bluuebunny/crossref_metadata_2025_split huggingface dataset:
Characterization of Hydrothermal Tobelitic Veins from Black Shale, Oquirrh Mountains, Utah
Authors: Wilson Paula N. , Parry W. T. , Nash W. P. 
Published: August 2006

AbstractHydrothermal tobelitic phyllosilicates modeled as ISII (R3) ordering with a minimum of 2–3% and a maximum of 6–8% interstratified smectite occur in veins and as replacement of fossils in hydrothermally altered black shale. These heavy metal-rich phyllosilicate veins formed during a Mesozoic-aged, regional-scale hydrothermal event that affected an area which encompasses the Mercur Au district (Wilson and Parry, 1990a, 1990b). Associated minerals include kaolinite, quartz, chlorite, Fe-oxides, I/S (R1, 45% smectite), and pyrite. N and O contents of NH4 phyllosilicates determined by microprobe analysis range from 0.19 to 1.78 and 48.6 to 52.9 elemental wt. %, respectively. Infrared absorption analysis indicates N occurs as NH4+. Very high O analyses are probably caused by contamination with kaolinite. A representative structural formula for the tobelitic material is [(NH4)0.36K0.36Na0.03]-(Al1.91Mg0.13Fe0.03)(Si3.21Al0.79)O10(OH1.88F0.12).Correlation plots of data from microprobe analyses indicate an atypically high correlation between interlayer charge and octahedral layer charge and no correlation between (K+Na) and N. More typical correlations between N and (K+Na) and between interlayer charge and tetrahedral layer charge are obtained if 2–8% of a beidellitic smectite are factored out of the analyses. This amount of smectite is consistent with modeling of X-ray diffraction data using the computer program NEWMOD (Reynolds, 1985).Possible sources of NH4 are from introduction by hydrothermal fluids or from thermal degradation of organic matter prevalent within the host rocks during low-grade metamorphism. The occurrence of NH4 phyllosilicate veins in unoxidized shale and the limited occurrence of NH4 phyllosilicates within the host shales suggests a hydrothermal source for the NH4.
Further Investigations on the Rehydration Characteristics of Rectorite
Authors: Kawano Motoharu , Tomita Katsutoshi 
Published: August 2006

AbstractThe rehydration and rehydroxylation properties of homoionic rectorites (saturated with Ca2+, Mg2+, Na+, or K+) were further investigated. The rehydration properties of the rectorite were characterized as follows: (1) basal spacings of rehydrated materials after heating above 500°C changed to 22.5 Å for H2O-complexes, 26.85 Å for ethylene glycol-complexes, and 27.65 Å for glycerol-complexes; (2) rehydrated Ca- and Mg-materials exhibited single layer hydrates at <50% RH, and rehydrated K-material showed double layer hydrates at 80% RH; (3) IR absorption spectra due to rehydrated H2O and OH exhibited the same or very close absorption intensities and frequencies to each other; (4) DTA-TGA curves of rehydrated materials indicated that the amount of rehydrated H2O approached about 4.2 wt. %, and about one-half of OH was rehydroxylated after heating at 800°C; and (5) interlayer cations of expandable layer components became non-exchangeable after heating above 500°C. These results suggest the following rehydration mechanism of rectorite: the interlayer cations migrate into the hexagonal holes of the SiO4 network by thermal dehydration. The cations migrated below 400°C easily return to the interlayer space and their original hydrated configurations have been recovered completely on rehydration. However, those migrated above 500°C are fixed to the hexagonal holes but water molecules are regained in the interlayer space. Consequently, electrostatic effects of interlayer cations on formation of water molecule layers are considerably reduced.
Crystallochemical Study of a Population of Particles in Smectites from a Lateritic Weathering Profile
Authors: Petit S. , Prot T. , Decarreau A. , Mosser C. , Toledo-Groke M. C. 
Published: August 2006

AbstractIn the copper deposit of Salobo 3A (Brazil), nontronite-like clay samples were found at the bottom of the weathering blanket. Samples were fractionated first by sedimentation and then by a HGMS method. From XRD data, it was found that the samples are essentially smectite with kaolinite in very small quantities. The average structural formula of the smectite, presented in the traditional manner, is:

Chemical analyses show that the smectite samples contain a population of clay particles whose chemistry ranges between a nontronite end-member and an Al-Mg beidellite end-member.Spectroscopic studies by FTIR, Mössbauer, and ESR show that the three major octahedral cations (Al, Fe, Mg) are present in each octahedral sheet of the smectite, forming a solid solution, and that the chemical trends of the smectite clay detected at a “macroscopic” scale (associated clay particles) can also be observed at the unit cell scale.
Solid-State Intercalation of Naphthalene and Anthracene into Alkylammonium-Montmorillonites
Authors: Ogawa Makoto , Shirai Hidenori , Kuroda Kazuyuki , Kato Chuzo 
Published: August 2006

