bluuebunny/crossref_metadata_2025_split huggingface dataset:
hk-Ordering in Aluminous Nontronite and Saponite Synthesized Near 90°C: Effects of Synthesis Conditions on Nontronite Composition and Ordering
Authors: Farmer V. C. , McHardy W. J. , Elsass F. , Robert M. 
Published: August 2006

AbstractIn studies on the fate of aluminium in the environment, nontronite and saponite have been obtained by synthesis in reducing alkaline conditions close to those prevailing in poorly drained soils developed from limestones. The two minerals obtained have different structures and organizations corresponding to two different growth and/or maturation mechanisms. High-resolution transmission electron microscopy of ultrathin sections of a synthetic aluminous nontronite embedded in resin showed the presence of crystallites consisting of two to ten co-terminating parallel layers, indicating synchronous growth. Electron diffraction showed that the individual crystallites had hk-ordering, i.e., orientation of layers with respect to the six-fold pseudosymmetry of the unit cell. Deposits of a synthetic saponite included hk-ordered crystallites and crinkled films with turbostratic stacking. The two saponite phases had slightly different b dimensions. Lattice fringe images of sections of saponite embedded in resin showed a high angular disorientation of the layers in the stacking direction, suggesting multiple nucleation and growth of individual layers, subsequently aggregated with imperfect parallelism.Exploration of the synthetic conditions of the aluminous nontronite indicated that calcium was essential for an hk-ordered product. Syntheses using potassium or sodium hydroxides and carbonates for pH control gave poorly organized nontronites. Hydrazine was not essential for nontronite formation, but better crystallized products—judging by their IR spectra—were obtained in its presence by maintaining reducing conditions in the early stages of synthesis. Attempts to prepare ferruginous beidellites under similar conditions to those in which aluminous nontronites formed were unsuccessful.
Reaction Path Approach to Mineral Weathering Reactions
Authors: Steinmann Philipp , Lichtner Peter C. , Shotyk William 
Published: August 2006

AbstractCommercial spreadsheet programs allow calculation of reasonable reaction paths for weathering of silicate minerals in a dilute acidic aqueous solution. These calculations use reaction coefficients of simplified weathering reactions and ignore speciation in the aqueous solution. The method is illustrated using the example of dissolution of microcline. When plotted on a log-log activity diagram, the obtained reaction paths are clearly curved, unlike the straight lines shown in most recent geochemistry textbooks. The calculated reaction paths are strongly dependent on the initial pH of the solution. At higher pH the speciation in the solution must be included in the calculations. The most important speciation reactions (the dissociation of H2O and H4SiO4) can be easily included using commercial mathematical programs. p ]The presented examples include closed systems with different initial pH values and an open system case describing the evolution of a soil profile. All reaction paths calculated using the simplified methods agree well with those obtained using sophisticated modeling codes.
The Use of Color to Quantify the Effects of pH and Temperature on the Crystallization Kinetics of Goethite under Highly Alkaline Conditions
Authors: Nagano Tetsushi , Nakashima Satoru , Nakayama Shinichi , Senoo Muneaki 
Published: August 2006

AbstractThe crystallization kinetics of goethite were studied colorimetrically under highly alkaline conditions (pH 10.1–12.2) at temperatures from 40° to 85°C. Color changes during crystallization from fresh precipitates, plotted on a*-b* colorimetric diagrams, were used to discriminate between pure goethite and mixtures of goethite and hematite. Only the b* value increased as goethite crystallization proceeded, and even a minor increase in the a* value revealed the existence of hematite. The rate of goethite crystallization, estimated from the b* value, could be modeled by a pseudo-first-order rate law. This rate depended both on pH and on temperature. Apparent activation energies for the reactions of 56.1 kJ/mol at pH 11.7 and 48.2 kJ/mol at pH 12.2 were estimated from Arrhenius plots.
Infrared Spectroscopy Study of Tetrahedral and Octahedral Substitutions in an Interstratified Illite-Smectite Clay
Authors: Srasra E. , Bergaya F. , Fripiat J. J. 
Published: August 2006

