The electric field gradient in synthetic fayalite α-Fe2SiO4 at moderate temperatures

This work reports on the evaluation of the electric field gradient (efg) in synthetic fayalite α-Fe₂SiO₄ using three different procedures: (1) experimental, with single-crystal Mössbauer spectroscopy (SCMBS) on the three principal sections of an α-Fe₂SiO₄ sample for several temperatures in the range 20?°C?≤?T?≤?300?°C; (2) semiquantitative, with the on-line calculation of the efg from three-dimensional difference electron densities, and (3) a fully quantitative method with cluster molecular orbital calculations based on the density functional theory. The experimental efg is in good agreement with our previously published low-temperature data as well as with the results obtained by the fully quantitative approach. In the latter case, large cluster sizes (up to 97 atoms) are necessary to obtain quantitative agreement with experiment. This is also considered as being responsible for the lack of correspondence with the semiquantitative efg on M1. Previously reported symmetry violations on the M2 site are also confirmed by our SCMBS measurements.     

Electronic structure and electric field gradient calculations of Al2SiO5 polymorphs

 The electronic structure of the three polymorphs of Al₂SiO₅, andalusite, sillimanite, and kyanite, is studied by linearized-augmented-plane-wave (LAPW) calculations using the WIEN code. Total energy calculations verify, in agreement with recent pseudopotential calculations, that andalusite is the most stable phase, followed by sillimanite and kyanite.We determine the electronic charge density distribution and find strong polarizations on all oxygen ions. We identify different polarizations due to Al or Si neighbors which depend on their respective distances to the oxygen atom. The chemical bonding is not purely ionic in nature but has important covalent contributions. Electric field gradients (EFGs) at all sites are calculated and agree well (within 10%) with available experimental data on Al. We identify the origin of the EFGs and demonstrate its relation to the nearest-neighbor coordination and the resulting anisotropy of the electronic charge distribution. Received: 22 March 2000 / Accepted: 3 August 2000     

The charge density distribution and antiferromagnetic properties of azurite Cu3[CO3]2(OH)2

 The structure and bonding in azurite are investigated on the basis of accurate single-crystal X-ray diffraction data. Both spherical IAM and pseudoatom models have been used in the refinements. The deformation electron density: dynamic (IAM) and static (pseudoatom) are mapped for the CO₃ group and for Cu(1) and Cu(2) squares in different sections. The carbonate group in azurite, not constrained to have trigonal symmetry, exhibits peaks in both static and dynamic maps which result from σ-bonds between C–sp² hybrid orbitals and O–p orbitals with some delocalisation of density in the dynamic map because of the thermal motion of oxygens. For the analysis of crystal fields and for the multipole calculations, coordinate systems on the Cu-atoms have been chosen as for a Jahn-Teller octahedron, but with the normal to the square as the z-axis instead of the absent apical oxygens. In both Cu squares there are peaks which result from single Cu–O σ-bonds. Most remarkable is the preferential occupation of the non-bonding 3d orbitals of Cu-atoms being above and below the Cu-squares. The centre of these peaks for the Cu(1)-atom makes an angle with the c-axis ∼53° in the ac plane. This direction corresponds to the maximum magnetic susceptibility at ambient temperature. The real atomic charges of Cu-atoms in azurite determined from multipoles are close to Cu⁺¹. The occupancies of the 3d atomic orbitals show that non-bonding orbitals in both Cu-atoms are most populated, in contrast to bonding orbitals, as is typical for the Jahn-Teller octahedron. The absence of apical oxygens makes this effect even more pronounced. It is suggested that the antiferromagnetic structure below 1.4 K will be collinear and commensurate with b′=2b. Received: 8 September 2000 / Accepted: 6 March 2001     

Study of the electron density in MgO, (Mg0.963Fe0.037)O and Cu2O by the maximum entropy method and multipole refinements: comparison between methods

