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1.
Enthalpies of solution of synthetic clinopyroxenes on the join CaMgSi2O6-Mg2Si2O6 have been measured in a melt of composition Pb2B2O5 at 970 K. Most of the measurements were made on samples crystallized at 1600°–1700°C and 30 kbar pressure, which covered the range 0–78 mole per cent Mg2Si2O6, and whose X-ray patterns could be satisfactorily indexed on the diopside (C2/c) structure. For the reaction: Mg2Si2O6→-Mg2Si2O6 enstatite diopside the present data, in conjunction with previous and new measurements on Mg2Si2O6 enstatite, determine ΔH° ~ 2 kcal and WH (regular solution parameter) ~ 7 kcal. These values are in good agreement with those deduced by Saxena and Nehru (1975) from a study of high temperature, high pressure phase equilibrium data under the assumption that the excess entropy of mixing is small, but, in light of the recent theoretical treatment of Navrotsky and Loucks (1977, Phys. Chem. Min.1, 109–127), the meanings of these parameters may be ambiguous.Heat of solution measurements on Ca-rich binary diopsides made by annealing glasses at 1358°C in air gave slighter higher values than the higher temperature high pressure samples. This may be evidence for some (Ca, Mg) disorder of the sort postulated by Navrotsky and Loucks (1977, Phys. Chem. Min.1, 109–127), although no differences in heat of solution dependent on synthesis temperature in the range 1350°–1700°C could be found in stoichiometric CaMgSi2O6.  相似文献   

2.
Experiments using V2O5 as a high-temperature solvent have produced compositional reversals defining the miscibility gap between enstatite and diopside on the join Mg2Si2O6-CaMgSi2O6 between 925° and 1,175° C at atmospheric pressure. These experiments locate an equilibrium near 1,000° C among diopside, protoenstatite, and orthoenstatite; they verify the stable coexistence of diopside and protoenstatite above 1,000° C and disprove the hypothesis that orthoenstatite has a stability field which is continuous from temperatures below 1,000° C to the solidus. The phase relations suggest that the orthorhombic low-Ca pyroxene on the solidus in this system (formerly identified as orthoenstatite) is a phase distinct from the orthoenstatite stable with diopside at low subsolidus temperatures. Data locating the orthoenstatite-diopside miscibility gap validate the use at low pressures of symmetric orthopyroxene and asymmetric clinopyroxene solution models in this system.  相似文献   

3.
We have investigated grain boundary diffusion rates in enstatite by heating single crystals of quartz packed in powdered San Carlos olivine (Mg0.90Fe0.10)2SiO4 at controlled oxygen fugacities in the range 10?5.7 to 10?8.7?atm and temperatures from 1350° to 1450?°C for times from 5 to 100?h at 1?atm total pressure. Following the experiments, the thickness of the coherent polycrystalline reaction rim of pyroxene that had formed between the quartz and olivine was measured using backscatter scanning imaging in the electron microprobe. Quantitative microprobe analysis indicated that the composition of this reaction phase is (Mg0.92Fe0.08)2Si2O6. The rate of growth of the pyroxene increases with increasing temperature, is independent of the oxygen fugacity, and is consistent with a parabolic rate law, indicating that the growth rate is controlled by ionic diffusion through the pyroxene rim. Microstructural observations and platinum marker experiments suggest that the reaction phase is formed at the olivine-pyroxene interface, and is therefore controlled by the diffusion of silicon and oxygen. The parabolic rate constants determined from the experiments were analyzed in terms of the oxide activity gradient across the rim to yield mean effective diffusivities for the rate-limiting ionic species, assuming bulk transport through the pyroxene layer. These effective diffusivities are faster than the lattice diffusivities for the slowest species (silicon) calculated from creep experiments, but slower than measured lattice diffusivities for oxygen in enstatite. Thus, silicon grain boundary diffusion is most likely to be the rate-limiting process in the growth of the pyroxene rims. Also, as oxygen transport through the pyroxene rims must be faster than silicon transport, diffusion of oxygen along the grain boundaries must be faster than through the lattice. The grain boundary diffusivity for silicon in orthopyroxenite is then given by D¯gbSiδ=(3.3±3.0)×10?9f0.0O2e?400±65/RT?m3s?1, where the activation energy for diffusion is in kJ/mol, and δ is the grain boundary width in m. Calculated growth rates for enstatite under these conditions are significantly slower than predicted by an extrapolation from similar experiments performed at 1000?°C under high pressure (hydrous) conditions by Yund and Tullis (1992), perhaps due to water-enhancement of diffusion in their experiments.  相似文献   