AbstractInfrared spectroscopy is used to distinguish between octahedral and tetrahedral substitutions in an interstratified illite-smectite clay. The Hofmann-Klemen (Li) test suggests that the AlMg□ and FeMg□ octahedral vacancies are preferentially occupied by Li after thermal treatment at 250°C. The ammonium (Chourabi-Fripiat) test reveals the beidellitic character by the formation of two OH stretching modes upon deammonation. The illitic layers are not affected since K is not exchangeable.
The Microstructure of Three Na+ Smectites: The Importance of Particle Geometry on Dehydration and Rehydration
Authors: Hetzel Frederic , Tessier Daniel , Jaunet Anne-Marie , Doner Harvey 
Published: August 2006

AbstractRecent pedological evidence of the widespread distribution of beidellites in soils indicates the need for a greater knowledge of the effect of charge location on the microstructural organization of Na+ smectite in gels. After equilibration at a suction pressure of 3.2 kPa before and after desiccation, TEM observations showed large differences between a beidellite and both a low and high charge montmorillonite. Monolayers were rare; individual layers were instead organized in particles with larger interparticle distances. This has implication for theories relating swelling pressures to interlayer distances or surface areas and implies the need for a geometrical approach to the study of swelling in smectites. Location of isomorphous substitution in the tetrahedral sheet of smectites results in an increased lateral extension of overlapping layers. This was reflected in a greater capacity to rehydrate after desiccation. Increased number of layers in particles were found with increasing surface charge density. The geometric organization of the particles is critical to the understanding of the ability of Na+ smectite to hold water against an applied suction.
The Quantity of Reduced Nickel in Synthetic Takovite: Effects of Preparation Conditions and Calcination Temperature
Authors: Titulaer Mark K. , Jansen J. Ben H. , Geus John W. 
Published: August 2006

AbstractTakovite, Ni6Al2(OH)i6CO3-5H2O, with molar Ni/Al ratios of 2.5 and 3 is prepared by precipitation at pH levels of 7 and 10, periods of reaction of 3 and 20 hr, and calcination temperatures varying between 120° and 8 5 3°C. The quantity of reduced Ni is determined as a function of the calcination temperature, and the solid phases remaining after reduction are determined with XRD. The Ni/Al ratio, pH of precipitation, and calcination temperature are important preparation conditions. A precursor of a Ni/Al ratio of 2.5 precipitated at a pH-level of 10 exhibits on reduction metallic Ni particles of about 15 nm irrespective of the drying or calcination temperature. After reduction, a considerable amount of NaAlO2 is present. Metallic Ni particles of 6 nm are present in a reduced precursor of Ni/Al ratio of 2.5 precipitated at a pH-level of 7. The size of the Ni particles present in a reduced precursor of Ni/Al ratio of 3 precipitated at a pH-level of 10 rises from 4–8 nm to 16 nm after calcination at temperatures increasing from 120° to 853°C. The last precursor contains much less sodium, and shows after reduction a disordered NiO phase containing some alumina. Especially, the takovite with the molar Ni/Al ratio of 2.5, thoroughly washed to remove Na, and calcined at T ≤ 260°C before reduction of Ni provides a promising catalyst for the production of hydrogen-carbon monoxide flows out of methane and steam.
Stable Isotope Geochemistry of Kaolinite from the “White Section,” Black Ridge, Clermont, Central Queensland: Implications For The Age And Origin of the “White Section”
Authors: Zhou Taihe , Dobos Stephen K. 
Published: August 2006

AbstractKaolinite from the Black Ridge, Clermont, has relatively low δ18O (12.3‰ to 14.8‰) and very low δD values with a large variation (−120‰ to −85‰). Comparison of these data with those from the nearby Denison Trough and elsewhere in eastern Australia, together with previous studies of the mineralogy of the sedimentary rocks, suggests that extensive kaolinization of the “White Section” resulted from weathering during the Late Triassic to Early Jurassic periods. The relatively large variation in δD values of kaolinite probably derives from post-formational isotopic exchange with other fluids.The similarity between δ18O values of kaolinites from Black Ridge and from the Denison Trough suggests that the small Miclere-Black Ridge basin may have been part of the Denison Trough before the Late-Triassic inversion. The preservation of original δD values in kaolinite at Black Ridge indicates that unlike the Denison Trough, which was reburied at more than 1000 m, the Miclere-Black Ridge basin was not rebuffed at great depth during the Mesozoic period.
27Al Mas NMR and Aluminum X-Ray Absorption Near Edge Structure Study of Imogolite and Allophanes
Authors: Ildefonse Ph. , Kirkpatrick R. J. , Montez B. , Calas G. , Flank A. M. , Lagarde P. 
Published: August 2006

