bluuebunny/crossref_metadata_2025 huggingface dataset:
Kaolinization of Bauxite: A Study in the Vlasenica Bauxite Area, Yugoslavia. I. Alteration of Matrix
Authors: Dangić Adam
Published: September 2006

The kaolinization of bauxite has generally been thought to be a simple process of epigenetic resilification. A study of the karstic boehmitic bauxites in the Vlasenica region of Yugoslavia, however, shows that kaohnization took place in a rather complex manner, in which the alteration was caused by the percolation of siliceous water descending through the deposit by means of cracks, fissures, etc. The matrix of one such Vlasenica deposit was found to be more highly kaolinized than the oolitic fraction. Based on a mineralogical and geochemical examination of matrix material, the following pattern of zoned alteration was identified: kaolinitic zone-boehmite enrichment zone-original bauxite. In the kaolinitic zone, well-crystallized kaolinite, formed by the reaction of dissolved silica with boehmite, has replaced all other minerals in the matrix. This Si metasomatism was accompanied by an outward migration of Al and resulted in the formation of a transition zone in which new boehmite partly replaces both kaolinite and hematite (Al remobilization). A thermodynamic model of the process has been established on the basis of stability diagrams calculated for the mineral assemblages in the alteration zones and in the deposit as a whole.
Role of Structural Hydrogen in the Reduction and Reoxidation of Iron in Nontronite
Authors: Lear Paul R. , Stucki Joseph W.
Published: September 2006

The effects of reduction and reoxidation of octahedral Fe3+ on the exchange of structural hydrogen in nontronite were determined using tritium (3H) as a label element. The uptake of H from the surrounding solution of nontronite suspensions increased as the reduction of structural Fe3+ increased. Similarly, the loss of H from the structure increased as the reduction increased. The results are generally consistent with a reduction mechanism involving the loss of structural OH, leaving the affected Fe sites with less than six-fold coordination. The attenuation of increased negative charge on the clay layer, however, was less than predicted by such a mechanism.

During the reoxidation of reduced nontronite in suspension, about one-third of the H remaining as part of the structure following reduction was lost, whereas twice that amount of H was incorporated into the structure from the surrounding solution. A reoxidation mechanism is proposed whereby H2O from the surrounding solution is incorporated into the mineral structure followed by the elimination of a hydrogen ion, returning the Fe to six-fold coordination. This mechanism implies the reversibility of Fe reduction in nontronite.
Influence of Al Substitution and Crystal Size on the Room-Temperature Mössbauer Spectrum of Hematite
Authors: Murad Enver , Schwertmann Udo
Published: September 2006

Mössbauer spectra of 15 hematites with Al substitutions between 0 and 10 mole % were taken at room temperature. X-ray powder diffraction indicated dimensions of these hematites in the c-direction to range upwards from 27 nm to crystals large enough to show no line broadening. The Mössbauer spectra showed that magnetic hyperfine fields decreased both with increasing Al-for-Fe substitution and with decreasing crystal size. These relationships indicate that hyperfine field variations cannot, as has been done in the past, be unequivocally related to Al substitution alone. Hyperfine field reductions were paralleled by Mössbauer line broadening due to hyperfine field distributions. Only the hematites heated to 1000°C showed a significant variation of quadrupole splittings with Al substitution. No dependence of quadrupole splitting on crystal size was observed, indicating no detectable distortion of coordination polyhedra in the particle size range studied.
Hydrothermal Synthesis and Characterization of Cobalt Clays
Authors: Bruce Linda A. , Sanders John V. , Turney Terence W.
Published: September 2006

Reaction of mixtures of cobalt nitrate, colloidal silica, and a metal hydroxide (MOH) under hydrothermal conditions produced a range of cobalt hydroxysilicates, the components of which depended upon the identity of M, temperature, and reactant ratios. At 250°C, if M = Na, a smectite of composition Na0.06Co3.07Si3.95O10(OH)2 (I) was produced. If M = K, either a mica, KCo2.5Si4O10(OH)2 (II), intermediate between di- and trioctahedral, or a Si-deficient mica, KCo3Si3.75O10(OH)2 (III), was formed depending upon the reactant ratios. Similarly, if M = Cs, either a vermiculite or a 2:1 layer silicate intermediate between a mica and a brittle mica was produced. If M = Li, only the non-clay mineral Li2CoSiO4 was formed. Tetraalkylammonium hydroxides (NR4OH, R = methyl, ethyl, or propyl) yielded chrysotile. All phases were characterized by elemental analysis, transmission electron microscopy, and X-ray powder diffraction. Further characterization of smectite I was undertaken by diffuse reflectance, infrared, and X-ray photoelectron spectroscopy. The layer charge in these clays appears to stem from cation vacancies within an almost trioctahedral sheet and, possibly, within the tetrahedral sheets. Some of the cobalt present had tetrahedral coordination geometry, but its location was not determined.
Influence of Citric and Tannic Acids on Hydroxy-Al Interlayering in Montmorillonite
Authors: Goh Tee Boon , Huang P. M.
Published: September 2006

