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1.
The metastable superheated solutions are liquids in transitory thermodynamic equilibrium inside the stability domain of their vapor (whatever the temperature is). Some natural contexts should allow the superheating of natural aqueous solutions, like the soil capillarity (low T superheating), certain continental and submarine geysers (high T superheating), or even the water state in very arid environments like the Mars subsurface (low T) or the deep crustal rocks (high T). The present paper reports experimental measurements on the superheating range of aqueous solutions contained in quartz as fluid inclusions (Synthetic Fluid Inclusion Technique, SFIT) and brought to superheating state by isochoric cooling. About 40 samples were synthetized at 0.75 GPa and 530-700 °C with internally-heated autoclaves. Nine hundred and sixty-seven inclusions were studied by micro-thermometry, including measuring the temperatures of homogenization (Th: L + V → L) and vapor bubbles nucleation (Tn: L → L + V). The Th-Tn difference corresponds to the intensity of superheating that the trapped liquid can undergo and can be translated into liquid pressure (existing just before nucleation occurs at Tn) by an equation of state. Pure water (840-935 kg m−3), dilute NaOH solutions (0.1 and 0.5 mol kg−1), NaCl, CaCl2 and CsCl solutions (1 and 5 mol kg−1) demonstrated a surprising ability to undergo tensile stress. The highest tension ever recorded to the best of our knowledge (−146 MPa, 100 °C) is attained in a 5 m CaCl2 inclusion trapped in quartz matrix, while CsCl solutions qualitatively show still better superheating efficiency. These observations are discussed with regards to the quality of the inner surface of inclusion surfaces (high P-T synthesis conditions) and to the intrinsic cohesion of liquids (thermodynamic and kinetic spinodal). This study demonstrates that natural solutions can reach high levels of superheating, that are accompanied by strong changes of their physico-chemical properties.  相似文献   

2.
Most submarine gas hydrates are located within the two-phase equilibrium region of hydrate and interstitial water with pressures (P) ranging from 8 to 60 MPa and temperatures (T) from 275 to 293 K. However, current measurements of solubilities of methane in equilibrium with hydrate in the absence of a vapor phase are limited below 20 MPa and 283.15 K, and the differences among these data are up to 30%. When these data were extrapolated to other P-T conditions, it leads to large and poorly known uncertainties. In this study, in situ Raman spectroscopy was used to measure methane concentrations in pure water in equilibrium with sI (structure one) methane hydrate, in the absence of a vapor phase, at temperatures from 276.6 to 294.6 (±0.3) K and pressures at 10, 20, 30 and 40 (±0.4%) MPa. The relationship among concentration of methane in water in equilibrium with hydrate, in mole fraction [X(CH4)], the temperature in K, and pressure in MPa was derived as: X(CH4) = exp [11.0464 + 0.023267 P − (4886.0 + 8.0158 P)/T]. Both the standard enthalpy and entropy of hydrate dissolution at the studied T-P conditions increase slightly with increasing pressure, ranging from 41.29 to 43.29 kJ/mol and from 0.1272 to 0.1330 kJ/K · mol, respectively. When compared with traditional sampling and analytical methods, the advantages of our method include: (1) the use of in situ Raman signals for methane concentration measurements eliminates possible uncertainty caused by sampling and ex situ analysis, (2) it is simple and efficient, and (3) high-pressure data can be obtained safely.  相似文献   

3.
The Newtonian viscosity of synthetic rhyolitic liquids with 0.15-5.24 wt% dissolved water was determined in the interval between 580 and 1640 °C and pressures of 1 atm and 5-25 kbar. Measurements were performed by combining static and accelerated (up to 1000g) falling sphere experiments on water-bearing samples, with high temperature concentric cylinder experiments on 0.15 wt% H2O melts. These methods allowed viscosity determinations between 102 and 107 Pa s, and cover the complete range of naturally occurring magmatic temperatures, pressures, and H2O-contents for rhyolites.Our viscosity data, combined with those from previous studies, were modeled by an expression based on the empirical Vogel-Fulcher-Tammann equation, which describes viscosities and derivative properties (glass transition temperature Tg, fragility m, and activation volume of viscous flow Va) of silicic liquids as a function of P-T-X(H2O). The fitted expressions do not account for composition-dependent parameters other than X(H2O) and reproduce the entire viscosity database for silicic liquids to within 3.0% average relative error on log η (i.e. std. error of estimate of 0.26 log units).The results yield the expected strong decrease of viscosity with temperature and water content, but show variable pressure dependencies. Viscosity results to be strongly affected by pressure at low pressures; an effect amplified at low temperatures and water contents. Fragility, as a measure for the deviation from Arrhenian behavior, decreases with H2O-content but is insensitive to pressure. Activation volumes are always largely negative (e.g., less than −10 cm3/mol) and increase strongly with H2O-content. Variations in melt structure that may account for the observed property variations are discussed.  相似文献   

