bluuebunny/crossref_metadata_2025_split huggingface dataset:
“Dealumination” and Aluminum Intercalation of Vermiculite
Authors: de la Caillerie Jean-Baptiste D'Espinose , Fripiat José J. 
Published: August 2006

AbstractDealumination of vermiculite was carried out using (NH4)2SiF6 solutions. The dealuminated products were studied by high-resolution solid state 29Si and 27Al nuclear magnetic resonance. A decrease in the cation-exchange capacity (CEC) resulted from the partial removal of Al from the tetrahedral layer, which decreased the framework negative charge, and from the partial replacement of Mg by Al in the octahedral layer, which increased its positive charge contribution. The lowest CEC was obtained by swelling the structure with butyl-ammonium prior to the reaction with (NH4)2SiF6. Thus, CECs in the range observed for beidellite were measured; however, the lowest (Al/Si)IV ratio was still more than twice as high as in beidellite. In addition, the dealumination reaction yielded noncrystalline silica as a by-product.In contact with a solution of Al hydroxypolymer (Al13), the dealuminated vermiculite showed no 18-Å reflection characteristic of Al13-intercalated smectite; instead it showed an ill-defined interstratification. For some samples, however, a significant increase in the specific surface area (as much as 230 m2/g) was observed, suggesting that an intercalation of Al moieties did occur. The 27Al resonance spectra of the intercalated structure showed at least two components in octahedral coordination. On thermal activation, a resonance line attributable to pentacoordinated Al was observed.
Hydrophobicity of Siloxane Surfaces in Smectites as Revealed by Aromatic Hydrocarbon Adsorption from Water
Authors: Jaynes W. F. , Boyd S. A. 
Published: August 2006

AbstractThe nature of the siloxane surface in smectites was investigated by measuring the adsorption of aromatic hydrocarbons from water by organo-clays. The organo-clays were prepared by replacing the hydrophilic, inorganic exchange cations of a series of smectites with the small, hydrophobic organic cation, trimethylphenylammonium (TMPA). Smectites with a range in charge densities were used that resulted in different TMPA contents in the organo-clays. Adsorption isotherms of benzene, alkylbenzenes, and naphthalene from water by the TMPA-smectites indicated that sorption was inversely related to TMPA content. The Langmuir form of the isotherms suggests that the aromatic compounds adsorb to the clay surface. Possible adsorptive sites in TMPA-smectites are limited to the TMPA cations and the siloxane oxygen surfaces. Because sorption increased as layer charge and TMPA content decreased, the organic compounds must adsorb to the siloxane surfaces.Calculations based on an adsorbed compound monolayer, which was estimated by fitting adsorption data to the Langmuir equation, and the N2 specific surface area of each TMPA-clay, indicate that the surface area occupied by each adsorbed molecule increases as the planar area of the molecule increases. This strongly indicates that the planar surfaces of the compounds adsorb directly to the clay surface. Apparently, the TMPA cations function to keep the smectite interlayers open. Interactions between the phenyl groups of TMPA cations on opposing interlayer clay surfaces may act to increase the size of the adsorptive regions. These results show that the siloxane surfaces of smectites can effectively adsorb aromatic hydrocarbons from water if the hydrophilic, inorganic exchange cations are replaced with small, hydrophobic organic cations. The strong adsorption of hydrophobic organic molecules from water demonstrates the hydrophobicity of the siloxane surfaces in smectites.
Detection of Trace Amounts of Erionite Using X-Ray Powder Diffraction: Erionite in Tuffs of Yucca Mountain, Nevada, and Central Turkey
Authors: Bish David L. , Chipera Steve J. 
Published: August 2006

AbstractRecent data in the biological literature suggest that the natural zeolite erionite may be more tumorigenic than asbestos minerals. Because of its potential biological importance, a technique has been developed to facilitate detection of erionite in tuffaceous rocks to a lower limit of detection (LLD) between 100 and 500 ppm. The method involves the use of automated X-ray powder diffraction instrumentation with long count times, as much as 360 s/step. The presence of interfering phases, such as smectite or clinoptilolite, raises the LLD. Ethylene glycol solvation of smectite improves the LLD, and profile fitting with clinoptilolite-bearing mixtures improves quantification. Application of these methods to tuffs from central Turkey allowed improved detection and more accurate quantification compared with previous scanning electron microscope examinations. Use of these methods with tuffs from Yucca Mountain, Nevada, the potential site for the nation's first high-level radioactive waste repository, showed that erionite occurs sporadically. Erionite is found only in the altered zone directly above the lower vitrophyre of the Topopah Spring Member. This altered zone is anomalous in that is contains a variety of zeolites that are either rare or absent in other Yucca Mountain tuffs. It appears that erionite is restricted to fractures and must have formed under unusual and variable conditions in the altered zone.
Origin and Diagenesis of Clay Minerals in the Monterey Formation, Santa Maria Basin Area, California
Authors: Compton John S. 
Published: August 2006

