Interaction of cations on octahedral and tetrahedral sites in simple spinels

The cation distribution in the partly inversed binary spinel is usually treated in terms of octahedral site preference energies. Such a model is based on the assumption of ideal cation mixing in each position. The present version of theory includes explicitly the interaction between altervalent cations on octahedral and tetrahedral sites by using a simple regular model of mixing. The values of octahedral site preference energies as well as the site interaction energies are readily obtained from experimental data on the temperature dependence of the inversion parameter.     

Partitioning of divalent transition elements between octahedral sheets of trioctahedral smectites and water

Using trioctahedral smectites synthesized at low temperature (25 and 75°C). partition coefficients have been determined for M²⁺ transition metals (Mn, Fe, Co, Ni, Cu, Zn) between octahedral sheets of smectites and water. These coefficients D_(M²⁺?Mg) = (M²⁺)/(Mg) solid/(M²⁺)/(Mg) liquid have high values near 10⁴ for Cu, 1000 for Ni, Co, Zn, 300 for Fe and 30 for Mn. All transition metals are strongly stabilized in the magnesian solid phase, even Mn which leads to noncrystallized products. Within the range of experimental uncertainties, it is found that tetrahedral substitution of Si by Al and differences in temperature (from 25 to 75°C) have no influence on partition coefficients. Experimental data are closely related to thermodynamic properties of the cations and on this basis other partition coefficients can be calculated, for the (M²⁺ ? Fe²⁺) pair for instance. The behaviour of transition metals is explained using crystal field theory.     

DFT study of the cation arrangements in the octahedral and tetrahedral sheets of dioctahedral 2:1 phyllosilicates

Quantum mechanical calculations based on the density functional theory (DFT) are used to study the crystal structures of dioctahedral 2:1 phyllosilicates. The isomorphous cation substitution is investigated by exploring different substitutions of octahedral Al³⁺ by Mg²⁺ or Fe³⁺, tetrahedral substitution of Si⁴⁺ by Al³⁺, and different interlayer cations (IC) (Na⁺, K⁺, Ca²⁺, and Mg²⁺). Samples with different kinds of layer charges are studied: only tetrahedrally charged, only octahedrally charged, or mixed octahedral/tetrahedral charged. The effect of the relative arrangements of these substitutions on the lattice parameters and total energy is studied. The experimental observation of segregation tendency of Fe³⁺ and dispersion tendency of Mg²⁺ in the octahedral sheet is reproduced and explained with reference to the relative energies of the octahedral cation arrangements. These energies are higher than those due to the IC/tetrahedral and IC/octahedral relative arrangements. The tetrahedral and octahedral substitutions that generate charged layers also tend to be dispersed. The octahedral cation exchange potentials change with the IC-charge/ionic radius value.     

Distribution of Fe in the octahedral sheet of trioctahedral micas by polarized EXAFS

The distribution of Fe atoms within the octahedral sheet of a series of trioctahedral micas has been investigated by polarized Fe K-edge EXAFS spectroscopy. Single crystals have been oriented in the X-ray beam with the layer plane at 35° with respect to the electric field vector. At this “magic angle”, contributions to the EXAFS spectrum of nearest cation shells are equal to those recorded on a completely disoriented powder. The average number of Fe and Mg cations surrounding each Fe atom has been determined and compared with those deduced from NMR spectra. It is shown that the distribution of Fe atoms is not random, the deviation from this distribution depending on the fluorine content. The agreement between these independent results proves the reliability of the structural information deduced from EXAFS and NMR spectra as well as the usefulness of these two methods in analyzing the local distribution of cations in minerals.     

Effects of dry density and exchangeable cations on the diffusion process of sodium ions in compacted montmorillonite

As a part of the safety assessment of the geological disposal of high-level radioactive waste, the effects of dry density and exchangeable cations on the diffusion process of Na⁺ ions in compacted bentonite were studied from the viewpoint of the activation energy for diffusion. The apparent self-diffusion coefficients of Na⁺ ions in compacted Na-montmorillonite and in a Na- and Ca-montmorillonite mixture were determined by one-dimensional, non-steady diffusion experiments at different temperatures and dry densities. A unique change in activation energy as a function of dry density was found for the Na⁺ ions in compacted Na-montmorillonite. The activation energy suddenly decreased from 18.1 to 14.1 kJ mol^− 1 as the dry density increased from 0.9 to 1.0 Mg m^− 3, whereas it increased to 24.7 kJ mol^− 1 as the dry density increased to 1.8 Mg m^− 3. Examination of the effect of exchangeable cations on the activation energies determined that the activation energies were almost constant, approximately 25 kJ mol^− 1, for the montmorillonite specimens at a dry density of 1.8 Mg m^− 3. However, three different activation energy values were obtained at a dry density of 1.0 Mg m^− 3. These findings cannot be explained by the conventional diffusion model (the pore water diffusion model), which suggests that the predominant diffusion process alternates among pore water diffusion, interlayer diffusion, and external surface diffusion.     

