Electronic structure of spinel

The fundamental band gap between conduction and valence bands in aluminate spinels has been found to be at least 8·1 eV; the optical reflectivity peak at this energy possibly represents the lowest-energy exciton. In crystals with non-stoichiometric Al/Mg ratios, the intensity of this first reflection peak appears to decrease with increasing Al/Mg ratio; however, the peak energies themselves are essentially independent of stoichiometry. It seems likely that spinel and olivine in spinel-structure will have electronic transport behavior similar to that of olivine in its normal structure.     

Systematics of the spinel structure type

Systematic trends in the geometry of 149 oxide and 80 sulfide binary and ternary spinels have been examined from the standpoint of ionic radius and electronegativity. The mean ionic radii of the octahedral and tetrahedral cations, taken together, account for 96.9 and 90.5% of the variation in the unit cell parameter, a, of the oxides and sulfides, respectively, with the octahedral cation exerting by far the dominant influence in sulfides. The mean electronegativity of the octahedral cation exerts an additional, but small, influence on the cell edge of the sulfides. The equation a=(8/3√d)d _tet+(8/3)d _oct, where d _tet and d _oct are the tetrahedral and octahedral bond lengths obained from the sum of the ionic radii, accounts for 96.7 and 83.2% of the variation in a in the oxides and sulfides, respectively, again testifying to the applicability of the hard-sphere ionic model in the case of the spinel structure. Comparison of observed and calculated u values for 94 spinels indicates that up to 40% of the experimentally measured anion coordinates may be significantly in error. In addition to these compounds, u values are given for 52 spinels for which no data have previously been determined. Diagrams are presented for the rapid interpretation of the internal consistency of published data and the prediction of the structural parameters of hypothetical or partially studied spinels.     

Cation distribution and structure modelling of spinel solid solutions

 This paper presents an improved generalisation of cation distribution determination based on an accurate fit of all crystal-chemical parameters. Cations are assigned to the tetrahedral and octahedral sites of the structure according to their scattering power and a set of bond distances optimised for spinel structure. A database of 295 spinels was prepared from the literature and unpublished data. Selected compositions include the following cations: Mg²⁺, Al³⁺, Si⁴⁺, Ti⁴⁺, V³⁺, Cr³⁺, Mn²⁺, Mn³⁺, Fe²⁺, Fe³⁺, Co²⁺, Ni²⁺, Zn²⁺ and vacancies. Bond distance optimisation reveals a definite lengthening in tetrahedral distance when large amounts of Fe³⁺ or Ni²⁺ are present in the octahedral site. This means that these cations modify the octahedral angle and hence the shared octahedral edge, causing an increase in the tetrahedral distance with respect to the size of the cations entering it. Some applications to published data are discussed, showing the capacity and limitations of the method for calculating cation distribution, and for identifying inconsistencies and inaccuracies in experimental data. Received: 19 February 2001 / Accepted: 1 June 2001     

Band theoretical studies of the electronic structure of oxides

The O^2? ion is a useful concept in ionic solids. Its electron density and large polarizability is well described by the Watson sphere model. The large variation in the electronic structure of oxides is illustrated by discussing the ionic MgO, the partly ‘covalent’ Cu₂O, and TiO and NbO which have defects with respect to the ideal NaCl structure. The variation in physical properties is shown for the oxides in the rutile structure ranging from the insulating TiO₂, the metallic RuO₂ to the ferromagnetic CrO₂. Electron densities, total energies and densities of states are used to study these materials.     

Energetics of metamorphic crystallization

Metamorphic crystallization necessitates nucleation of new grains. Associated with this process is an energy barrier which requires an input of energy sufficient to make the net change of free energy with nucleus growth decrease so that the process of grain crystallization will proceed. Temperature increase and elastic strain are widely accepted as capable of including metamorphic crystallization. Evaluation of these suggests that an energy input on the order of 0.x cal gm^?1 is commonly enough to overcome the energy barrier and induce metamorphic crystallization. Both processes are necessarily timebound to the time of energy input. Conservative quantitative evaluations of the increase in interfacial free energy by grain size reduction, and of the energy increase resulting from increased dislocation density of grains, show that energetically, these may be equally capable of inducing metamorphic crystallization. These processes can store energy in the system; later release of that energy by metamorphic crystallization may occur under stress and temperature conditions much different from those that accompanied the input of the energy. Furthermore, the formation of a new set of grains will necessarily eliminate the evidence of the precursor state, whether fine granulation or a condition of high dislocation density in the grains of the system.Experiments have demonstrated the existence and properties of tiny short-lived hot spots on the surfaces of sliding solids. From this we infer the likelihood of such high spot temperatures being realized at grain boundaries during penetrative deformation. The energy concentrated at these spots may help to overcome the energy barrier to nucleation and grain growth and may stimulate formation of stable grains and the progressive elimination of metastable grains during deformation. This is a syntectonic process, but recognizing that syntectonic metamorphic crystallization is most characteristic of regionally dynamothermally metamorphosed terranes, the importance of grain boundary hot spots in providing energy for metamorphic crystallization may be very great.     