AbstractThe clay mineralogy of the Miocene Monterey Formation was determined for onshore and offshore sequences in the Santa Maria basin area, California. The <0.1-μm fraction of clayey, opal-CT porcelanites, siliceous mudstones, and dolostones from the Pt. Pedernales area consists of mixed-layered illite/smectite (I/S) that contains < 10% illite layers. The underlying Tranquillon Volcanics and Obispo Tuff, the presence of bentonite beds, zeolite minerals, and unaltered volcanic ash beds in the Monterey Formation, and the highly smectitic composition of the I/S suggest that a significant amount of the I/S formed from the alteration of vitreous volcanic ash. The alteration of volcanic glass to smectite coincides with the transformation of biogenic opal-A (mostly diatoms) to opal-CT. Alteration of volcanic glass to smectite may inhibit the opal-A to opal-CT transformation by removing pore-water Mg, promote dolomite precipitation by raising the pH, alter the Sr isotopic composition of the pore waters, and provide an additional source of silica to these predominantly biogenic siliceous rocks. The 0.1- to 2-μm fraction contains mica minerals (discrete illite, biotite, and muscovite) as well as I/S. Clayey, opal-A diatomites from the overlying Sisquoc Formation contain detrital kaolinite and random (R = 0) I/S, but the percent illite layers in the I/S is uncertain.The <0.1-μn fraction of quartz rocks from the Lions Head area and the offshore B-2 well is far more variable, and contains random or ordered (R = 1) I/S, kaolinite, and chlorite. Corrensite was observed at the base of the Lions Head area. The percent illite layers in the I/S increases from 10% to 80% over a stratigraphic depth of 0.8 km that corresponds to a present-day temperature range of 80 to 115°C. Initial illitization of smectite coincides with the opal-CT to quartz transformation. Ordered (R = 1) I/S is associated with abundant diagenetic kaolinite and dolomite in several metabentonite beds. The dominance of sodic plagioclase over K-feldspar, and the absence of kaolinite and chlorite in rocks of equivalent age that have not undergone illitization suggest that limited availability of K results in the alteration of smectite to kaolinite, chlorite, and possibly late dolomite. Minor amounts of clinoptilolite were found in opal-A and opal-CT rocks. Minor to trace amounts of analcime and mordenite were tentatively identified, primarily in quartz rocks.
FTIR Study of Deuterated Montmorillonites: Structural Features Relevant to Pillared Clay Stability
Authors: Bukka Krishna , Miller J. D. , Shabtai Joseph 
Published: August 2006

AbstractFTIR studies of six partially-deuterated montmorillonites (MS) reveal the presence of two O-D stretching bands, one between 2702–2728 cm-1 and another near 2680 cm-1. For homoionic (Li, Na, Mg, Ca, or La) Wyoming-type MS, the position of the higher frequency band, designated as (O-D)h, is between 2714–2728 cm-1, whereas for homoionic Cheto-type MS it is between 2702–2706 cm-1. The lower frequency band, designated as (O-D)1, is in the narrow range of 2674–2684 cm-1. Resolution of two corresponding O-H bands, appearing near 3670 and 3635 cm-1, was observed only after partial dehydroxylation of the smectites. The changes in the relative intensities of the two O-D stretching bands as a function of the smectite type and of the Lewis acidity (charge density) of the exchangeable ion were determined. For Wyoming-type MS, the intensity of the (O-D)h band is much lower than that of the (O-D)l band, whereas for Cheto-type MS, the intensity of the (O-D)h band is about equal or slightly higher than that of the (O-D)l band. The observed resolution can be ascribed tentatively to the presence of (at least) two types of octahedral OH groups in the smectites, the (O-D)h band being assigned to AlMgOH and the (O-D)1 band to AlAlOH groups. Pillaring of Cheto-type MS with hydroxy-Al13 oligocations resulted in products showing much higher thermal stability between 400–600°C compared to that of identically pillared Wyoming-type MS. Compositional and other factors, e.g., CEC values and mode of pillaring, may cause this difference in stability.
The Interaction of Polysaccharides with Silver Hill Illite
Authors: Gu Baohua , Doner Harvey E. 
Published: August 2006