4.
Thermodynamic parameters for the reaction: $$\begin{gathered} Mg_2 Si_2 O_6 = Mg_2 Si_2 O_6 \hfill \\ enstatite clinopyroxene \hfill \\ \end{gathered} $$ in the system CaO-MgO-SiO2 have been deduced from phase equilibrium and enthalpy of solution data. From the regular solution theory, the seventeen currently available reversed experimental compositions of coexisting enstatite and clinopyroxene, presumed to be ordered diopside, lead, by a statistical regression, to the following best fit parameters: ΔH o=6.80 kJ ΔS o=2.75 J/K W H Cpx =24.47 kJ (regular solution enthalpy parameter) W V Cpx =0.105 J/bar (regular solution volume parameter). The derived parameters are not significantly affected by the (necessary) choice of W Opx in the range 20–50 kJ. The above values are in very good agreement with deductions from the solution calorimetry on synthetic CaMgSi2O6-Mg2Si2O6 clinopyroxenes of Newton et al. (1979), which also places bounds on possible departures from the optimal values of these parameters. The calorimetric data may also be interpreted in terms of a Bragg-Williams cooperative-disordering model (Navrotsky and Loucks, 1977), in which diopside-structure clinopyroxene and a ‘relaxed’ low-Ca clinopyroxene (‘Fe-free pigeonite’) approach each other in composition, structural state, and stability with increasing temperature. The ΔH o parameter deduced from the regular solution theory is reinterpreted as the enthalpy change of enstatite to Mg2Si2O6 pigeonite; the ΔH o of the transformation of enstatite to the diopside structure would, in this case, be considerably larger than 6.8 kJ. The curvature of the enthalpy of solution data, explained by the regular solution theory in terms of M2-site energetics (involving W H cpx ), is reinterpreted as due to disordering and ‘relaxation’ in the Navrotsky-Loucks model. Although the regular solution theory with the best-fit parameters accounts for all of the reversed enstatite and diopside compositions to within 18 ° C, and is a convenient representation of the phase equilibria for purposes of geothermometry, the disordering model is, at the present level of knowledge, equally valid and allows for a region of stability of two coexisting clinopyroxenes.  相似文献   

5.
Our experimental simulations of the exhumation path of mantle peridotites show that high‐temperature (1400 °C) decompression of lherzolite from 14 to 13 and 12 GPa results in exsolution of interstitial blebs of diopside and Mg2SiO4 (wadsleyite) lamellae from majoritic garnet. At lower pressures (from 8 to 5 GPa, at T = 1400 °C) only enstatite exsolves as blebs at garnet boundaries. Continuous high‐temperature decompression from 14 to 7 GPa produces zoned majoritic garnet containing blebs of exsolved pyroxenes inside garnet rims. No intracrystalline precipitation of pyroxene was observed in garnet, although such lamellae are found in some natural garnet peridotites. The explanation appears to be the three orders of magnitude difference in grain size between experimental and natural specimens. Our data suggest that Mg2SiO4 and diopside exsolutions reflect the deepest point of the exhumation path of garnet peridotites, whereas enstatite precipitation may be restricted to garnets with less majoritic component at shallower depths.  相似文献   

6.
Three methods of geothermometry, currently used for spinel lherzolites, are refined based on new experiments on subsolidus phase equilibria of olivine, pyroxenes and spinel in CaO-MgO-Al2O3-SiO2 and natural rock systems at 16 kb and 1200 °C. Although quasi-thermodynamic modelling is employed, the methods are essentially based on the pyroxene solvus, alumina contents in clinopyroxene and orthopyroxene. Increasing alumina contents in pyroxenes reduce enstatite and diopside components in clinopyroxene and orthopyroxene, respectively. Thus, neglect of alumina in pyroxenes causes underestimates of temperatures by the solvus method.The three geothermometers were tested by applying them to homogeneous spinel lherzolites which were especially selected for this purpose. Coincidence of the three temperatures thus estimated gives confidence in the effectiveness of the geothermometers.They were also applied to spinel lherzolite nodules in basalts and intrusive lherzolites described in the literature. It was found that equilibration temperature of the nodules varies from 1000 °C to 1300 °C, i.e., temperatures somewhat higher than have been generally thought. In contrast to the nodules, the intrusive spinel lherzolites show extensive disequilibrium, which is probably due to retrogressive metamorphism suffered by the intrusives.  相似文献   

