Four pyroxenes with compositions En48Fs48Wo4, En47·5Fs47·5Wo5, En45Fs45Wo10 and En40Fs40Wo20, synthesized at 1200°C at atmospheric pressure, were heat-treated at 500, 600, 700, and 800°C for various lengths of time. These pyroxenes are variously ordered with respect to Fe2+ and Mg2+ without unmixing. The Fe2+-Mg2+ distribution over the two nonequivalent sites M1 and M2, determined through Mössbauer spectroscopy, is found to be a function of both temperature and concentration of Ca2+ at the M2 site. The preference of Fe2+ for the M2 site increases with decreasing temperature and increasing Ca2+. These data can be used to determine cation equilibration temperatures of lunar and terrestrial pigeonites. The lunar pigeonites usually indicate equilibration temperatures of 700–860°C, except the pigeonite from rock 14053, which may have been subjected to shock heating due to meteoritic impact. 相似文献
Cooling rates have been determined for twelve group IVA iron meteorites using a ternary (Fe-Ni-P) model that simulates the growth of the Widmanstätten pattern. The new ternary model is governed by a set of differential diffusion equations that are coupled through the phase growth velocity and elemental concentration profiles. Measured ternary diffusivities and phase diagram solubilities were extrapolated below 500°C for use in the model. The model is more sophisticated than previous ones in that P as well as Ni gradients are calculated, ternary α-γ tie lines are allowed to vary, and ternary diffusivities are used.Output from the simulation is used to create a family of cooling rate curves on plots of central taenite Ni vs. log taenite half-width for each meteorite. A comparison of measured data to the cooling rate curves yields unique meteorite cooling rates. The measured cooling rates for the twelve IVA irons vary inversely with Ni content by over an order of magnitude (4–200°C/Myr). It is proposed that the group IVA irons were accommodated at various depths in an asteroidal-sized body. 相似文献
Gases trapped in lavas of three main flows of the Ardoukôba eruption (8 to 15 November, 1978) have been analysed by mass spectrometry. These analyses concern both plagioclase phenocrysts and microcrystalline mesostasis. Fluids are released between 500°C and 1200°C, and consist of H2O, CO2, CO, N2, SO2, HCl, H2, CH4 with traces of hydrocarbons and H2S. The total content is less than 0.3–0.4 wt. % of samples with about 0.1–0.15 wt % of H2O. No significant variation among the three flows is observed. Plagioclase phenocrysts are less abundant in fluids than the mesostasis (～2/3). The gases trapped in these phenocrysts are richer in CO and organic compounds, whereas mesostasis contain more H2O, CO2 and SO2. CO is likely produced by reduction of CO2 and H2O with carbon during either analyses or eruption itself, or is of primary origin. In the latter case, gas composition suggests an entrapment temperature of about 1200°C ± 75°C. Kinetic study of the water and carbon dioxide release allows to calculate the diffusion characteristics of these fluids. Water and carbon dioxide behave rather similarly. Plagioclase gives a single activation energy value (8 Kcal/mole), while mesostasis gives two values (8 Kcal/mole, 15 Kcal/mole). Diffusion coefficients at 20°C are estimated to fall in the range 10?13 · 10?12 cm2 · sec?1. 相似文献
Relaxation experiments on vitreous SiO2, densified at 900°C, 20 kbar to a permanent density of 2.36 g cm?3 yield an activation energy of69 ± 5kcal mol?1 in the temperature range 700–800°C. The data can be used to estimate minimum cooling rates, maximum depositional temperatures or maximum thicknesses of shock-metamorphosed rocks containing diaplectic glasses, if relaxation of a glass densified under dynamic conditions is assumed to be similar to that of statically densified glass. 相似文献