AbstractIntercalation of naphthalene and anthracene into alkyltrimethylammonium (CnH2n+1(CH3)3N+; n = 8, 12, 14, 16, and 18)-montmorillonites was carried out by novel solid-solid reactions at room temperature. Octyltrimethylammonium(C8)-montmorillonite did not form an intercalation compound with either naphthalene or anthracene. Naphthalene was intercalated into both dodecyltrimethylammonium(C12)- and octadecyltrimethylammonium(C18)-montmorillonites to give intercalation compounds. On the other hand, the solid-solid reaction between dodecyltrimethylammonium(C12)- or tetradecyltrimethylammonium(C14)-montmorillonite and anthracene gave only partly intercalated compounds while hexadecyltrimethylammonium(C16)- and octadecyltrimethylammonium(C18)-montmorillonites gave single phase intercalation compounds. The hydrophobic interactions between alkylammonium-montmorillonites and the aromatic compounds are thought to be the driving force for the solid-state intercalation. The extent of the increase in the basal spacing may also be involved in the different reactivity.
Clay Dispersion and Hydraulic Conductivity of Clay-Sand Mixtures as Affected by the Addition of Various Anions
Authors: Frenkel H. , Levy G. J. , Fey M. V. 
Published: August 2006

AbstractThe effect of anions on clay dispersion and the hydraulic conductivity (HC) of clay-sand mixtures has received little attention. This study investigates the effect that adding small amounts of anions has on the dispersivity and HC of reference clays. Mixtures of 3 and 6 g 100 g−1 kaolinite, smectite, and illite with quartz sand were packed in columns. The columns were saturated with Ca and then leached with 1 molc m−3 of one of the following organic and inorganic Na salts: chloride, hydroxide, EDTA, silicate, citrate, formate, oxalate, hexametaphosphate, orthophosphate, tartrate, or humate. Changes in HC and clay concentration in the effluent were measured and clay dispersion was evaluated as a function of the various anions added. In the kaolinite clay-sand mixtures, a significant amount of clay was observed in the effluent for all anions tested, and the HC increased above its original value. The HC of smectite clay-sand mixtures decreased following the addition of the various anions. Dispersed clay appeared in the effluent only upon addition of citrate or hexametaphosphate. In the latter two cases, the HC started to increase once maximum clay concentration appeared in the effluent. Clay concentration in the effluent of smectite was one order of magnitude lower than that of kaolinite. Illite clay-sand mixtures showed dispersion behavior intermediate between smectite and kaolinite but behaved in the same way as kaolinite with respect to HC changes.
Dithionite as a Dissolving Reagent for Goethite in the Presence of Edta and Citrate. Application to Soil Analysis
Authors: Rueda Elsa H. , Ballesteros María C. , Grassi Reynaldo L. , Blesa Miguel A. 
Published: August 2006

AbstractA synergistic effect of reductant and complexant is observed in the dissolution of goethite by dithionite and citrate or EDTA. The rate data are interpreted using the surface complexation approach to describe the interface of the reacting oxide. Adsorption of both S2O42− (D) and complexant (L) generates three surface complexes that define the dissolution behavior: ≡ Fe-D, ≡ Fe-L, and dimeric
surface complexes. The initial rate increases at lower pH values because of increased surface complexation conditional formation constants. At pH values below 4, however, the fast decomposition of S2O42− gives rise to a rapid depletion of reductant, and total dissolution is not observed. It is shown that for best analytical results in soil analysis, EDTA is a better complexant than citrate; the iron extracted in one dithionite-EDTA treatment at pH 5–6, under N2 at 315 K is not increased by increasing the number of extractions, and is equivalent to the total extractable iron found by previous procedures.
Low Temperature Experimental Investigation of the Effect of High pH Naoh Solutions on the Opalinus Shale, Switzerland
Authors: Chermak J. A. 
Published: August 2006

AbstractBatch reactor experiments were performed at 150°C, 175°C, and 200°C to determine the effect of high pH NaOH solutions on the mineralogy of the Opalinus shale. In these experiments, the change in solution quench pH at 25°C, solution composition, and mineralogy were monitored as a function of time for up to ≈40 days. Runs were performed in 50 ml titanium hydrothermal reactor vessels. Each reactor was charged with 0.5–5.0 g of the 80–200 mesh size fraction of Opalinus shale, and 25 ml of solution (0.1 and 0.01 M NaOH). The general sequence of reaction products observed under these high pH conditions include first the formation of analcime, followed by vermiculite, and finally Na-rectorite formation.
Formation of Allophane and Beidellite during Hydrothermal Alteration of Volcanic Glass Below 200°C
Authors: Kawano Motoharu , Tomita Katsutoshi 
Published: August 2006