AbstractThis paper compares the results of 27Al nuclear magnetic resonance spectroscopy (NMR) and Al-K-edge X-ray Absorption Near Edge Structure (XANES) of natural imogolite and allophanes and some crystalline reference minerals. All soil allophanes studied contain 4-coordinated Al (AlIV). The highest relative proportion of AlIV, 21% of the total Al, was found in Si-rich allophane. This value is close to that found in spring allophanes, which were previously considered to be different from soil allophanes. For a quantitative determination of the AlIV/Altotal ratio, NMR is more reliable than XANES, because of the sensitivity of the chemical shift to low AlIV concentrations, but XANES may be used even if paramagnetic impurities (mostly Fe) are present. Al-K XANES also yields more information than NMR on the local environment of AlVI and especially site multiplicity. AlVI XANES of imogolite and allophanes are similar regardless of the Al/Si ratio. They yield two well-resolved resonances with maxima near 1568 and 1570 eV, which indicates the presence of a unique AlVI site by comparison with crystalline references. The presence of only one AlVI site indicates that imogolite and allophanes have an octahedral sheet with a structure similar to 2/1 dioctahedral phyllosilicates but different from gibbsite or kaolinite, previously considered as structural analogues. The 27AlIV MAS NMR peak maxima of allophanes are between 58.6 and 59.8 ppm, in the range observed for crystalline and amorphous framework alumino-silicates, and less positive than those of sheet silicates, which are typically in the range 65–75 ppm. 27Al-H1 CPMAS NMR spectra suggest that both AlIV and AlVI have Al-O-H linkages.
Effects of the Structure of Silica-Alumina Gel on the Hydrothermal Synthesis of Kaolinite
Authors: Satokawa Shigeo , Osaki Yasushi , Samejima Soichiro , Miyawaki Ritsuro , Tomura Shinji , Shibasaki Yasuo , Sugahara Yoshiyuki 
Published: August 2006

AbstractKaolinite was hydrothermally synthesized from two kinds of silica-alumina gels to examine the effect of the structure of the starting material. Two kinds of gels were prepared by precipitation at different pH conditions (pH = 9.6 and 4.2) from solutions containing water glass and aluminum sulfate. Na ions in the gels were removed with a resin before the hydrothermal treatment, but a slight amount of sulfate ions was still present in the gels. The nuclear magnetic resonance spectra of the starting gels suggested that the gel prepared at pH 9.6 consists of networks with alternating SiO4- and A1O4-tetrahedra (partially AlO6-octahedra), whereas the gel prepared at pH 4.2 consists of a sheet structure related to allophane. After the hydrothermal treatment at 220°C for 9 days, kaolinite particles with spherical shape were obtained from the former gel, and platy kaolinite was crystallized from the latter one. The difference in morphology of synthetic kaolinite was attributable to the structures of the starting gels, and the pH values in the hydrothermal reactions were not very significant to the morphology.
Evaluation of Standard Free Energies of Formation of Clay Minerals by an Improved Regression Method
Authors: Varadachari Chandrika , Kudrat Mahammad , Ghosh Kunal 
Published: August 2006

AbstractAn improved regression method for the evaluation of standard free energies of formation (ΔG°f) of clay minerals is here proposed in an attempt to remove some of the limitations of the earlier method (Chen, 1975). Particularly, this method suggests a procedure for the assignment of rankings for Σ ΔG°f, i values. Moreover, an iterative least-squares fitting technique is applied to solve the exponential equation to obtain the estimated ΔG°f. The estimated ΔG°f data for the various standard clay minerals are derived and compared with data available in the literature; in general, there is good agreement between the values. It is also shown how the regression method can be extended to clay minerals of variable composition. The ΔG°f's for several such minerals have been evaluated; a large number of combination equations required for such computations have been listed, so that for other similar minerals the process of evaluation of ΔG°f is greatly simplified.
FTIR Reflectance vs. EPR Studies of Structural Iron in Kaolinites
Authors: Delineau Thierry , Allard Thierry , Muller Jean-Pierre , Barres Odile , Yvon Jacques , Cases Jean-Maurice 
Published: August 2006