The formation of hydroxy-Al-interlayered montmorillonite was affected by complexing organic acids. Montmorillonite (<2.0 μm) was aged for three months at an initial pH of 5.0 or 6.0 in AlCl3 solutions containing citric or tannic acid at organic acid/Al molar ratios from 0 to 1.0. The Al/clay ratio in the system was 900 meq Al3+/100 g of montmorillonite. Ion-exchange experiments revealed that organically complexed Al ions have both positive and negative charges. Evidence from X-ray powder diffraction, electron microscopic examination, measurements of specific surface, cation-exchange capacity, organic carbon, and the nature of sorbed Al indicates that citric and tannic acids influence differently the hydroxy-Al interlayer formation in montmorillonite. Hydroxy-Al-citrate can be adsorbed as interlayers in montmorillonite, but hydroxy-Al-tannate exists principally as a separate phase binding the clay particles. The differences observed between the influence of citric and tannic acids on Al interlayering are probably due to their differences in molecular weight (size) and structure.
Electron Microscopic Investigations of Iron Oxyhydroxides and Accompanying Phases in Lateritic Iron-Crust Pisolites
Authors: Amouric M. , Baronnet A. , Nahon D. , Didier P.
Published: September 2006

Pisolites from an iron crust in western Senegal were studied by conventional and high-resolution electron microscopy to determine their internal structure and the genetic processes that led to their formation. Each pisolite consisted of a concentric structure of hematite rimmed by goethite. Two types of goethite were distinguished: (1) large (≃ 0.6 μm long and 0.06 μm wide), euhedral laths arranged in fibrous aggregates of slightly misoriented grains devoid of internal defects as shown by their two-dimensional lattice images, and (2) a matrix of smaller (≃400 Å), anhedral grains surrounded by the larger laths. Based upon the crystal habit and the presence or absence of internal alveoles, the large goethite laths probably grew at the expense of the matrix goethite. Poorly crystalline kaolinite, presumably formed from well-crystalline precursor kaolinite, and clusters of partially dissolved quartz grains were also imaged. In addition, two uncommon phases were found—maghemite in topotactic relationship with hematite and a layered, Fe-rich, mica-like mineral with a 2M superstructure. Unlike kaolinite, this latter phase was likely in equilibrium with iron oxyhydroxides. Substituted Al probably was released during goethite recrystallization, and mass transfers probably took place through the heterogeneous porosity (i.e., large voids and cracks coupled with fine pores) revealed by transmission electron microscopy.
Expansion of Smectite by Laurylamine Hydrochloride: Ambiguities in Transmission Electron Microscope Observations
Authors: Lee Jung Hoo , Peacor Donald R.
Published: September 2006

Treatment of smectite with laurylamine hydrochloride was verified to cause expansion of d(001) which may be retained and observed in ion-milled samples by transmission electron microscopy. The spacings between layers as observed in lattice fringe images, however, are variable and may be as small as 10 Å. The method therefore produces ambiguities in differentiating between some smectites and illites, similar to those that have been found for untreated samples; e.g., on this basis, expanded layers may be inferred to be smectite, but layers with d-values approaching 10 Å may be either illite or smectite. Expansion also destroys the original rock texture, which, therefore, must be observed using only untreated samples.
Lysis of Erythrocytes by Silicate Minerals
Authors: Oscarson D. W. , Van Scoyoc G. E. , Ahlrichs J. L.
Published: September 2006

In vitro studies of the destruction (lysis) of bovine red blood cells (erythrocytes) by some silicate minerals showed the reaction to be complete in less than 1 hr and very destructive to the cell membrane. The activity as lysing agents was found to be in the order smectites > silica > palygorskite ≃ sepiolite > chrysotile > kaolinite. Different compositions (Fe, Al, Mg, Li, vacancy) of the octahedral sheet of the smectite and fibrous clay minerals did not appreciably alter their hemolytic activity. The most active particle size range for kaolinite and montmorillonite was 0.2-2 μm. Structural folding of palygorskite reduced lysis suggesting that edge surfaces and silanol groups are important in this process. Aluminum oxides and hydroxides caused no lysis, and coatings of positively charged aluminum-hydroxy polymers on montmorillonite, silica, palygorskite, and kaolinite significantly reduced lysis.
Acidic Properties of Montmorillonite in Selected Solvents
Authors: Loeppert R. H. , Zelazny L. W. , Volk B. G.
Published: September 2006

Montmorillonites saturated with Al3+, H+-Al3+, and K+ were titrated in H2O, acetonitrile (AN), and dimethylformamide (DMF) to investigate the acidic properties of the clay in these solvents and to evaluate the application of nonaqueous titration procedures for studies of the acidic properties of 2:1 swelling clays. Samples were titrated with tetramethylammonium hydroxide using a combination glass electrode for Potentiometric determination. Titers of base required to reach the final Potentiometric endpoints were greater in AN than in DMF and H2O. The larger titers in AN compared to H2O were attributed to pH-dependent sites for which an inflection was not observed in the latter solvent. Titration curves of Al-saturated montmorillonite in AN showed evidence of a salt-induced hydrolysis which was confirmed by titration curves of salt extracts. The hydrolysis reaction was more evident in AN than in H2O and was probably due to a disruption of the H2O structure by AN and a polarization of the H2O of solvation. The hydrolysis reaction was enhanced in the presence of excess salt due to the ion exchange of H+ from the exchange surface. These studies indicate that acidic properties of clays may be drastically altered in organic solvents. The acidic properties may be used to advantage, for example, in the determination of edge-site acidity. In addition, they have implications concerning possible chemical reactions and/or alterations of clay in organic solvents.
Multiple Cation-Exchange Capacity Measurements on Standard Clays Using a Commercial Mechanical Extractor
Authors: Jaynes W. F. , Bigham J. M.
Published: September 2006