The reaction of montmorillonite to mixed-layer clay: the effect of interlayer alkali and alkaline earth cations

The Wyoming bentonite was saturated with alkali and alkaline earth cations and allowed to react hydrothermally for one month at 300°C, and one week and one month at 400°C. Generally, the rate of formation of collapsed layers for the alkali clays was inversely related to interlayer hydration energy. This pattern of reaction is expected if layer dehydration results from an attraction between negatively charged 2:1 layers and the positive interlayer cation. In this mechanism, the greater the hydration energy of the interlayer region, the greater the charge that must develop on the 2:1 layers to cause dehydration, and, therefore, the slower the reaction rate. Reaction rate for the alkaline earth clays was directly related to interlayer hydration energy. Clays saturated with cations of hydration energy equal to or greater than Na⁺ did not react at 300°C, and ceased to react at 50% expandable layers at 400°C. Those saturated with cations of lower hydration energy continued to form mica-like layers with increasing run time at both 300° and 400°C. Clays saturated with monovalent cations reacted by a process of gradual transformation of smectite layers into collapsed layers, whereas those with divalent cations reacted directly from the smectite structure to form a rectorite-like phase.     

Hydration thermodynamics of the SWy-1 montmorillonite saturated with alkali and alkaline-earth cations: A predictive model

The aim of the present work was to study the thermodynamic equilibria between water and a homo-ionic montmorillonite SWy-1 saturated by different cations. The choice of this smectite is justified by the large set of experimental data available from the literature for eight different interlayer cations: Na⁺, K⁺, Rb⁺, Cs⁺, Mg²⁺, Ca²⁺, Sr²⁺, and Ba²⁺. In particular, studies by [Cases et al., 1992], [Cases et al., 1997] and [Bérend et al., 1995] are providing heat of adsorption data, pairs of desorption-adsorption isotherms, and information about the partition of adsorption-desorption water molecules between external surfaces and internal spaces. By calculating the effective amount of hydration water as the difference between the so-called gravimetric water and the surface covering water, a thermodynamic model was then developed, based on the concept of Ransom and Helgeson (1994) considering an asymmetric subregular binary solid solution between a fully hydrated and a anhydrous smectite. A set of six thermodynamic parameters ( and four Margules parameters) was extracted by a least square method from measurements of enthalpies of adsorption and paired adsorption-desorption isotherms for each interlayer cation. These six initial parameters were then used to determine a complete set of standard thermodynamic hydration parameters (, heat capacity, molar volume, and number of interlayer H₂O) and quantify, for each cation, the number of moles of hydration water molecules as a function of relative humidity and temperature. The validation of the standard state thermodynamic properties of hydration for each end member was carried out using three approaches: (1) a comparison with experimental isotherms obtained on hetero-ionic and homo-ionic SWy-1 smectite at different temperatures; (2) a comparison with the experimental integral enthalpy and entropy of hydration of the SWy-1 smectite; and (3) a comparison with experimental isotherms acquired on various smectites (Upton, MX80, Arizona) with different layer charges.Eventually, the present work demonstrates that, from a limited number of measurements, it is possible to provide the hydration thermodynamic parameters for hydrated smectites with different compositions and under different conditions of temperature and relative humidity, using the newly developed predictive model.     

Microinclusions in dark gray diamond crystals of octahedral habit from Yakutian kimberlites

Micrometer-sized inclusions in dark gray diamond crystals of octahedral habit from Yakutian kimberlites were studied by analytical scanning electron microscopy and analytical transmission electron microscopy. In addition to peridotite-suite silicate inclusions (enstatie and olivine), which were previously studied in detail as macroinclusions in perfect diamond crystals, there are abundant inclusions of native metals (Fe-Cr and Fe-Cr-Ti intermetallic compounds and metallic Fe), sulfides (Fe-Ni sulfide, polydymite, and chalcopyrite), and carbonates (calcite). Rare grains of ilmenite, fluorite, apatite, zircon, phlogopite, and some other minerals were also found. The gray and black colors of diamonds were previously attributed to the presence of graphite. Although this phase was identified in the electron diffraction patterns of all the samples, its content was very low. Microinclusions of induced octahedral morphology composed of intimate enstatite-calcite intergrowths were also found. Possible deep processes responsible for the formation of diamonds with such a peculiar inclusion association are discussed in light of new data on experimental synthesis. Original Russian Text ? S.V. Titkov, A.I. Gorshkov, N.G. Zudin, I.D. Ryabchikov, L.O. Magazina, A.V. Sivtsov, 2006, published in Geokhimiya, 2006, No. 11, pp. 1209–1217.     

