bluuebunny/crossref_metadata_2025_split huggingface dataset:
Interaction of Uranyl Ions with Synthetic Zeolites of Type A and the Formation of Compreignacite-Like and Becquerelite-Like Products
Authors: Brindley G. W. , Bastovanov Marija 
Published: August 2006

AbstractUranyl acetatye solutions, ranging in concentration from about 100 ppm to 3700 ppm, were re-acted with the Na-, K-, and Ca- forms of zeolite A. The crystalline products from the Na- and K-A zeolites resembled compreignacite (K2O·6UO3·11H2O) and from the Ca-A, becquerelite (CaO·6UO3·11H2O). With higher concentrations of uranyl acetate, only X-ray-amorphous products were obtained. The compreignacite-like products gave sharp X-ray powder diffraction patterns and were indexed with orthorhombic, quasi-hexagonal unit cells which showed a significant variation of the axial ratio b/a from values just greater than, to values just less than √3. The becquerelite-like phase was always accompanied by unreacted zeolite. Compreignacite was synthesized from uranyl acetate and KOH solutions at room temperature over a period of several days.
Surface Properties of Allophane, Halloysite, and Imogolite
Authors: Theng B. K. G. , Russell M. , Churchman G. J. , Parfitt R. L. 
Published: August 2006

AbstractThe adsorption of sodium, chloride, and phosphate ions by allophane, imogolite, and halloysite has been studied in relation to the surface structure of the mineral samples. The high adsorption of phosphate (>200 μmole/g) and chloride (10–30 meq/100 g at pH 4) by allophane is ascribed to the small particle size of allophane, its high surface area (∼800 m2/g), and the presence at the surface of Al-OH-Al groups and defect sites. In contrast, halloysite has a relatively large particle size and a Si-O-Si surface. Accordingly, the adsorption of phosphate (5–10 μmole/g) and chloride (1 meq/100 g) by halloysite is very much lower as compared with allophane. Phosphate adsorption by halloysite is also related to particle morphology and the number of edge sites. Thus, a sample consisting entirely of spheroidal particles adsorbed only 5 μmole/g at a solution concentration of 1 × 10−4 M, whereas the tubular types of comparable surface area adsorbed 7–10 μmole/g at the same concentration. This is because spheroidal halloysite particles have few, if any, edge sites at which phosphate can adsorb. The relative degree of order and hydration of halloysite, as indicated by infrared spectroscopy, also affects phosphate adsorption. However, this factor is apparently less important than particle morphology and surface structure. Although imogolite also has an Al-OH-Al surface, it contains relatively few defect sites where phosphate can adsorb. Consequently, much less phosphate (120 μmole/g) was adsorbed as compared with allophane.
Solubility of Two High-Mg and Two High-Fe Chlorites Using Multiple Equilibria
Authors: Kittrick J. A. 
Published: August 2006

AbstractHigh-Mg chlorites from Vermont and Quebec and high-Fe chlorites from Michigan and New Mexico were equilibrated at room temperature in the near-neutral pH range. Gibbsite, kaolinite, and hematite of known stability were added to the samples to control unmeasurable variables at calculable levels. Equilibrium solution compositions were obtained from undersaturation and from supersaturation. Other indicators of equilibrium were good agreement between successive analyses over a long period of time, between duplicate samples, between independent systems, and between independent measures of equilibrium. All four chlorites were stable relative to brucite and, with a few exceptions, relative to talc under the conditions of study. When in equilibrium with gibbsite, the pH − ½Mg2+ value of the chlorites ranged from 6.3 to 6.5, at a pH4SiO4 value of 4.0. These values are in good agreement with prior estimates of chlorite stability. The calculated standard free energy of formation of the chlorites is dependent upon solution Fe2+ calculated from the sample Eh and assumed equilibrium with hematite, with the assumption that the Fe2+-Fe3+ couple is at the same Eh as the sample.
Crystal-Chemical Study of Layered [Al2Li(OH)6]+X−·nH2O
Authors: Serna Carlos J. , Rendon Jose L. , Iglesias Juan E. 
Published: August 2006