4.
In situ X-ray diffraction measurements of KAlSi3O8-hollandite (K-hollandite) were performed at pressures of 15–27 GPa and temperatures of 300–1,800 K using a Kawai-type apparatus. Unit-cell volumes obtained at various pressure and temperature conditions in a series of measurements were fitted to the high-temperature Birch-Murnaghan equation of state and a complete set of thermoelastic parameters was obtained with an assumed K′300,0=4. The determined parameters are V 300,0=237.6(2) Å3, K 300,0=183(3) GPa, (?K T,0/?T) P =?0.033(2) GPa K?1, a 0=3.32(5)×10?5 K?1, and b 0=1.09(1)×10?8 K?2, where a 0 and b 0 are coefficients describing the zero-pressure thermal expansion: α T,0 = a 0 + b 0 T. We observed broadening and splitting of diffraction peaks of K-hollandite at pressures of 20–23 GPa and temperatures of 300–1,000 K. We attribute this to the phase transitions from hollandite to hollandite II that is an unquenchable high-pressure phase recently found. We determined the phase boundary to be P (GPa)=16.6 + 0.007 T (K). Using the equation of state parameters of K-hollandite determined in the present study, we calculated a density profile of a hypothetical continental crust (HCC), which consists only of K-hollandite, majorite garnet, and stishovite with 1:1:1 ratio in volume. Density of HCC is higher than the surrounding mantle by about 0.2 g cm?3 in the mantle transition zone while this relation is reversed below 660-km depth and HCC becomes less dense than the surrounding mantle by about 0.15 g cm?3 in the uppermost lower mantle. Thus the 660-km seismic discontinuity can be a barrier to prevent the transportation of subducted continental crust materials to the lower mantle and the subducted continental crust may reside at the bottom of the mantle transition zone.  相似文献   

5.
Superliquidus metal-silicate partitioning was investigated for a number of moderately siderophile (Mo, As, Ge, W, P, Ni, Co), slightly siderophile (Zn, Ga, Mn, V, Cr) and refractory lithophile (Nb, Ta) elements. To provide independent constrains on the effects of temperature, oxygen fugacity and silicate melt composition, isobaric (3 GPa) experiments were conducted in piston cylinder apparatus at temperature between 1600 and 2600 °C, relative oxygen fugacities of IW−1.5 to IW−3.5, and for silicate melt compositions ranging from basalt to peridotite. The effect of pressure was investigated through a combination of piston cylinder and multi-anvil isothermal experiments between 0.5 and 18 GPa at 1900 °C. Oxidation states of siderophile elements in the silicate melt as well as effect of carbon saturation on partitioning are also derived from these results. For some elements (e.g. Ga, Ge, W, V, Zn) the observed temperature dependence does not define trends parallel to those modeled using metal-metal oxide free energy data. We correct partitioning data for solute interactions in the metallic liquid and provide a parameterization utilized in extrapolating these results to the P-T-X conditions proposed by various core formation models. A single-stage core formation model reproduces the mantle abundances of several siderophile elements (Ni, Co, Cr, Mn, Mo, W, Zn) for core-mantle equilibration at pressures from 32 to 42 GPa along the solidus of a deep peridotitic magma ocean (∼3000 K for this pressure range) and oxygen fugacities relevant to the FeO content of the present-day mantle. However, these P-T-fO2 conditions cannot produce the observed concentrations of Ga, Ge, V, Nb, As and P. For more reducing conditions, the P-T solution domain for single stage core formation occurs at subsolidus conditions and still cannot account for the abundances of Ge, Nb and P. Continuous core formation at the base of a magma ocean at P-T conditions constrained by the peridotite liquidus and fixed fO2 yields concentrations matching observed values for Ni, Co, Cr, Zn, Mn and W but underestimates the core/mantle partitioning observed for other elements, notably V, which can be reconciled if accretion began under reducing conditions with progressive oxidation to fO2 conditions consistent with the current concentration of FeO in the mantle as proposed by Wade and Wood (2005). However, neither oxygen fugacity path is capable of accounting for the depletions of Ga and Ge in the Earth’s mantle. To better understand core formation, we need further tests integrating the currently poorly-known effects of light elements and more complex conditions of accretion and differentiation such as giant impacts and incomplete equilibration.  相似文献   