Distribution of Fe among octahedral sites and its effect on the crystal structure of pumpellyite

Two pumpellyites with the general formula W ₈ X ₄ Y ₈ Z ₁₂O_56-n (OH) _n were studied using ⁵⁷Fe Mössbauer spectroscopic and X-ray Rietveld methods to investigate the relationship between the crystal chemical behavior of iron and structural change. The samples are ferrian pumpellyite-(Al) collected from Mitsu and Kouragahana, Shimane Peninsula, Japan. Rietveld refinements gave Fe(X):Fe(Y) ratios (%) of 41.5(4):58.5(4) for the Mitsu pumpellyite and 46(1):54(1) for the Kouragahana pumpellyite, where Fe(X) and Fe(Y) represent Fe content at the X and Y sites, respectively. The Mössbauer spectra consisted of two Fe²⁺ and two Fe³⁺ doublets for the Mitsu pumpellyite, and one Fe²⁺ and two Fe³⁺ doublets for the Kouragahana pumpellyite. In terms of the area ratios of the Mössbauer doublets and the Fe(X):Fe(Y) ratios determined by the Rietveld refinements, Fe²⁺(X):Fe³⁺(X):Fe³⁺(Y) ratios are determined to be 22:14:64 for the Mitsu pumpellyite and 27:8:65 for the Kouragahana pumpellyite. By applying the Fe²⁺:Fe³⁺-ratio determined by the Mössbauer analysis and the site occupancies of Fe at the X and Y sites given by the Rietveld method together with chemical analysis, the resulting formula of the Mitsu and Kouragahana pumpellyites are established as Ca₈(Fe _0.88 ²⁺ Mg_0.68Fe _0.77 ³⁺ Al_1.66)_Σ3.99(Al_5.67Fe _2.34 ³⁺ )_Σ8.01Si₁₂O_42.41(OH)_13.59 and Ca₈(Mg_1.24Fe _0.65 ²⁺ Fe _0.46 ³⁺ Al_1.66)_Σ4.01(Al_6.71Fe _1.29 ³⁺ )_Σ8.00Si₁₂O_42.14(OH)_13.86, respectively. Mean Y–O distances and volumes of the YO₆ octahedra increase with increasing mean ionic radii, i.e., the Fe³⁺→Al substitution at the Y site. However, change of the sizes of XO₆ octahedra against the mean ionic radii at the X site is not distinct, and tends to depend on the volume change of the YO₆ octahedra. Thus, the geometrical change of the YO₆ octahedra with Fe³⁺→Al substitution at the Y site is essential for the structural changes of pumpellyite. The expansion of the YO₆ octahedra by the ionic substitution of Fe³⁺ for Al causes gradual change of the octahedra to more symmetrical and regular forms.     

Microinclusions in diamonds of octahedral habit from kimberlites of Shandong Province, Eastern China

Microinclusions in octahedral diamond crystals from kimberlites of Shandong Province, eastern China, have been studied with analytical scanning electron microscopy. Native iron, tungsten, and lead; Fe-Cr intermetallic compounds; polydymite; ilmenite; halite; and matlockite (PbFCl) have been identified on the crystal surfaces. Microinclusions of native iron and chrome, Fe-Cr intermetallic compounds, pentlandite, Cr-free garnet, calcite, and apatite, as well as a relatively large (100 × 270 μm) inclusion representing an intergrowth of clinopyroxene, calcite, and apatite, have been revealed on the surfaces of fresh chips of the samples. The deep geological processes that could have resulted in the formation of such unusual mineral assemblages are discussed in the light of new experimental data.     

Dissolution of silica from montmorillonite: effect of solution chemistry

The rate of silica removal from two montmorillonites (Chambers and Polkville) has been measured as a function of time, temperature, solution composition, and exchange ion on the clay. Silica removal rate increased with temperature from 200 to 350°C, decreased with time, and could be approximated initially by a parabolic rate law. Solution composition influenced silica removal rate by determining the exchange population of the clay; silica removal is most rapid when K-exchange ions are present. Thus increasing the concentration of K⁺ accelerated silica removal, whereas increasing the concentration of Na⁺, Ca²⁺, and Mg²⁺ inhibited silica removal. Activation energies for silica removal range from 5 to 10 kcal/mol. The largest values are associated with the largest concentrations of inhibitor ions in solution. Activation energies of this magnitude suggest that the rate-limiting step for silica removal is transport through a hydrated, expanded interlayer space. Application of experimental results to diagenesis in moderately to deeply buried sediments suggests that K⁺ uptake by montmorillonite may precede and accelerate illite formation.     