Sequential cation-exchange capacity (CEC) measurements were obtained from standard clays using a mechanized, variable-rate leaching device. The device consists of a motorized screwjack and as many as 24 leaching tubes coupled to 60-ml plastic syringes. Controlled withdrawal of the syringe plungers produces a vacuum that permits samples in the leaching tubes to be extracted at a uniform rate. A single, 8-hr leaching of clays with 35 ml of salt solution was found to be comparable to multiple saturations or displacements using a centrifuge. CECs consistent with published values were obtained for reference 2:1 clay minerals using both acetate and chloride salts of Na, Ca, and Mg. Potassium-exchange capacities were also successfully measured following in situ thermal treatment of samples in the leaching tubes. Variations in measured CECs for kaolin-group minerals due to salt intercalation were minimized by using chloride rather than acetate salts and by washing with a dilute aqueous solution of the saturating cation following initial saturation. The mechanical extractor significantly reduced the effort required to perform conventional CEC determinations without sacrificing analytical precision.
Mixed-Layer Illite/Smectite Minerals in Tertiary Sandstones and Shales, San Joaquin Basin, California
Authors: Ramseyer Karl , Boles J. R.
Published: September 2006

The southern San Joaquin Valley contains more than 7 km of sedimentary fill, largely Miocene and younger in age. Ancient depositional environments ranged from alluvial fans at the basin margins to turbidite fans toward the basin center. Mixed-layer illite/smectite (I/S) dominates the <2-μm fraction of Miocene shales, and kaolinite is abundant in Miocene sandstones. I/S from carbonate-cemented sandstones contains 5–20% more smectite layers than I/S from uncemented sandstones. The timing of cementation correlates with the proportion of smectite layers in the I/S, suggesting that cementation slowed the illitization process. Smectite and I/S with > 80% expandable layers occur at present burial temperatures of 120°-l 40°C in Miocene sandstones and shales. This highly expandable I/S is restricted to areas covered by thick deposits (1000-2500 m) of Pleistocene sediments. Rocks of similar age and at equivalent temperatures, but covered by <900 m of Pleistocene sediments, contain I/S having low expandabilities (<30%).

Microprobe analyses of 16 discrete smectite and smectite-rich I/S clays indicate an average montmorillonite composition of:
$$\left( {C{a_{0.2}}{K_{0.15}}N{a_{0.1}}} \right)\left( {A{l_{3.0}}F{e^{3 + }}_{0.35}M{g_{0.75}}T{i_{0.03}}} \right)\left( {S{i_{7.7}}A{l_{0.3}}} \right){O_{20}}{\left( {OH} \right)_4} \cdot n{H_2}O.$$ Smectite in I/S-rich clays of Gulf Coast shales has a similar composition except for lower octahedral Al/ Fe ratios (Al/FeVI = 3.1), compared with the San Joaquin samples (Al/FeVI = 8.6).

Residence time at different temperatures appears to be an important influence on the percentage of smectite layers in I/S from the San Joaquin basin. Areas containing I/S with high expandabilities (e.g., 95% smectite layers) have a time-temperature index (TTI) of 4.0-4.5 at 120°C, whereas areas containing I/S with low expandabilities (e.g., 30% smectite layers) have a TTI of 5.0. Present data suggest that highly expandable I/S changed to slightly expandable I/S over a narrow temperature interval (10°-20°C). Differences in the potassium availability from detrital components and in the K+/H+ activity ratios of pore water do not appear to be related to the differences in the percentage of smectite layers of these I/S clays.
Pathways of Smectite Illitization
Authors: Bethke Craig M. , Vergo Norma , Altaner Stephen P.
Published: September 2006

Junction probability diagrams show variation in both composition and layer arrangement in mixed-layer clay minerals. These diagrams can represent short-range and long-range ordered, random, and segregated interstratifications. Mineralogical analyses of illite/smectite from shale cuttings, bentonites, and hydrothermally altered tuffs define characteristic reaction pathways through these diagrams. Shale and bentonite analyses fall along pathways joining smectite and illite on diagrams showing nearest-neighbor (R1) layer arrangements. Transition from random to R1-ordered interstratifications occurs in shale samples containing 60–70% illite layers, and in bentonites containing 55–67% illite layers. Analyses of alteration products, however, fall near a line connecting rectorite and illite, which represents the maximum degree of R1 layer ordering. No mineralogical evidence is available to suggest that these alteration samples formed from a smectite precursor. All samples develop next-nearest (R2) and thrice-removed (R3) neighbor ordering along similar pathways. Transition to R2 ordering occurs gradually in samples composed of 65–80% illite layers, and samples containing more than 85% illite layers may show strong R3 ordering.
High-Resolution Imaging of Ordered Mixed-Layer Clays
Authors: Klimentidis Robert E. , MacKinnon Ian D. R.
Published: September 2006

High-resolution transmission electron microscopy (HRTEM) has been used to examine illite/smectite from the Mancos Shale; rectorite from Garland County, Arkansas; illite from Silver Hill, Montana; Na-smectite from Crook County, Wyoming; corrensite from Packwood, Washington; and diagenetic chlorite from the Tuscaloosa Formation. Thin specimens were prepared by ion milling, ultramicrotome sectioning, and/or grain dispersal on a holey carbon substrate. Some smectite-bearing clays were also examined after intercalation with dodecylamine hydrochloride (DH). Intercalation of smectite with DH proved to be a reliable method for HRTEM imaging of expanded smectite (d (001) = 16 Å) which could then be distinguished from unexpanded illite (d (001) = 10 Å). Lattice fringes of basal spacings of DH-intercalated rectorite and illite/smectite showed a 26-Å periodicity. These data support X-ray powder diffraction (XRD) studies which suggest that these samples are ordered, interstratified varieties of illite and smectite. The ion-thinned, unexpanded corrensite sample showed discrete crystallites containing 10-Å and 14-Å basal spacings corresponding to collapsed smectite and chlorite, respectively. Regions containing disordered layers of chlorite and smectite were also noted. Crystallites containing regular alternations of smectite and chlorite layers were not common. These HRTEM observations of corrensite did not corroborate XRD data. Particle sizes parallel to the c axis ranged widely for each sample studied, and many particles showed basal dimensions equivalent to more than five layers. For all illite, smectite, and illite/ smectite particles examined, crystallite sizes of about 20 Å in the basal dimension were not observed.
Magnetic Ordering At 4.2 And 1.3 K in Nontronites of Different Iron Contents: A 57Fe Mössbauer Spectroscopic Study
Authors: Cardile C. M. , Johnston J. H. , Dickson D. P. E.
Published: September 2006