AbstractExperimental alteration of volcanic glass has been carried out in distilled water at 200°C and 150°C. The formation and transformation processes of alteration products have been examined by scanning electron microscopy (SEM), transmission electron microscopy (TEM), X-ray powder diffraction (XRD), infrared absorption analysis, and X-ray photoelectron spectroscopy. SEM and TEM clearly show that amorphous aluminum-silicate coatings with allophane particles precipitate on the surface of volcanic glass during the earliest alteration stage. Noncrystalline flaky and/or fibrous materials are formed from the allophane aggregates and from the amorphous coatings as new reaction products. The flaky and/or fibrous materials curl inward and transform into 100–500 nm circular smectite. The Al/Si atomic ratio of 1.09 for allophane decreases progressively to 0.65 for smectite through 0.86 for noncrystalline transitional material. The smectite has d(06) spacing of 1.497 Å and consists mainly of Si, Al, and small amounts of Fe, Ca, and Na.
Adsorption of Cations on Imogolite and their Effect on Surface Charge Characteristics
Authors: Harsh James B. , Traina S. J. , Boyle J. , Yang Ying 
Published: August 2006

AbstractNoncrystalline aluminosilicates termed allophane and imogolite are common constituents of spodosols, soils derived from volcanic ash, and many inceptisols. The surface charge characteristics of their synthetic analogues may be used to better understand their ion retention properties. In this study, we determined the point of zero salt effect (PZSE) by potentiometric titration of allophanes with Al/Si ratios of 1.12, 1.52, and 2.04 and of imogolite with an Al/Si ratio of 2.02. We also used microelectrophoresis to determine the point of zero charge (PZC) at the particle shear plane for the same materials in CI solutions of Li, Na, Cs, and tetramethyl ammonium. The PZSE decreased with decreasing Al/Si ratio for the allophanes, but the imogolite PZSE was much lower than that of the allophane with 2.04 Al/Si. The PZC was always higher than the PZSE of the same material, especially for imogolite. The results are best explained if cations reside within the hollow tubes of imogolite. This conclusion is supported by a fluorescence study that showed that only quenchers smaller than the inner diameter of the imogolite tube could fully quench Ce-imogolite.
Adsorption and Spectroscopic Studies on the Interactions of Cobalt(III) Chelates with Clays
Authors: Kaneyoshi Masami , Yamagishi Akihiko , Tanaguchi Masahiro , Aramata Akiko 
Published: August 2006

AbstractThe interactions of the following three kinds of racemic and enantiomeric cobalt(III) chelates with montmorillonite and saponite are studied: [Co(en)3]3+ (en = ethylenediamine), [Co(diNOsar)]3+ (diNOsar = (1,8-dinitro-3,6,10,13,16,19-hexaazabicyclo[6,6,6]-eicosane)cobalt(III))and [Co(diAMsar)]3+ (diAMsar = (1,8-diamino-3,6,10,13,16,19-hexaazabicyclo-[6,6,6]eicosane)-cobalt(III)). At neutral pH, these complexes are adsorbed as a trivalent cation up to 90%–100% of the cation exchange capacity of a clay. No difference is observed in the maximum adsorption amount between the racemic and enantiomeric isomers. The basal spacings of the clay-chelate adducts are determined by the X-ray diffraction measurements of non-oriented powder samples: 14.3 Å for [Co(en)3]3+ montmorillonite, 16.5 Å for [Co(diNOsar)]3+ montmorillonite, and 16.9 Å for [Co(diAMsar)]3+ montmorillonite. The results imply that the chelates form a monolayer in the interlayer space. From the one-dimensional Fourier analyses of the diffraction pattern of [Co(diNOsar)]3+ montmorillonite, the chelate is concluded to be adsorbed with its three-fold symmetry axis in parallel with the layer surface. This is in contrast with the previous results of [Ru(phen)3]2+ and [Ru(bpy)3]2+, which are adsorbed with their three-fold symmetry axes perpendicular to the surface. The conclusion is consistent with the angular dependence of the infrared absorption spectrum of the film of the adduct.
Boxwork Fabric of Halloysite-Rich Kaolin Formed by Weathering of Anorthosite in the Sancheong Area, Korea
Authors: Jeong Gi Young , Kim Soo Jin 
Published: August 2006