6.
Quantitative thermodynamic calculations that involve aqueous fluids have proved difficult because of the complexity of the interactions that occur within the fluids. Existing thermodynamic models are difficult to apply to mixed solvent or highly saline solutions at P > 0.3 GPa and T > 300 °C. This work constructs a method for activity-composition calculations in saline, mixed solvent, supercritical aqueous solutions. Mixing is formulated on a mole-fraction scale in terms of a set of independent end-members that describe composition and speciation within the solution. The ideal mixing term takes speciation into account and avoids problems with the common ion effect. Non-ideal interactions are represented by an activity coefficient term that combines a limited form of Debye-Hückel and a van Laar formulation. This approach, referred to as the DH-ASF model, is thermodynamically valid over a wide range of P, T and fluid composition. The value of the model lies in its broad applicability, and small number of calibration parameters. Experimental data from the literature for the systems NaCl-H2O, KCl-H2O, H2O-SiO2-CO2, H2O-NaCl-CO2, H2O-NaCl-SiO2 and for H2O-albite melts have been used to calibrate the DH-ASF model. Calculations were performed using Thermocalc, computer software that calculates equilibria for mineral-based chemical systems.1 The model represents the data to within experimental error in most cases. Conditions modelled include pressures between 0.2 and 1.4 GPa, temperatures between 500 and 900 °C, and xH2O from 0.1 to 1. Calibrated parameters are consistent with expectations based on the conceptual model for the fluid, and are relatively insensitive to changes in pressure and temperature for most examples. The DH-ASF model is thermodynamically valid for a range of P-T conditions that includes pressures from 0.1 to 2 GPa and temperatures from 200 to 1000 °C. A lack of experimental data restricts calibration of the model for many end-members. However, it may be possible to neglect parameters associated with end-members present in small amount. In this case, or with new experimental data for calibrations, the DH-ASF model allows previously inaccessible geological systems and processes to be modelled.  相似文献   

7.
The composition and evolution of a metallic planetary core is determined by the behavior with pressure of the eutectic and the liquidus on the Fe-rich side of the Fe-FeS eutectic. New experiments at 6 GPa presented here, along with existing experimental data, inform a thermodynamic model for this liquidus from 1 bar to at least 10 GPa. Fe-FeS has a eutectic that becomes more Fe-rich but remains constant in T up to 6 GPa. The 1 bar, 3 GPa, and 6 GPa liquidi all cross at a pivot point at 1640 ± 5 K and FeS37 ± 0.5. This liquid/crystalline metal equilibrium is T-x-fixed and pressure independent through 6 GPa. Models of the 1 bar through 10 GPa experimental liquidi show that with increasing P there is an increase in the T separation between the liquidus and the crest of the metastable two-liquid solvus. The solvus crest decreases in T with increasing P. The model accurately reproduces all the experimental liquidi from 1 bar to 10 GPa, as well as reproducing the 0-6 GPa pivot point. The 14 GPa experimental liquidus ( [Chen et al., 2008a] and Chen et al., 2008b) deviates sharply from the lower pressure trends indicating that the 0-10 GPa model no longer applies to this 14 GPa data.  相似文献   

