bluuebunny/crossref_metadata_2025_split huggingface dataset:
The Effect of Unequal Ionic Size on the Swelling Pressure in Clays
Authors: Huerta Marlene M. , Curry Joan E. , McQuarrie Donald A. 
Published: August 2006

AbstractIn this paper, we use the unequal radius modified Gouy-Chapman theory to evaluate the effect of the ionic size of the electrolyte on the swelling pressures (II) in different clay systems immersed in electrolytic solutions. First the model is applied to a 1:1 electrolyte to show that the coion size is only important at surface charge densities much lower than those found in typical clay systems. The swelling pressure is calculated and the results are compared with experimental data. Literature ionic radii values are used to show the dependence of the swelling pressure on the specific counterions present. Next the model is applied to a 1:1 and 2:1 electrolyte mixture with unequal-sized counterions to show the swelling pressure is highly dependent on both counterion sizes. The unequal and same-sized cases are compared.
Reactions between Clay Volatiles and Calcite Reinvestigated
Authors: Heller-Kallai Lisa , Miloslavski Irena 
Published: August 2006

AbstractCalcite crystals exposed to clay volatiles react with some components of these volatiles, giving rise to a variety of surface morphologies. F, Cl, and S in different proportions were detected by electron microprobe analysis of the calcite surfaces. Under identical experimental conditions, volatiles from every clay mineral examined caused a specific morphology and chemical composition of the calcite surfaces, but these varied with temperature of the calcite. Changes in pH values and mass spectra of the volatiles after passage through calcite demonstrate that even on rapid heating some clay volatile-calcite reactions occur at temperatures as low as 150°C. Species other than those detectable by electron microprobe analysis also participate in the reactions in which CO2 is liberated.
Influence of Fe(II) on the Formation of the Spinel Iron Oxide in Alkaline Medium
Authors: Jolivet J. P. , Belleville P. , Tronc E. , Livage J. 
Published: August 2006

AbstractFe(II) and Fe(III) in various proportions were coprecipitated by NH3 at pH ≈ 11. The Fe(II)/Fe(III) ratio (x) was varied from 0.10 to 0.50. After stabilization by aging at pH ≃ 8 in anaerobic conditions, hydrous precipitates were characterized by electron microscopy, Mössbauer spectroscopy, and kinetics of dissolution in acidic medium. At any x value, all stable products exhibited the structure of (oxidized) magnetite. For x ≤ 0.30, two distinct species were coexisting: the one (“m”) was made up of ca. 4nm-sized particles with a low Fe(II) content (Fe(II)/Fe(III) ≈ 0.07), and the other (“M”) consisted of particles of larger, more or less distributed sizes, and composition Fe(II)/Fe(III) ≈ 0.33; “M” increased relative amount with increasing x. For x ≥ 0.35, “M” was the only constituent and its Fe(II)/Fe(III) ratio was equal to x. “M” is identified with (nonstoichiometric) magnetite, whereas “m” is likely to be an oxyhydroxide. Mechanisms of formation are discussed, and a phase diagram is proposed which schematizes the evolution of the coprecipitation products with x and with time. Addition of Fe(II) after the precipitation of Fe(III), instead of coprecipitation, yielded very similar results.
The Interlayer Collapse During Dehydration of Synthetic Na0.7-Beidellite: A 23Na Solid-State Magic-Angle Spinning NMR Study
Authors: Kloprogge J. Theo , Jansen J. Ben H. , Schuiling Roelof D. , Geus John W. 
Published: August 2006

AbstractThe dehydration and migration of the interlayer cation of the synthetic beidellite Na0.7Al4.7Si7.3O20-(OH)4·nH2O, were studied with solid-state 23Na and 27Al MAS-NMR, heating stage XRD, and thermogravimetric analyses (TGA, DTA). The 23Na MAS-NMR of Na-beidellite at 25°C displays a chemical shift of 0.2 ppm, which indicates a configuration comparable with that of Na+ in solution. Total dehydration proceeds reversibly in two temperature ranges. Four water molecules per Na+ are gradually removed from 25° to 85°C. As a result, the basal spacing decreases from 12.54 Å to 9.98 Å and the Na+ surrounded by the two remaining water molecules is relocated in the hexagonal cavities of the tetrahedral sheet. The chemical shift of 1.5 ppm exhibited after the first dehydration stage illustrates the increased influence of the tetrahedral sheet. The high local symmetry is maintained throughout the entire first dehydration stage. During the second dehydration, which proceeds in a narrow temperature range around 400°C, the remaining two water molecules are removed reversibly without any change of the basal spacing.
Alkali Cation Selectivity and Surface Charge of 2:1 Clay Minerals
Authors: Xu Shihe , Harsh James B. 
Published: August 2006