Strain path partitioning within thrust sheets: microstructural and petrofabric evidence from the Moine Thrust zone at Loch Eriboll,northwest Scotland

Quartz c axis fabrics and microstructures have been investigated within a suite of quartzites collected from the Loch Eriboll area of the Moine Thrust zone and are used to interpret the detailed processes involved in fabric evolution. The intensity of quartz c axis fabrics is directly proportional to the calculated strain magnitude. A correlation is also established between the pattern of c axis fabrics and the calculated strain symmetry.Two kinematic domains are recognized within one of the studied thrust sheets which outcrops immediately beneath the Moine Thrust. Within the upper and central levels of the thrust sheet coaxial deformation is indicated by conjugate, mutually interfering shear bands, globular low strain detrital quartz grains whose c axes are aligned sub-parallel to the principal finite shortening direction (Z) and quartz c axis fabrics which are symmetric (both in terms of skeletal outline and intensity distribution) with respect to mylonitic foliation and lineation. Non-coaxial deformation is indicated within the more intensely deformed and recrystallized quartzites located near the base of the thrust sheet by single sets of shear bands and c axis fabrics which are asymmetric with respect to foliation and lineation.Tectonic models offering possible explanations for the presence of kinematic (strain path) domains within thrust sheets are considered.     

对煤炭地质行业非劳动因素参与分配的探讨

非劳动要素与分配的问题，引起了理论界的高度重视。作为地勘行业的煤炭地质单位，如何确立非劳动要素参与分配的机制，是摆在煤炭地质单位劳资工作者面前的新课题。通过”资本参与分配、技术要素参与分配、管理要素参与分配”等三个方面的分析，对目前煤炭地质单位非生产要素参与分配的现状及实施的前提条件作了进一步的探讨，并就如何确立非生产要素参与分配的分配体系提出了看法。     

Deformation mechanisms in some cover thrust sheets from the external French Alps

Rocks from two parts of the Ultradauphinois Zone of the external French Alps have been examined, and the mechanisms by which they were deformed have been assessed from petrographic data. Jurassic and Triassic limestones deformed by pressure solution, dissolving non-ferroan-calcite and precipitating ferroan-calcite. Calcite pressure shadows are usually less elliptical in shape than pyrite pressure shadows, and grain boundary sliding is therefore thought to have played a significant role. Eocene rocks deformed by a variety of mechanisms. Limestones show mylonitic textures, whereas limestone conglomerates with a quartz-sandstone matrix deformed by pressure solution of calcite and grain boundary sliding of quartz. A model for enhanced diffusion of silica along mica seams is proposed to account for planar quartz-mica boundaries. Greywackes deformed by incongruent pressure solution, involving the metamorphic reaction of feldspar to mica and quartz, coupled with the replacement of feldspar by calcite.     

自然界中ZnS-CdS完全类质同象系列的发现和初步研究

过去认为在自然界中的Cd只能有限替代ZnS中的Zn。但是，近几年笔者在研究贵州牛角塘镉锌矿床时，经电子探针、扫描电镜和透射电镜等多种方法的研究，发现锌硫化物中的Cd主要以类质同象存在，其含量可从0．8％增至37．93％；镉硫化物中的Zn同样主要以类质同象存在，其含量为2．43％～38．64％。锌硫化物与镉硫化物成渐变的过渡关系，并且Zn与Cd成很好的负相关关系，相关系数达0．99以上，形成ZnS-CdS的完全类质同象系列。这一发现无论在矿物学，还是在地球化学和矿床学上都具有重要的理论意义和实用价值。     

Clustering of cations in amphiboles

The OH^? stretching frequencies of clino-amphiboles are known to depend on the cations to which the OH^? is co-ordinated, and the intensities of the corresponding infra-red (ir) absorption bands have been used to obtain evidence as to the occupancy of the M1 and M3 sites. However, the possible effects on the method arising from clustering together of like cations, or of the mutual avoidance of like cations (anti-clustering), have not hitherto been explicitly analysed. A model is set up which permits these to be systematically explored. The results are exemplified for occupation of M1 and M3 by (Fe, Mg). Clustering of Fe increases the frequency of both Fe₃ and Mg₃ triads, though not equally, and the effect of anti-clustering is in the opposite sense. The effect on the frequencies of MgFe₂ and Mg₂Fe triads is much more complicated and the sense of the changes depends on both the overall Fe content and on the degree of clustering or anti-clustering.     

Effect of compacton on chemistry of solutions expelled from montmorillonite clay saturated in sea water

The total mineralization of solutions squeezed out of montmorillonite clay saturated in sea water was determined at different overburden pressures. The subsequent fractions of expelled solutions were also analysed for various anions (Cl^?, SO^2-₄, HCO^?₃, F^?) and cations (Na⁺, K⁺, Mg²⁺, Ca²⁺, B³⁺). The results indicate that the concentrations of squeezed-out solutions during the initial stages of compaction (at pressures up to 35 kg/cm²) are slightly higher than that of interstitial solution present initially. The concentration of squeezed-out solution goes through a maximum, or at least remains constant, before starting to decrease with increasing overburden pressure.