 The electron densities determined by the maximum entropy method and by the multipole refinement approach are compared with each other, in terms of some topological properties according to the Bader formalism (Laplacian and eigenvalues of the Hessian matrix of the electron density at the critical points). The cases of MgO, (Mg,Fe)O and Cu₂O are examined. The best agreement is observed for the critical points along the Mg–O, (Mg,Fe)–O and Cu–O directions, whereas larger discrepancies occur at the other critical points. Plots of the electron densities generated by the maximum entropy method and the multipole formalism along the most representative crystallographic directions contribute to elucidating the comparison between approaches. Received: 3 July 2001 / Accepted: 7 March 2002     

The influence of Al2O3 on the H2O content in periclase and ferropericlase at 25 GPa

In this paper I present results of IR spectroscopic measurements of water solubility in Al-bearing periclase and ferropericlase (Mg# = 88) synthesized at 25 GPa and 1400–2000 °C. The IR spectra of their crystals show narrow absorption peaks at 3299, 3308, and 3474 cm^?1. The calculated H₂O contents are 11–25 ppm in periclase (Al₂O₃ = 0.9–1.2 wt.%) and 14–79 ppm in ferropericlase (Al₂O₃ = 0.9–2.9 wt.%). Ferropericlase contains more H₂O and Al₂O₃ than periclase at 1800–2000 °C. I suggest that addition of Al₂O₃ does not influence the solubility of water in ferropericlase but can favor the additional incorporation of Fe₂O₃ into the structure. The incorporation of Fe³⁺ into ferropericlase increases water solubility as a result of iron reduction to Fe²⁺. It is shown that water has limited solubility in ferropericlase from mantle peridotite; therefore, ferropericlase cannot be considered an important hydrogen-bearing mineral in the lower mantle.     

Ab initio Hartree–Fock study and charge density analysis of beryl (Al4Be6Si12O36)

 An ab initio Hartree–Fock calculation on beryl structure has been performed and the wave function has been used for an analysis of the electron density. The equilibrium geometry, determined by minimizing the energy with respect to cell parameters and fractional coordinates, is in good agreement with structural experimental measurements; small differences in length between the various Si–O bonds of the structure are well reproduced by the calculation. The two non-equivalent oxygen atoms (O1 and O2) of beryl show different electron distributions. In particular, the valence shell charge concentration (VSCC) of O1 (the bridge between two Si ions) has a torus-like shape, showing a bulge on the external side of the Si–O–Si angle and a thinning on the internal side of it; by contrast O2 has two lone pairs which are approximately located on the line for O2, normal to the plane passing, on average, through the atoms O2, Si, Be and Al. The electron density of each oxygen is strongly polarized toward the Si ions and much less polarized towards the other cations. Such features of the VSCC of the oxygens can be recast in terms of the valence bond theory, to explain the observed differences in bond lengths. By calculating the potential inside the channels of the beryl structure, predictions could be made about the positions occupied by alkali cations, which are often found in natural minerals belonging to the beryl group: results agree in general with experimental findings, but foresee a shift of such cations off the central positions located on the six fold symmetry axis. Additionally, calculations of position and orientation of H₂O inside the channel, in the alkali-free beryl, locate the molecule close to the basal plane, with the H⋯H axis parallel to [001] or oriented at 40^∘ from it. Received: 12 December 2001 / Accepted: 6 April 2002     

天然电场选频测深法在地下水勘探中的异常理论分析与实践应用

选频法是音频大地电场法的进一步应用与发展。本文通过实践应用说明选频法在浅层地下水勘探中的有效性,并对选频法测深极距(MN)与地下水埋深之间的关系开展对比分析和初步理论研究。首先,采用水平交变电场、交变磁场共同作用下的均匀半空间中低阻导电球体简化地质地球物理模型,对选频法测深曲线开展正演计算;然后,对选频法在广西“十二五”农村饮水安全工程应用中的131口钻井出水量情况进行统计,并对其中98口钻井的钻探情况开展详细列表统计分析,对比研究测深曲线异常处MN极距大小与实际钻探出水深度之间的关系。理论分析与实践应用表明,选频法在浅层地下水勘探中效果明显,是一种确定浅层地下水井位的有效方法;同时,实践统计结果表明,选频法测深法异常曲线处MN极距的大小与实际钻探出水深度之间存在1∶1的近似关系,验证了理论模拟计算结果的正确性;另外,本文的研究成果表明,在浅层(<200 m)天然电磁法勘探中,天然电场观测值的大小除了与大地的电阻率、信号的频率有关外,还与电极距大小是相关的。     