AbstractA critical demand in environmental modeling and a desirable but elusive goal of research on the ion exchange properties of the charged solid surface has been to determine the selectivity coefficient from fundamental properties of the ions and surface. We developed a Hard and Soft Acid and Base (HSAB) Model to describe exchangeable cation selectivity on solid surfaces. Our previous work has shown that the model quantitatively describes alkali cation exchange on clay minerals in terms of the absolute electronegativity and softness of the exchangeable cations and two fitting parameters:αandβ. This study was conducted to determine the relationship betweenαandβand surface charge characteristics of 2:1 clays. The layer charge and cation selectivity of seven smectites and one vermiculite were used. The regression of log Kvoagainst four combinations of charge properties was performed and the appropriate relationship betweenα,β, and surface charge was selected based on both statistical criteria (R2) and their consistency with the assumptions of the HSAB model. The selected model was then cross-validated using separate cation exchange data from the literature. It was found thatαandβare linearly related to the amount of charge arising from mineral tetrahedral and octahedral sites, respectively. These results make it possible to predict the alkali cation selectivity of 2:1 clay minerals from their chemical composition data and the alkali cation properties.
Natural and Synthetic Copper Phyllosilicates Studied by XPS
Authors: Mosser Christine , Mosser Aimé , Romeo Michelangelo , Petit Sabine , Decarreau Alain 
Published: August 2006

AbstractX-ray photoelectron spectroscopy (XPS) has been used to characterize the bonding state of Cu2+, Si4+, Al3+, and O2− ions in structural (octahedral and interlamellar) or adsorbed position in phyllosilicates. Five smectites, 5 kaolinites, and 1 chrysocolla with Cu(II) in known positions (octahedral, interlamellar, or surface adsorbed) have been investigated. Their spectra were compared with those of pure Cu metal and of pure Cu(I) and Cu(II) oxides.The line for Cu 2p3/2 (binding energy of 935.4 eV) and well-defined shake-up lines (binding energy of about 943 eV) observed after 1 hr of X-ray irradiation are characteristic of Cu(II) in phyllosilicate octahedral sites. But due to the photoreduction effect, they show Cu(I) oxidation states (Cu 2p3/2, binding energy of 933.2 eV and near absence of shake-up lines) for the phyllosilicates with adsorbed Cu or in interlamellar positions. The kinetics of photoreduction distinguishes octahedral from interlamellar positions, and the latter from a surface adsorbed position. The enlargement of the FWHM (full width at half maximum) of XPS lines has been used to describe crystallochemical parameters linked to local ordering around the probe cations. Crystallization produces decreasing O 1 s and Cu 2p (octahedral cation) line widths but has no effect on the Si 2p (tetrahedral cation) line width. The enlargement of FWHM for all ion lines of the lattice is linked to the nature (Cu > Mg > Al) and the number and amount of structural cations in the phyllosilicates.
An Electron Optical investigation of Aluminosilicate Cements in Silcretes
Authors: Singh Balbir , Gilkes R. J. , Butt C. R. M. 
Published: August 2006

AbstractSilcretes developed within the in situ regolith in the Barr Smith Range, Western Australia, were investigated using optical and electron-beam techniques. One of the cementing agents in these silcretes showed gel-like optical properties and had a variable aluminosilicate chemical composition at the scale of electron microprobe analysis so that it might be considered as allophane-like material. High resolution transmission electron microscopy demonstrated that the material consists of a fine-grained and poorly ordered kaolinite embedded in a matrix of amorphous silica.
Three Zones for Illite Formation During Burial Diagenesis and Metamorphism
Authors: Eberl D. D. 
Published: August 2006