AbstractBoxwork fabric in which numerous thin or thick halloysite walls are interconnected into a microscopically porous cellular pattern is widely developed in the halloysite-rich kaolin formed by weathering of anorthosite in Sancheong, Korea. Studies using optical microscopy, scanning electron microscopy, and transmission electron microscopy have been carried out in order to elucidate the detailed features and origin of the boxwork.In the early stage of weathering, halloysite spheres formed in etch pits on the walls of microstructural discontinuities in the slightly weathered rock. With further weathering, the halloysite spheres grew to discs or flattened globules, which in turn coalesced to form large planar halloysite plates amid narrow fissures. The halloysite plates were detached by dissolution of the plagioclase in groundwater. Continued growth of the halloysite tubes in the plates resulted in the wrinkling of the plates. Finally, the plagioclase was completely dissolved by groundwater, leaving the boxwork of wrinkled halloysite walls and large pores. The relatively high rigidity of the boxwork is due to the compact agglomeration of halloysite tubes within the wrinkled halloysite walls.Cation balance calculation shows that Al was significantly mobilized during the formation of the boxwork in the weathering environment. The well-developed microfissures, the high dissolution rate of the calcic plagioclase, and the rapid flow of groundwater in a mountainous topography with relatively steep (20°) slope have been the factors controlling the formation of the porous boxwork in the halloysite-rich kaolin of the Sancheong area.
Development of Ammonium-Saponites from Gels with Variable Ammonium Concentration and Water Content at Low Temperatures
Authors: Kloprogge J. Theo , Breukelaar Johan , Jansen J. Ben H. , Geus John W. 
Published: August 2006

AbstractAmmonium-saponite is hydrothermally grown at temperatures below 300°C from a gel with an overall composition corresponding to (NH4)0.6Mg3Si3.4Al0.6O10(OH)2. The synthetic saponite and coexisting fluid have been characterized by means of X-ray powder diffraction, X-ray fluorescence, Induced Coupled Plasma-Atomic Emission Spectroscopy, thermogravimetric analysis, transmission electron microscopy, CEC determination using an ammonia selective electrode, and pH measurement. In the crystallization model developed, crystallization started with the growth of individual tetrahedral layers with an aluminum substitution not controlled by the A1IV/A1VI ratio in the gel and hydrothermal fluid, on which the octahedral Mg layers can grow. During the synthesis, individual sheets stacked to form thicker flakes while lateral growth also took place. The remaining A1VI partly replaced ammonium as the interlayer cation.
Comparison of I/S Transformation and Maturity of Organic Matter at Elevated Temperatures
Authors: Velde B. , Lanson B. 
Published: August 2006

AbstractComparing the state of reaction advancement of I/S (illite content of illite/smectite mixed layer minerals) and organic matter (vitrinite reflectance) in instances of high temperature gradients allows one to observe the evolution of geologic materials under extreme conditions. In a geothermally heated sedimentary series (Salton Sea area, California), both clays and organics have reacted to completion in the temperature gradient range of 200°-400oC/km during heating episodes of 104 years. We observed an instance of rapid heating, through magmatic intrusion into the Meso-Paleozoic eastern Paris Basin sedimentary series in late Permian time, which induced changes in the organic material, but where clays are apparently unaffected.
Implications of Linearly Correlated Oxygen and Hydrogen Isotopic Compositions for Kaolinite and Illite in the Magnus Sandstone, North Sea
Authors: Fallick A. E. , Macaulay C. I. , Haszeldine R. S. 
Published: August 2006

AbstractAuthigenic kaolinite and illite are important diagenetic minerals in the Magnus Sandstone, a giant oil reservoir in the northern North Sea. These clay minerals, separated from three wells, show considerable ranges in their oxygen isotopic composition (δ8OSMOW = +9 to + 16%) and hydrogen isotopic composition (δDSMOW = - 55 to - 105%). The variations in δ18O and δD are positively linearly correlated with a high degree of statistical significance for both kaolinite and illite:Kaolinite:n=12;δD=6.1δ18O−169;r=0.66(>95%)Illite:n=11;δD=5.9δ18O−159;r=0.78(>99%).Formation of the clays in a pore fluid of uniform isotopic composition over a range of temperatures appears unlikely. It is suggested that the observed relationships between clay mineral δ18O and δD are perhaps best explained by a model of precipitation at more or less constant temperature from pore fluids which varied isotopically across the oilfield. The isotopic composition of the formation waters would then lie along the line: δDw = 6.2 δl8Ow - 50. This is most plausibly interpreted as a mixing line with suggested minimal endmembers at (δ18O, δD) values of (+4, -24) and (-4, -76). The first of these represents reasonable isotopic values for Magnus Sandstone formation waters. Although δ18O of the second is compatible with an evolved Cretaceous meteoric water, its δD value is difficult to understand in the context of the model.
Changes in Particle Morphology During Illitization: An Experimental Study
Authors: Whitney Gene , Velde Bruce 
Published: August 2006