AbstractThe substitution of Fe3+ in the kaolinite structure is studied by EPR spectrometry and by FTIR spectrometry on a large set of kaolins from different origins (sedimentary and primary ores, soil kaolins). The IR bands at 3598 and 875 cm−1, observed in the literature only in the case of disordered kaolins or in Fe-rich environments (synthetic, lateritic), are revealed by high-resolution IR analysis, whatever the origin and the total Fe content of the samples. The EPR bands corresponding to Fe3+ substituted in sites II of the octahedral sheet increase when the IR absorbance near 3600 cm−1 increases. Two IR absorption bands near 4465 cm−1 and 7025 cm−1 are observed for the first time, both in transmission and diffuse reflectance on all samples. These bands are assigned to the combination of the 3598 and 875 cm−1 bands and to the first harmonic of the band at 3598 cm−1, respectively. The area of the band at 4465 cm−1 in diffuse reflectance is quantitatively correlated to the abundance of Fe3+ located in centers II as measured by ESR. This directly confirms the assignment of the two IR bands at 3598 and 875 cm−1 to OH stretching and deformation vibration bands in octahedral FE3+ environment in the kaolinite structure, respectively. Effects due to the size of particles and to the main kaolins impurities on the near infrared spectra, are also discussed.
Transformations of Synthetic Birnessite as Affected by pH and Manganese Concentration
Authors: Tu Shihua , Racz Geza J. , Goh Tee Boon 
Published: August 2006

AbstractThe amount of Mn2+ adsorbed or removed from solution by birnessite is several times greater than its reported cation exchange capacity. Extractability of the sorbed Mn2+ decreases with aging. It is uncertain whether the sorbed Mn2+ is oxidized on the surface or incorporated into the structure of birnessite. Using X-ray powder diffractometry and transmission electron microscopy, a study was conducted to examine the mineralogical alteration of birnessite after treatment with various concentrations of MnSO4 and solution pH.The sorbed Mn2+ was not directly oxidized and remained on the birnessite surface. The sorption of Mn2+ was followed by alteration of birnessite with the formation of new Mn minerals. The specific Mn minerals formed were governed by the pH of the reaction, and the rate of the transformation was determined by Mn2+ concentration and pH. Nsutite and ramsdellite were identified at pH 2.4, crypto-melane at pH 4, groutite at pH 6, and manganite at pH 8. Other Mn minerals formed at these and other pH levels could not be identified. As the concentration of Mn in the solution decreased, the time required to form new minerals from the birnessite increased. The newly formed phases were the result of structural conversion since dissolution of birnessite and reprecipitation of new phases were not observed.
Properties of Hydroxy-Al and -Cr Interlayers in Montmorillonite
Authors: Dubbin W. E. , Goh Tee Boon , Oscarson D. W. , Hawthorne F. C. 
Published: August 2006

AbstractIn environments contaminated with Cr, the interlayers of expandable layer silicates may serve as sinks for this potentially toxic element. As a means of determining the potential for smectites to serve as sinks for Cr, the precipitation products of Al and Cr in the interlayers of a montmorillonite were examined. Five montmorillonite (SWy-1) clay suspensions were treated with preweighed amounts of AlCl3 and CrCl3 to give five Al/(Al + Cr) molar ratios (1.0, 0.67, 0.5, 0.33, 0) with a total trivalent cation (M3+) concentration of 600 cmol(+)/kg clay. The clay-cation suspensions were titrated with 0.1 N NaOH to give a NaOH/M3+ molar ratio of 2.5. Analysis of the solid-phase reaction products showed that the cation exchange capacity and specific surface of all clays were reduced. Chromium reduced the exchangeability of the interlayers while Al increased the thermal stability. X-ray diffraction analysis revealed that all Al-containing interlayer materials formed similar gibbsitelike polymers. Data from infrared spectroscopy indicated that both Al and Cr were present within the same polymer. Differential thermal analysis and thermogravimetric tracings showed that the rapid collapse of the interlayer in the Cr end-member upon heating was due to a low-temperature loss of hydroxyls. It was not possible to identify all interlayer structures in the Cr end-member. Data from X-ray photoelectron spectroscopy showed all Cr to be Cr(III). Displacement of the interlayer material became more difficult as Cr content increased. The least exchangeable interlayers, therefore, may be found in environments containing the most Cr.
Molecular Structure and Binding Sites of Cobalt(II) Surface Complexes on Kaolinite from X-Ray Absorption Spectroscopy
Authors: O'Day Peggy A. , Parks George A. , Brown Gordon E. 
Published: August 2006