Energetics of Hydrothermal Ore Deposition

The process of hydrothermally concentrating trace metals into ores is endothermic. The necessary energy is supplied as heat either directly from the mantle or by igneous bodies. For epithermal ores, heat from intrusives causes advective circulation of hydrothermal fluids, which leach ore components from various source rocks. If minerals that precipitate from the circulating fluid are to reach ore concentrations, then the plutonic heat source must provide energy at a rate sufficient for adequate mass transport, roughly 10¹⁴ kJ/a, and must continue for about 10⁶ a. To power a continuing hydrothermal circulation cell to form an ore deposit, such plutons should be intruded within an area less than about 50 km in diameter and with a frequency at least as often as every 25 ka.

The rarity of mineral districts results principally from the enormous heat requirements of the processes that generate major mineralization. Consequently, in mineral exploration, an initial objective ideally is to find evidence of extraordinarily persistent heat and fluid flow.     

Energetics of Indian winter monsoon

The Indian subcontinent is characterized by complex topography and heterogeneous land use-land cover. The Himalayas and the Tibetan Plateau are spread across the northern part of the continent. Due to its highly variable topography, understanding of the prevailing synoptic weather systems is complex over the region. The present study analyzes the energetics of Indian winter monsoon (IWM) over the Indian subcontinent using outputs of mesoscale model (MM5) forced with National Center for Environmental Prediction/National Center for Atmospheric Research (NCEP/NCAR), US, initial and boundary conditions. MM5 modeling framework, designed to simulate or predict mesoscale atmospheric circulations, is having a limited-area, non-hydrostatic and terrain following 12 sigma levels. The IWM energetics is studied using MM5 model outputs. Prior to this model’s validity and deviation from the corresponding observations (NCEP/NCAR) is assessed. The model’s overestimation/underestimation of wind, temperature and specific humidity at upper troposphere proves that the model has difficulty in picking up corresponding fields at all the model grid points because of terrain complexity over the Himalayas and Tibetan Plateau. Hence, the model fields deviate from the corresponding observations. However, model results match well with the winter global energy budget calculated using reanalysis dataset by Peixoto and Oort (1992). It suggests MM5 model’s fitness in simulating large scale synoptic weather systems. And, thus the model outputs are used for calculation of energetics associated with IWM. It is observed that beyond \(15^{{\circ }}\hbox {N}\) lower as well as upper level convergence of diabatic heating, which represents continental cooling and sinking of heat from atmosphere to land mass (i.e., surface is cooler than surrounding atmosphere) dominates. The diabatic heating divergence (cooling of continents) is found over ocean/sea and whole of the China region, Tibetan and central Himalayas (because of excess condensation than evaporation). The adiabatic generation of kinetic energy depends on the cross isobaric flow (north to south in winter, i.e., the present study shows strong circulation during IWM). It is found that wind divergence of model concludes lower level convergence over study region (i.e., strong winter circulation in the model fields).     

Geothermometry of spinel lherzolites

Three methods of geothermometry, currently used for spinel lherzolites, are refined based on new experiments on subsolidus phase equilibria of olivine, pyroxenes and spinel in CaO-MgO-Al₂O₃-SiO₂ and natural rock systems at 16 kb and 1200 °C. Although quasi-thermodynamic modelling is employed, the methods are essentially based on the pyroxene solvus, alumina contents in clinopyroxene and orthopyroxene. Increasing alumina contents in pyroxenes reduce enstatite and diopside components in clinopyroxene and orthopyroxene, respectively. Thus, neglect of alumina in pyroxenes causes underestimates of temperatures by the solvus method.The three geothermometers were tested by applying them to homogeneous spinel lherzolites which were especially selected for this purpose. Coincidence of the three temperatures thus estimated gives confidence in the effectiveness of the geothermometers.They were also applied to spinel lherzolite nodules in basalts and intrusive lherzolites described in the literature. It was found that equilibration temperature of the nodules varies from 1000 °C to 1300 °C, i.e., temperatures somewhat higher than have been generally thought. In contrast to the nodules, the intrusive spinel lherzolites show extensive disequilibrium, which is probably due to retrogressive metamorphism suffered by the intrusives.     