8.
The heat capacity (Cp) of two synthetic spessartine samples (Sps) was measured on 20-30 mg-size samples in the temperature range 2-864 K by relaxation calorimetry (RC) and differential scanning calorimetry (DSC). The polycrystalline spessartine samples were synthesized in two different laboratories at high pressures and temperatures from glass and oxide-mixture starting materials and characterized by X-ray powder diffraction and electron-microprobe analysis. The low-temperature heat capacity data show a prominent lambda transition with a peak at 6.2 K, which is interpreted to be the result of a paramagnetic-antiferromagnetic phase transition. The DSC data around ambient T agree excellently with the RC data and can be represented by the Cp polynomial for T > 250 K:
  相似文献   

9.
Multi-anvil press experiments were performed using a single cell assembly containing six different compositions. This set-up allows a careful sampling of the miscibility gap for given P-T conditions. Shrinking of the miscibility gap in the Fe-S-Si system has been studied from 4 to 12 GPa up to 2200 K, demonstrating a stable immiscible zone up to 4 GPa and 2200 K and its closure at higher pressures. Presence of both S and Si in the Earth’s core is suggested by chondritic models. Therefore, its composition is inherited from processes at pressures higher than 4 GPa. This evolution of the Fe-S-Si miscibility gap is linked with the change in the local short-range order in Fe and Fe-S liquids. Our results indicate that core formation under reducing conditions would be affected by immiscibility for planetesimals up to size of the Moon. Furthermore, due to the difference in wetting properties between the two immiscible liquid phases, the S-rich metal phase would control the chemical exchange between liquid metals and silicates during early differentiation in planetesimals.  相似文献   

10.
We use a lattice vibrational technique to derive thermophysical and thermochemical properties of the pure elements aluminum and iron in pressure–temperature space. This semi-empirical technique is based on either the Mie–Grüneisen–Debye (MGD) approach or an extension of Kieffer’s model to incorporate details of the phonon spectrum. It includes treatment of intrinsic anharmonicity, electronic effects based on the free electron gas model, and magnetic effects based on the Calphad approach. We show that Keane’s equation of state for the static lattice is better suitable to represent thermodynamic data for aluminum from 1 bar to pressures in the multi-megabar region relative to Vinet’s universal and the Birch–Murnaghan equation of state. It appears that the MGD and Mie–Grüneisen–Kieffer approach produce similar results, but that the last one better represents heat capacity below room temperature. For iron we show that the high temperature behavior of thermal expansivity can be explained within the Calphad approach by a pressure-dependent Curie temperature with a slope between –1 and 0 K/GPa.  相似文献   

11.
A non-stoichiometric sample of spinel with composition T(Mg0.4Al0.6)M(Al1.8□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 KT0 and its first pressure derivative K′ were refined simultaneously providing the following coefficients: V0 = 510.34(6) Å3, KT0 = 171(2) GPa, K′ = 7.3(6). This KT0 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 KT0 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).  相似文献   

12.
A means for estimating pressures in natural samples based on both the coupled substitution (Na+)[1+] (Ti + [VI]Si)[4+] = (M)[2+] (Al + Cr)[3+], and the classic pyroxene-stoichiometry majorite-substitution into garnet at high-pressure, is derived for garnets with majoritic chemistry. The technique is based on a compilation of experimental data for different bulk compositions. It is compositionally and thermally robust and can be used to estimate pressures experienced by natural materials during formation of majoritic garnet. In addition, it can be used either retrospectively, or in new experimental studies to establish the pressures of crystallization of reaction products, and determine if disequilibrium is recorded by the chemistries of majoritic garnets. Pressures are calculated based on majoritic chemistries in chondritic meteorites and diamond inclusions. Majoritic garnets associated with Mg perovskite in shocked L chondrites (n = 4) yield uniform pressures of 23.8 ± 0.2 GPa that are slightly higher than pressures recorded by majoritic garnet in shock-derived melt veins in L chondrites (22.4 ± 0.6 GPa; n = 5). Similar pressures are also exhibited by shock-derived majoritic garnets in H chondrites (22.2 ± 1.1 GPa; n = 3). Diamond inclusions with eclogitic and peridotitic majoritic garnet chemistries exhibit mean pressures of 10.7 ± 2.7 GPa (n = 30) and 8.3 ± 1.6 GPa (n = 15) respectively, consistent with a sub-lithospheric origin. However, pressures defined by majoritic diamond inclusions from Jagersfontein (22.3 ± 0.8 GPa and 16.9 ± 1 GPa), Monastery (15.7 ± 7 GPa) and Kankan (15.5 ± 0.2 GPa) show that these inclusions originated from the mantle transition zone. Thus, this new single-phase method for pressure estimation has unmatched potential to map the depth of formation of garnets with majoritic chemistries that occur as diamond inclusions in all parageneses except those that include Ca silicate perovskite. The derived pressures confirm the sub-lithospheric origin of eclogitic majoritic diamond inclusions, and thus provide a more comprehensive picture of the important role of storage of oceanic lithosphere in the transition zone.  相似文献   

