Placing constraints on phase equilibria and thermophysical properties in the system MgO-SiO2 by a thermodynamically consistent vibrational method

We use a lattice vibrational technique to derive thermophysical and thermochemical properties and phase equilibria in the system MgO-SiO₂ at pressures and temperatures relevant to Earth’s mantle. The technique is based on an extension of Kieffer’s model to incorporate details of the phonon spectrum, and it includes treatment of intrinsic anharmonicity. We use a least squares inversion technique applied to available experimental data, and show that it results in an accurate representation of thermodynamic properties and sound wave velocities of high-pressure phases in the system MgSiO₃. The vibrational method has been validated against laboratory experimental data in the temperature range between 0 and 2500 K and at pressures between 1 bar and 30 GPa. The technique results in a phase diagram consistent with the majority of thermophysical and thermochemical data. It is shown that intrinsic anharmonicity affects significantly slopes and positions of the phase boundaries. Our analysis indicates inconsistencies in a number of data sets of thermophysical properties for stishovite, majorite and ortho-enstatite necessitating new measurements. For akimotoite elasticity data at high-pressure and high-temperature conditions and 1 bar heat capacity measurements are needed. For stishovite elasticity measurements are necessary to reconcile elasticity data with V-P-T measurements. Additionally V-P-T measurements at pressures higher than 10 GPa are needed, which should be reconciled with V-P-T data at lower pressures. Raman and infrared spectroscopic data are necessary for both clino-enstatite and majorite. Additionally structural data are needed to resolve the discrepancy between values for the degree of disorder in majorite. Volume expansion data for ortho-enstatite are needed and effects causing differences in measured volume expansion should be elucidated.     

Phase changes and thermodynamic properties of CaTiO3. Spectroscopic data,vibrational modelling and some insights on the properties of MgSiO3 perovskite

The effect of pressure (up to 21 GPa at room temperature) and temperature (up to 1570 K at room pressure) on the Raman spectrum of CaTiO₃ is presented. No significant changes, which could be attributed to a major structural change, are observed in the spectra up to 22 GPa. The pressure shifts of the Raman modes can be related to a significant compression of the Ti-O bond. Discontinuous changes in the spectra upon heating may be related to phase changes observed by calorimetry and X-ray diffraction. The important temperature shifts of some low-frequency modes can be related to an increase in the Ti-O-Ti angle in agreement with the X-ray data showing a decrease of the structural distortion with increasing temperature. These data are compared to those available for MgSiO₃-perovskite and show that CaTiO₃ is a good structural analogue for MgSiO₃-perovskite. The present spectroscopic data are used to calculate the specific heat and entropy of CaTiO₃. The role of the low frequency modes in the calculations is emphasized. Good agreement is observed between calculated and experimentally determined values in the 0–1300 K temperature range. A similarly defined model is proposed for MgSiO₃-perovskite. It is found that the entropy lies between 57 and 64 J/mol/K at 298 K and between 190 and 200 J/mol/K at 1000 K in agreement with the values inferred from experimental equilibrium data. Finally we briefly discuss the values of the Grüneisen parameters of both perovskites inferred from macroscopic and microscopic data.     

陕西关中盆地粉质黏土热物理性质研究

关中盆地浅层地热能资源十分丰富,但目前开采程度仍有待提高。土壤的热物理性质在很大程度上决定了其工程特性,对浅层地热能在开发利用过程中所涉及的基本理论和开发方法等具有较大影响。通过室内试验对西安市、咸阳市、渭南市和宝鸡市范围内的粉质黏土的热物理性质开展研究,对试验数据进行了分析,进而揭示了粉质黏土比热容、导温系数和热导率的宏观变化规律。结果表明: 粉质黏土的热导率为0.82~2.65 W/(m·K),导温系数为0.001 28~0.004 86 m²/h,比热容为0.77~1.53 kJ/(kg·K); 随着含水率的增大,热导率整体呈减小趋势,且数值分布范围缩小; 比热容总体随导温系数的增大而减小; 导温系数随热导率的增大呈线性增大,且相关系数均较高。研究可为工程实践过程中开发利用浅层地热提供一定的理论基础。     