AbstractA layered double hydroxide with a chemical composition [Al2Li(OH)6]+X− · nH2O, where X− is an interlayer anion, has been synthesized hydrothermally at 130°C from aluminum-tri-(sec-butoxide) and lithium carbonate. Electron micrographs showed the product to have a platy morphology with distinct hexagonal symmetry, which has been corroborated by selected area electron diffraction patterns corresponding to a projection of the structure on its (001) plane. Evidence for a superlattice with a = 5.32 Å was obtained, indicating cation ordering among octahedral sites. X-ray powder diffraction data also can be interpreted by reference to a hexagonal supercell with dimensions a = 5.32 Å and c = 15.24 Å. The arrangement of the octahedral sites appears to be that of gibbsite, but with the vacancies filled with lithium cations. Anions must be present between the sheets to balance the charge. A complete assignment of the observed infrared lattice vibrations can be made for the anion [Al2LiO6] with the ideal D3d symmetry for motions within one octahedral sheet. The results show that [Al2Li(OH)6]+X− · nH2O is a hydrotalcite-like compound with the octahedral cations largely ordered. The general formula for hydrotalcite-like compounds, [M2+1−xM3+x(OH)2]x+Xm−x/m · nH2O, should be extended to include the monovalent lithium cation.
Hydrolysis and Dehydration Reactions of Exchangeable Cu2+ on Hectorite
Authors: McBride M. B. 
Published: August 2006

AbstractElectron spin resonance (ESR) analysis of Cu2+-hectorite suspensions provides evidence for the surface-induced hydrolysis of Cu(H2O)62+ at low pH and surface-inhibited hydrolysis (or precipitation) at high pH. Dehydration of the hectorite by heating to 110°C appears to promote hydrolysis in high pH clays further. Heating to even higher temperatures removes ligand water from Cu2+, allowing the metal ion to coordinate with silicate oxygen atoms. The planar Cu(H2O)42+ ion predominates in the interlamellar regions of hectorite that has been air dried or heated to temperatures of 110°C or lower, but more extreme thermal treatment changes the apparent orientation of the Cu2+-ligand axes as some or all of the four water ligands are removed, A loss in ESR signal intensity upon heating Cu2+-hectorite above 110°C is evidence for lowered symmetry of the dehydrated, surface-coordinated Cu2+ ion.
Layer Charge Heterogeneity in Vermiculites
Authors: Lagaly Gerhard 
Published: August 2006

AbstractThe broad charge heterogeneity typical of nearly all smectites is not necessarily characteristic of vermiculites. In addition to vermiculites with pronounced heterogeneity, minerals with no or only limited charge heterogeneities are known. Layer charge and charge heterogeneity of 25 vermiculites were determined by alkylammonium ion exchange. The comparison of experimental basal spacings with dL/n-plots provided a simple determination of the average charge density. The spacings of high-charged vermiculites (≥0.8 eq/(Si,Al)4O10) with paraffin-type interlayers follow a straight line in the dL/n-plots. Lower-charged vermiculites were recognized by stepwise increasing spacings due to mono-, two-, or three-layer chain packings. Charge heterogeneity produced a superposition of the dL/n-curves for different charges, and the basal reflections of some of the alkylammonium derivatives became nonintegral.
Hydrolysis and Decomposition of Hectorite in Dilute Salt Solutions
Authors: Kreit J. F. , Shainberg I. , Herbillon A. J. 
Published: August 2006

AbstractThe hydrolysis and decomposition of M-hectorite (M being Na, Li, Mg, or Ca) in dilute solutions of M-chlorides were studied by recording the changes in electrical conductivity (EC) of the clay suspensions with time, and by chemical analyses of the interclay solutions and resulting solid phases. The rate of hydrolysis of the hectorites in suspension, as evaluated by the change of EC with time, was found to decrease with increase in salt concentration (to zero for Na-hectorite in NaCl concentration of 47 meq/liter), and to decrease with increase in the valency of the adsorbed cation (the rate of hydrolysis of Ca-hectorite was one sixth of that of Na-hectorite). The rate of Na-hectorite hydrolysis was determined by the concentration of protons at the clay surface as calculated from the diffuse double layer theory.Conversely, in suspensions of Al-hectorite saturated with Na, the hydrolysis rates were not dependent on the electrolyte concentrations. This result can be explained by assuming that the hydroxy-Al polymers at the clay surface determine the proton concentration at the clay surface. Hectorites saturated with structural cations (such as Mg and Li) are chemically more stable than those saturated with Na and Ca. The presence of Li and Mg at the clay surface slowed down the diffusion release of these octahedral ions to the clay surface, compared with Na and Ca hectorite, respectively.
Alteration of Andesite in Wet, Unstable Soils of Oregon's Western Cascades
Authors: Glasmann J. R. 
Published: August 2006