13.
The sulfur concentration at pyrrhotite- and anhydrite-saturation in primitive hydrous basaltic melt of the 2001-2002 eruption of Mt. Etna was determined at 200 MPa, T = 1050-1250 °C and at log fO2 from FMQ to FMQ+2.2 (FMQ is Fayalite-Magnetite-Quartz oxygen buffer). At 1050 °C Au sample containers were used. A double-capsule technique, using a single crystal olivine sample container closed with an olivine piston, embedded in a sealed Au80Pd20 capsule, was developed to perform experiments in S-bearing hydrous basaltic systems at T > 1050 °C. Pyrrhotite is found to be a stable phase coexisting with melt at FMQ-FMQ+0.3, whereas anhydrite is stable at FMQ+1.4-FMQ+2.2. The S concentration in the melt increases almost linearly from 0.12 ± 0.01 to 0.39 ± 0.02 wt.% S at FeS-saturation and from 0.74 ± 0.01 to 1.08 ± 0.04 wt.% S at anhydrite-saturation with T ranging from 1050-1250 °C. The relationships between S concentration at pyrrhotite and/or anhydrite saturation, MgO content of the olivine-saturated melt, T, and log fO2 observed in this study and from previous data are used to develop an empirical model for estimating the magmatic T and fO2 from the S and MgO concentrations of H2O-bearing olivine-saturated basaltic melts. The model can also be used to determine maximum S concentrations, if fO2 and MgO content of the melt are known. The application of the model to compositions of melt inclusions in olivines from Mt. Etna indicates that the most primitive magmas trapped in inclusions might have been stored at log fO2 slightly higher than FMQ+1 and at T = 1100-1150 °C, whereas more evolved melts could have been trapped at T ? 1100 °C. These values are in a good agreement with the estimates obtained by other independent methods reported in the literature.  相似文献   

14.
Detrital zircons from the Ob, Yenisey, Lena, Amur, Volga, Dnieper, Don and Pechora rivers have been analyzed for U-Th-Pb, O and Lu-Hf isotopes to constrain the growth rate of the preserved continental crust in Greater Russia. Four major periods of zircon crystallization, 0.1-0.55, 0.95-1.3, 1.45-2.0 and 2.5-2.9 Ga, were resolved from a compilation of 1366 zircon U/Pb ages. The Archean zircons have δ18O values lying between 4.53‰ and 7.33‰, whereas Proterozoic and Phanerozoic zircons have a larger range of δ18O values in each of the recognized U/Pb time intervals with maximum δ18O values up to 12‰. We interpret the zircons with δ18O between 4.5‰ and 6.5‰ to have been derived from a magmatic precursor that contains little or no sedimentary component. The variable δ18O values of the zircons were used to constrain the 176Lu/177Hf ratios of the crustal source region of the zircons, which, in turn, were used to calculate Hf model ages (TDMV). The crustal incubation time, the time difference between primitive crust formation (dated by TDMV) and crustal melting (dated by zircon U/Pb age), varies between 300 to 1000 Myr for the majority of analyzed zircon grains, but can be up to 2500 Myr. The average TDMV Hf model age weighted by the fraction of zircons in the river load is 2.12 Ga, which is in reasonable agreement with the area-weighted average of 2.25 Ga. The TDMV Hf model age crustal growth curve for zircons with mantle-like δ18O values (4.5-6.5‰), weighted by area, shows that growth of the Great Russian continental crust started at 4.2 Ga, and that there are two principal periods of crustal growth, 3.6-3.3 Ga and 0.8-0.6 Ga, which are separated by an interval of low but more or less continuous growth. An alternative interpretation, in which the average 176Lu/177Hf ratio (0.0115) of the continental crust is used for the Paleoproterozoic zircons from the Lena River, lowers the average TDMV age of these grains by about 500 Myr and delays the onset of significant crustal growth to 3.5 Ga.The two principal growth periods recognized in Greater Russia differ from those identified from the Gondwana and the Mississippi river basin, which show peaks at 1.7-1.9 and 2.9-3.1 Ga (Hawkesworth and Kemp, 2006a) and 1.6-2.2 and 2.9-3.4 Ga (Wang et al., 2009), respectively. The older 3.6-3.3 Ga or 3.5-3.3 Ga peak for Greater Russia is slightly older than the older Gondwana-Mississippi peaks, whereas the younger 0.8-0.6 Ga peak is distinctly younger than the youngest peak in either Gondwana or the Mississippi river basin. This suggests that the two major peaks of crustal growth identified in Gondwana and the Mississippi river basin may not be global periods of enhanced continental growth and that the major periods of crustal growth may differ from continent to continent.  相似文献   