The 57Fe Mössbauer spectra of six nontronite samples were measured at appropriate temperatures of 4.2 and 1.3 K. Three of the nontronites gave a complex magnetic hyperfine spectrum showing magnetic ordering at 4.2 K, and the other three required a lower temperature of 1.3 K to produce similar magnetic ordering. The spectra were computer-fitted with three closely overlapping sextets which are considered to arise from: (1) Fe3+ that is ordered magnetically in the cis-octahedral sites with a greater number of neighboring tetrahedral Fe3+ ions (51 T); (2) the cis-octahedral site with the greater number of neighboring Si4+ ions (46 T); and (4) the tetrahedral sites (41 T). In an untreated sample a further sextet corresponding to interlayer Fe3+ (36 T) was identified. The magnetic ordering was complicated and not directly related to the iron content of these sites. It probably depended also on the overall composition and structural order of the particular nontronite. The ordering appears to have been essentially two-dimensional, consistent with the layer structure of this material.
Dehydration of K-Exchanged Montmorillonite at Elevated Temperatures and Pressures
Authors: Koster van Groos A. F. , Guggenheim Stephen
Published: September 2006

The dehydration temperature of K-montmorillonite, obtained by ion exchange of a Na-mont-morillonite, was determined at pressures to 2 kbar, using high-pressure differential thermal analysis. Dehydration reactions were found at about 50° and 100°C above the liquid-vapor curve of water. At pressures above the critical point of water the dehydration temperatures increased only slightly. The temperature of the first dehydration reaction is 10°C higher than for Na-montmorillonite, indicating a slightly greater stability of the hydration shell around the potassium interlayer cation. The second dehydration reaction occurs at a slightly lower temperature. The data were used to determine the enthalpy of the dehydration ΔH(dh) and the bonding enthalpy of the interlayer water ΔH(iw) at 1 atm. The first dehydration reaction of the K-exchanged montmorillonite has a ΔH(dh) = 46.16 ± 0.06 kJ/mole and a ΔH(iw) = 7.8 ± 0.5 kJ/mole, whereas for the second reaction, ΔH(dh) = 56.7 ± 2 kJ/mole and ΔH(iw) = 19.8 ± 2 kJ/mole. These values compare with a ΔH(dh) = 46.8 ± 0.3 kJ/mole and a ΔH(iw) = 7.8 ± 0.5 kJ/mole for the first dehydration reaction of the Na-montmorillonite and a ΔH(dh) = 62.9 ± 2 kJ/mole and ΔH(iw) = 27.1 ± 2 kJ/mole for the second dehydration.
Reactions of the Conjugated Dienes Butadiene and Isoprene Alone and with Methanol Over Ion-Exchanged Montmorillonites
Authors: Adams J. M. , Clapp T. V.
Published: September 2006

The reactions of simple conjugated dienes over divalent and trivalent transition metal-exchanged montmorillonites yield, in the absence of nucleophiles, a variety of products. Some of these products are a result of Diels-Alder cycloaddition reactions, whereas others are indicative of carbocation intermediates, i.e., other dimers, oligomers, and isomerization products of these intermediates. The reactions in sealed cells between 20° and 150°C show trends in the yields of the various product groups. Dimers of butadiene and isoprene formed by cycloaddition (i.e., 4-vinylcyclohexene and the monoterpene p-menthadiene (limonene)) were formed at low temperatures (20–50°C). As the temperature was raised, the total yield of dimers increased and higher oligomers were formed along with isomerization products of the dimers and oligomers. The products of cycloaddition, however, did not increase markedly. The type of solvent used for the reaction was found to influence the reactivity, e.g., the use of 1,4-dioxan rather than chloroform led to a reduction in total conversion and also to a markedly higher degree of selectivity. In the presence of a suitable nucleophile (methanol), both dienes gave the 1,4-addition product predominantly, which suggests that an allylic carbocation intermediate was involved. The use of an interlayer-supported nickel complex, [HNi(P(OEt)3)4]+, produced the only large scale polymerization observed in this work.
Mössbauer Spectroscopic Study of the Iron Mineralogy of Post-Glacial Marine Clays
Authors: Torrance J. Kenneth , Hedges Sheila W. , Bowen Lawrence H.
Published: September 2006

Three post-glacial marine clays from eastern Canada and one marine clay from Japan have been studied by Mössbauer spectroscopy to ascertain their iron mineralogy. Small amounts of hematite (in two samples) and magnetite (in one sample) were found in the Canadian clays, and hematite was detected in the Japanese clay. The major spectral components were ferrous and ferric doublets, consistent with X-ray powder diffraction results that show chlorite, mica, and amphibole in the Canadian samples and smectite in the Japanese sample. Citrate-dithionite extraction removed hematite and most of the magnetite from these samples. Acid-base extraction also removed chlorite and some mica from the Canadian samples. Samples treated by these extractions had appreciably lower geotechnical yield stresses at given water contents.
Expandable Phyllosilicate Reactions with Lithium on Heating
Authors: Lim C. H. , Jackson M. L.
Published: September 2006