AbstractThe clay-polysaccharide interaction is of practical importance in the formation and stabilization of soil aggregates. This study examined the adsorption of three synthetic polysaccharides (PSS) and one soil PSS on Silver Hill illite. The adsorption of PSS was influenced by both the adsorbed cations on the adsorbents and the charge characteristics of the polymers. The adsorbed cations formed different surface complexes with the clay surfaces, with varying ability to screen the surface negative charge and thereby influenced the adsorption of charged polymers. Na-illite adsorbed substantially higher amounts of the cationic PSS, but lower amounts of the anionic PSS, than hydroxy-Al illite. The adsorption of the nonionic PSS was, however, little influenced by those adsorbed cations. The adsorption of the soil PSS resembled that of anionic PSS. However, it yielded linear adsorption isotherms due to the heterogeneous nature of the soil PSS. The adsorption of the three synthetic PSS on Na-illite was in the general order: cationic > nonionic > anionic, confirming that electrostatic forces played a role in the adsorption of charged polymers. pH and ionic strength influenced the adsorption of the charged PSS, because of their influences on the charge characteristics of both the polymer and the clay, and on polymer conformation. This study indicates that surface charge properties of both clays and organic polymers and the presence of polyvalent cations in the system are important factors influencing the complexation between soil clays and organic constituents.
Synthesis of Expandable Fluorine Mica From Talc
Authors: Tateyama Hiroshi , Nishimura Satoshi , Tsunematsu Kinue , Jinnai Kazuhiko , Adachi Yasuo , Kimura Mitsuru 
Published: August 2006

AbstractExpandable fluorine micas were synthesized using talc and Na2SiF6 at 800°C for 2 hours in air, nitrogen, argon, and under vacuum. Gaseous SiF4, generated from Na2SiF6, and the resultant amorphous sodium silicofluoride formed during the reaction between talc and Na2SiF6 below 900°C are taking active part in the formation of expandable micas because the intensity of the 12.5 Å reflection of expandable micas decreases as the gas flow increases in the furnace. Expandable micas seem to be formed by the transformation from talc taking place without the entire disruption of the original atomic arrangement. This takes place with the loss of one Mg2+ from an octahedral site and by the intercalation of every two Na+ into the interlayer site of talc. Infrared absorption and thermal analyses show that expandable micas include a small amount of OH− in their structures.
19F MAS-NMR Study of Structural Fluorine in Some Natural and Synthetic 2:1 Layer Silicates
Authors: Huve Laurent , Delmotte Luc , Martin Pascal , Le Dred Ronan , Baron Jacques , Saehr Daniel 
Published: August 2006

AbstractHigh-resolution solid-state, fluorine-19, magic-angle spinning-nuclear magnetic resonance spectroscopy (MAS-NMR) was used to study natural and synthetic fluorinated 2:1 layer silicates of known composition. This technique enabled us to determine directly the coordination of structural fluorine and it was found to be sensitive to both the chemical nature of the octahedral elements (Al, Mg, Li) and the type of octahedral sheet (di- or trioctahedral). The observed chemical shifts at −132, −152, −176 and −182 ppm (relative to CFC13) were assigned to different environments of fluorine. The results were then used to characterize synthetic 2:1 layer silicates with unknown octahedral composition.
Modeling Boron Adsorption on Kaolinite
Authors: Singh Shivi P. N. , Mattigod Shas V. 
Published: August 2006