AbstractX-ray absorption spectroscopy (XAS) was used to determine the local molecular environment of Co(II) surface complexes sorbed on three different kaolinites at ambient temperature and pressure in contact with an aqueous solution. Interatomic distances and types and numbers of backscattering atoms have been derived from analysis of the extended X-ray absorption fine structure (EXAFS). These data show that, at the lowest amounts of Co uptake on kaolinite (0.20–0.32 µmol m−2), Co is surrounded by ≈6 O atoms at 2.04–2.08 Å and a small number or Al or Si atoms (N = 0.6–1.5) at two distinct distances, 2.67–2.72 Å and 3.38–3.43 Å. These results indicate that Co bonds to the kaolinite surface as octahedrally coordinated, bidentate inner-sphere mononuclear complexes at low surface coverages, confirming indirect evidence from solution studies that a fraction of sorbed Co forms strongly bound complexes on kaolinite. In addition to inner-sphere complexes identified by EXAFS spectroscopy, solution studies provide evidence for the presence of weakly bound, outer-sphere Co complexes that cannot be detected directly by EXAFS. One orientation for inner-sphere complexes indicated by XAS is bidentate bonding of Co to oxygen atoms at two Al-O-Si edge sites or an Al-O-Si and Al-OH (inner hydroxyl) edge site, i.e., corner-sharing between Co octahedra and Al and Si polyhedra. At slightly higher surface sorption densities (0.51–0.57/ µmol m−2), the presence of a small number of second-neighbor Co atoms (average NCo < 1) at 3.10–3.13 Å indicates the formation of oxy- or hydroxy-bridged, multinuclear surface complexes in addition to mononuclear complexes. At these surface coverages, Co-Co and Co-Al/Si distances derived from EXAFS are consistent with edge-sharing between Co and Al octahedra on either edges or (001) faces of the aluminol sheet in kaolinite. Multinuclear complexes form on kaolinite at low surface sorption densities equivalent to <5% coverage by a monolayer of oxygen-ligated Co octahedra over the N2-BET surface area. These spectroscopic results have several implications for macroscopic modeling of metal ion uptake on kaolinite: 1) Primary binding sites on the kaolinite surface at low uptake are edge, non-bridging Al-OH inner hydroxyl sites and edge Al-O-Si bridging oxygen sites, not Si-OH sites typically assumed in sorption models; 2) specific adsorption of Co is via bidentate, inner-sphere complexation; and 3) at slightly higher uptake but still a small fraction of monolayer coverage, formation of Co multinuclear complexes, primarily edge-sharing with Al-OH octahedra, begins to dominate sorption.
The Nature of Polynuclear OH-Al Complexes in Laboratory-Hydrolyzed and Commercial Hydroxyaluminum Solutions
Authors: Wang Wei-Zi , Hsu Pa Ho 
Published: August 2006

AbstractLaboratory-hydrolyzed and commercial OH-Al solutions were characterized using kinetics of Al-ferron color development, kinetics of structural OH neutralization with H+, 27Al NMR spectroscopy, and sulfate precipitation. The results showed that the Al13 complexes having the Keggin structure were dominant only in fresh, laboratory-hydrolyzed OH-Al solutions of OH/Al molar ratio = 1.8 and above. These species gradually converted to other polynuclear forms that reacted with ferron slowly, were not detectable by 27Al NMR spectroscopy, and yielded different basic Al sulfates following Na2SO4 addition. These more stable complexes can best be interpreted to have a Al(OH)3-fragment structure. In the three commercial aluminum chlorohydrate (ACH) solutions studied, Al13 complexes accounted for a small portion of the total Al present. More than 80% of the Al was present as species that were not detectable with NMR spectroscopy and resembled the slow-reacting complexes in aged, laboratory-hydrolyzed OH-Al solutions. Small portions of the slow-reacting complexes appeared to be submicron particulates that acted as nuclei for gibbsite formation or aggregates of Al13 complexes that dispersed to Al13 upon dilution. Polyaluminum chloride (PA) solution resembled the moderately aged laboratory-hydrolyzed OH-Al solutions.