AbstractAlteration products of andesite cobbles from wet soils formed in volcanic colluvial material were studied using petrographic, electron microscope, X-ray powder diffraction, and thermal techniques. Augite phenocrysts altered by congruent dissolution leaving voids which were subsequently filled with smectite. Plagioclase also altered to produce micrometer-size spheroidal aggregates of smectite. Halloysite was not observed within the altered cobbles, although it was abundant in the soil matrix. The formation of smectite in the altered cobbles was probably favored by the restrictive drainage of the microenvironment in combination with wet soil conditions.
Berthierine and Chamosite in Coal Measures of Japan
Authors: Iljima Azuma , Matsumoto Ryo 
Published: August 2006

AbstractBerthierine (formerly chamosite) occurs as concretions, lenses, and bands in carbonaceous, kaolinitic shale of freshwater coal-swamp deposits in Paleogene and Upper Triassic coal measures of Japan. Textural relations in thin sections of the Triassic berthierine rocks and a siderite-kaolinite-berthierine-quartz assemblage in Paleogene rocks indicate that the berthierine formed by reaction of siderite with kaolinite. The transformation of siderite and kaolinite to berthierine and quartz occurs progressively under reducing conditions between 65° and 150°C and at burial depths of 2–5 km. Utatsu berthierine is an aluminous, low-Mg variety as compared with berthierine pellets in modern marine and estuarine sediments and in ancient marine ironstones. Fe is the dominant octahedral cation with Fe2+ ≫ Fe3+. The composition of the berthierine varies between different morphological types. Utatsu berthierine transformed to ferrous chamosite when kaolinite in the host shale changed to pyrophyllite. These transformations are estimated to have occurred at ∼160°C and at a burial depth of ∼3 km.
Catalytic Action of Copper on the Oxidation of Structural Iron in Vermiculitized Biotite
Authors: Sayin Mahmut 
Published: August 2006

AbstractThe ferrous iron content of two vermiculitized biotites decreased by treatment with 0.1 N salts of copper at 70°C from 9.1–14% to 1.8–2.6%. Presumably, interlayer copper ions acted as a catalyst (here, an electron carrier) for the oxidation of iron by dissolved oxygen. The oxidized iron was ejected from the structure and formed crystalline iron minerals, such as hematite and goethite. Weight loss determinations, chemical, and X-ray powder diffraction data suggest that Cu(II) ions were polymerized to hydroxy-hydrous compounds in the interlayer space. Poor exchangeability of the resultant complex is attributed to the formation of strong electrostatic attractions between OH groups of the interlayer complexes and silicate oxygens.
Thermodynamic Characterization of Clay/Electrolyte Systems
Authors: Neal C. , Thomas A. G. , Truesdale V. W. 
Published: August 2006

AbstractClay/electrolyte systems are best characterized using a new variable, notional interfacial content (NIC). The NIC approach emphasizes that any division of the total amount of a species present in a clay/electrolyte system into that part which ‘belongs’ to the clay and that part which ‘belongs’ to solution is necessarily arbitrary. It carries out this division by choosing one of the species as a reference species and defining it as being completely in a notional bulk solution which had the same composition, but not extent, as the real bulk solution. The NIC of each of the other species present, that is that part of their total amount not in the notional bulk solution, therefore represents the amounts of those species ‘belonging’ to the clay.The NIC concept is universal and hence encompasses several other, older terms. For example, by choosing different reference species, the variables hitherto called ‘water adsorption’ and ‘negative adsorption’ (which have been used to describe the same phenomenon) may be obtained. Similarly, certain earlier definitions of exchangeable and adsorbed cations (some being pragmatic are not included) as well as that of ion surface excesses may be accounted for. The NIC approach thus provides a rationalization of several earlier terms which are, in fact, plagued by a multiplicity of definition which makes their use very complicated.
Mixed-Layer Kerolite/Stevensite from the Amargosa Desert, Nevada
Authors: Eberl Dennis D. , Jones Blair F. , Khoury Hani N. 
Published: August 2006