AbstractReinterpretation of published data for shale cuttings from the Gulf of Mexico sedimentary basin identifies three reaction zones for illite formation with increasing depth for well CWRU6. In a shallow zone (1.85 to 3 km), non-expanding illite-like layers formed primarily by the coalescence of smectite 2:1 layers around interlayer K+. In a middle zone (3 to 4 km), illite crystals neoformed from solution as coarser K-bearing phases and smectite were dissolved by organic acids. In the deepest zone (>4 km), illite recrystallized as less stable illite crystals dissolved, and more stable illite crystals grew during mineral ripening. The progressive loss of radiogenic argon in the deepest zone yielded a constant apparent age for the clays with depth, an effect previously attributed to “punctuated diagenesis.” The above hypothesis for illite formation emphasizes the need to establish the zone (i.e., the reaction mechanism) from which shales were derived before making detailed geologic interpretations based on illite mineralogy.
Quantitative Analysis of Mixtures of 1M And 2M1 Dioctahedral Micas by X-Ray Diffraction
Authors: Tettenhorst Rodney T. , Corbató Charles E. 
Published: August 2006

AbstractInvestigation of a naturally occurring mixture of dioctahedral micas prompted an examination of X-ray diffraction (XRD) techniques for obtaining quantitative estimates of 1M and 2M1 mica proportions. A method for determining quantitative estimates has been developed that includes the effect of preferred orientation of mica particles as described by the March function. A diagram is presented from which the percentage of 2Mı and the March parameter (r) can be obtained from two peak-area ratios: 2.80 Å/5.0 Å and 2.80 Å/2.58 Å, which are measured on observed XRD patterns of mica mixtures. The ability of this peak-area ratio diagram to predict reasonably accurate proportions of 1M and 2Mı micas was tested by comparing calculated and observed XRD patterns over a range of 2θ values from 16° to 40° for size-fractionated mixtures. Lack of accurate crystal-structure data for dioctahedral 1M mica proved an impediment to obtaining improved quantitative estimates of mica proportions.
Chemisorption of Benzene on Cu-Montmorillonite as Characterized by FTIR and 13C MAS NMR
Authors: Hinedi Z. R. , Johnston C. T. , Erickson C. 
Published: August 2006

AbstractSorption of benzene onto Cu-montmorillonite was characterized by Fourier transform infrared (FTIR) spectroscopy and 13C magic angle spinning nuclear magnetic resonance (MAS NMR). Under anhydrous conditions, chemisorption of benzene in the interlamellar region of Cu-montmorillonite led to the formation of a dark red surface complex that exhibited a vibrational spectrum similar to that of doped poly-p-phenylene. When the benzene sorption reaction was carried out under high relative humidity conditions, polymerization of benzene did not occur. The FTIR spectrum of the surface complex formed under wet conditions exhibited vibrational bands that could not be assigned to those of the parent benzene molecule or to those of previously observed chemisorbed Type I or Type II complexes. 13C MAS NMR spectra of 13C-enriched benzene sorbed onto Cu-montmorillonite powder showed the presence of two groups of peaks that could be assigned to aromatic and aliphatic carbon respectively.
Considerations and Applications of the Illite/Smectite Geothermometer in Hydrocarbon-Bearing Rocks of Miocene to Mississippian Age
Authors: Pollastro Richard M. 
Published: August 2006

AbstractEmpirical relationships between clay mineral transformations and temperature provide a basis for the use of clay minerals as geothermometers. Clay-mineral geothermometry has been applied mainly to diagenetic, hydrothermal, and contact- and burial-metamorphic settings to better understand the thermal histories of migrating fluids, hydrocarbon source beds, and ore and mineral formation.Quantitatively, the most important diagenetic clay mineral reaction in sedimentary rocks is the progressive transformation of smectite to illite via mixed-layer illite/smectite (I/S). Changes in both the illite/smectite ratio and ordering of I/S, as determined from X-ray powder diffraction profiles, correlate with changes in temperature due to burial depth. Although the smectite-to-illite reaction may be influenced by several factors, reaction progress appears to be strongly controlled by temperature. Studies show that the model proposed by Hoffman and Hower in 1979 is applicable in burial diagenetic settings from about 5 to 330 Ma, and includes most rocks about Miocene to Mississippian in age. Reliability of the I/S geothermometer is, however, dependent upon a good understanding of the rock's original clay-mineral composition.Changes in the ordering of I/S are particularly useful in the exploration for hydrocarbons because of the common coincidence between the temperatures for the conversion from random-to-ordered I/S and those for the onset of peak, or main phase, oil generation. Here, the utility of the I/S geothermometer is reviewed in hydrocarbon-bearing rocks of Miocene to Mississippian age. Using three common applications, the I/S geothermometer is compared to other mineral geothermometers, organic maturation indices, and grades of indigenous hydrocarbons. Good agreement between changes in ordering of I/S and calculated maximum burial temperatures or hydrocarbon maturity suggests that I/S is a reliable semiquantitative geothermometer and an excellent measures of thermal maturity.
An Experimentally Derived Kinetic Model for Smectite-to-Illite Conversion and Its Use as a Geothermometer
Authors: Huang Wuu-Liang , Longo John M. , Pevear David R. 
Published: August 2006

