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1.
A solution model is developed for rhombohedral oxide solid solutions having compositions within the ternary system ilmenite [(Fe 2+ s Ti 4+ 1–s ) A (Fe 2+ 1–s Ti 4+ s ) B O3]-geikielite [(Mg 2+ t Ti 4+ 1–t ) A (Mg 2+ 1–t Ti 4+ t ) B O3]-hematite [(Fe3+) A (Fe3+) B O3]. The model incorporates an expression for the configurational entropy of solution, which accounts for varying degrees of structural long-range order (0s, t1) and utilizes simple regular solution theory to characterize the excess Gibbs free energy of mixing within the five-dimensional composition-ordering space. The 13 model parameters are calibrated from available data on: (1) the degree of long-range order and the composition-temperature dependence of the transition along the ilmenite-hematite binary join; (2) the compositions of coexisting olivine and rhombohedral oxide solid solutions close to the Mg–Fe2+ join; (3) the shape of the miscibility gap along the ilmenite-hematite join; (4) the compositions of coexisting spinel and rhombohedral oxide solid solutions along the Fe2+–Fe3+ join. In the course of calibration, estimates are obtained for the reference state enthalpy of formation of ulvöspinel and stoichiometric hematite (–1488.5 and –822.0 kJ/mol at 298 K and 1 bar, respectively). The model involves no excess entropies of mixing nor does it incorporate ternary interaction parameters. The formulation fits the available data and represents an internally consistent energetic model when used in conjuction with the standard state thermodynamic data set of Berman (1988) and the solution theory for orthopyroxenes, olivines and Fe–Mg titanomagnetite-aluminate-chromate spinels developed by Sack and Ghiorso (1989, 1990a, b). Calculated activity-composition relations for the end-members of the series, demonstrate the substantial degree of nonideality associated with interactions between the ordered and disordered structures and the dominant influence of the miscibility gap across much of the ternary system. The predicted shape of the miscibility gap, and the orientation of tie-lines relating the compositions of coexisting phases, display the effects of coupling between the excess enthalpy of solution and the degree of long-range order. One limb of the miscibility gap follows the composititiontemperature surface corresponding to the ternary second-order transition.  相似文献   

2.
The black shale-hosted selenide vein-type deposit at Tilkerode, eastern Harz, Germany, has specular hematite enclosed in clausthalite (PbSe). The specular hematite has Ti and V in amounts of up to ~1 wt.% TiO2 and ~3 wt.% V2O5, and subordinate, but important, contents of Mo (22–372 ppm) and B (up to 68 ppm). The Tilkerode hematite serves as a reference for hydrothermal hematite formed at relatively low temperatures (<150 °C). The composition of the Tilkerode hematite is compared with that of two generations of specular hematite from itabirite-hosted iron-ore deposits in the Quadrilátero Ferrífero of Minas Gerais, Brazil. The first generation of specular hematite represents an early tectonic hematitisation of dolomitic itabirite at Águas Claras and occurs as fine-grained crystals. Reconnaissance data indicate that the Águas Claras hematite is poorer in Ti and V, relative to the Tilkerode hematite, but has ~5–10 ppm B and ~7–11 ppm Li. The second generation of specular hematite defines the pervasive tectonic foliation of the Gongo Soco iron ore. This hematite has Ti contents of up to ~2 wt.% TiO2 and subordinate amounts of V (62–367 ppm); its B and Li concentrations are mostly below <2 ppm B and <1 ppm Li. The presence of Ti and B in the Tilkerode hematite can be explained by highly saline, B-bearing fluids that were capable of mobilising otherwise immobile Ti. The Mo signature of the Tilkerode hematite suggests that Mo was derived from the host black shale. In Minas Gerais, B and Li were incorporated into the early tectonic hematite from saline fluids at relatively low temperatures (Águas Claras) and then released during metamorphic hematite growth at higher temperatures, as suggested by the foliation-defining hematite without B–Li signature (Gongo Soco).  相似文献   

