bluuebunny/crossref_metadata_2025_split huggingface dataset:
Hydrothermal Effects on Cesium Sorption and Fixation by Clay Minerals and Shales
Authors: Komarneni Sridhar , Roy Della M. 
Published: September 2006

AbstractThe effects of hydrothermal conditions on the sorption and fixation of cesium by various clay minerals and shales were investigated. Hydrothermal heating, which may be expected in a radioactive waste repository, altered the clay minerals and shales and led to a decrease in their cation-exchange capacity. Cesium sorption greatly decreased in micaceous vermiculite and in well-crystallized illites containing vermiculite upon hydrothermal treatment at 400°C and 300 bars pressure due to complete layer collapse. However, poorly crystallized illites heated as above showed either a small increase or only a slight decrease in Cs sorption because of partial layer collapse. These studies show that the decrease in Cs sorption is greater in well-crysallized illites than in poorly crystallized illites when treated similarly under hydrothermal conditions. Hydrothermal heating of Cs-sorbed and Cs-saturated samples increased the amount of Cs fixation in all minerals and shales as a result of collapse of the layers. For example, a sample of the Conasauga shale fixed only 18% of sorbed Cs before treatment but fixed 47% after hydrothermal treatment at 200°C and 300 bars pressure. Thus, hydrothermal conditions in a shale repository may be beneficial after leaked radioactive Cs ions are taken up by clay minerals in shales.
The Influence of Aluminum on Iron Oxides. VI. The Formation of Fe(II)-Al(III) Hydroxy-Chlorides, -Sulfates, and -Carbonates as New Members of the Pyroaurite Group and Their Significance in Soils
Authors: Taylor R. M. , McKenzie R. M. 
Published: September 2006

AbstractIn the absence of oxygen, Fe(II) chloride, sulfate, and carbonate solutions react at pH 6.5 to 7 with aluminum hydroxide suspensions to form new Fe(II)-Al(III) hydroxy anion compounds of the pyroaurite group. The Fe(II)-Al(III) hydroxy-chloride and -sulfate compounds are isostructural with Fe(II)- Fe(III) “green rust” compounds with A1 essentially substituting for Fe(III). Where CO32- is the only anion in the system, an Fe(II)-Al(III) compound isostructural with hydrotalcite is formed. Either in the dried or wet state, these compounds are unstable in air due to oxidation of Fe(II). Oxidation of the dried sample in air yields akaganeite or aluminous ferrihydrite, whereas, if the sample is maintained in a moist condition and oxidized by air under water, lepidocrocite or aluminous goethite is produced along with small amounts of ferrihydrite. On X-ray powder diffraction, the lepidocrocite so formed commonly shows no diagnostic (020) basal reflection, or one with a markedly reduced intensity. The products of oxidation, and the rapidity of their formation, appear to be dependent on the composition of the initial double hydroxy compound and the conditions under which the oxidation is carried out.The green colored compounds commonly observed in gleyed soils also rapidly become yellow brown on exposure to air, and difficulty arises in the identification of the Fe oxide phases assumed to be present. Similar conditions and reactants to those involved in the formation of the compounds described above are expected in these soils, and it is suggested that Fe(II)-Al(III) members of the pyroaurite group may form in such an environment.
Formation and Characterization of Clay Complexes with Bitumen from Athabasca Oil Sand
Authors: Czarnecka Eliza , Gillott J. E. 
Published: September 2006

AbstractMontmorillonite, kaolinite, illite, and chlorite were found to adsorb bitumen and its pentane-soluble and pentane-insoluble fractions. The formation of clay-bitumen complexes is influenced by the nature of the exchangeable cation on the clay and by the solvent carrier which stabilizes the bituminous compounds. Ca-clays adsorb organic compounds more strongly than sodium forms except in the presence of nitrobenzene. Solvents of high dielectric constant, such as nitrobenzene, promote ionization so that the ion-exchange mechanism of adsorption is favored, whereas solvents of lower dielectric constant, such as chloroform, tend to solvate rather than to dissociate bitumens. The behavior of the montmorillonite-bi- tumen complex in variable relative humidity indicates that organic molecules adsorb primarily on external surfaces and cause the clay to become less hydrophilic than prior to treatment. Clay-organic complexes are sufficiently stable to resist powerful organic solvents. The clay-organic complex separated from the Athabasca oil sand behaves similarly during chemical treatment to complexes formed between bitumen and the four reference clay minerals.
Water Vapor Isotherms and Heat of Immersion of Na- and Ca-Montmorillonite Systems. III. Thermodynamics
Authors: Keren R. , Shainberg I. 
Published: September 2006