AbstractThe smectite-to-illite conversion during shale diagenesis has recently been used to constrain the estimate of a basin's thermal history. We have systematically investigated the kinetics for the conversion of a Na-saturated montmorillonite (SWy-1) to a mixed-layer smectite/illite as a function of KCl concentration (from 0.1 to 3 moles/liter) over a temperature range of 250° to 325°C at 500 bars in cold-seal pressure vessels using gold capsules. The results show that the conversion rate can be described by a simple empirical rate equation-dS/dt = A · exp(-Ea/RT) · [K+] · S2where S = fraction of smectite layers in the I/S, t = time in seconds, A = frequency factor = 8.08 × 10-4 sec-1, exp = exponential function, Ea = activation Energy = 28 kcal/mole, R = gas constant, 1.987 cal/deg-mole, T = temperature (degree Kelvin), [K+] = K+ concentration in molarity (M) in the fluid.The results also show that Ca2+ in solutions barely affects the illitization rate, whereas Mg2+ significantly retards the rate. The retardation, however, is not as severe as previously reported. Na+ ion can significantly retard the rate only if the concentration is high.We found that by assuming a range 0.0026-0.0052 moles/liter (100-200 ppm) of K+, concentrations similar to the value typically reported in oil field brines, the present kinetic model can reasonably predict the extent of the smectite-to-illite conversion for a number of basins from various depths and age. This narrow range of potassium concentrations, therefore, is used to model the smectite-to-illite conversion in shale when the actual chemical information of pore fluid is not available.The kinetic equation has been tested using field data from a large variety of geologic settings worldwide (i.e., the Gulf of Mexico, Vienna Basin, Salton Trough Geothermal Area, East Taiwan Basin, Huasna Basin, etc). The results show that the equation reasonably predicts the extent of the reaction within our knowledge of the variables involved, such as burial history, thermal gradients, and potassium concentration.
Chlorite Geothermometry: A Review
Authors: de Caritat Patrice , Hutcheon Ian , Walshe John L. 
Published: August 2006

AbstractChlorite minerals, found in a great variety of rocks and geological environments, display a wide range of chemical compositions and a variety of polytypes, which reflect the physicochemical conditions under which they formed. Of particular importance for studies dealing with ore deposit genesis, metamorphism, hydrothermal alteration or diagenesis is the paleotemperature of chlorite crystallization. However, in order to understand the relationship between chlorite composition and formation temperature and hence use chlorite as a geothermometer, one must determine how other parameters influence chlorite composition. These parameters may include fO2 and pH of the solution and Fe/(Fe + Mg) and bulk mineral composition of the host rock.Four approaches to chlorite geothermometry, one structural and three compositional, have been proposed in the past: 1) a polytype method based on the (largely qualitative) observation that structural changes in chlorite may be partly temperature-dependent (Hayes, 1970); 2) an empirical calibration between the tetrahedral aluminum occupancy in chlorites and measured temperature in geothermal systems (Cathelineau, 1988), which has subsequently been modified by several workers; 3) a six-component chlorite solid solution model based upon equilibrium between chlorite and an aqueous solution, which uses thermodynamic properties calibrated with data from geothermal and hydrothermal systems (Walshe, 1986); and 4) a theoretical method based on the intersection of chlorite-carbonate reactions and the CO2-H2O miscibility surface in temperature-XCO2 space, which requires that the composition of a coexisting carbonate phase (dolomite, ankerite, Fe-calcite or siderite) be known or estimated (Hutcheon, 1990). These four approaches are reviewed and the different calculation methods for the compositional geothermometers are applied to a selection of chlorite analyses from the literature. Results of this comparative exercise indicate that no single chlorite geothermometer performs satisfactorily over the whole range of natural conditions (different temperatures, coexisting assemblages, Fe/(Fe + Mg), fO2, etc.). Therefore, chlorite geothermometry should be used with caution and only in combination with alternative methods of estimating paleotemperatures.
Origin, Diagenesis, and Mineralogy of Chlorite Minerals in Devonian Lacustrine Mudrocks, Orcadian Basin, Scotland
Authors: Hillier S. 
Published: August 2006