3.
Samples prepared by the novel method based on the thermal decomposition at 700 °C in air of mixed Fe and Ni oxinates were characterized by thermogravimetric analysis, X-ray diffraction, magnetization measurements, and variable-temperature Mössbauer spectroscopy. It is found that the combustion treatment produces Ni-hematite and trevorite, the fraction of the latter increasing with the increment of Ni in the metal oxinates. Results indicate that the substitution of Ni2+ for Fe3+ in the hematite structure, which was found to be less than 5.3 mol%, is accompanied by the presence of oxygen and structural vacancy sites. Both the metal replacement and the presence of defects cause the a and c cell hematite parameters to decrease. The Néel temperature and the difference between the saturation fields for the antiferromagnetic AF and the weakly ferromagnetic WF phases are also found to decrease with nickel content. These effects are due to the fact that the magnetic behavior of hematite depends on the presence of Ni, vacancy sites, and lattice distortion. The large decrease in the Néel temperature with Ni doping suggests that structural vacancies are also present On the contrary, Ni incorporation does not appreciably affect the Morin temperature and the temperature range in which both AF and WF phases coexist. It is suggested that these effects are probably due to the differing effects that Ni and defects can produce on the magnetic dipolar and the single ion anisotropies.  相似文献   

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Sorption of geosorbents including soils and sediments is a key process controlling the fate and transport of hydrophobic organic compounds (HOCs) in the environment. HOC sorption has been generally correlated to the nature and content of organic matter present in the geosorbents. However, several environments can have organic matter contents low enough so that clay mineral surfaces are the dominant sorbents, including low-organic carbon soils, some ground water aquifers, atmospheric water droplets (e.g. clouds, fogs, and raindrops), and engineered environmental systems (e.g. clay barriers). Furthermore, several previous studies demonstrated that clays or clay components in soils sorb HOCs higher than expected, especially those compounds containing strong polar functionalities. Because many environmentally related HOCs including a significant portion of pesticides and herbicides contain polar functional groups, studying the interactions of these compounds with mineral surface at the molecular level is of great theoretical and practical importance. In the present study, we studied sorption of a series of nonionic pesticides (e.g. dichlobenil, carbaryl, alachlor, metolachlor, monuron, diuron, cyanazine) containing polar functional groups and a polycyclic aromatic hydrocarbon, naphthalene, as a control on a reference smectite (SWy-2) saturated with K^+ using combined batch sorption and FTIR methodologies.  相似文献   

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8.
 Using the high-pressure differential thermal analysis (HP-DTA) system in a cubic multianvil high-pressure apparatus, we measured the melting points of portlandite, Ca(OH)2, up to 6 GPa and 1000 °C. We detected endothermic behavior at the temperature and pressure conditions of 800 °C and 2.5 GPa, 769 °C and 3.5 GPa, 752 °C and 4.0 GPa, 686 °C and 5.0 GPa, and 596 °C and 6.0 GPa, respectively, due to melting of portlandite. By in situ X-ray studies under pressure, the melting of portlandite was observed at 730 °C and 4.32 GPa and at 640 °C and 5.81 GPa, respectively. Results of both HP-DTA and X-ray studies were consistent within experimental error. The melting is congruent and has a negative Clapeyron slope, indicating that liquid Ca(OH)2 has higher densities than crystalline portlandite in this pressure range. Received: 19 June 1999 / Revised, accepted: 11 September 1999  相似文献   

9.
The stability and pressure–volume equation of state of iron–silicon alloys, Fe-8.7 wt% Si and Fe-17.8 wt% Si, have been investigated using diamond-anvil cell techniques up to 196 and 124 GPa, respectively. Angular–dispersive X-ray diffractions of iron–silicon alloys were measured at room temperature using monochromatic synchrotron radiation and an imaging plate (IP). A bcc–Fe-8.7 wt% Si transformed to hcp structure at around 1636 GPa. The high-pressure phase of Fe-8.7 wt% Si with hexagonal close-packed (hcp) structure was found to be stable up to 196 GPa and no phase transition of bcc–Fe-17.8 wt% Si was observed up to 124 GPa. The pressure–volume data were fitted to a third-order Birch–Murnaghan equation of state (BM EOS) with zero–pressure parameters: V0=22.2(8) Å3, K0=198(9) GPa, and K0=4.7(3) for hcp–Fe-8.7 wt% Si and V0=179.41(45) Å3, K0=207(15) GPa and K0=5.1(6) for Fe-17.8 wt% Si. The density and bulk sound velocity of hcp–Fe-8.7 wt% Si indicate that the inner core could contain 3–5 wt% Si.  相似文献   