低频谐变电偶极源激发的地下电磁场的闭式解

研究偶极子源产生的电磁场在地下或水下无线电通信和地球物理勘探领域有着重要的应用价值。偶极子和介质的作用往往导致Sommerfeld型积分的解。为了深入揭示电磁波在地下的分布与传播规律,本文针对有耗媒质中为获得大探测深度和长距离通信使用的低频发射天线,在准静态近似条件下导出了水平电偶极子产生的下电磁场Sommerfeld型积分解的闭式表达式。这些公式适用于任意场区和除奇异点以外的任何场点,与数值积分相比,可显著提高计算速度。利用闭合表达式,本文还提出了一种新的场区划分方法。     

Efficiency removal of phenol, lead and cadmium by means of UV/TiO2/H2O2 processes

A variety of processes can be used in treatment of industrial wastewaters. The relatively newest of which is photo catalysis with titanium dioxide which may also be used plus hydrogen peroxide to improve the treatment rate. In this study, photo catalysis/ hydrogen peroxide processes had been employed for the removal of phenol, lead and cadmium by three different pHs of 3.5, 7 and 11. The treatment tests were also accomplished without UV irradiation. In both experiments, the variables were pH and concentrations of reagent chemicals, but the detention time was kept constant (180 min). Results indicated that the optimum efficiencies of phenol and Cd removal were 76 % and 97.7 % at pH=11, respectively, and for lead, it was 98.8% in all pHs. In other words, no pH dependency was regarded for lead treatment. These results were all obtained by simultaneous use of UV irradiation with 3 mL/L H₂O₂ and 0.8 g/L TiO₂. Finally, the best pH for treatment, when all the three contaminants are presented is considered to be at 11. These results should be regarded by all industrial treatment plants which have experienced the problem of these three special contaminants in their effluents.     

Ion acoustic instability of HPT particles,FAC density,anomalous resistivity and parallel electric field in the auroral region

During the magnetic storm of 21st March 1990, the DE-1 spacecraft encountered the auroral region at high invariant latitude at altitudes ranging from a few thousand kilometers in the ionosphere to many earth radii in the magnetosphere. The magnetic field perturbations interpretable as field aligned current (FAC) layers and the electrostatic turbulence possibly due to electrostatic ion acoustic instability driven by these currents are shown. The critical drift velocity of Hot Plasma Torus (HPT) electrons and the growth rate of ion acoustic wave as a function of electron to ion temperature ratio (T _e/T_i) for low and high current densities and energy of HPT electrons are found out. The intense FAC destabilizes the ion acoustic wave and the resultant electrostatic turbulence creates an anomalous resistivity. The current driven resistivity produces parallel electric field and high power dissipation. The anomalous resistivityη, potential difference along the auroral field lines V_t|, intensity of electric field turbulenceE _t| and power produced per unit volumeP are computed. It is found that the change in westward magnetic perturbation increasesJ _t|, η, V_t|, E_t| andP. Hence HPT electrons are heated and accelerated due to power dissipation during magnetically active periods in the auroral region. Concerning, applications, such HPT electrons can be used in particle accelerators like electron ring accelerator, smokatron etc.     