FAMOUS basalt 527-1-1 (a high-Mg oceanic pillow basalt) has three generations of spinel which can be distinguished petrographically and chemically. The first generation (Group I) have reaction coronas and are high in Al2O3. The second generation (Group II) have no reaction coronas and are high in Cr2O3 and the third generation (Group III) are small, late-stage spinels with intermediate Al2O3 and Cr2O3. Experimental synthesis of spinels from fused rock powder of this basalt was carried out at temperatures of 1175–1270°C and oxygen fugacities of 10?5.5 to 10?10 atm at 1 atm pressure. Spinel is the liquidus phase at oxygen fugacities of 10?8.5 atm and higher but it does not crystallize at any temperature at oxygen fugacities less than 10?9.5. The composition of our spinels synthesized at 1230–1250°C and 10?9 atmfO2 are most similar to the high-Cr spinels (Group II) found in the rock. Spinels synthesized at 1200°C and 10?8.5 atmO2 are chemically similar to the Group III spinels in 527-1-1. We did not synthesize spinel at any temperature or oxygen fugacity that are similar to the high-Al (Group I) spinel found in 527-1-1. These results indicate that the high-Cr (Group II) spinel is the liquidus phase in 527-1-1 at low pressure and Group III spinel crystallize below the liquidus (～1200°C) after eruption of the basalt on the sea floor. The high-Al spinel (Group I) could have crystallized at high pressure or from a magma enriched in Al and perhaps Mg compared to 527-1-1. 相似文献
The conductivity of four igneous rocks with, 49, 65, 77, and 84% SiO2 was measured as a function of temperature in the interval from 20° to 1280°C; measurements were made in a vacuum of 10?3 torr. No simple relationships were found between conductivity and SiO2 content or versus major element groupings such as Na2O=K2O=CaO and TiO2=Cr2O3=Al2O3=Fe2O3=FeO. An analytical expression was obtained between conductivity and the albite-quartz ratio, valid for temperatures between 300° and 1200°C. It was necessary to compute the CIPW norm in order to obtain the albite and quartz percentages. The onset of melting apparently occurred between 600° and 700°C. Petrography performed on two samples after cooling showed 70 and 85% partial melting. Three conduction regions were identified: 1) below 300°C, 2) between 300°C and 600°C, and 3) above 600°C. Different activation energies obtained for the heating and cooling intervals confirm that the sample undergoes textural changes in the heating-cooling cycle. Activation energy increments of 0.1 and 0.2 eV per decade of albite-quartz ratio were obtained. 相似文献
The effects of temperature, fO2 and composition on the electrical conductivity of silicate liquids have been experimentally determined from 1200 to 1550°C under a range of fO2 conditions sufficient to change the oxidation state of Fe from predominantly Fe2+ to Fe3+. Oxidation of ferrous to ferric iron in the melt has no measurable effect on the conductivity of melts with relatively low ratios of divalent to univalent cations. Under strongly oxidizing conditions a minor decrease of conductivity is detected inth highΣM2/ΣM+ ratios. It is concluded that for purposes of estimating the conductivity of magmatic liquids, fO2 may be ignored to a first approximation. Both univalent and divalent cation transport is involved in electrical conduction. Melts relying heavily on divalent cations for conduction, i.e. melts with relatively large ΣM2+/ΣM+ ratios, show strong departures from Arrheenius temperature dependence with the apparent activation energies decreasing steadily as the temperature increases. Conductivities dominated by the univalent cations, in melts with relatively small ΣM2+/ΣM+ ratios, show classical Arrhenius temperature dependence. These observations are discussed in terms of the general characteristics of the melt structure.Compositional variations within the magmatic range account for much less than an order of magnitude variation in electrical conductivity at a fixed temperature. This observation, combined with previous measurements of the conductivity of olivine (A. Duba, H.C. Heard and R. Schock, 1974) make it possible to state with reasonable confidence that melts occurring within the mantle will be more conductive by 3–4 orders of magnitude than their refractory residues. Potential applications to geothermometry are discussed. 相似文献