AbstractChlorite and corrensite are common clay minerals in lacustrine mudrocks from the Devonian Orcadian Basin, Scotland. The relationship of their occurrence to vitrinite reflectance data demonstrate that they are authigenic minerals, formed during burial diagenesis/metamorphism at temperatures of ≥120°C. Whole rock mineralogical and chemical analyses show that chlorite authigenesis occurred by reactions between the detrital dioctahedral clay mineral assemblage and dolomite that was formed under early evaporitic conditions in the lacustrine environment.XRD and electron microprobe analyses indicate that phases intermediate between corrensite and chlorite are probably mixed-layer chlorite/corrensite with a tendency towards segregation of layer types. Chemically, the conversion of corrensite to chlorite involves an increase in Al for Si substitution in tetrahedral sites, but there is no change in the Fe/Mg ratio of octahedral cations. There is also no relationship of mixed-layer proportions to paleotemperature; only a general paleotemperature interval of approximately 120° to 260°C in which a range of phases between corrensite and chlorite occurs. Chlorite polytypes are exclusively IIb, indicating the formation of this polytype at diagenetic temperatures.The occurrence of corrensite and Mg-rich chlorite in evaporite and carbonate successions is probably a reliable indicator of diagenetic alteration at temperatures of ≥ 100°C. Burial diagenetic reactions between dioctahedral clay minerals and Mg-rich carbonates may possibly explain many occurrences of corrensite and Mg-rich chlorite in such rocks.
Chlorite Polytype Geothermometry
Authors: Walker Jeffrey R. 
Published: August 2006

AbstractSince the initial studies of chlorite polytypes, it has been suggested that the stability of the various polytypes may be a function of the temperature at which the mineral formed; however, few studies have been performed in which polytypes of chlorite in a specific suite of samples have been determined and correlated with temperature. A review of the reported occurrences of type I chlorite indicates that other factors, including grain size of the host rock, may be at least as important as temperature in controlling the stability of these polytypes. Results of systematic studies in areas of diagenesis and very low-grade metamorphism suggest that type-II chlorite is stable at temperatures well below 200°C and that it can form as the initial chlorite phase without passing through any intermediate polytypic stages. The conditions under which type-I polytypes occur are somewhat restricted, and cognizance of those restrictions will help to direct future studies of chlorite polytype transformations. These studies should focus on the structural details of polytype transformations; on the relationship of polytype stability to pressure, composition and kinetics; and on experimental calibration of the transformations.
Dimepiperate Adsorption and Hydrolysis on Al3+-, Fe3+-, Ca2+-, and Na+-Montmorillonite
Authors: Pusino A. , Liu W. , Gessa C. 
Published: August 2006

AbstractThe adsorption of the herbicide dimepiperate S-(α;α-dimethylbenzyl)-1-piperidinecarbothioate on homoionic Fe3+-, Al3+-, Ca2+-, and Na+-montmorillonite was studied in aqueous medium. The adsorption is described well by the Freundlich equation. The adsorption capacity decreases in the order Fe3+ > Al3+ > Ca2+ > Na+ clay. The dimepiperate adsorption from chloroform solution was also investigated by analytical, spectroscopic, and X-ray powder diffraction techniques. IR results suggest that the adsorption involves the interaction of the thioester carbonyl group of dimepiperate possibly with the surrounding water of metal ions. On Al3+ and Fe3+ clays, this interaction leads to hydrolysis of the thioester bond and formation of the thiol and carbamic acid derivatives that yield α-methylstyrene and piperidine, respectively.