叶蜡石化蚀变过程中的元素活动性与流体性质:以山西五台地区白云叶蜡石矿为例

热液蚀变过程中的元素活动性与流体性质对深入理解矿物稳定性和成矿作用具有重要的意义。本文以华北克拉通中北部山西五台地区的白云叶蜡石矿为例,研究了蚀变过程中元素迁移特征和流体性质。该矿体围岩以绿片岩相酸性火山岩为主,岩性为绢云钠长石英片岩并夹有少量的绿泥钠长片岩。矿区内蚀变分带明显,可分为早期的黄铁绢英岩化(绢云母-石英-黄铁矿)和晚期叠加的叶蜡石化(叶蜡石-伊利石-高岭石-石英),而金矿化则主要发育于黄铁绢英岩化带内。Log fo2-pH相图模拟结果显示,早期黄铁绢云岩化蚀变热液具有弱酸性至偏中性(pH=5.24~5.87)和较低氧逸度(位于黄铁矿+黄铜矿稳定相区内)特征;而引起叶蜡石化蚀变的热液具有强酸性(pH=2.07~2.20)和高氧逸度(位于HM缓冲线以上)特征。质量平衡迁移分析结果显示,随着叶蜡石化蚀变作用的增强,叶蜡石矿石中的Al2O3行为较稳定,SiO2、Na2O和K2O含量相对于围岩绢云钠长石英片岩呈不同程度的迁入,而其余氧化物大量活化迁出。微量元素Nb、Ta、Th、U、Rb和Ga含量相对升高,Th/U比值略有升高;Sr、Ba、Zr、Hf明显亏损,Zr/Hf比值从34~41下降到17~22。稀土元素均发生一定程度的活化迁移,且轻稀土迁出程度更高。Y/Ho比值(28~32)高于球粒陨石的Y/Ho(26~28),表明Y-Ho在叶蜡石化蚀变过程中表现出不同的地球化学行为。Eu负异常明显增大,这可能与长石的分解关系密切。围岩绢云钠长石英片岩中金属元素含量较高且Au与As含量之间呈明显正相关性,但在叶蜡石矿石中大部分金属元素含量均低于检出限,说明金属元素在叶蜡石化蚀变作用过程中发生了强烈的活化迁移,这与岩相学上叶蜡石矿石中可见港湾状细粒赤铁矿而缺乏黄铁矿的特征吻合。本文研究结果表明叶蜡石化过程中,大量的所谓不活动元素(如P、Ti、Zr、Hf、Y和Ho等)发生了显著迁移并导致Zr/Hf和Y/Ho比值的解耦,并伴随着大量金属元素的迁出,说明叶蜡石化不利于金矿化的形成。     

Structural and chemical characterization of synthetic (Na,K)-richterite solid solutions by EMP, HRTEM, XRD and OH-valence vibrational spectroscopy

The composition and structure of synthetic (Na,K)-richterites have been characterized by EMP, HRTEM, XRD and FTIR methods. Despite the fact that the syntheses were done on bulk compositions along the richterite-K-richterite binary, EMP analyses and FTIR spectra indicate that the amphiboles are not simple solid solutions of the two richterite endmembers richterite and K-richterite alone, but tremolite and Mg-cummingtonite components are also present in considerable amounts. HRTEM observations show that the amphiboles are structurally well ordered. Only a very few chain multiplicity faults are present. XRD examination reveals lattice parameters of 9.9055 Å, 17.9844 Å, 5.2689 Å and 104.212° for richterite and 10.0787 Å, 17.9877 Å, 5.2715 Å and 104.878° for K-richterite endmembers. The unit cell volumes are 909.90 ų and 923.61 ų for richterite and K-richterite, respectively. The lattice parameters a and β for K-richterite are considerably larger than those published previously implying that those were not determined for pure K-richterite. The positions of the characteristic OH-stretching vibrations in the IR for sodium-potassium (3729.8–3734.8 cm^?1) and vacancies (3671.1–3675.4 cm^?1) on the A-site are in agreement with earlier determinations. Using synthetic tremolite as a standard the vacancy concentration on the A-site of the synthetic (Na,K)-richterites was determined quantitatively by FTIR-spectroscopy. The OH-stretching vibration of this synthetic tremolite is at 3674.5 cm^?1. It is assigned to a local coordination with 3 Mg (2 M₁+M₃) as nearest neighbors and with 2 Ca (M₄) as next nearest neighbors. A well resolved band with a smaller intensity is located at 3669.2 cm^?1, which is attributed to a configuration including Ca+Mg on M₄ instead of only Ca.     