Numerical modeling of major element distribution between chromian spinel and basaltic melt, with application to chromian spinel in MORBs

A set of empirical equations is developed which allows calculation of chromian spinel composition in equilibrium with a basaltic melt under a known set of conditions. These equations are calibrated with published experimental data for the temperature range from 1,093 to 1,490 °C and a pressure of up to 20 kbar. It is demonstrated that the composition of chromian spinel from the experiments, which crystallizes from basaltic, boninitic, and komatiitic melt and varies from high-Al to high-Cr, and high-Fe³⁺ can be successfully reproduced using the suggested model. The composition of chromian spinel has been calculated using the glass composition for a set of primitive basaltic lavas using the suggested set of empirical equations. Good agreement between the calculated composition and composition of rims of chromian spinel included in glass is achieved for compositionally diverse spinel from a Hawaiian sample and 15 MORB samples. The Fe₂O₃ content in the chromian spinels is, however, often variable and higher than the calculated Fe₂O₃ content. Additional calculations using 76 published MORB glass analyses reproduced most of the MORB chromian spinel range, except for the most Cr- and Mg-rich. The crystallization of these Cr-rich chromian spinels likely occurred from a more primitive Al-poor melt than that of the 76 MORB glasses. An example of a more primitive glass can occasionally be found as glass inclusions in these Cr- and Mg-rich chromian spinel microphenocrysts.     

High-temperature elasticity of magnesioferrite spinel

The elastic moduli of magnesioferrite spinel, MgFe₂O₄, and their temperature dependence have been determined for the first time by ultrasonic measurements on a polycrystalline specimen. The measurements were carried out at 300 MPa and to 700°C in a gas-medium high-pressure apparatus. On heating, both the elastic bulk (K _S) and shear (G) moduli decrease linearly to 350°C. By combining with extant thermal-expansion data, the values for the room-temperature K _S and G, and their temperature derivatives are as follows: K ₀ = 176.3(7) GPa, G ₀ = 80.1(2) GPa, (∂K _S/∂T) _P = −0.032(3) GPa K⁻¹ and (∂G/∂T) _P = −0.012(1) GPa K⁻¹. Between 350 and 400°C, there are abrupt increases of 1.4% in both of the elastic moduli; these closely coincide with the magnetic Curie transition that was observed by thermal analyses at about 360°C.     

Surface structure effects on direct reduction of iron oxides by Shewanella oneidensis

The atomic and electronic structure of mineral surfaces affects many environmentally important processes such as adsorption phenomena. They are however rarely considered relevant to dissimilatory bacterial reduction of iron and manganese minerals. In this regard, surface area and thermodynamics are more commonly considered. Here we take a first step towards understanding the nature of the influence of mineral surface structure upon the rate of electron transfer from Shewanella oneidensis strain MR-1 outer membrane proteins to the mineral surface and the subsequent effect upon cell “activity.” Cell accumulation has been used as a proxy for cell activity at three iron oxide single crystal faces; hematite (001), magnetite (111) and magnetite (100). Clear differences in cell accumulation at, and release from the surfaces are observed, with significantly more cells accumulating at hematite (001) compared to either magnetite face whilst relatively more cells are released into the overlying aqueous phase from the two magnetite faces than hematite. Modeling of the electron transfer process to the different mineral surfaces from a decaheme (protoporphyrin rings containing a central hexacoordinate iron atom), outer membrane-bound cytochrome of S. oneidensis has been accomplished by employing both Marcus and ab initio density functional theories. The resultant model of electron transfer to the three oxide faces predicts that over the entire range of expected electron transfer distances the highest electron transfer rates occur at the hematite (001) surface, mirroring the observed cell accumulation data. Electron transfer rates to either of the two magnetite surfaces are slower, with magnetite (111) slower than hematite (001) by approximately two orders of magnitude. A lack of knowledge regarding the structural details of the heme-mineral interface, especially in regards to atomic distances and relative orientations of hemes and surface iron atoms and the conformation of the protein envelope, precludes a more thorough analysis. However, the results of the modeling concur with the empirical observation that mineral surface structure has a clear influence on mineral surface-associated cell activity. Thus surface structure effects must be accounted for in future studies of cell-mineral interactions.     