The temperature dependence of water diffusivity in rhyolite melts over the range 650–950°C and [PT(H2O] = 700 bars is evaluated from water concentration-distance profiles measured in glass with an ion microprobe. Diffusivities are exponentially dependent on concentration over this temperature range and vary from about 10?8 cm2/s at 650°C to about 10?7 cm2/s at 950°C at 2 wt.% water. Water solubility also varies with temperature at a rate of ?0.14 wt. per 100°C increase. The avtivation energy (Ea) appears to be constant at 19 ± 1kal/mole for 1, 2,and 3 wt.% H2O. Comparison of these data with results for cation diffusion indicates that this value is a minimum Ea for diffusion of any species in a rhyolite melt.Compensation plots of log10D0 (the frequency factor) versus Ea indicate that hydrous rhyolite melts follow the same trend as anhydrous basalts. D0 increases for H2O and Ca2+ [1] as Ea decreases. This suggests that these molecules may diffuse by different mechanisms than do monovalent cations, and that hydration of the melt affects diffusion of Ca2+ and H2O differently than it does monovalent cation diffusion. The results imply that dramatic increases in cation diffusivities by hydration [1] may occur with additions of less than 1 wt.% H2O. 相似文献
Phase equilibria in a natural garnet lherzolite nodule (PHN 1611) from Lesotho kimberlite and its chemical analogue have been studied in the pressure range 45–205 kbar and in the temperature range 1050–1200°C. Partition of elements, particularly Mg2+Fe2+, among coexisting minerals at varying pressures has also been examined. High-pressure transformations of olivine(α) to spinel(γ) through modified spinel(β) were confirmed in the garnet lherzolite. The transformation behavior is quite consistent with the information previously accumulated for the simple system Mg2SiO4Fe2SiO4. At pressures of 50–150 kbar, a continuous increase in the solid solubility of the pyroxene component in garnet was demonstrated in the lherzolite system by means of microprobe analyses. At 45–75 kbar and 1200°C, the Fe2+/(Mg + Fe2+) value becomes greater in the ascending order orthopyroxene, Ca-rich clinopyroxene, olivine and garnet. At 144–146 kbar and 1200°C, garnet exhibits the highest Fe2+/(Mg + Fe2+) value; modified spinel(β) and Ca-poor clinopyroxene follow it. When the modified spinel(β)-spinel(γ) transformation occurred, a higher concentration of Fe2+ was found in spinel(γ) rather than in garnet. As a result of the change in the Mg2+Fe2+ partition relation among coexisting minerals, an increase of about 1% in the Fe2SiO4 component in (Mg,Fe)2SiO4 modified spinel and spinel was observed compared with olivine.These experimental results strongly suggest that the olivine(α)-modified spinel(β) transformation is responsible for the seismic discontinuity at depths of 380–410 km in the mantle. They also support the idea that the minor seismic discontinuity around 520 km is due to the superposition effect of two types of phase transformation, i.e. the modified spinel(β)-spinel(γ) transformation and the pyroxene-garnet transformation. Mineral assemblages in the upper mantle and the upper half of the transition zone are given as a function of depth for the following regions: 100–150, 150–380, 380–410, 410–500, 500–600 and 600–650 km. 相似文献
Chemical studies of two ophiolite suites and of selected mid-oceanic rift (MOR) regions indicate the presence of certain magmatic compositions: basalt, Fe-enriched basalt, and sodium granite (plagiogranite). There is a notable lack of evidence for melts of intermediate composition (i.e. 50–60 wt.% SiO2). To determine possible relationships between basic rocks (basalts and gabbros) and acidic rocks (plagiogranites) a primitive basalt was fractionated at low pressure, under anhydrous conditions, and at different oxygen fugacities near the iron-wustite buffer and slightly above the quartz-fayalite-magnetite buffer. Samples of this basalt were taken to slightly above liquidus temperatures and then cooled at rates ranging from 1 to 2°C/hr. A liquid line of descent characterized by an Fe enrichment was delineated by quenching these experiments from a final temperature in the range of 1200 to 1000°C and analyzing the residual liquid (glass). After 95% crystallization of olivine, plagioclase, calcium pyroxene, and ilmenite, the residual liquid was an Fe-enriched basalt. This Fe-enriched basalt became immiscible at a temperature of about 1010°C. The immiscible phases produced were a more Fe-enriched basaltic liquid and a granitic liquid. The