15.
Considerable advances in our understanding of physicochemical properties of geological fluids and their roles in many geological processes have been achieved by the use of synthetic fluid inclusions. We have developed a new method to synthesize fluid inclusions containing organic and inorganic material in fused silica capillary tubing. We have used both round (0.3 mm OD and 0.05 or 0.1 mm ID) and square cross-section tubing (0.3 × 0.3 mm with 0.05 × 0.05 mm or 0.1 × 0.1 mm cavities). For microthermometric measurements in a USGS-type heating-cooling stage, sample capsules must be less than 25 mm in length. The square-sectioned capsules have the advantage of providing images without optical distortion. However, the maximum internal pressure (P; about 100 MPa at 22 °C) and temperature (T; about 500 °C) maintained by the square-sectioned capsules are less than those held by the round-sectioned capsules (about 300 MPa at room T, and T up to 650 °C).The fused silica capsules can be applied to a wide range of problems of interest in fluid inclusion and hydrothermal research, such as creating standards for the calibration of thermocouples in heating-cooling stages and frequency shifts in Raman spectrometers. The fused silica capsules can also be used as containers for hydrothermal reactions, especially for organic samples, including individual hydrocarbons, crude oils, and gases, such as cracking of C18H38 between 350 and 400 °C, isotopic exchanges between C18H38 and D2O and between C19D40 and H2O at similar temperatures. Results of these types of studies provide information on the kinetics of oil cracking and the changes of oil composition under thermal stress.When compared with synthesis of fluid inclusions formed by healing fractures in quartz or other minerals or by overgrowth of quartz at elevated P-T conditions, the new fused-silica method has the following advantages: (1) it is simple; (2) fluid inclusions without the presence of water can be formed; (3) synthesized inclusions are large and uniform, and they are able to tolerate high internal P; (4) it is suitable for the study of organic material; and (5) redox control is possible due to high permeability of the fused silica to hydrogen.  相似文献   