A method using Li saturation and heating to 250°C to differentiate montmorillonite from beidellite and nontronite has been developed. The test utilizes three washings with 3 M LiCl and two washings with 0.01 M LiCl in 90% methanol to prevent dispersion. An 'infinitely thick’ sample (6–8 mg/cm2) on a glass slide is used to avoid the effects of the reaction of a thin clay film with sodium of the slide when it is heated at 250°C. Solvation with glycerol rather than ethylene glycol is used, because all of the Li smectites studied expanded to some extent in ethylene glycol after the heating. The smectites included several montmorillonites, a nontronite, and saponites. The presence of interstratified montmorillonite and beidellite layers was clearly shown by the test for several smectite samples, including the so-called beidellites from Beidell, Colorado, and Chen-yuan, Taiwan, and several soil clays. The test thereby provides more mineralogical information than the often-used arbitrary dividing point between montmorillonite and beidellite at 50% tetrahedral charge. Heating the Li-saturated clays at 250°C caused substitution of 35 to 125 meq/100 g of nonexchangeable Li. These amounts exceeded the changes in cation-exchange capacity plus Li by 4 to 21 meq/100 g, except for the end-member beidellite from the Black Jack mine, Idaho. Fusion with LiNO3 at 300°C could not be used to differentiate between smectites instead of washing with LiCl solution and heating to 250°C, because fused montmorillonite subsequently expanded to 18 Å with glycerol. Large increases in nonexchangeable Li were caused by the fusion of smectites, a vermiculite, and two partially expanded micas.
The Lorentz-Polarization Factor and Preferred Orientation in Oriented Clay Aggregates
Authors: Reynolds R. C.
Published: September 2006

A closed-form equation was derived that describes the powder-ring distribution factor as a function of 2θ, soller slit collimation, and σ*, which is defined as the standard deviation of an axially symmetrical Gaussian orientation function. Methods were developed for measuring σ* in the reflection mode by means of a θ/2θ diffractometer. Six experimental arrangements for a sedimentary chlorite showed widely different intensity ratios of the 001/005 reflections and gave a standard deviation of ±5.8% when corrected by the theory. The absolute integrated intensities of the 003 reflection from eleven illite samples provided an eight-fold maximum range which, when corrected, yielded a standard deviation of ±7.7%.

The intensity distributions within each of two X-ray powder diffraction patterns obtained from instruments with different soller-slit configurations could not be directly compared at low diffraction angles unless corrections, based on σ*, were introduced to allow for the differences in axial divergence.
Ordered Interstratification of Dehydrated and Hydrated Na-Smectite
Authors: Moore D. M. , Hower John
Published: September 2006

The 001 spacing of Na-smectite was found to vary from 9.6 Å at 0% relative humidity (RH) to 12.4 Å at 60-65% RH. The 9.6-Å spacing corresponds to dehydrated Na-smectite, and the 12.4-Å corresponds to Na-smectite with one water layer. A regular series of intermediate values resulted from ordered interstratification of the 9.6- and 12.4-Å units. Ordered interstratification was confirmed by the presence of a 001 spacing of 9.6 + 12.4 Å = 22 Å. This peak appeared under experimental conditions at about 35% RH. It appeared for calculated simulations of ordered stacking of 50/50 mixtures (±10%) of 9.6- and 12.4-Å units. The 004 peak of this 22-Å spacing interacted with the 002 of the 9.6-Å spacing of ordered mixtures of more than 50% 9.6-Å units and with the 002 of the 12.4-Å spacing of ordered mixtures of more than 50% 12.4-Å units. The result of this interaction was a complex peak, the position of which was a function of the ratio of 9.6- and 12.4-Å units. This complex peak was noted for experimental and for calculated conditions. Calculated tracings assuming ordered stacking matched the experimental tracings closely, whereas those assuming random stacking did not.

Ordering was apparently due to the interaction of the positive charge of the interlayer cation repelling the positive charge of the hydrogens of the hydroxyl ions, one above and one below, closest to the interlayer space. The collapse of a single interlayer space (dehydration) brought the interlayer cation closer to the hydrogens of the hydroxyls causing the hydroxyls to rotate such that the hydrogens shifted toward the adjacent interlayer spaces. Collapse of these two interlayer spaces was therefore more difficult. This same mechanism helps explain ordering in illite/smectite. The difference is that hydration/dehydration is quick and reversible, whereas the change from smectite to illite is slow and irreversible.
Relationship Between Illite/Smectite Diagenesis and Hydrocarbon Generation in Lower Cretaceous Mowry and Skull Creek Shales of The Northern Rocky Mountain Area
Authors: Burtner Roger L. , Warner Maurice A.
Published: September 2006