AbstractThe integral thermodynamic quantities of adsorbed water on Na- and Ca-montmorillonite have been calculated from water adsorption isotherms on Na- and Ca-montmorillonite at 298° and 313°K and from one adsorption isotherm and calorimetric measurements at 298°K. The integral entropy values decrease and then increase as the amount of adsorbed water approaches zero. In both systems, the curves approach the entropy value of free liquid water at the high content water. The thermodynamics of adsorbate on a non-inert adsorbent is discussed in some detail. The two-isotherm method gives the energy change of the water phase only, whereas the colorimetric method gives the energy change of the whole system (clay, exchangeable cations, and the adsorbed water). Only when the energy changes in the solid phase are negligible (=inert surface) should the two methods give similar results. An hypothesis was developed to explain the entropy-change data of water adsorbed on clay surfaces, in which the clay surface behaves as a non-inert adsorbent.
Kaolins: Sources of Differences in Cation-Exchange Capacities and Cesium Retention
Authors: Lim C. H. , Jackson M. L. , Koons R. D. , Helmke P. A. 
Published: September 2006

AbstractSeven kaolins from Georgia (southeastern U.S.A.), ranging from high to low commercial grade, were characterized by X-ray powder diffraction and chemical techniques to establish that the variation in quality was caused by impurities. The Ca and Cs cation-exchange capacities (CEC) varied from 2.67 to 8.17 and from 3.29 to 8.77 meq/100g, respectively. Selective dissolution and correlation analyses strongly indicated that expandable 2:1 minerals, particularly smectite (1.2-5.9%), were responsible for most of the observed variations in Ca CEC (r = 0.85*). The external surface CEC of kaolinite ranged from 0 to 1 meq/ 100 g. The positive significant correlation (r = 0.90**) between the Ca CEC and the K-mica content (03.9%) suggested that Ca CEC may be related to the degree of mica weathering through an expandable mineral stage.The Cs-retention capacity (0.19–1.14 meq/100 g) was closely related to Cs-measured vermiculite content (r = 0.80*), and this content plus specific surface (R = 0.93**) or mica content (R = 0.86*). The Cs retention appeared to be primarily related to the presence of interlayer wedges at mica/vermiculite XY interfaces.
Kaolinite, Smectite, and K-Rectorite in Bentonites: Relation to Coal Rank at Tulameen, British Columbia
Authors: Pevear D. R. , Williams V. E. , Mustoe G. E. 
Published: September 2006

AbstractThe Tulameen coal field is part of an Eocene nonmarine basin which received extensive volcaniclastic sediments due to its location within an active magmatic arc. Bentonite partings in the coal originally consisted of glassy rhyolitic tephra with phenocrysts of sanidine, biotite, and quartz. During the initial alteration, which took place within the swamp or shortly after burial, glass was transformed to either smectite-cristobalite-clinoptilolite or to smectite-kaolinite. The formation of kaolinite depended on the degree of leaching of silica and alkalies in the swamp environment. Some beds are nearly 100% kaolinite and can be designated as tonsteins. The smectite shows no evidence of interlayering; the kaolinite is well ordered. During alteration, sodium, originally a component of the glass, was lost from the system.A later thermal event, which affected only the southern part of the basin, metamorphosed the smectite to a regularly interstratified illite/smectite with 55% illite layers and rectorite-type superlattice (IS-type). The source of potassium was dissolution of sanidine. Vitrinite reflectance measurements of the coal suggest that the smectite was stable to 145–160°C, at which temperature it transformed to K-rectorite.The absence of randomly interstratified intermediates, even in beds rich in potassium, suggests that the transformation of smectite to K-rectorite was controlled by a steep thermal gradient possibly resulting from local magmatism or circulating geothermal fluids.
Negative Adsorption in Clay-Water Systems with Interacting Double Layers
Authors: Helmy A. K. , Natale I. M. , Mandolesi M. E. 
Published: September 2006

AbstractA relation was derived which describes negative adsorption (salt exclusion) in systems in which double layer interaction takes place but where the surface potential remains finite, such as in clay pastes and sediments. Exclusion volumes calculated for montmorillonite pastes in equilibrium with 1:1 type electrolytes were found to compare favorably with data obtained by F. A. M. de Haan in an earlier study.
Structure of Some Allophanes from New Zealand
Authors: Parfitt Roger Lyndhurst , Hemni Teruo 
Published: September 2006