10.
The hydration state of Na- and K-exchanged clinoptilolite from Castle Creek (Idaho, U.S.A.) has been measured by a pressure titration method to 300 °C and P H2O<30 bars. The water content of clinoptilolite can be predicted as a function of water activity and temperature with the equation: a H2O = [exp[[−ΔH h /nRT] + [ΔS h /nR] − 1/nRT· [W1 X h + W2 X h 2]− ln(X a/X h)]]−1 where T is degrees in Kelvin, ΔH h is the standard molal enthalpy of hydration, ΔS h is the entropy of hydration, X h and X a are, respectively, the mole fractions of the hydrous and anhydrous components of the solid solution, W 1 and W 2 are interaction parameters, n is the maximum number of moles of H2O per formula unit (based on 12 oxygens), and R is the gas constant. This equation can be used to locate clinoptilolite-H2O isohydrons in a H2O-T space below the liquid-vapor equilibrium curve of water. The standard molal Gibbs free energy of hydration is −47.62 ± 5.52 kJ/mol H2O and −5.40 ± 2.71 kJ/mol H2O for the Na- and K-clinoptilolite, respectively. These standard-state thermodynamic properties of clinoptilolite hydration are in good agreement with previous data at low H2O pressures. The experiments indicate that clinoptilolite progressively dehydrates with increasing temperature at pressures along the liquid-vapor equilibrium curve. Kinetic data above 150 °C show that clinoptilolite dehydration and hydration reactions are fast and reversible and that steady-state hydration states are attained in minutes. Received: 19 June 1998 / Revision, accepted 14 December 1998  相似文献   

11.
Omphacite is an important mineral component of eclogite. Single-crystal synchrotron X-ray diffraction data on natural (Ca, Na) (Mg, Fe, Al)Si2O6 omphacite have been collected at the Advanced Photon Source beamlines 13-BM-C and 13-ID-D up to 47 GPa at ambient temperature. Unit cell parameter and crystal structure refinements were carried out to constrain the isothermal equation of state and compression mechanism. The third-order Birch–Murnaghan equation of state (BM3) fit of all data gives V 0 = 423.9(3) Å3, K T0 = 116(2) GPa and K T0′ = 4.3(2). These elastic parameters are consistent with the general trend of the diopside–jadeite join. The eight-coordinated polyhedra (M2 and M21) are the most compressible and contribute to majority of the unit cell compression, while the SiO4 tetrahedra (Si1 and Si2) behave as rigid structural units and are the most incompressible. Axial compressibilities are determined by fitting linearized BM3 equation of state to pressure dependences of unit cell parameters. Throughout the investigated pressure range, the b-axis is more compressible than the c-axis. The axial compressibility of the a-axis is the largest among the three axes at 0 GPa, yet it quickly drops to the smallest at pressures above 5 GPa, which is explained by the rotation of the stiffest major compression axis toward the a-axis with the increase in pressure.  相似文献   

12.
The ambient pressure elastic properties of single-crystal TiO2 rutile are reported from room temperature (RT) to 1800 K, extending by more than 1200 oK the maximum temperature for which rutile elasticity data are available. The magnitudes of the temperature derivatives decrease with increasing temperature for five of the six adiabatic elastic moduli (C ij ). At RT, we find (units, GPa): C 11=268(1); C 33=484(2); C 44=123.8(2); C 66=190.2(5); C 23=147(1); and C 12=175(1). The temperature derivatives (units, GPa K−1) at RT are: (∂C 11/∂T) P =−0.042(5); (∂C 33/∂T) P =−0.087(6); (∂C 44/∂T) P =−0.0187(2); (∂C 66/∂T) P =−0.067(2); (∂C 23/∂T) P =−0.025; and (∂C 12/∂T) P −0.048(5). The values for K S (adiabatic bulk modulus) and μ (isotropic shear modulus) and their temperature derivatives are K S =212(1) GPa; μ=113(1) GPa; (∂K S /∂T) P =−0.040(4) GPa K−1; and (∂μ/∂T) P =−0.018(1) GPa K−1. We calculate several dimensionless parameters over a large temperature range using our new data. The unusually high values for the Anderson-Gròneisen parameters at room temperature decrease with increasing temperature. At high T, however, these parameters are still well above those for most other oxides. We also find that for TiO2, anharmonicity, as evidenced by a non-zero value of [∂ln (K T )/∂lnV] T , is insignificant at high T, implying that for the TiO2 analogue of stishovite, thermal pressure is independent of volume (or pressure). Systematic relations indicate that ∂2 K S /∂TP is as high as 7×10−4 K−1 for rutile, whereas ∂2μ/∂TP is an order of magnitude less. Received: 19 September 1997 / Revised, accepted: 27 February 1998  相似文献   

13.
<正>There is a general consensus that Plate Tectonics can explain metallogenesis based on the collisions between oceanic and continental crust.For instance,the large-sized porphyry copper deposits that occur along the Cordillera of the Andes around the east coast of the Pacific,and in the Phillipines,Malaysia and Indonesia along the western coast of the Pacific that sit upon the massive Pacific plates.They are considered to be typical of deposits resulting from collision between the oceanic and continental crust.Many experts,however,have long held a negative view about whether the collision between  相似文献   