The percentage of expandable layers in illite/smectite (I/S) mixed-layer clay decreases with increasing temperature and depth in a section through marine Cretaceous shales in the Champlin 1 Hartley Federal well in the Powder River basin, Wyoming. This systematic change in I/S expandability is evidence that low-expandable I/S in Cretaceous shales of the northern Rocky Mountain area reflects, at least in part, thermal alteration during burial diagenesis. In eastern Montana and western North Dakota where I/S in the Lower Cretaceous Mowry and Skull Creek source rocks is diagenetically unaltered, only trace amounts of hydrocarbons have been found in the Lower Cretaceous and other Cretaceous sandstones. Elsewhere in the northern Rocky Mountain-Great Plains region, hydrocarbons in the Lower Cretaceous Muddy Sandstone and its equivalents occur within or immediately adjacent to areas in which I/S clay in the Mowry and Skull Creek shales has been diagenetically altered during burial. Altered I/S and thermally mature organic matter, as defined by Rock-Eval pyrolysis values, coexist in these source rocks. Both may be used as maturation indicators in the search for Cretaceous-source hydrocarbons in the northern Rocky Mountain area.
Composition of Some Smectites and Diagenetic Illitic Clays and Implications for their Origin
Authors: Nadeau P. H. , Bain D. C.
Published: September 2006

Chemical analysis by X-ray fluorescence (XRF) and calculated structural formulae of clay-size fractions of smectites from Cretaceous bentonites and illitic clays from Cretaceous, Devonian, and Ordovician bentonites and Jurassic and Permian sandstones indicate the nature and extent of various types of ionic substitution. The determination of tetrahedral (Al, Si) and octahedral (Al, Mg, Fe) composition shows the variable chemistry of these materials. Structural formulae of the illitic clays show that they have tetrahedral charges between 0.4 and 0.8 per half unit cell, and can be divided into phengitic types having octahedral charges of 0.2-0.4 and muscovitic types having octahedral charges <0.2. Evaluation of the formulae in the light of X-ray powder diffraction (XRD) and transmission electron microscopy (TEM) data shows that the occupancy of non-exchangeable interlayer sites (predominantly K) varies from 47% to 90% of that of ideal muscovite. In some minerals as much as 20% of these sites is occupied by ammonium ions (determined independently). The amount of surface silicate charge balanced by non-exchangeable cations versus that balanced by exchangeable cations has been examined in conjunction with TEM data and suggests that in most samples the charges are about equal. The octahedral composition of smectites in Cretaceous bentonites precludes their having served as transformation precursors for most of the Cretaceous illitic bentonites. The results suggest that these illitic clays originated by neoformation.
K/Ar Systematics of Bentonite and Shale in a Contact Metamorphic Zone, Cerrillos, New Mexico
Authors: Aronson James L. , Lee Mingchou
Published: September 2006

To test the ability of illitic clay minerals to retain argon, K/Ar ages were measured on grain-size separates from the Cretaceous Mancos Shale and associated bentonites that have been transformed into K-bentonite near the contact with a large Tertiary igneous stock. The ages of size separates of illite/ smectite from the K-bentonite nearest the contact were internally concordant and matched the hornblende K/Ar age of the stock. In contrast, K/Ar data from clay size fractions from shales adjacent to each K-bentonite were internally discordant with measured ages that were much greater than the age of the intrusion. Thus, significant radiogenic argon was retained by fine-grained detrital illite, even in shale samples very near the igneous contact. These results are convincing evidence that illitic clay minerals are excellent K/Ar clocks under conditions prevailing in sedimentary and diagenetic environments.
Vanadium Chlorite from a Sandstone-Hosted Vanadium-Uranium Deposit, Henry Basin, Utah
Authors: Whitney Gene , Northrop H. Roy
Published: September 2006

An unusual vanadium chlorite precipitated during the formation of a vanadium-uranium ore deposit in the Henry Basin, southeastern Utah. The ore deposit formed by reduction and precipitation of U and V in the presence of organic matter at the interface between a stagnant brine and overlying, circulating meteoric water. Some samples of the vanadium chlorite (heated before analysis) contain ≥ 10% V2O5. In fresh samples, most of the vanadium is in the trivalent oxidation state. X-ray powder diffraction data suggest that Fe and V are concentrated preferentially in the interlayer hydroxide sheets of the chlorite. A d(060) value of 1.52 Å indicates that the chlorite probably has a dioctahedral structure which is distended by the presence of octahedral Fe and V. The vanadium ore zone is flanked by peripheral zones containing perfectly ordered chlorite/smectite. This chlorite/smectite contains much less V than the pure chlorite. This chlorite may have formed by the progressive precipitation of vanadium-rich interlayer hydroxide sheets in the mixed-layer chlorite/smectite in the most reducing portion of the ore zone. The pure chlorite is a IIb polytype, which, for nonvanadiferous analogs, is ordinarily found in high-temperature environments; however, no evidence exists to show that these rocks have ever been exposed to elevated temperatures. In fact, the presence of unreacted smectite in a potassium-rich setting and the low vitrinite reflectance of coalified plant debris indicate a low-temperature history for these sediments.
The Nature of Vermiculite in Adirondack Soils and Till
Authors: April Richard H. , Hluchy Michele M. , Newton Robert M.
Published: September 2006

The clay and bulk mineralogy of soil and till from 26 Adirondack watersheds was studied. The materials consist typically of quartz, K-feldspar, plagioclase, mica, vermiculite, and kaolinite. Talc, smectite, halloysite, and hornblende are present in some samples. The clay fraction of the soils is composed predominantly of vermiculite, likely derived from the transformation of a mica precursor, and kaolinite. The soil vermiculite commonly contains hydroxy-Al interlayers which are especially prevalent in the B-horizon samples. Despite significant variation in the type of bedrock and the composition of heavy mineral assemblages in these watersheds, the clay mineralogy is remarkably uniform. This finding supports earlier suggestions that the occurrence of vermiculite in soils is more dependent on climate than on the nature of the parent material.
Supergene Vermiculitization of A Magnesian Chlorite: Iron and Magnesium Removal Processes
Authors: Proust Dominique , Eymery Jean-Paul , Beaufort Daniel
Published: September 2006