granitic liquid is similar in composition to the naturally occurring plagiogranites found in small volumes in ophiolites and in certain MOR regions. It is therefore concluded that silicate liquid immiscibility could be the petrogenetic process responsible for producing plagiogranite in some MOR regions and in some ophiolites. On the other hand, plagiogranites in ophiolites and MOR rock suites having andesitic and dacitic composition rocks may have evolved under conditions more closely approximating equilibrium crystallization and/or they may have evolved at high water pressures. The available experimental data suggest that amphibole would crystallize early and yield SiO2-enriched liquids at depths greater than 4.5 km for PH2O's in the range 0.6–1.0 Ptotal.The major problem in interpreting any of the natural plagiogranites as products of silicate liquid immiscibility is the fact that neither the Fe-enriched conjugate liquid or its crystalline equivalent has been described in the ophiolite or MOR literature. The identification of this Fe-rich conjugate magma is essential in any rock suite if a completely convincing case for silicate liquid immiscibility is to be made. 相似文献
It has been an enigma that in the Tieschitz, H3, and other unequilibrated chondrites the silicates show quench textures yet their metallic minerals, according to the Wood [6] model, appear to have cooled extremely slowly.In Tieschitz, spherical metallic chondrules up to 500 μm in diameter, with textures indicating an origin as liquid droplets, consist of polycrystalline intergrowths of α(kamacite), γ(taenite) and troilite. Interface Ni compositions of contiguous α (～5 wt.%) and γ (～50 wt.%) grains define equilibrium tie-line relationships in the Fe-Ni system indicating equilibration to ～350°C (620 K). Polycrystalline γ(taenite) is multi-zoned with respect to Ni and is interpreted as the relict of a primary solidification structure. A mechanism whereby Ni compositional heterogeneities were produced in γ(taenite) by the rapid, non-equilibrium cooling of FeNiS melts during chondrule formation is discussed.Comparisons with lunar metal globules indicate solidification rates for Tieschitz metallic chondrules in the range 1–106 K/s. It is suggested that before or during aggregation, sub-solidus cooling in the temperature range ～700–1400°C with cooling times of days to weeks allowed the preservation of a relict solidification structure in metallic chondrules. At a temperature of ～700°C accretion and shallow burial (1–10 m) on the surface of the Tieschitz parent body provided insulation with slower cooling required to nucleate and grow α(kamacite) from the heterogeneous γ(taenite) under equilibrium conditions by the process of solid state diffusion proposed by Wood [6]. The cooling rate (1 K/106 yr) through 500°C derived using the Wood model is shown to be an underestimate of the real cooling rate of Tieschitz metal through that temperature, since it does not take into account Ni heterogeneities produced at higher temperatures. A rough estimate of the post-accretional cooling rate is obtained from the average size of α(kamacite) grains(<100 μm) andTeqα ～ 350°C indicating a cooling rate of the order of<1K/103yr through 500°C. 相似文献
Experimental study of the phase boundary for the disproportionation of the inverse spinel Mg2SnO4 into its isochemical mixed oxides indicates a slope dP/dT = 40 ± 10bars/°K. This positive slope is consistent with the large entropies of inverse (relative to normal) spinels predicted from high-temperature entropy-molar volume systematics. Thermodynamic data do not support the existence of a distinctly negative slope for the proposed disproportionation of Mg2SiO4 normal spinel. Evidence from X-ray and phase equilibria studies suggests the possibility that Si4+, Mg2+, and Fe2+ share the octahedral sites in silicate spinels under mantle conditions. The consequences of this partial inverse character are a positive slope for the postulated spinel-mixed oxide phase boundary near 650 km depth, removal of a widely accepted constraint on mantle-wide convection, and anomalous elasticity-density behaviour within the transition zone. 相似文献