AbstractAllophane samples from soils, pumice, and stream beds have been studied by electron optical, infrared absorption, X-ray fluorescence, gas chromatography, and phosphate adsorption methods. The allophane particles were hollow spherules or polyhedra 35 and 50 Å in diameter with molar Al/Si ratios close to 2.0. The thickness of the wall of the spherules was estimated to be 7 Å. For the pumice allophanes, the wall was largely composed of imogolite structural units (OH)3Al2O3SiOH. Defects or pores were present in the wall and probably were the sites where phosphate was adsorbed. It is suggested that these allophanes with molar Al/Si ratios close to 2.0 should be called “proto-imogolite” allophane.Two soil allophanes had a similar structure to the allophane from Stratford pumice, but small amounts of layer silicates, including halloysite, were also present in the soil samples, as indicated by infrared bands at 470, 1030, and 1100 cm−1. The allophane from the stream bed at Silica Springs had an infrared spectrum similar to feldspathoids, and it did not have the imogolite structure.
Effect of Chemical Pretreatment on X-Ray Powder Diffraction Characteristics of Clay Minerals Derived from Volcanic Ash
Authors: Brewster Gordon Ross 
Published: September 2006

AbstractThe effects of NaOAc removal of carbonates, H2O2 removal of organic materials, and sodium citrate-bicarbonate-dithionite (SCBD) removal of iron oxides upon the X-ray powder diffraction (XRD) characteristics of clay minerals present within weathered volcanic ash deposits were examined. All pretreatments of samples derived from the Ae and Bhf horizons containing volcanic ash resulted in dramatic increases in XRD peak intensities, while the treatment of IIC-horizon samples resulted in subdued XRD peak intensities. Also, the chemical treatments produced an apparent increase in the amount of expandable clay minerals within the Ae horizon, due probably to the hydrolysis and removal of interlayer Al3+ when H2O2 and SCBD were used. Hence, poorly ordered and pedogenically modified vermiculite or vermiculite/montmorillonite interstratifications became “weathered” by H+ attack and Al3+ removal in a manner similar to the natural processes which take place in the acid and eluvial A horizon. In addition, possible XRD peak modification due to the dilution of crystalline clay concentrations by amorphous clay-size material appeared to be subordinate to the laboratory-induced chemical alteration of the weathered clay minerals.
Adsorption of Cadmium and Cobalt on Montmorillonite as a Function of Solution Composition
Authors: Egozy Yair 
Published: September 2006

AbstractAdsorption of Co2+ and Cd2+ on Wyoming montmorillonite was studied by the batch equilibration technique, as a function of salt concentration (0.01–4 M NaCl and NaNO3), pH (5.0–6.5), adsorbate concentration (trace-10−2 moles/liter), and presence of complexing ions. Comparison was made with the adsorbability of Sr2+, known to follow simple ion-exchange equations. The distribution coefficients for Co and Cd in noncomplexing media varied with salt concentration (from ∼500 liters/kg in 0.01 M Na+ to ∼10 liters/kg in 1 M Na+; pH = 5), but to a lesser extent than that of Sr. Adsorbability varied also with pH (∼1 order of magnitude/pH unit), especially at high ionic strength, compared to a negligible pH effect on Sr. The distribution coefficients of Cd and Co decreased with increasing loading on the clay at a very low percentage (0.2%) of the ion-exchange capacity compared to Sr (20%). These data suggest two classes of sites participating in the adsorption of Cd and Co.The adsorbability of Cd in highly concentrated chloride solution (>1 M) was less than 1 liter/kg, presumably because of the chloride complex formation. This effect increased with increasing pH. The low adsorbability of Cd on montmorillonite from concentrated NaCl solution is promising with respect to its use as a tracer for monitoring flow through formations containing montmorillonite.
Selective Adsorption of Zinc on Halloysite
Authors: Wada Koji , Kakuto Yasuko 
Published: September 2006