16.
We present an integrated study of geochemistry, petrofabrics and seismic properties of strongly sheared eclogites from the Chinese Continental Scientific Drilling (CCSD) project in the Sulu ultrahigh-pressure (UHP) metamorphic terrane, eastern China. First, geochemical data characterize diverse protoliths of the studied eclogites. The positive Eu- and Sr-anomalies, negative Nb anomaly and flat portion of heavy rare earth elements in coarse-grained rutile eclogites (samples B270 and B295) suggest a cumulate origin in the continental crust, whereas the negative Nb anomaly and enrichment of light rare earth elements in retrograde eclogites (samples B504, B15 and B19) imply an origin of continental basalts or island arc basalts. Second, P-wave velocities (Vp) of three typical eclogite samples were measured under confining pressures up to 500 MPa and temperatures to 700 °C. At 500 MPa and room temperature, the mean Vp reaches 8.50-8.53 km/s in samples B270 and B295 but drops to 7.86 km/s in sample B504, and the P-wave anisotropy changes from 1.7-2.7% to 5.5%, respectively. The pressure and temperature derivatives of Vp are larger in the retrograde eclogite than in fresh ones. Third, the electron backscatter diffraction (EBSD) measurements of the eclogites reveal random crystal preferred orientation (CPO) of garnet and pronounced CPO of omphacite, which is characterized by a strong concentration of [001]-axes sub-parallel to the lineation and of (010)-poles perpendicular to the foliation. The asymmetric CPO of omphacite in sample B270 recorded a top-to-the-south shear event during subduction of the Yangtze plate. The calculated fastest Vp is generally sub-parallel to the lineation, but a different deformation environment during exhumation could form second-order variations in omphacite CPO and affect the Vp distribution in eclogites (e.g., the fastest Vp is at ~ 35° from the foliation in sample B295). Comparison between measured and calculated seismic properties indicates that the CPO of omphacite controls the seismic anisotropy of eclogites at high pressure, and compositional layering and retrograde minerals will increase the anisotropy. Calculated P-wave velocities agree well with velocities measured at 500 MPa and room temperature for fresh eclogites, but much higher than those of retrograde eclogite. As a case study, the laboratory-derived Vp-P and Vp-T relationships were used to estimate P-wave velocities of eclogites and peridotites beneath the Western Superior Province, Canada. The results indicate that besides the fabric-induced anisotropy, the direction dependence of pressure and temperature derivatives of Vp can significantly increase seismic anisotropy of eclogites with depth, which results in eclogites being an important candidate for the seismic anisotropy in the upper mantle. Due to their very high density and velocity, garnet-rich eclogites within peridotite could be detected in seismic reflections in subduction zones.  相似文献   

17.
Chloride and hydrosulfide are the principal ligands assumed to govern transport of copper in hydrothermal fluids. Existing solubility experiments suggest that Cu(I)-hydrosulfide complexes are dominant compared to chloride complexes at low salinities in alkaline solutions (H2S(aq)/HS− pH buffer), and may be important in transporting Cu in low density magmatic vapors, potentially controlling the liquid-vapor partitioning of Cu. This study provides the first in situ evidence of the solubility of copper sulfides and the nature and structure of the predominant Cu species in sulfur-containing fluids at temperatures up to 592 °C and pressures of 180-600 bar. XANES and EXAFS data show that at elevated T (?200 °C), Cu solubility occurs via a linear Cu complex. At 428 °C in alkaline solutions, Cu is coordinated by two sulfur atoms in a distorted linear coordination (angle ∼150-160°). This geometry is consistent with the species predicted by earlier solubility studies. In addition, in situ measurements of the solubility of chalcocite in 2 m NaHS solutions performed in this study are in remarkably good agreement with the solubilities calculated using available thermodynamic data for Cu(I)-hydrosulfide complexes, also supporting the interpretation of speciation in these studies and validating the extrapolation of low-T thermodynamic properties for to high P-T. Data on phase separation for the 2 m NaHS solution show that while significant amounts of copper can be partitioned into the vapor phase, there is no indication for preferential partitioning of Cu into the vapor. This is consistent with recent partitioning experiments conducted in autoclaves by Pokrovski et al. (2008a) and Simon et al. (2006). XANES data suggest that the species present in the low density phase is very similar to that present in the high density liquid, i.e., , although Cu(HS)(H2S)0 cannot be excluded on the basis of XAS data.  相似文献   

18.
High temperature elasticity of single crystal potassium chloride has been studied by the Rectangular Parallelepiped Resonance (RPR) method up to 870 K (? 3.8 times the Debye temperature, ?). The elastic stiffness moduli, C 11 and C 44, decrease linearly with temperature while C 12 increases slightly with temperature. The RPR method is particularly suited to measurements of elasticity at high temperatures, since no glues (which decompose at high temperature) are used to connect the transducers to a specimen. As a consequence, the measured spectrum closely approximates the theoretical spectrum of a specimen freely suspended in space with no external contact. The present elasticity data permits the investigation of the thermodynamic properties of potassium chloride far above the Debye temperature when used together with the previous zero-pressure data on thermal expansivity and heat capacity. The equation of state of potassium chloride is virtually unaffected by anharmonicity, even at T/?=3.8. One result is that the thermal pressure for KCl above the Debye temperature linearly increases with temperature. There is also small dependence on volume, in contrast to NaCl where there is no dependence on volume.  相似文献   