14.
Karst in Vietnam covers an area of about 60,000 km2, i.e. 18 % of the surface of the country. The country has an annual average temperature of 24@, an annual average rainfall of 2300 mm and a relative humidity of about 90%. Karst in Vietnam is typified by peak cluster-depression landscapes ranging in elevation from 200 to over 2000 m. Tower and coastal karst landscapes also exit. Because of naturally favourable conditions, karst ecosystems are diverse and very rich. Higher plants (cormophytes) are abundant. They are represented by approximately 2000 species, 908 genera, 224 families, 86 orders and 7 phyla. They form a thick vegetation cover of evergreen tropical rainforest. Knowledge about lower plants is limited. The fauna is rich and diverse. Phyla such as Protozoa, Vermes, Mollusca and Arthropoda are yet ill known. Preliminary results show that the phylum Chordata is represented by 541 species from 80 families, 40 orders and 5 classes. There exist many precious and rare mammals, in particular some en  相似文献   

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Two examples are given for comparing applications and limitations of four methods which can be used to deal with error propagation in geochemical calculations.The examples indicate that the Monte Carlo method can also be employed to evaluate the effect of covariance.A special function of the method for covariance matrix shown here can reveal the correlations of middle variables relative to the independent primary variables.  相似文献   

17.
The technique of mineral prediction by pattern recognition has been developed through the applicationof computerized pattern recognition to geological exploration. The principles and computing method of thistechnique as well as some characteristics of its application in geological exploration are expounded in thispaper. Some of the study results gained by the authors in this aspect are also given. which include classifica-tion of oil-field waters. evaluation of gossans of main ore deposits in China, prediction of ore resources inthe Dachang Sn-polymetallic field. and appraisal of Pb and Sn anomalies and prediction of mineral re-sources in southern Hunan. Some of the prediction results have been proved correct.  相似文献   

18.
The distribution of mineral deposits, characterised as barite deposits, hematite-rich auriferous deposits and auriferous tourmaline–sulfide deposits, displays a regional sulfate–hematite–sulfide zoning along the thrust-delineated limbs of the Mariana anticline, in the south-eastern part of the Quadrilátero Ferrífero of Minas Gerais, Brazil. Cross-cut relationships of barite veins and sulfide lodes indicate that sulfidation occurred in a late-tectonic context, which is here attributed to the collapse of the ~0.6-Ga Brasiliano thrust front. Reconnaissance S-isotopic data from barite and pyrite (Antônio Pereira barite deposit and its adjacent gold deposit, respectively), and arsenopyrite (Passagem de Mariana gold deposit), suggest a new interpretation for the hydrothermal fluid overprint in the Mariana anticline. The Antônio Pereira barite has Δ33S values that are near zero, constraining the sulfate source to rocks younger than 2.45 Ga. The barite-δ34S values are between +19.6 and +20.8?‰. The Passagem arsenopyrite and tourmaline have Co/Ni ratios that define a positive linear trend with the Antônio Pereira pyrite. The latter has homogenous δ34S values, between +8.8 and +8.9?‰, which are compatible with thermochemical reduction of aqueous sulfate with the S-isotopic composition of the Antônio Pereira barite.  相似文献   

19.
The validity of the thermodynamic cBΩ model is tested in terms of the experimentally determined diffusion coefficients of He in a natural Fe-bearing olivine (Fo90) and a synthetic end-member forsterite (Mg2SiO4) over a broad temperature range (250–950 °C), as reported recently by Cherniak and Watson (Geochem Cosmochim Acta 84:269–279, 2012). The calculated activation enthalpies for each of the three crystallographic axes were found to be (134 ± 5), (137 ± 13) and (158 ± 4) kJ mol?1 for the [100], [010] and [001] directions in forsterite, and (141 ± 9) kJ mol?1 for the [010] direction in olivine, exhibiting a deviation of <1 % with the corresponding reported experimental values. Additional point defect parameters such as activation volume, activation entropy and activation Gibbs free energy were calculated as a function of temperature. The estimated activation volumes (3.2–3.9 ± 0.3 cm3 mol?1) of He diffusion in olivine are comparable with other reported results for hydrogen and tracer diffusion of Mg cations in olivine. The pressure dependence of He diffusion coefficients was also determined, based on single experimental diffusion measurements at 2.6 and 2.7 GPa along the [001] direction in forsterite at 400 and 650 °C.  相似文献   

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