AbstractZn- and Ca-adsorption equilibria of five Ca-saturated halloysite samples were measured at equilibrium Zn concentrations up to 10−2 M in 10−4 to 10−2 M CaCl2. The results were interpreted on KCaZn vs. [Zn]/CEC (%) plots, where KCaZn is the selectivity coefficient (= [Zn][Ca]/[Ca][Zn]), Zn and Ca represent the adsorbed species, and CEC is the cation-exchange capacity. All Zn adsorption occurred at cation-exchange sites, and 0.77 to 36.0 meq Zn/100 g clay, which constitutes 9 to 83% of the CEC, was adsorbed with “high selectivities” (KCaZn > 10). The higher values were found for two spherical and one “filmy” halloysites, whereas the lower values were found for two tubular halloysites. The magnitude of their 001 intensity, hydration in interlayer space, CEC, and “free” iron oxide content did not correlate with the selective Zn adsorption, but a good correlation was found between the proportion of “high selectivity” sites for Zn and proportion of “high affinity” sites for H+. The adsorption of Zn at the “high selectivity” sites was not completely reversible, and KCaZn values >1000 were recorded in 0.5 M CaCl2 for Zn which occupied 10–40% of the exchange sites. Selective Zn adsorption decreased with decreasing pH, and all adsorbed Zn was extracted with 0.1 M HCl.
Fe2+-Fe3+ Transformations in Clay and Resin Ion-Exchange Systems
Authors: Gerstl Z. , Banin A. 
Published: September 2006

AbstractThe pH, Eh, electrical conductivity (EC), and the amounts and valency of replaceable iron were measured periodically on Fe2+- and Fe3+-saturated montmorillonite and cation-exchange resin at three temperatures. Differences in the pattern of change of pH, Eh, and EC with time appear to be related more to the histories and modes of preparation of the systems than to intrinsic differences in the hydrolysis of the iron in them. Electron transfer reactions involving crystal components of the clay can cause oxidation of adsorbed Fe2+ ions; the activation energy (Ea) for oxidation on the clay's surface was 6 kcal/mole, less than a third of the activation energy reported for Fe2+ oxidation in solution. In the Fe2+-resin, where Ea = 10.7 kcal/mole, perturbed surface-water molecules may act as electron acceptors enhancing Fe2+ oxidation.Polymerization and precipitation of the adsorbed iron is affected by the necessity to maintain electroneutrality, the ability of the iron-hydroxy ions and small polymers to move about in the voids of the ion exchanger, and the steric hindrance posed by the matrix of the ion exchanger to the formation of large polymers. In resin, little or no iron precipitates, probably due both to steric hindrance and the inability of the resin to release ionic components to maintain electroneutrality. In clays, steric hindrance is small, and Al and Mg are released from the crystal to maintain electroneutrality, thus the precipitation of iron is abundant and is controlled by the rate of release of Al and Mg from the crystal.
Manganese Minerals in Clays: A Review
Authors: Chukhrov F. V. , Gorshkov A. I. , Rudnitskaya E. S. , Beresovskaya V. V. , Sivtsov A. V. 
Published: September 2006

AbstractVernadite (MnO2·nH2O) is a mineral with a poorly ordered structure. Its synthetic analogue is designated δ-MnO2. Birnessite and vernadite are independent mineral species and cannot be described further under the same name. They have similar hexagonal unit-cell parameters, a0, but different c0 parameters. Rancieite has a structure similar to that of birnessite. Calcium bearing, 14-Å birnessite occurring in nature was first described by the authors. In addition to the todorokite having the parameters a0 = 9.75 Å, b0 = 2.84 Å, and c0 = 9.59 Å, other species of natural todorokite are known having a0 parameters that are multiples of 4.88 Å equal to 14.6 and 24.40 Å, the b0 and c0 parameters being the same.
Dehydroxylation of Dioctahedral Phyllosilicates
Authors: Heller-Kallai L. , Rozenson I. 
Published: September 2006

AbstractMössbauer spectroscopy of dioctahedral phyllosilicates showed that on dehydroxylation iron which originally occupied M(2) and M(l) sites became, respectively, 5- and 6-coordinated. The 6-coordinated sites are very distorted. No migration of cations occurs in the course of heating the specimens for 1–3 hr at 600°–700°C.By using a combination of several physicochemical methods, different successive stages of the dehydroxylation process could be distinguished: (1) migration of protons; (2) localized dehydroxylation of individual associations without significant change in the overall configuration of the octahedral sheets; and (3) loss of most of the hydroxyl groups with concomitant changes in the cell dimensions. Penetration of Li into the octahedral sheets does not affect the course of the reaction, but reduces the dehydroxylation temperature and the stability of the products.Dehydroxylation was preceded by or associated with the oxidation of any divalent iron present. Fe3+ derived from Fe2+ was indistinguishable by Mössbauer spectroscopy from iron initially present in the trivalent form. High concentrations of Fe lower the dehydroxylation temperature and reduce the stability of the dehydroxylate to the extent that partial disintegration may precede complete dehydroxylation.
Adsorption of Organic Diacids and Sodium Polyacrylate Onto Montmorillonite
Authors: Siffert B. , Espinasse P. 
Published: September 2006