The experiments in the model system CaMgSi2O6–(Na2CO3, CaCO3)–KCl are performed at 5 GPa and 1400–1600 °C in order to study the phase relations, including liquid immiscibility, in the chloride–carbonate–silicate systems with application to alkali and chlorine-rich liquids preserved in kimberlitic diamonds. Experiments in the boundary joins of the system demonstrated that both the carbonate–silicate and chloride–carbonate melts are homogeneous; while high-temperature (above 1800 °C) liquid immiscibility is assumed for the chloride–silicate join of the above system. Addition of silicate component into the chloride–carbonate melts and chloride component into the carbonate–silicate melts results in splitting of the homogeneous liquids into the immiscible chloride–carbonate brine and carbonate–silicate melt. Carbonate–silicate and chloride–carbonate branches of the miscibility gap converge within the carbonate-rich region of the system. Regular temperature evolution of the shape and size of the miscibility gap is deduced. With decreasing temperature, the convergence point moves toward more Si-rich compositions, expanding fields of homogeneous chloride–carbonate silica-saturated melts. This effect is governed by the precipitation of the silicate phases even from silica-bearing chloride–carbonate melts. In addition, experiments revealed regular evolution of both Cl-bearing carbonate–silicate melt and Si-bearing chloride–carbonate brine toward the low-temperature chlorine–bearing carbonatitic liquid with decreasing temperature. These trends are similar to the evolution of the melt and brine inclusions in some diamonds from Botswana, Brazil, Canada, and Yakutia, indicating their growth during cooling. The model for interaction of the chloride–carbonate brine with the mantle rocks is developed on the basis of the present experimental data. This model is applied to the chlorine-enriched kimberlites of the Udachnaya–East pipe. 相似文献
High-pressure phase relations in ZnSiO3 and Zn2SiO4 were investigated at about 1000°C and in the pressure range of 100–500 kbar, using a double-staged split-sphere type of high-pressure apparatus.Clinopyroxene-type ZnSiO3 transforms directly into a polymorph with the ilmenite structure at 120 kbar. The hexagonal unit cell dimensions of the ZnSiO3 ilmenite are determined to be under ambient conditions.The following reactions are also recognized at about 1000°C: and: The stabilities of silicate ilmenites, especially the absence of ilmenite of transition metal silicate composition, is discussed. It is pointed out that data on phase relations in zinc silicates may be informative for the consideration on those in magnesium silicates under very high pressures. It is suggested that the silicate ilmenite may be a major constituent in the lower mantle. 相似文献
Data for the diffusion of cations in pyroxenes are relevant to a variety of sub-solidus processes including order-disorder and exsolution. Similar data must also be available if the reliability of geobarometers and geothermometers involving pyroxenes is to be assessed. Two types of diffusion experiment have been performed to determine cation diffusion rates in pyroxenes: (1) interdiffusion between single crystals of diopside and polycrystalline sinters enriched in Al and Fe, and (2) interdiffusion between single crystals of diopside and a glass of the same composition which was isotopically enriched in26Mg and43Ca. Following high-temperature annealing for periods up to several hundred hours, analysis of the diffusion couples, using an electron microprobe and an ion microprobe respectively, failed to show any measurable diffusion profiles. From these “null result” experiments the diffusion coefficients (D) for Al and Fe in diopside are estimated to be less than4×10?14cm2s?1 at 1200°C, and values ofD for Ca and Mg in diopside are estimated to be less than7 × 10?14cm2s?1 at 1250°C. These rates are significantly slower than published tracer-type diffusion data for Ca and Al.A review of studies of order-disorder, microstructural coarsening, and diffusion in pyroxenes suggest that activation energies for cation exchange are typically in excess of 60 kcal mol?1. Transport rates will be assisted, and activation energies lowered by sample non-stoichiometry, inhomogeneities, high dislocation densities and the presence of water.The collective data for Al, Mg and Ca diffusion in diopside indicate diffusion coefficients? 10?15cm2s?1 at 1200°C. A comparison with data for diffusion in garnet, olivine and spinel suggests that pyroxenes may have the highest blocking temperatures. 相似文献