19.
We have carried out a comparative Rb-Sr, Sm-Nd and Lu-Hf isotopic study of a progressively deformed hercynian leucogranite from the French Massif Central, belonging to the La Marche ductile shear zone, in order to investigate the respective perturbation of these geochronometers with fluid induced deformation. The one-meter wide outcrop presents a strongly deformed and mylonitized zone at the center, and an asymmetric deformation pattern with a higher deformation gradient on the northern side of the zone. Ten samples have been carefully collected every 10 cm North and South away from the strongest deformed mylonitic zone. They have been analyzed for a complete major, trace element data set, oxygen isotopes, Rb-Sr, Sm-Nd and Lu-Hf isotopic systematics.We show that most of major and trace elements except SiO2, alkaline elements (K2O, Rb), and some metal transition elements (Cu), are progressively depleted with increasing deformation. This depletion includes REE + Y, but also HFS elements (Ti, Hf, Zr, Nb) which are commonly considered as immobile elements during upper level processes. Variations in elemental ratios with deformation, e.g. decrease in LREE/MREE- HREE, Nd/Hf, Th/Sr, increase in Rb/Sr, U/Th and constant Sr/Nd, lead to propose the following order of element mobility: U ? Th > Sr = Nd ? Hf + HREE. We conclude in agreement with previous tectonic and metallogenic studies that trace element patterns across the shear zone result from circulation of oxidizing F-rich hydrothermal fluids associated with deformation. A temperature of the fluid of 470-480 °C can be deduced from the δ18O equilibrium between quartz-muscovite pairs.Elemental fractionation induces perturbation of the Rb-Sr geochronometer. The well-defined 87Rb/86Sr-87Sr/86Sr correlation gives an apparent age of 294 ± 19 Ma, slightly younger than the 323 ± 4 Ma age of leucogranites in this area. This apparent age is interpreted as dating event of intense deformation and fluid circulation associated with mass transfer, and exhumation of the ductile crust shortly after the leucogranite emplacement. Sm-Nd and Lu-Hf isochron-type diagrams do not define any correlation, because of the low fractionated Sm/Nd and Lu/Hf ratios. Isotopic data demonstrate that only the Lu-Hf geochronometer system is not affected by fluid circulation and gives reliable TDM age (1.29 ± 0.03 Ga) and εHf signatures. By contrast, the Sm-Nd geochronometer system gives erroneous old TDM ages of 2.84-4 Ga. There is no positive εNd-εHf correlation, because of decreasing εNd values with deformation at constant εHf values. However, εNd-εHf values remain in the broad εNd-εHf terrestrial array, which strongly indicates that fluid-induced fractionation can contribute to the width of the terrestrial array. The strong εHf negative values of the leucogranite are similar to metasedimentary granulitic xenoliths from the French Massif Central and confirm the generation of the leucogranite by several episodes of reworking of the lower crust.  相似文献   

20.
We perform first principles molecular dynamics simulations of Mg2SiO4 liquid and crystalline forsterite. On compression by a factor of two, we find that the Grüneisen parameter of the liquid increases linearly from 0.6 to 1.2. Comparison of liquid and forsterite equations of state reveals a temperature-dependent density crossover at pressures of ∼12-17 GPa. Along the melting curve, which we calculate by integration of the Clapeyron equation, the density crossover occurs within the forsterite stability field at P = 13 GPa and T = 2550 K. The melting curve obtained from the root mean-square atomic displacement in forsterite using the Lindemann law fails to match experimental or calculated melting curves. We attribute this failure to the liquid structure that differs significantly from that of forsterite, and which changes markedly upon compression, with increases in the degree of polymerization and coordination. The mean Si coordination increases from 4 in the uncompressed system to 6 upon twofold compression. The self-diffusion coefficients increase with temperature and decrease monotonically with pressure, and are well described by the Arrhenian relation. We compare our equation of state to the available highpressure shock wave data for forsterite and wadsleyite. Our theoretical liquid Hugoniot is consistent with partial melting along the forsterite Hugoniot at pressures 150-170 GPa, and complete melting at 170 GPa. The wadsleyite Hugoniot is likely sub-liquidus at the highest experimental pressure to date (200 GPa).  相似文献   

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