AbstractOrganic diacid (oxalic and succinic) adsorption onto montmorillonite is feasible, but weak (~1 mg/g). The comparison of chemical and radiochemical determinations reveals that 80% of the acid in contact with the smectite is used to attack the clay lattice. The pH is the main parameter involved in adsorption, and fixation passes through a minimum for pH 6 to 7. Polyacrylate adsorption is also weak (~1.5 mg/g). It changes with the nature of the exchangeable cation of smectite. Its pH-dependence displays a pronounced maximum for a value corresponding to the pKa of the acidic functions (pH ~6.8), and a minimum at about pH 8. On the assumption that a polyacrylate macromolecule is 100% hydrolyzed, it follows that the-COOH groups carried by 20% hydrolyzed Polyacrylamide molecules (such as those used in the tertiary recovery of petroleum) contribute at the very most to 10% of the total adsorption onto clay. Fixation, therefore, involves predominantly protonation of the amide functions at the edge surfaces of the clay. The acidic functions play a minor role in the adsorption phenomenon in that they affect the length of the macromolecule. The extent of this contribution, however, is virtually impossible to estimate.
Precise Identification of Illite/Smectite Interstratifications by X-Ray Powder Diffraction
Authors: Środoń Jan 
Published: September 2006

AbstractThe thickness of the two-layer ethylene glycol complex of dioctahedral smectites varies under room conditions between 17.3 and 16.5 Å because of such factors as layer charge density, type of interlayer cation, and relative humidity. Neglecting this variability can give up to 30% error in the X-ray powder diffraction estimation of the smectite:illite ratio of the mixed-layer structures. Three methods have been developed for the interpretation of X-ray powder diffraction patterns of glycolated mixed-layer illite/smectite which take layer-spacing variability into account. The methods include a technique for quantifying the degree of layer ordering. In addition, the proposed techniques minimize the error due to the influence of domain size on positions of reflections. The experimental error can be kept below 5% or below 1% smectite layers, depending on the method applied, provided that the peak positions are measured with the accuracy of ± 0.02°2θ.
Formation, Compositions, and Properties of Hydroxy-Al- and Hydroxy-Mg-Montmorillonite
Authors: Brindley G. W. , Kao Chih-Chun 
Published: September 2006

AbstractHydroxy-Al- and hydroxy-Mg-montmorillonite were prepared by treating dispersed Na-montmorillonite with aluminum and magnesium nitrate solutions and titrating with NaOH solutions so that the OH/Al ratio varied from zero to 3.0 and the OH/Mg ratio from zero to 2.0. External precipitation of Al and Mg hydroxides was observed when the OH/M ratios (M = metal) approached 3 and 2, respectively. From chemical analyses of the initial Na-montmorillonite and the hydroxy-metal montmorillonites, structural formulae were derived by assuming that the silicate layer compositions remained unchanged. Prior to the addition of NaOH, the average interlayer material approximated in composition to [Al(OH)2]+ and [Mg(OH)]+. With additions of NaOH the interlayer compositions moved progressively towards Al(OH)3 and Mg(OH)2. When the hydroxy interlayers approached completion, external precipitation was observed. X-ray powder diffraction data showed that the hydroxy-Mg products have less tendency to swell in ethylene glycol and water, and greater thermal stability than the hydroxy-Al products. Initially, when the average interlayer compositions were near Al(OH)2 and Mg(OH), swelling followed more nearly the normal behavior.
Automated Digital Image Processing for Volume Change Measurement in Triaxial Cells
Authors: Gachet P , Geiser F , Laloui L , Vulliet L 
Published: September 2006

Abstract
An automated digital image processing technique is presented for the measurement of specimen volume change during triaxial testing.A digital camera is fixed at a constant distance from the triaxial cell. Pictures taken at various intervals are processed (e.g., using contouring techniques) to extract specimen volume and thus volumetric strain.A calibration procedure requiring a rigid specimen is used to correlate specimen image with specimen volume. The accuracy of the method is discussed on the basis of experimental results. This technique is of particular interest for cases where conventional use of pore-water volume exchange cannot be used to extract total volumetric strain, as is the case when testing unsaturated soils.