AbstractMixed-layer clays composed of randomly interstratified kerolite/stevensite occur as lake and/or spring deposits of probable Pliocene and Pleistocene age in the Amargosa Desert of southern Nevada, U.S.A. The percentage of expandable layers of these clays, determined from computer-simulated X-ray diffractograms, ranges from almost 0 to about 80%. This range in expandabilities most likely results from differences in solution chemistry and/or temperature at the time of formation. An average structural formula for the purest clay (sample P-7), a clay with about 70% expandable layers, is:
$${\left[ {\left( {M{g_{2,72}}A{l_{0,07}}F{e_{0.03}}L{i_{0.09}}} \right)\left( {S{i_{3.96}}A{l_{0.04}}} \right){O_{10}}{{\left( {OH} \right)}_2}} \right]^{ - 0.21}}{\left[ {X_{0.21}^ + } \right]^{ + 0.21}}.$$The data suggest that talc, kerolite, and stevensite form a continuous structural series based on layer charge.
Influence of Relative Humidity on the Crystallization of Fe(III) Oxides from Ferrihydrite
Authors: Torrent J. , Guzman R. , Parra M. A. 
Published: August 2006

AbstractFerrihydrite prepared in different manners was kept under relative humidities ranging from 75 to 100% and at temperatures of 45° and 55°C for 180 days. Ferrihydrite transformed to hematite and goethite at relative humidities close to 100%, but at lower relative humidities the transformation was less pronounced and hematite was highly favored over goethite. Increasing temperature also favored hematite over goethite, and Al substitution completely prevented goethite formation. These results suggest that hematite can form in relatively dry, warm soils or sediments, although more slowly than in moister environments.
Effect of Exchangeable Ions and Ionic Strength on Boron Adsorption by Montmorillonite and Illite
Authors: Keren R. , O'Connor G. A. 
Published: August 2006

AbstractThe effects of exchangeable Na and Ca and the ionic strength of NaCl and CaCl2 solutions on the boron adsorption by the Na and Ca forms of montmorillonite and illite at pH 9 were studied. The boron adsorption by montmorillonite was greater for the Ca form than for the Na form at any boron activity in solution and at any ionic strength. For example, the amount of boron adsorbed by Na- and Ca-montmo-rillonite was 2.9 and 4.3 μmole/g, respectively, at an ionic strength of 0.36 and a boron activity of 0.875 mmole/liter in equilibrium solution. The boron adsorption by illite was much greater than by montmorillonite. For example, the amount of boron adsorbed by Na-montmorillonite and Na-illite was 1.5 and 8.7 μmole/g, respectively, at an ionic strength of 0.02 and a boron activity of 0.5 mmole/liter. However, the nature of the exchangeable cation had little effect on the boron adsorption by illite. The effect of the ionic strength on the boron adsorption by Na-montmorillonite was greater than that observed for either Camontmorillonite or illite. The data suggest that the negative electric field around the clay particles is one of the main factors controlling boron adsorption at alkaline pHs.
Surface Properties of Sepiolite from Amboseli, Tanzania, and Its Catalytic Activity for Ethanol Decomposition
Authors: Dandy A. J. , Nadiye-Tabbiruka M. S. 
Published: August 2006

AbstractThe catalytic activity of sepiolite from Amboseli, Tanzania, for the dehydration and dehydrogenation of ethanol at 150°–300°C has been studied using a flow reactor. Both reactions occur, but the catalyst activity decreases with use. The products include water, carbon dioxide, ethene, ethanal (acetaldehyde), diethyl ether, but-1,3-diene, but-2-enal (crotonaldehyde), and an unidentified aromatic compound. The proportions change with temperature, the dehydrogenation reaction being favored at the higher temperatures. The BET surface areas of the sepiolite are 316 m2/g (nitrogen adsorption at — 197°C) and 212 m2/g (ethanol vapor adsorption at 25°C, assuming a molecular cross-sectional area of 24.6 Å2), indicating a possible greater penetration of pores and channels by nitrogen compared with ethanol vapor under these conditions. The pore-size distribution reveals that approximately 55% of the surface area measured by nitrogen adsorption is contributed by micropores.
Oxidation and Reduction of Structural Iron in Chlorite at 480°C
Authors: Borggaard Ole K. , Lindgreen Holger B. , Mørup Steen 
Published: August 2006