An X-ray powder diffraction study of a vermiculitized chlorite in an amphibole schist near Limoges, France, shows the following weathering sequence: chlorite → ordered interstratified chlorite/vermiculite → vermiculite. Mössbauer spectroscopy indicates that vermiculitization proceeded by the release of ferrous iron from the 2:1 mica layer of the chlorite. The ferric iron content of the vermiculite product is almost the same as that of the initial chlorite. Infrared spectroscopy and chemical microprobe analyses show that Mg was preferentially extracted from the hydroxide sheet of the chlorite, whereas the Si and Al contents progressively increased to the point of the formation of a pure dioctahedral aluminous vermiculite. The Si, Al, and Mg removal processes support currently accepted vermiculitization mechanisms, but the behavior of Fe is slightly different. In this weathering sequence, vermiculitization does not appear to have taken place by the oxidation of Fe2+, but rather, by the simultaneous leaching of Fe2+ and Mg.
X-Ray Photoelectron Spectroscopic Study of the Effect of Heating on Montmorillonite Containing Sodium and Potassium Cations
Authors: Seyama Haruhiko , Soma Mitsuyuki
Published: September 2006

The effect of heating on montmorillonites containing exchangeable Na and K has been studied by X-ray photoelectron spectroscopy (XPS). The surface composition of the unheated montmorillonite was consistent with the bulk composition, but after the sample recrystallized at 1100°C, the surface abundance of Na increased, whereas that of K decreased. Because Na and K were not present in the high-temperature crystalline products, this behavior suggests that a noncrystalline material separated from the crystalline products. The Na 1s binding energy and KL23L23 Auger kinetic energy of montmorillonite were comparable with those of Na in typically ionic compound, such as NaCl. These electron energies became smaller and larger, respectively, on heating and approached those of feldspar (albite). The K 2p3/2 binding energy of montmorillonite increased slightly on heating. The K 2p3/2 binding energy of heated sample of montmorillonite was also comparable with that of feldspar (orthoclase). These results suggest that Na and K were incorporated into feldspar-like noncrystalline materials.
Current Problems with the Nomenclature of Phyllosilicates
Authors: Zvyagin B. B.
Published: September 2006

The nomenclature of phyllosilicates is discussed in relation to structural variations of layers and interlayers. Some discrepancies in the nomenclature which arose due to historical reasons and different viewpoints may be reconciled if the choice of the construction units (layers or their parts) is related to definite sets of structures for which these units are common. Features of idealized models approximating real structures should be considered for classification and derivation of nomenclature sets, whereas priority is given to structural variations before lattice and symmetry characteristics. Layer polymorphs, pseudo-polytypes, polytypes (both simple and complex), and OD structures are distinguished. Particular results obtained for micas as a model example of phyllosilicates in relation to modular structures in general are considered in an Appendix.
Quantitative X-Ray Diffraction Analysis of Clay-Bearing Rocks From Random Preparations
Authors: Środoń Jan , Drits Victor A. , McCarty Douglas K. , Hsieh Jean C. C. , Eberl Dennis D.
Published: September 2006

An internal standard X-ray diffraction (XRD) analysis technique permits reproducible and accurate calculation of the mineral contents of rocks, including the major clay mineral families: Fe-rich chlorites + berthierine, Mg-rich chlorites, Fe-rich dioctahedral 2:1 clays and micas, Al-rich dioctahedral 2:1 clays and micas, and kaolinites. A single XRD pattern from an air-dried random specimen is used. Clays are quantified from their 060 reflections which are well resolved and insensitive to structural defects. Zincite is used as the internal standard instead of corundum, because its reflections are more conveniently located and stronger, allowing for a smaller amount of spike (10%). The grinding technique used produces powders free of grains coarser than 20 µm and suitable for obtaining random and rigid specimens.

Errors in accuracy are low, <2 wt. % deviation from actual values for individual minerals, as tested on artificial shale mixtures. No normalization is applied and thus, for natural rocks, the analysis is tested by the departure of the sum of the measured components from 100%. Our approach compares favorably with other quantitative analysis techniques, including a Rietveld-based technique.
Microtextures and the Origin of Muscovite-Kaolinite Intergrowths in Sandstones of the Utrillas Formation, Basque Cantabrian Basin, Spain
Authors: Arostegui Javier , Irabien María Jesús , Nieto Fernando , Sangüesa Javier , Zuluaga María Cruz
Published: September 2006

Muscovite-kaolinite intergrowths found in Albian sandstones of the Basque Cantabrian basin (northern Spain) were studied by optical, scanning and electron microscopy and electron microprobe analysis. Kaolinitization begins at grain edges, forming the characteristic fanned-out textures, and propagates toward the interior along the cleavages of muscovite. Kaolinite and muscovite occur as thick packets, being free of interlayering. Phase boundaries between both minerals show bidimensional crystallographic continuity, and no intermediate phases have been identified. The data obtained suggest that muscovite only supplied a template suitable for the epitactic crystallization of kaolinite, while Al was available in sufficient amounts due to the dissolution of detrital K-feldspar. Very small packets of magnetite or maghemite showing a coherent orientation with the kaolinite crystals have been recognized, and could be responsible for the small Fe contents usually detected in electron microprobe analyses of kaolinite.