AbstractBoron adsorption at constant ionic strength [0.09 ± 0.01 moles/liter of KClO4 or Ca(ClO4)2] on 0.2−2 μm clay fraction of pretreated kaolinite was modeled using both phenomenological equations and surface complexation reactions. Phenomenological equations were expressed as linear relationships between the distribution coefficient and adsorption density or equilibrium concentration. The normalized form of the isotherms allowed the distribution coefficient to be predicted over a wide range of adsorption densities or equilibrium concentrations and pH. The Langmuir isotherm revealed a weak two-part linear trend supported by a similar behavior of the van Bemmelen-Freundlich isotherm. Potential adsorption mechanisms were assessed from these isotherms. The bases for the inner-sphere (surface coordination) and outer-sphere (ion-pair) surface reactions were postulated, and equations were developed and incorporated into the generalized triple-layer surface-complexation model [TL(g)-SCM]. Boron adsorption was best modeled using the inner-sphere complexes. The results confirm that the generalized triple-layer surface-complexation model can provide information regarding plausible reactions at the substrate/aqueous interface. Intrinsic constants for postulated surface reactions were derived as fitting parameters over a range of pH and initial boron concentrations.
Sodium and Chloride Sorption by Imogolite and Allophanes
Authors: Su Chunming , Harsh James B. , Bertsch Paul M. 
Published: August 2006

AbstractThe surface excesses of Na and Cl on synthetic imogolite and allophanes with varying Al/Si molar ratios in 0.10 M and 0.01 M NaCl solutions were determined using 22Na and 36Cl as ion probes. The point of zero net charge (PZNC) values ranged from 4.1 to 8.4, increasing with the Al/Si molar ratio for the allophanes, and was highest for imogolite (Al/Si = 2.01). The PZNC values were significantly lower than the point of zero charge (PZC) values previously determined by microelectrophoresis for the same material, indicating that Na resided within the shear plane to a greater extent than Cl. The PZNC values of allophanes were lower than their PZSE values, indicating that permanent charge existed in allophanes, and increased as Al/Si decreased. Conversely, the PZNC of imogolite was higher than its point of zero salt effect (PZSE) determined by potentiometric titration. Adsorption of Cl on imogolite from 0.1 and 0.01 M NaCl solutions below pH 8.4 and of Na from 0.1 M NaCl solutions between pH 5 and 8.4 exceeded the proton charge determined by potentiometric titration. There was no direct evidence of permanent charge in imogolite and excess Cl adsorption could not be entirely explained by simultaneous intercalation of Na and Cl. Isomorphic substitution of Al in tetrahedral sites was shown to increase with decreasing Al/Si by 27Al high-resolution solid-state nuclear magnetic resonance (NMR) spectra of allophanes, and was absent in imogolite. The chemical shifts of Al(4) and Al(6) were similar in allophanes (63.0–64.7 ppm and 6.1–7.8 ppm, respectively) and the chemical shift of Al(6) was 9.4 in imogolite.
Electroacoustic Study of Adsorption of Cetylpyridinium Chloride on Kaolinite
Authors: Rowlands William N. , Hunter Robert J. 
Published: August 2006

AbstractAdsorption of cetylpyridinium chloride (CPC) onto kaolinite can be followed using the electroacoustic effect. The dynamic mobility, measured at a frequency of 1 MHz, varies from about −2 to +1 × 10−8 m2 V−1 s−1 in a number of steps, reflecting the adsorption of two separate layers, with the bilayer being more obvious, especially at pH 5–8. The behaviour at different pHs reflects the different charge characteristics of the basal cleavage planes and the crystal edges. When the amount of added CPC is equal to the cation exchange capacity of the clay, the kinetic charge changes from negative to positive and there is a pronounced break in the conductivity curve. It is also possible to estimate the edge to face area from such measurements and so obtain a measure of the aspect ratio of the clay crystallites. The (minimum) value for this clay is about 5:1.
Reaction of OH-Al Polymers with Smectites and Vermiculites
Authors: Hsu Pa Ho 
Published: August 2006

AbstractFive montmorillonites, one hectorite, and two vermiculites were treated with OH-Al solutions containing rapid- and slow-reacting polymers of similar concentrations. With all smectites, both rapid- and slow-reacting OH-Al polymers were much more preferentially adsorbed than monomeric species. Relatively slow-reacting OH-Al polymers were more preferentially adsorbed than rapid-reacting ones. The average basicity of the adsorbed Al was 2.46, which was close to that of the OH-Al polymers in the original solution. The OH-Al polymers that enter the interlayer resemble those in original solutions.With vermiculites, the solution concentration of rapid-reacting OH-Al polymers was much reduced after reaction. The average basicity of the adsorbed Al was 1.99, which was considerably lower than that in the original solution. It is postulated that OH-Al polymers break to monomeric Al ions and then enter the clay. The monomeric Al species that enter the clay interlayers hydrolyze and polymerize in situ and become fixed. The H+ ions released from hydrolysis convert the rapid-reacting OH-Al polymers to monomeric Al in solution. Limited amounts of slow-reacting polymers were adsorbed because of their resistance to acid depolymerization.
Horace-Bénédict de Saussure, a Forerunner in 1794–95 of Experimental Weathering
Authors: Carozzi Albert V. 
Published: August 2006