Partition of magnesium and iron between Olivine and spinel,and between pyroxene and spinel

Partition of Fe²⁺ and Mg between coexisting (Mg, Fe)₂SiO₄ spinel and (Mg, Fe)SiO₃ pyroxene was investigated at pressures 80 and 90 kbar and at temperatures 840 and 1050° C, using tetrahedral-anvil type of high pressure apparatus. Olivine-spinel solid solution equilibria in the system Mg₂SiO₄-Fe₂SiO₄ were discussed in the light of the partition reaction. Partition of Fe²⁺ and Mg in both olivine-spinel and pyroxene-spinel systems can not be regarded as that between ideal solid solutions. By applying the simple solution model for the partition of Fe²⁺ and Mg, sign of the heat of mixing was estimated to be positive for all olivine, spinel and pyroxene. Relative concentration of Fe²⁺ in spinel in the pyroxene-spinel system is likely to cause some change in the chemical composition of modified spinel () or spinel () in the transition zone of the mantle. A considerable change is also expected in the transition pressure of to ( + ) and ( + ) to .Presented at the symposium Recent Advances in the Studies of Rocks and Minerals at High Pressures and Temperatures held in Montreal, 1972. Jointly sponsored by the International Mineralogical Association and the Commission on Experimental Petrology.     

Gaps in cubic closest packing: from MgO via spinel to the pharmacosiderite crystal structure type

Numerous ordered defect structures are known that are related to the sodium chloride (or MgO) structure type, thus they are basically cubic closest packed (ccp) arrangements with vacancies. For example the NbO type is an MgO type in which one quarter each of the anions and the cations are missing compared to the ccp in such a way that both anions and cations are in square-planar coordination. In spinel, Al₂MgO₄, one half of the octahedrally coordinated cations are missing compared with the MgO type and only one eighth of the tetrahedrally coordinated sites within the ccp are occupied. What these cases have in common is that all these derivatives are rather dense. This is different in pharmacosiderite, K[Fe₄(OH)₄As₃O₁₂]. 6 to 7H₂O, where one half of the anion positions, three quarters of the octahedral sites and five eighth of the tetrahedral sites remain vacant, compared to the spinel type. Pharmacosiderite is a wide open porous structure with zeolitic properties. We are illustrating these relationships using a Bärnighausen symmetry tree and by tables relating the various structure types to each other.     

Energetics of glasses in the system diopside-anorthite-forsterite

Enthalpies of mixing in glasses in the experimentally accessible region of the system Di-An-Fo are generally less than 4 kJ/mol in magnitude. Enthalpies of mixing of liquids in this and in several other petrologically relevant melts are also small; thus, if magmas of different compositions mix isothermally, the heat released or absorbed can be neglected in any consideration of the thermal evolution of the magmas, unless melting or crystallization takes place. The enthalpy of vitrification of Mg₂SiO₄ (to form a hypothetical glass at 700°C) is estimated to be 61±4 kJ/mol, in contrast to the enthalpy of fusion at 1500°C, 89±12 kJ/mol (Navrotsky et al. 1989). This suggests an average difference in heat capacity ( C _p) between liquid and crystal of 35 J/K. mol, half that estimated by Ghiorso and Carmichael (1980, 1987).     

Effects of non-stoichiometry on the spinel structure at high pressure: Implications for Earth’s mantle mineralogy

A non-stoichiometric sample of spinel with composition ^T(Mg_0.4Al_0.6)^M(Al_1.8□_0.2)O₄ was investigated by single-crystal X-ray diffraction in situ up to about 8.7 GPa using a diamond anvil cell. The P(V) data were fitted using a third-order Birch-Murnaghan equation of state and the unit-cell volume V₀, the bulk modulus K_T0 and its first pressure derivative K′ were refined simultaneously providing the following coefficients: V₀ = 510.34(6) Å³, K_T0 = 171(2) GPa, K′ = 7.3(6). This K_T0 value represents the lowest ever found for spinel crystal structures. Comparing our data with a stoichiometric and natural MgAl₂O₄ (pure composition) we observe a decrease in K_T0 by about 11.5% and a strong increase in K′ by about 33%. These results demonstrate how an excess of Al accompanied by the formation of significant cation vacancies at octahedral site strongly affects the thermodynamic properties of spinel structure. If we consider that the estimated mantle composition is characterized by 3-5% of Al₂O₃ this could imply an Mg/Al substitution with possible formation of cation vacancies. The results of our study indicate that geodynamic models should take into account the potential effect of Mg/Al substitution on the incompressibility of the main mantle-forming minerals (olivine, wadsleyite, ringwoodite, Mg-perovskite).     