Textural relationships between authigenic kaolinite and deformation microstructures in the intergrowths, combined with previous information about burial conditions, show that alteration proceeded during a late stage of the diagenetic history, related to the uplift of the studied materials as a result of the Alpine orogeny.
Mineralogy of Dickite and Nacrite From Northern Taiwan
Authors: Chen Pei Yuan , Wang Ming Kuang , Yang Deng Shiu
Published: September 2006

Nacrite and dickite are found in two localities in northern Taiwan. One, containing nacrite and dickite, is associated with a gold-enargite deposit as a vug-filling clay in the Chinkushih (CKS) mine district near the northern coast. The other is the occurrence of dickite in the interstices of a Miocene coarse-grained quartzose sandstone in the Nanshihchiao (NSC) area, near Taipei city. X-ray diffraction (XRD), differential thermal analysis (DTA), scanning electron microscope (SEM), and petrographic examinations were used to characterize the mineralogical features. Nacrite most often takes the unusual form of rhombic platelets, and dickite is commonly elongated in habit with the shapes possibly related to their origin. Based on geological evidence, we believe that both nacrite and dickite are of hydrothermal origin. In the CKS area, the formation of nacrite and dickite is related to the hypogene gold-enargite mineralization. In contrast, the transformation of dickite in the NSC area is due to the influence of the raised temperatures of sandstone formation, resulting from volcanic activity during the Kungkuan stage after the deposition of the sandstone.
Molecular Physiology of the Neural Circuit for Calcineurin-Dependent Associative Learning inCaenorhabditis elegans
Authors: Kuhara Atsushi , Mori Ikue
Published: September 2006

How learning and memory is controlled at the neural circuit level is a fundamental question in neuroscience. However, molecular and cellular dissection of the neural circuits underlying learning and memory is extremely complicated in higher animals. Here, we report a simple neural circuit for learning behavior inCaenorhabditis elegans, where the calcium-activated phosphatase, calcineurin, acts as an essential modulator. The calcineurin mutanttax-6showed defective feeding state-dependent learning behavior for temperature and salt. Surprisingly, defective associative learning between temperature and feeding state was caused by malfunctions of two pairs of directly connected interneurons, AIZ and RIA, in the mature nervous system. Monitoring temperature-evoked Ca2+concentration changes in the AIZ–RIA neural pathway revealed that starvation, a conditioning factor, downregulated AIZ activity through calcineurin during associative learning between temperature and feeding state. Our results demonstrate the molecular and physiological mechanisms of a simple neural circuit for calcineurin-mediated associative learning behavior.
Layer-Specific Touch-Dependent Facilitation and Depression in the Somatosensory Cortex during Active Whisking
Authors: Derdikman Dori , Yu Chunxiu , Haidarliu Sebastian , Bagdasarian Knarik , Arieli Amos , Ahissar Ehud
Published: September 2006

Brains adapt to new situations by retuning their neurons. The most common form of neuronal adaptation, typically observed with repetitive stimulations of passive sensory organs, is depression (responses gradually decrease until stabilized). We studied cortical adaptation when stimuli are acquired by active movements of the sensory organ. In anesthetized rats, artificial whisking was induced at 5 Hz, and activity of individual neurons in layers 2–5 was recorded during whisking in air (Whisking condition) and whisking against an object (Touch condition). Response strengths were assessed by spike counts. Input-layer responses (layers 4 and 5a) usually facilitated during the whisking train, whereas superficial responses (layer 2/3) usually depressed. In layers 2/3 and 4, but not 5a, responses were usually stronger during touch trials than during whisking in air. Facilitations were specific to the protraction phase; during retraction, responses depressed in all layers and conditions. These dynamic processes were accompanied by a slow positive wave of activity progressing from superficial to deeper layers and lasting for ∼1 s, during the transient phase of response. Our results indicate that, in the cortex, adaptation does not depend only on the level of activity or the frequency of its repetition but rather on the nature of the sensory information that is conveyed by that activity and on the processing layer. The input and laminar specificities observed here are consistent with the hypothesis that the paralemniscal layer 5a is involved in the processing of whisker motion, whereas the lemniscal barrels in layer 4 are involved in the processing of object identity.
Novel Agonist Monoclonal Antibodies Activate TrkB Receptors and Demonstrate Potent Neurotrophic Activities
Authors: Qian Ming D. , Zhang Jie , Tan Xiang-Yang , Wood Andrew , Gill Davinder , Cho Seongeun
Published: September 2006

Tyrosine kinase receptor B (TrkB) mediates neurotrophic effects of brain-derived neurotrophic factor (BDNF) to increase neuronal survival, differentiation, synaptic plasticity, and neurogenesis. The therapeutic potential of TrkB activation using BDNF has been demonstrated well in several preclinical models of CNS diseases, validating TrkB as a promising drug target. Therefore, we aimed to develop TrkB-specific receptor agonists by using a monoclonal antibody approach. After generation of hybridoma clones and assessment of their binding and functional activity, we identified five mouse monoclonal antibodies that show highly selective binding to TrkB and that induce robust activation of TrkB signaling. Epitope mapping studies using competition analysis showed that each of the monoclonal antibodies recognizes a unique binding site on TrkB, some of which are distinct from BDNF docking sites. These antibodies behave as true agonists based on their ability to both activate proximal and secondary signaling molecules downstream of TrkB receptors and promote neuronal survival and neurite outgrowth. The binding affinities and the functional efficacy of these antibodies are comparable to those of BDNF, whereas they do not bind to the p75 low-affinity neurotrophin receptor at all. Therefore, they could represent novel reagents to explore the pathophysiological roles of TrkB and its potential therapeutic utility in treating CNS disorders.