AbstractSmectite was reacted at several temperatures between 200°C and 500°C to produce interstratified illite/smectite (I/S) with different proportions of expandable layers. Dispersed and sedimented products were examined using a transmission electron microscope. Particle size and aspect ratio showed no systematic change as a function of reaction extent during R0 illitization. However, particles exhibited rounded edges during the early stages of the reaction, suggesting some dissolution of primary smectite. Additionally, increasing particle contrast in the electron beam suggests thickening of particles with increasing reaction extent. The thickening of particles is thought to be produced by the nucleation and precipitation of secondary illite layers on primary smectite layers. In the most extensively reacted I/S, particles have become aggregated into clumps or quasicrystals by lateral growth of illite layers. Internal uniformity of crystallographic alignment of individual growing crystals within each aggregate was reflected in the increasing frequency of 60° and 120° interfacial angles within each aggregate. In highly illitic I/S, these aggregates took on an overall euhedral form and became crystallographically contiguous, producing single crystal electron diffraction patterns.
Rietveld Refinement and Fourier-Transform Infrared Spectroscopic Study of the Dickite Structure at Low Temperature
Authors: Bish David L. , Johnston Clifford T. 
Published: August 2006

AbstractThe full structure of dickite from St. Claire, Pennsylvania, including hydrogen atoms, was refined in space group Cc using time-of-flight neutron powder diffraction data obtained at 12 K and Rietveld refinement/difference-Fourier methods (Rwp = 2.62%, reduced χ2 = 1.915, 113 variables, a = 5.1474(6)Å, b = 8.9386(10)Å, c = 14.390(2)Å, and ß = 96.483(1)°). The non-hydrogen structure is essentially identical to published structures for dickite, but the hydrogen positions are distinct. The inner hydroxyl group is approximately parallel to the (001) plane, inclined by 1.3° towards the tetrahedral sheet. Contrary to published low-temperature infrared (IR) spectra, there is no evidence that dickite possess lower symmetry at low temperatures although there is tentative evidence for statistical occupancy of H3 on more than one site. Low-temperature IR spectra of St. Claire and Wisconsin dickites do not show evidence for more than four hydroxyl groups and are consistent with the reported structure. Upon cooling from 300 to 15 K, the position of the OH3 stretching band increased from 3710 to 3731 cm−1. This large, positive shift in frequency was attributed to the increase in the internuclear O-H3 ⋯ O distance upon cooling. The frequency of the 3655 cm−1 band initially decreased by 2 cm−1 to 3653 cm−1 upon cooling from 300–125 K; however, the band increased in frequency by 1 cm−1 upon further cooling to 15 K. This unusual change in frequency upon cooling is consistent with the assignment of this band to OH2 and OH4. The position of the OH1 stretching band decreased from 3622 to 3620 cm−1 upon cooling, which was attributed, in part, to the observed increase in the Al-O(H1)-Al angle at low temperature.
The Surface Coulomb Energy and Proton Coulomb Potentials of Pyrophyllite {010}, {110}, {100}, and {130} EDGES
Authors: Bleam William F. , Welhouse Gereon J. , Janowiak Mark A. 
Published: August 2006

AbstractThis paper describes structural models of four pyrophyllite edge faces: {010}, {110}, {100}, and {130}. Water molecules chemisorbed to Lewis acid sites stabilize edge faces both crystallochemically and electrostatically. The detailed assignment of protons to surface oxygens and the orientation of OH bond-vectors both influence the surface Coulomb energy.The geometry chosen for the electrostatic calculations was infinite pyrophyllite ribbon the thickness of a single phyllosilicate layer and the width of 50 to 70 unit cells. Such a phyllosilicate ribbon has only two edges, a top and bottom, which were simulated using the edge-face models mentioned above. About 94% of the surface Coulomb energy is confined to the edge-face repeat unit. The surface Coulomb energies of the four edge faces are on the order of 2–3 nJ/m, varying ± 1 nJ/m with proton assignment. The Coulomb potential, measured either within the layer or parallel to the layer, has a distinct negative trend near the edge face that can be traced to chemisorbed water molecules. Finally, the correlation between proton Coulomb potentials at the edge face and the coordination environment of the protons is poor, obscured by long-range interactions.