AbstractAn iron-rich chlorite, ripidolite, was oxidized by air-heating at 480°C, i.e., below the dehydroxylation temperature and subsequently reduced in hydrogen at the same temperature. On the basis of chemical, differential thermal, infrared, Mössbauer, and X-ray powder diffraction analyses, Fe(II) seems to be present only in the 2:1 layer of the original chlorite in a type of site similar to that of Fe(II) in biotite, with OH in cis-positions. These data also suggest that octahedral Al and Fe(III) are located in the hydroxide sheet of the original chlorite. The structural changes of the mineral due to the oxidation and the subsequent reduction appear limited to minor structural rearrangements and, perhaps, to the introduction of OH in both cis- and trans-positions. The results of the investigation are in agreement with a reaction of the form: [Fe(II)OH]+ ⇋ [Fe(III)O]+ + H(H+ + e−).
Polytypism of Micas: OD-Interpretation, Stacking Symbols, Symmetry Relations
Authors: Dornberger-Schiff K. , Backhaus K. -O. , Ďurovič S. 
Published: August 2006

AbstractFrom the symmetry point of view, micas may be classified as follows: those with all three octahedrally coordinated sites occupied by the same cation (homo-octahedral micas), those with only two of these sites occupied by the same cation (meso-octahedral micas), and those with the three sites occupied by different cations or by two different cations and a void, in an ordered manner (hetero-octahedral micas). For any of these three classes, mica polytypes, idealized in accordance with the generalized Pauling model, can be interpreted as OD structures consisting of octahedral OD layering and tetrahedral OD layering in which an interlayer cation plane is sandwiched between tetrahedral sheets. A mica layer built up by an octahedral sheet and two halves of tetrahedral sheets on either side consists of two OD packets linked by a two-fold rotation.The orientation of any OD packet may be given by a number from 0 to 5 (related to a hexagonal coordinate system). A dot behind or before these numbers is used to denote the position of the octahedral layer (number + dot = orientational character). The displacement of a packet against its predecessor is characterized by a vector from the origin of a packet pn (or qn-1) to the origin of the adjacent packet pn+1 (or p2n). These displacements may also be symbolized by numbers from 0 to 5 (displacement characters); a zero displacement is symbolized by *. Any mica polytype (ordered or disordered) can thus be described by a two-line symbol. The orientational characters are located on the first line, and the displacement characters on the second. Any symbol, therefore denotes unequivocally the stacking layers in a polytype. The space-group symmetry of ordered polytypes follows directly from the symbol.
Factors Affecting Orientation of OH-Vectors in Micas
Authors: Bookin A. S. , Drits V. A. 
Published: August 2006

AbstractThe orientation of the OH-vectors in hydroxyl groups of micas of different compositions, polytype modifications, and symmetry were calculated by the method of minimization of electrostatic energy. The orientations are strongly affected by the peculiarities of structures, and even slight deviations from the ideal dioctahedral periodicity can introduce a correction of as much as 10° to the value of the polar angle. Ordering of cations in octahedra lead to twisting of the OH-bond towards the octahedron with lower charge and larger dimension. The latter is less true for cation ordering in tetrahedra. Because of these factors and the dependence of the hydrogen position on the coordinates of heavy atoms, such calculations can give reliable results only if the structure has been refined with high precision. Different polytypes of micas displayed the same orientation of the OH-vectors with respect to the axes of a separate layer, if the stacking sequence did not introduce specific distortions of the 2:1 layer.
Origin of an Underclay as Revealed by Vertical Variations in Mineralogy and Chemistry
Authors: Rimmer Susan M. , Eberl Dennis D. 
Published: August 2006

AbstractRegular vertical variations in mineralogy and chemistry indicate that underclay beneath the Herrin (No. 6) coal in southwestern Illinois has undergone in situ alteration. Alteration resulted from the downward movement of hydrogen ions, as indicated by the progressive leaching of acid-sensitive minerals adjacent to the coal. Mineralogical trends observed in the underclay with increasing depth below the coal include: (1) a decrease in the expandability of mixed-layer illite/smectite (I/S); (2) an increase in the amount of ordered I/S with respect to randomly interstratified I/S; (3) an increase in the amount of discrete illite with respect to expandable clays; and (4) an increase in chlorite and calcite. Ordered I/S is the dominant mixed-layer clay where calcite is present, but randomly interstratified I/S dominates where calcite is absent. The pH of the underclay also increases with depth. These trends are consistent with an origin by acid leaching of a preexisting mineral assemblage that included illite, chlorite, and calcite. Other acid-alteration trends may be expected for different precursor minerals and for different leaching intensities and durations.