Interrelationship of the principal physicomechanical and thermophysical properties of coarse-grained frozen soils

The results of physical, mechanical and thermomechanical investigations of frozen coarse-grained soils with sandy clay aggregate are discussed. The authors propose a general classification of coarse-grained soils with fine aggregate, subdividing into skeleton and nonskeleton soils, and new methods for determination of their physicomechanical and thermal characteristics.

Special methods and formulae are given, that allow calculation of the main physicomechanical and thermal characteristics of coarse-grained soils in the same way as those of coarse particles and fine aggregates.

In common complex stability and deformation problems, and research on frozen, freezing and thawing soils, taking into account cryogenic and thermo mass transfer processes, it is proposed to investigate these soils on the basis of thermoelasticity and thermomechanics (rational thermodynamics).     

Geochemistry and petrogenesis of pyrophyllite deposit of Madrangjodi,Keonjhar district,Orissa

Pyrophyllite deposit at Madrangjodi is a large lensoidal massif overlain unconformably by Dhanjori quartzite and underlain by the parent Singhbhum granite (Phase — II). Pyrophyllite and quartz are the major minerals with minor to trace amounts of muscovite, chloritoid opaques and tourmaline. It is broadly divisible into lamellar, granular and schistose varieties. SiO₂ (66.90–74.36%) and Al₂O₃ (20.80–27.54%) are the major oxides. The major elements data indicate its derivation from Singhbhum granite with depletion of SiO₂ and increment of Al₂O₃. Trace and REE data are discussed to corroborate its genesis.     

京西门头沟叶腊石泥岩矿物学特征

我国含煤地层共伴生矿物种类较多,资源量较大,其中京西门头沟石炭-二叠纪煤系中的叶蜡石泥岩比较罕见,具有重要的开发利用价值。利用偏光显微镜、X射线衍射（XRD）、红外光谱（IR）、热分析（TA）、电子探针（EPM）等测试手段,从矿物学角度对北京西山门头沟红庙岭组叶腊石矿物学特征进行研究。结果表明,研究区泥岩叶腊石与硬水铝石、硬绿泥石等矿物共生,偏光显微镜下叶腊石通常呈隐晶或微晶鳞片状,定向分布。基于微区电子探针化学分析计算得出的叶腊石晶体结构化学式为：Al_1.9965（Si_3.9982 O₁₀）（O₂H_2.0180）。根据沉积地质背景和共生矿物组合特征,推断叶腊石的形成温度在300℃左右,认为京西门头沟区叶腊石为高岭石受到构造应力影响形成的动力变质矿物。     

Structural features of quench products of melts in the chloride-carbonate-silicate systems revealed by vibrational and X-ray spectroscopy

Quench products of melts synthesized at 5 GPa and 1500°C in model system CaMgSi₂O₆–Na₂CO₃(±CaCO₃)–KCl, were studied using vibrational (IR and Raman) and X-ray absorption spectroscopy (XANES). Correlations between structural peculiarities of the quenches with chemical composition are established. Increase of the CaMgSi₂O₆ content of the melts results in gradual substitution of the Са-bearing carbonate groups by Na-bearing, whereas Ca is progressively more bounded with silicate structural units. XANES spectra reveal that chlorine is predominantly present as (K _x Na_1–x )Cl complexes. XANES spectra also indicate distribution of potassium cations between chloride and silicate groups, although its partial bonding with carbonate groups in the melt is not excluded.     