The System Na2O-Al2O3-Fc2O3-SiO2 at 1 Atmosphere, and the Petrogenesis of Alkaline Rocks

Equilibria involving acmite, albite, nepheline, quartz, anda liquid phase constitute the petrologically important partof the system Na₂O–Al₂O₃–Fe₂O₂–SiO₂, and theunivariant and invariant relations provide useful analogiesfor a wide variety of alkaline igneous rocks. These relationsare dominated by the incongruent melting behaviour of acmite,which does not appear on the liquidus of the join acmite-nepheline-silica;instead, a broad field of hematite is present and acmite crystallizesonly from liquids containing potential sodium silicate. Consequently,the oversaturated and undersaturated eutectics, correspondingto granitic and nepheline syenitic liquids, are rich in sodiumsilicate and distinct from those found in Petrogeny's Residuasystem: the temperatures of the eutectics are 7285C and 7155C, respectively. Survival of peralkaline granite in the aluminouscontinental crust can be explained by the strongly peralkalinecomposition of the oversaturated eutectic. Magma of this typemay be the primitive granite of the non-orogenic zones. Theubiquitous alkali metasomatism around alkaline complexes canalso be interpreted in terms of residual liquids enriched inalkali silicates. Transition from undersaturated to oversaturatedliquids is possible by fractionation of hematite and a new processfor achieving the reverse transition has been found. This dependson the substitution of Fe³ for Al³ in feldspar and suggestsa more important role for syenite in any scheme of petrogenesis. Each of the two eutectics is linked to a corresponding peritecticat which hematite reacts to give acmite. The liquid at the undersaturated,quaternary reaction point is of ijolitic type, providing thefirst intimation that ijolite may represent a low-melting fractionin nature. The system Na₂O–Al₂O₃–Fe₂O₃–SiO₂thus constitutes the peralkaline residua system and on thisbasis a coherent picture of stable continental magmatism canbe constructed. Ijolite is seen as the low-melting fractionfrom a range of peralkaline compositions and from rocks suchas melilite basalt, while the frequently associated carbonatiteis considered to be the volatile-rich, fugitive material fromthe mantle. Such a relationship is consistent with the dualassociation of carbonatite with either ijolite or kimberliteunder different tectonic conditions. The more common syenite,nepheline syenite, and alkaline granite of the non-orogenicregions are regarded as low-melting fractions from basalticmaterials in the deep crust. Most of this activity, involvingmagmas of residual type, could thus be explained in terms ofpartial melting in the deep crust and upper mantle. A possiblemechanism for this would be arching of the rigid continentalcrust, the consequent relief of lithostatic load giving riseto melting, and the concentration of fugitive constituents,in the underlying zones.     

Competitive sorption of copper and lead at the oxide-water interface: Implications for surface site density

The competitive sorption of Cu(II) and Pb(II) to colloidal hematite was investigated as a function of pH and total metal concentration. Acid–base titrations of the hematite and single-metal sorption experiments for Cu and Pb at low to medium surface coverages were used to calibrate two surface complexation models, the triple layer model, and a 2-pK basic Stern model with ion-pair formation. The surface site density was systematically varied from 2 to 20 sites/nm². Three different metal surface complexes were considered: (1) an inner-sphere metal complex; (2) an outer-sphere metal complex; and (3) an outer-sphere complex of singly hydrolyzed metal cations. Both models provided excellent fits to acid–base titration and single-metal sorption data, regardless of the surface site density used. With increasing site density, ΔpK of the stability constants for protonation reactions increased and metal surface complexes decreased steadily. The calibrated models based on different site densities were used to predict competitive sorption effects between Cu and Pb and single-metal sorption at higher total metal concentrations. Precipitation of oversaturated solid phases was included in the calculations. Best predictions of competitive sorption effects were obtained with surface site densities between 5 and 10 sites/nm². The results demonstrate that surface site density is a key parameter if surface complexation models are exposed to more complex, multicomponent environments. We conclude that competitive metal sorption experiments can be used to obtain additional information about the relevant surface site density of oxide mineral surfaces.     