Evolution of spinel–pyroxene symplectite in spinel–lherzolites from the Horoman Complex,Japan

We examined the textural and geochemical characteristics of spinel-pyroxene symplectites in spinel-lherzolites collected from the lowest, middle, and upper parts (LZ1, MZ, and UZ1, respectively) of the Horoman Peridotite Complex, Japan. The modal proportion of the minerals within symplectite is almost the same, i.e., orthopyroxene:clinopyroxene:spinel = 2:1:1. The size of the symplectite minerals increases from the lowest through to the middle to the upper parts in the complex. The reconstructed major element composition of the bulk symplectites is intermediate between pyrope-rich garnet and olivine. The model garnet compositions of the LZ1satisfies garnet stoichiometry and those of the MZ and UZ1 are not consistent with garnet stoichiometry. The primitive mantle-normalized pattern in trace elements for the LZ1 symplectite is similar to that of pyrope-rich garnet from fertile peridotites, particularly in its enrichment of HREE and a positive Zr anomaly. Thus, the LZ1 symplectite has inherited both major and trace element signatures from pre-existing garnet whereas the compositions of the MZ and UZ1 symplectites were modified during and/or after breakdown of pre-existing garnet. Geochemical and textural variations of symplectites might basically correspond to temperature differences within the complex during upwelling of the Horoman Complex. The basal part of the complex (LZ1) experienced the lowest temperature decompression path in the complex, which resulted in less textural and chemical modification. On the other hand, the higher part of the complex (UZ1) experienced a relatively higher temperature decompression path than other parts of the complex, resulting in chemical equilibration among the constituent minerals and coarsening of the symplectite minerals. Selective enrichment of Sr and LREE in the symplectite may indicate that the metasomatism by a Sr- and LREE-rich melt/fluid occurred during and/or after the formation of symplectite.     

氧化铁涂层石英砂滤料表面特征研究

采用高温加热法制备氧化铁涂层石英砂(IOCS),研究固化温度、改性剂浓度等因素对滤料表面性能的影响,通过磨损实验分析氧化铁涂层的耐磨稳定性.研究结果表明,IOCS表面氧化铁涂层的厚度大约为30～60 μm,固化温度影响涂层的形态和成分,进而影响IOCS表面电位,涂层处理过程要求改性剂浓度大于1.0 mol/L.在实际滤池反冲洗产生的磨损强度范围内,涂层磨损剥离量随磨损次数增加逐渐减小,涂层质量最终趋于稳定.     

Dissolution rates of metals in Fe oxides: implications for sampling ferruginous materials with significant relict Fe oxides

A study of the pattern of dissolution of synthetic and natural Fe oxides in 6 M HCl indicates that the rate of element release from synthetic Fe oxides is strongly influenced by mineralogy and the level of element incorporation. Synthetic maghemite (γ-Fe₂O₃) samples are subject to much more rapid dissolution than goethite (FeOOH) and hematite (α-Fe₂O₃). In samples dominated by hematite and maghemite, Cu, Zn and particularly Pb, in comparison to Fe, are preferentially released during the early stages of dissolution. Similar patterns are apparent from the dissolution of hematite- and maghemite-dominated samples derived from natural gossan. Comparison of XRD scans with data from the dissolution of natural gossan samples transformed by incremental heating to hematite- and maghemite-dominated assemblages suggests that the degree of crystallinity may also be a significant factor in the release of elements incorporated in the Fe oxides. Ferruginous materials made up of varying proportions of goethite, hematite, maghemite, kaolinite and quartz are important sampling materials in a range of regolith environments. These are products of complex chemical and mechanical mobilization over long periods of geological time. If the patterns of Fe oxide dissolution in 6 M HCl and the release of incorporated metals reflect stability in such weathering regimes, knowledge of the retention characteristics of incorporated metals in different Fe oxide phases, as indicated by this study, will be useful in the planning and interpretation of geochemical surveys in such regions.