 2120 and 2040 cm-1 in the C≡N stretching region, suggesting that part of the ferrate(III) complex was reduced to ferrate(II) complex on the intercalation chiefly because pure K3Fe(III)(CN)6 and K4Fe(II)(CN)6·3H2O gives bands at 2120 and 2040 cm-1, respectively. On the intercalation of Fe(CN)64-, no change in the oxidation state of iron was observed. These features were confirmed by Mössbauer spectroscopy. In the IR spectra of material anion-exchanged in aqueous solution of Na2Fe(CN)5NO·2H2O, the intensity of bands due to N≡O (1940 cm-1) and C≡N stretching was much less than that observed for Na2Fe(CN)5NO·2H2O, indicating that most of N≡O ligand was eliminated during the intercalation. Four bands were observed in the C≡N stretching region: a band at 2143 cm-1 was assigned to C≡N groups in Fe(CN)5NO2-; a band at 2120 cm-1 was tentatively assigned to Fe(CN)5H2O2-; bands at 2040–2050 cm-1 were assigned to Fe(CN)5H2O3-.
High-Resolution Transmission Electron Microscopy and Electron Diffraction of Mixed-Layer Illite/Smectite: Experimental Results
Authors: Veblen David R. , Guthrie George D. , Livi Kenneth J. T. , Reynolds Robert C.
Published: August 2006

High-resolution transmission electron microscopy (HRTEM) and electron diffraction experiments have been performed on R1 and R> 1 illite/smectite (I/S) samples that from X-ray powder diffraction (XRD) experiments appear to contain well-ordered layer sequences. The HRTEM images confirmed earlier computer image simulations, which suggested that periodicities due to I/S ordering can be imaged in TEM instruments of moderate resolution. The experiments also confirmed that in instruments of this sort, the strongest contrast arising from the compositional difference between I and S layers occurs under rather unusual imaging conditions of strong overfocus. Some selected-area electron diffraction (SAD) patterns showed additional diffraction spots consistent with R1 and R3 ordering. SAD patterns and cross-fringes arising in HRTEM images from non-00lreciprocal lattice rows indicated that the stacking vectors of most adjacent 2:1 layers were not randomly oriented with respect to each other. Thus, the I/S was not fully turbostratic, but instead consisted of very thin, coherently stacked crystallites that extended across the fundamental particles postulated by Nadeau and coworkers.

S/(I + S) ratios were determined for about seventy HRTEM images obtained and interpreted by three different TEM operators. These ratios were consistent with those obtained from standard XRD procedures, suggesting that results obtained by XRD can be used to infer the initial structural state of mixed-layer I/S prior to treatment of samples for XRD experiments. The HRTEM experiments thus demonstrated that the two specimens examined consisted of ordered I/S existing as small crystals, most of which contained more layers than the fundamental particles of Nadeau and coworkers. The non-turbostratic stacking suggests an energetic interaction between the individual fundamental particles, leading to at least two alternative thermodynamic descriptions of these materials. Although the I/S crystals in the present experiments probably were disaggregated into fundamental particles during sample preparation for XRD, the I/S crystals appear to have separated only along the smectite interlayers. If the term “fundamental particle” is to be used for primary, untreated I/S, its original definition should be modified to include not only free particles, but also those that occur as layers within small crystals. It further should be recognized that these particles can interact thermodynamically and crystallographically with their neighbors.
Morphological, Chemical, and Isotopic Evidence for an Early Diagenetic Evolution of Detrital Smectite in Marine Sediments
Authors: Clauer Norbert , O'Neil James R. , Bonnot-Courtois Chantal , Holtzapffel Thierry
Published: August 2006

Mineralogical (XRD), morphological (transmission electron microscopy), chemical (major, rare-earth elements, and scanning-transmission electron microscopy), and isotope (Sr, O, H) measurements were made of marine detrital smectite from shales to study their reactions during early diagenesis. Albian, Aptian, and Palaeogene smectite samples were selected from Deep Sea Drilling Project drill cores taken in the Atlantic Ocean and from outcrops and drill cores from Belgium and northern France. Detrital, fake-like smectite particles seem to have adapted to their depositional environment by isochemical dissolution and subsequent crystallization of authigenic, lath-like particles. The major-element and rare-earth element compositions of both types of particles are similar. The Sr isotope chemistry suggests that the dissolution-crystallization process occurred soon after deposition in an almost closed chemical system. Except for slight changes in the amount of Fe and the oxygen isotope composition, the reaction took place without noticeable chemical exchange with the interstitial or marine environment. Such closed-system recrystallization of clay minerals may be a common diagenetic process if the water/rock ratio is small, as in shales.