Polarized electronic absorption spectra of Co2+ ions in the kieserite-type compounds CoSO4 · H2O and CoSeO4 · H2O

Polarized electronic absorption spectra of the kieserite-type compounds CoSO₄ · H₂O and CoSeO₄ · H₂O have been obtained at room temperature (spectral range 35 000-5000 cm^-1) and at liquid nitrogen temperature (visible spectral region), using microscope-spectrometric techniques. The spectra are interpreted and evaluated in terms of a tetragonal crystal field formalism for the d⁷ configuration, in regard to the pseudotetragonal elongation of the CoO₄(H₂O)₂ octahedra, known from previous X-ray structure investigations, employing the tetragonal parameters Dq, Dt, and Ds, and the Racah parameters B and C. The observed and calculated energy levels are in good agreement for the following parameter sets: CoSO₄ · H₂O: Dq=826, Dt=40, Ds=350, B=856, C=3580 cm^-1; CoSeO₄· H₂O: Dq=817, Dt=44, Ds=406, B=841, C=3490 cm^-1; corresponding ‘cubic’ crystal field strengths Dq_cub are 803 and 792 cm^-1, respectively. The values of Dq_(cub), Racah B and C are in the common range for Co²⁺ ions in (pseudo) octahedral fields of oxygen ligands, and their differences in CoSO₄· H₂O compared to CoSeO₄ · H₂O are consistent with somewhat different mean Co-O bond lengths and with a slightly higher covalent contribution to Co-O bonding in the selenate compound. The values found for the parameter Dt, which is directly correlated to the extent of tetragonal distortion, are much lower than expected from purely geometrical considerations, thus confirming a significantly higher position of H₂O ligands in the spectrochemical series compared to oxygen ligands belonging to SO₄ or SeO₄ groups.     

Phase Equilibria in the Ternary Systems KBr–K2B4O7–H2O and KCl–K2B4O7–H2O at 373 K

According to the compositions of the underground gasfield brines in the west of Sichuan Basin,the phase equilibria in the ternary systems KBr-K2B4O7-H2O and KCl-K2B4O7-H2O at 373 K were studied using the isothermal dissolution equilibrium method.The solubilities of salts and the densities of saturated solutions in these ternary systems were determined.Using the experimental data,phase diagrams and density-composition diagrams were constructed.The two phase diagrams were simple co-saturation type,each having an invariant point,two univariant curves and two crystallization regions.The equilibrium solid phases in the ternary system KBr-K2B4O7-H2O are potassium bromide （KBr） and potassium tetraborate tetrahydrate （K2B4O7·4H2O）,and those in the ternary system KCl-K2B4O7-H2O are potassium chloride （KCl） and potassium tetraborate tetrahydrate （K2B4O7·4H2O）.Comparisons of the phase diagrams of the two systems at different temperatures show that there is no change in the crystallization phases,but there are changes in the size of the crystallization regions.As temperature increases,the solubility of K2B4O7·4H2O increases rapidly,so the crystallization field of K2B4O7·4H2O becomes smaller.     

Behavior and effects of phosphorus in the system Na2O−K2O−Al2O3−SiO2−P2O5−H2O at 200 MPa(H2O)

The addition of phosphorus to H₂O-saturated and initially subaluminous haplogranitic (Qz–Ab–Or) compositions at 200 MPa(H₂O) promotes expansion of the liquidus field of quartz, a marked decrease of the solidus temperature, increased solubility limits of H₂O in melt at low phosphorus concentrations, and fractionation of melt out of the haplogranite plane (projected along an Or₂₈ isopleth) toward a peralkaline, silica-poor but quartz-saturated minimum composition. The partition coefficient for P₂O₅ between aqueous vapor and melt with an ASI (aluminum saturation index, mol Al/[mol Na+K])=1 is negligible (0.06), and consequently so are the effects of phosphorus on other melt-vapor relations involving major components. Phosphorus becomes more soluble in vapor, however, as the concentration of a NaPO₃ component increases via the fractionation of melt by crystallization of quartz and feldspar. The experimental results here corroborate existing concepts regarding the interaction of phosphorus with alkali aluminosilicate melt: phosphorus has an affinity for alkalis and Al, but not Si. Phosphorus is incorporated into alkali feldspars by the exchange component AlPSi_-2. For subaluminous compositions (ASI=1), the distribution coefficient of phosphorus between alkali feldspar and melt, D[P]Af/m, is 0.3. This value increases to D[P]Af/m=1.0 at a melt ASI value of 1.3. The increase in D[P]Af/m with ASI is expected from the fact that excess Al promotes the AlPSi_-2 exchange. With this experimental data, the P₂O₅ content of feldspars and whole rocks can reveal important facets of crystallization and phosphorus geochemistry in subaluminous to peraluminous granitic systems.     