AbstractIn a hitherto unpublished manuscript dated 1794–95, H.-B. de Saussure described three types of rudimentary laboratory experiments on weathering, each one lasting about 4 hours, undertaken on samples of jade, serpentine, feldspar, and mica schist. He submitted these samples to dry heating, heating with continuous addition of water, and heating with periodic addition of water. Experimentation was performed at temperatures of the order of 200–250°C, and Saussure seems to have realized that a reasonable increase of temperature was necessary for laboratory simulation of long-lasting geological processes. No changes were observed during dry heating whereas increasing alteration was noticed in the presence of water, particularly when heating was combined with periodic wetting. He concluded that these tests demonstrated his preconceived idea that weathering of minerals (mostly silicates) resulted from alternating periods of drying and wetting. This concept is basically very close, if not identical, to that underlying modern ideas on seasonal weathering.
Hydrophobic Nature of Organo-Clays as a Lewis Acid/Base Phenomenon
Authors: Norris J. , Giese R. F. , van Oss C. J. , Costanzo P. M. 
Published: August 2006

AbstractThe surface thermodynamic properties of a series of n-alkylammonium and quaternary ammonium treated clay films were determined by contact angle measurement of drops of test liquids using the Young equation for polar materials. The two clays were a Wyoming montmorillonite (SWy-1) and Laponite RD. For a series of primary n-alkyl (6 ≤ n ≤ 15) and several quaternary organic cations, the organo-clay (both SWy-1 and Laponite RD) showed very little change in the value of γLW compared to the equivalent ammonium-saturated clay. Also, γ⊕ remained small or increased slightly compared to the ammonium-saturated clay. For SWy-1 exchanged by both quaternary ammonium and primary n-alkylammonium cations, the value of γ⊖ was smaller (0.1 ≤ γ⊖ ≤ 15.8 mJ/m2) than for the ammonium-saturated clay (γ⊖ = 36.2 mJ/m2) and decreased linearly with the number of carbon atoms. The γ⊖ values for the organic cation-exchanged Laponite RD samples (24.2 ≤ γ⊖ ≤ 31.2 mJ/m2) were smaller than or comparable to the ammonium saturated clay (γ⊖ = 30.7 mJ/m2), and were relatively insensitive to the number of carbon atoms in the organic cation. Thus, for both clays the increased adsorption of organic molecules resulting from replacement of inorganic cations by organic cations is due primarily to the decrease in the value of the Lewis base parameter, γ⊖.
Effects of Structural Iron Reduction on the Hydraulic Conductivity of Na-Smectite
Authors: Shen Siyuan , Stucki Joseph W. , Boast Charles W. 
Published: August 2006

AbstractThe long-term impermeability of clay barriers in waste disposal facilities and hydraulic structures is of critical importance to environmental, agricultural, and industrial concerns. Changes in the oxidation state of Fe in the constituent clays of compacted clay barriers may degrade the hydraulic conductivity of these structures because other properties related to hydraulic conductivity, such as swelling, gel microstructure, and particle size, are greatly altered by the oxidation state. Two Na-saturated smectites (SWa-1 and API 25) were reduced by sodium dithionite (Na2S2O4), both in suspension and in situ after consolidation, to examine the effects of structural Fe reduction on hydraulic conductivity. Results indicated that the hydraulic conductivity depended on both the oxidation state and the consolidation history of the clay. The hydraulic conductivity of clay reduced in suspension before consolidation was lower than that of oxidized clay. Initially reduced smectite, thus, may be compactable to a less-permeable material with higher bulk density. But reduction of smectite in situ after consolidation increased the hydraulic conductivity and its variability. The oxidized state of clay liners should, therefore, be preserved.