The surface free energies of talc and pyrophyllite

The components of the interfacial surface tension of talc and pyrophyllite were determined by measuring the rate of the capillary rise of a number of liquids through thin, sedimented deposits of the powdered minerals. The rate of capillary rise of a liquid in a powder is related to the contact angle between the liquid and the solid by the Washburn equation. The contact angles thus derived were used to determine the apolar (Lifshitzvan der Waals) component, γ ^LW , and the polar, electronacceptor and electron-donor parameters, γ ^⊕ and γ ^? respectively, of the Lewis acid/base component of the total interfacial surface energy using the Young equation. The values of γ ^LW for talc and pyrophyllite (31.5 and 34.4 mJ/m²) are slightly smaller than for smectite clay minerals (e.g., the value for hectorite is 39.9 mJ/m²), the electron donor parameter values are roughly comparable for talc and pyrophyllite (γ ^⊕ = 2.4 and 1.7 mJ/m²) as are the values of the electron acceptor parameter (γ ^? = 2.7 and 3.2 mJ/m²). The well-known hydrophobicity of these two minerals is due to the remarkably small value (for silicate minerals) of γ ^?(γ^⊕ is normally small or zero for silicates and many other oxides). The small values of both γ ^⊕ and γ ^? mean that the Lewis acid/base interactions between talc or pyrophyllite and highly polar water molecules are very weak. In contrast, low-charge smectites, the minerals most similar chemically and structurally to talc and pyrophyllite, have much greater values of γ ^? (≥ 30 mJ/m²) and are hydrophyllic.     

Finite element modelling of elastic intraplate stresses due to heterogeneities in crustal density and mechanical properties for the Jabalpur earthquake region,central India

Deep lower crustal intraplate earthquakes are infrequent and the mechanism of their occurrence is not well understood. The Narmada-Son-lineament region in central India has experienced two such events, the 1938 Satpura earthquake and the 1997 Jabalpur earthquake, having a focal depth of more than 35 km. We have estimated elastic stresses due to the crustal density and mechanical properties heterogeneities along the Hirapur-Mandla profile passing through the Jabalpur earthquake region to analyse conditions suitable for the concentration of shear stresses in the hypocentral region of this earthquake. Elastic stresses have been computed by a finite element method for a range of material parameters. The results indicate that the shear stresses generated by the density heterogeneities alone are not able to locally enhance the stress concentration in the hypocentral region. The role of mechanical properties of various crustal layers is important in achieving this localization of stresses. Among a range of material parameters analysed, the model with a mechanically strong lower crust overlying a relatively weak sub-Moho layer is able to enhance the stress concentration in the hypocentral region, implying a weaker mantle in comparison to the lower crust for this region of central India.     

Physical properties of calcium aluminates from vibrational spectroscopy

Heat capacity (C_V) and entropy (S) as a function of temperature were calculated for phases in the CaO-Al₂O₃ system from vibrational spectra using a quasi-harmonic model. Calculated values of C_V at 298 K for the calcium aluminates may have uncertainties as small as ±1%, based on comparison with published calorimetric data for CaO, Al₂O₃, and CaAl₂O₄. For hibonite (CaAl₁₂O₁₉), we predict C_P as 519.3 J/mol-K and S as 391.7 J/mol-K, at 298 K. For grossite (CaAl₄O₇), calculated values of C_P as 195.9 J/mol-K and of S as 172.0 J/mol-K are slightly smaller than the available calorimetric data at 298 K, consistent with calorimetric data having been obtained from samples containing ∼10 wt% hibonite impurities. Thermal conductivity at 298 K (k₀) is predicted from peak widths of the vibrational modes using the damped harmonic oscillator model of a phonon gas. Calculations of k₀ for CaO and Al₂O₃ differ from the measurements by 17% and 5%, respectively. The discrepancy for lime is larger due to uncertainties in its peak widths. This comparison suggests that our results for the calcium aluminates should be more accurate than conventional measurements of k₀ which are commonly uncertain by ∼25%.     

福建省建瓯市井后叶蜡石矿床地质特征及找矿标志

建瓯市井后叶腊石矿是新探明的特大型矿床,资源储量约占全国叶蜡石查明总资源储量的近三分之一,为我国最大叶蜡石矿床。通过对井后叶蜡石矿的地层、构造、岩体以及围岩蚀变等地质特征分析,矿床为典型的火山热液成因类型,成矿方式以交代为主。