Biosorption of Pb, Cd, Cu and Zn from the wastewater by treated Azolla filiculoides with H2O2/MgCl2

The adsorption of heavy metals onto treated Azolla filiculoides by H₂O₂/MgCl₂, as a cosmopolitan free-floating waterfern, was investigated from aqueous solutions in the batch biosorption experiments. The maximum uptake capacities of the collected Azolla from rice field at the optimal conditions for Pb, Cd, Cu and Zn ions were approximately 228, 86, 62 and 48 mg/g (dry Azolla), respectively. On the other hand, the maximum uptake capacities of the collected Azolla from the Anzali International Wetland in the north part of Iran at the same conditions for these heavy metals were about 124, 58, 33 and 34 mg/g (dry Azolla), respectively. Such decrease of uptakes is due to the pollution of Anzali International Wetland, which reduces the capacity uptake of metals. The recovery of biosorbed heavy metals from the rice field Azolla was carried out by HCl and NaCl desorbents that the recovery of 64–86% and 51–72% was occurred, respectively.     

Crystal field transitions in Co2[Al4Si5]O18 cordierite and CoAl2O4 spinel determined by neutron spectroscopy

Inelastic magnetic neutron scattering has been used to determine the energy of the ⁴ A ₂→⁴ T ₂ transition in CoAl₂O₄ spinel and the δ₁ transition in Co₂[Al₄Si₅]O₁₈ cordierite. The observed crystal field splitting in Co-spinel is 485 meV (3900 cm⁻¹), which corresponds to a crystal field stabilization energy of 56.2 kJmol⁻¹. The transition energy of the δ₁ transition in Co-cordierite has been determined to be 21 meV (170 cm⁻¹). The present data demonstrate that magnetic neutron scattering can be used to measure crystal field transitions at energies of interest in the study of 3d-containing silicates. It may be used to measure transition energies when the use of optical spectroscopy is inappropriate. Received: 30 January 1997 / Accepted: 5 July 1997     

江西德兴铜矿区大坞河流域环境介质中Cu含量变化趋势

以2004年和2011年江西德兴铜矿开采区影响的大坞河流域共计140件水、土、底泥及种植物样品中Cu的含量为研究对象,参考国家标准对大坞河流域不同河段Cu污染进行评价,研究不同环境介质中Cu含量随时间变化的规律,并且探讨种植物中Cu元素的来源。研究表明,从空间上看大坞河源区和上游的样品超标率最高,分别达到70.3%和90.9%。7年间研究区环境介质中的Cu元素总体是趋于恶化的,除地表水和土壤中Cu含量有所降低外,其他环境介质中的Cu含量都有所增加,最明显的是2011年小白菜中的Cu元素含量是2004年的11.68倍。与种植物密切相关的地表水和对应土壤中Cu元素的变化规律存在较大差异,据此推断其Cu元素来源与元素形态、大气干湿沉降等因素有关。     

Using dimensional-regression analysis to predict the mean particle size of fragmentation by blasting at the Sungun copper mine

Arabian Journal of Geosciences - A methodology was founded on the basis of a dimensional analysis procedure, together with multivariate nonlinear regression analysis which is used to predict mean...