The diffusivity of18O in forsterite Mg2SiO4 has been measured in the temperature range 1150–1600°C. The activation energy of oxygen self-diffusion in this silicate is found to equal0.32 ± 0.04MJ/mol(77 ± 10kcal/mol), and there is no dependence of the diffusivity upon the oxygen partial pressure surrounding the samples. The diffusion profiles were analysed either with an ion probe or by means of the18O(p, α)15N nuclear reaction. The latter method made use of a resonance in the nuclear cross-section in the case of diffusion profiles shorter than 100 nm (1000Å); for diffusion profiles up to 4 μm the same reaction was used, but in a non-resonant mode. New data on creep in forsterite and natural olivine are also given, including the influence of the oxygen partial pressurepO2 which is zero for forsterite and proportional to(pO2)16 for natural olivine. From this set of data we infer the possible relationship between diffusion and creep for these materials. This relationship may be more complicated than that predicted by simple climb mechanism. 相似文献
The enstatite-diopside solvus in the system Mg2Si2O6-CaMgSi2O6 has been experimentally determined within the pressure range 5–40 kbars and the temperature range 900–1500°C. Experiments involving reversal of the phase boundaries by unmixing from glass starting material and by reaction of pure clinoenstatite and diopside showed difficulty in achieving equilibration due to persistence of metastable, subcalcic clinopyroxene and to the sluggishness of reaction rate. The experimental data showed that the temperature dependence of the diopside limb is less than previously accepted. At 1500°C and 30 kbars subcalcic diopside found by Davis and Boyd (1966) is shown to be metastable with respect to enstatite and more calcic diopside of composition En42.3Di57.7. The solvus widens with increasing pressure between 5 and 40 kbars at 1200°C, but at 900°C the pressure effect on the solvus is very small. The stability relationships of the four pyroxenes, protoenstatite, enstatite, iron-free pigeonite and diopside are summarized, based on data from the literature and the present study. 相似文献
Rheological properties of the crust and upper mantle are essential data that are needed in modelling the mechanical behaviour of the shallow part of the earth. The importance of such data has been seen in discussions about the strength profile of continen… 相似文献
High pressure experiments using the sink/float method have bracketed the density of hydrous iron-rich ultrabasic silicate melt from 1.35 to 10.0 GPa at temperatures from 1400 to 1860 °C. The silicate melt composition was a 50–50 mixture of natural komatiite and synthetic fayalite. Water was added in the form of brucite Mg(OH)2 and was present in the experimental run products at 2 wt.% and 5 wt.% levels as confirmed by microprobe analyses of total oxygen. Buoyancy marker spheres were olivines and garnets of known composition and density. The density of the silicate melt with 5 wt.% water at 2 GPa and 1500 °C is 0.192 g cm? 3 less than the anhydrous form of this melt at the same P and T. This density difference gives a partial molar volume of water in silicate melt of ～ 7 cm3 mol? 1, which is similar to previous studies at high pressure. The komatiite–fayalite liquids with 0 and 2 wt.% H2O, have extrapolated density crossovers with equilibrium liquidus olivine at 8 and 9 GPa respectively, but there is no crossover for the liquid with 5 wt.% H2O. These results are consistent with the hypothesis that dense hydrous melts could be gravitationally stable atop the 410 km discontinuity in the Earth. The results also support the notion that equilibrium liquidus olivine could float in an FeO-rich hydrous martian magma ocean. Extrapolation of the data suggests that FeO-rich hydrous melt could be negatively buoyant in the Earth's D″-region or atop the core–mantle-boundary (CMB), although experiments at higher pressure are needed to confirm this prediction. 相似文献