7.
The univariant high-pressure reaction of aluminous enstatite and spinel to pyrope and forsterite in the MgO-Al2O3-SiO2 system has been determined in the temperature range 900 °–1100 °C by hydrothermal reversals in the piston-cylinder apparatus using the low-friction NaCl pressure medium. A mixture of synthetic minerals, including an enstatite with 6 wt% Al2O3, with product and reactant assemblages in nearly equal amounts, was the starting material. The equilibrium pressure of 19.3±0.3 kbar at 1000 ° C and average dP/dT slope of 8.0 bars/ ° C confirm the strong curvature of the equilibrium below 1200 ° C deduced by Obata (1976) from a theoretical study of experimental Al2O3 isopleths of enstatite in the garnet field. His prediction of an absolute minimum pressure near 18 kbar of the garnet peridotite assemblage in the ternary system is undoubtedly correct.Three reversed determinations of the equilibrium Al2O3 content of enstatite in the presence of spinel +forsterite were made at points adjacent to the univariant curve. The points are 5.5 wt% Al2O3 at 950 ° C and 20 kbar, 6.2 wt% at 1000 ° C and 20 kbar and 7.2 wt% at 1080 ° C and 20 kbar. These values are somewhat higher than given by the MacGregor (1974) isopleth set and quite close to those predicted by Fujii (1976) from experimental synthesis data at higher temperatures, using the Wood and Banno (1973) model of ideal solution of the Mg2Si2O6 and MgAl2SiO6 components in enstatite to reduce the data.All of the available spinel-field isopleth data can be systematized with the use of the ideal solution model. A value of H 0 of 9000 cal fits the reduced data well, and is in agreement with the calorimetrically determined value of 8500±1900 calories. An accurate calculation of the dP/dT slope of the univariant equilibrium at 1000 ° C based on calorimetry gives 7±2bars/ °C, also in good agreement with experiment. Thus, all of the available experimental and calorimetric data are consistent with the ideal-solution aluminous enstatite model.The dP/dT slopes of the spinel-field isopleths are too large to permit their use as an accurate geobarometric scale. They do have considerable potential as a thermometric indicator for certain natural peridotites, however. The southwestern Oregon overthrust peridotite masses of Cretaceous age have enstatite of 5.6 wt% Al2O3 with spinel of nearly 80 mole% MgAl2O4. The present reduced isopleth data directly give 930 ° C for the equilibration, assuming 12 kbar pressure. A first order correction based on ideal solution departures from the ternary system, as suggested by Stroh (1976) gives 1000 ° C. Thus, the high temperatures deduced by Medaris (1972) are confirmed. The pressure cannot be deduced independently from the pyroxene Al2O3 contents.  相似文献   

8.
Summary The phase relations of K-richterite, KNaCaMg5Si8O22(OH)2, and phlogopite, K3Mg6 Al2Si6O20(OH)2, have been investigated at pressures of 5–15 GPa and temperatures of 1000–1500 °C. K-richterite is stable to about 1450 °C at 9–10 GPa, where the dp/dT-slope of the decomposition curve changes from positive to negative. At 1000 °C the alkali-rich, low-Al amphibole is stable to more than 14 GPa. Phlogopite has a more limited stability range with a maximum thermal stability limit of 1350 °C at 4–5 GPa and a pressure stability limit of 9–10 GPa at 1000 °C. The high-pressure decomposition reactions for both of the phases produce relatively small amounts of highly alkaline water-dominated fluids, in combination with mineral assemblages that are relatively close to the decomposing hydrous phase in bulk composition. In contrast, the incongruent melting of K-richterite and phlogopite in the 1–3 GPa range involves a larger proportion of hydrous silicate melts. The K-richterite breakdown produces high-Ca pyroxene and orthoenstatite or clinoenstatite at all pressures above 4 GPa. At higher pressures additional phases are: wadeite-structured K2SiVISiIV 3O9 at 10 GPa and 1500 °C, wadeite-structured K2SiVISiIV 3O9 and phase X at 15 GPa and 1500 °C, and stishovite at 15 GPa and 1100 °C. The solid breakdown phases of phlogopite are dominated by pyrope and forsterite. At 9–10 GPa and 1100–1400 °C phase X is an additional phase, partly accompanied by clinoenstatite close to the decomposition curve. Phase X has variable composition. In the KCMSH-system (K2CaMg5Si8O22(OH)2) investigated by Inoue et al. (1998) and in the KMASH-system investigated in this report the compositions are approximately K4Mg8Si8O25(OH)2 and K3.7Mg7.4Al0.6Si8.0O25(OH)2, respectively. Observations from natural compositions and from the phlogopite-diopside system indicate that phlogopite-clinopyroxene assemblages are stable along common geothermal gradients (including subduction zones) to 8–9 GPa and are replaced by K-richterite at higher pressures. The stability relations of the pure end member phases of K-richterite and phlogopite are consistent with these observations, suggesting that K-richterite may be stable into the mantle transition zone, at least along colder slab geotherms. The breakdown of moderate proportions of K-richterite in peridotite in the upper part of the transition zone may be accompanied by the formation of the potassic and hydrous phase X. Additional hydrogen released by this breakdown may dissolve in wadsleyite. Therefore, very small amounts of hydrous fluids may be released during such a decomposition. Received April 10, 2000; revised version accepted November 6, 2000  相似文献   

9.
Phase equilibria determined in high-pressure studies of the systems Mg2Si2O6-CaMgSi2O6 and MgSiO3-Mg3Al2Si3O12 can be used to estimate equilibration conditions of ultramafic rocks containing the assemblage enstatite + diopside + garnet. Garnet lherzolite nodules from kimberlites in northern Lesotho appear to have equilibrated in the upper mantle at depths ranging from 100 to 200 km and at temperatures in the range 900–1400°C. Temperature-depth points for these lherzolites form a trend that is interpreted as a segment of a fossil geotherm. The trend is inflected to higher temperatures at its deep end. Lherzolites that plot on the shallow limb of the geotherm have a granular texture whereas those that plot on the deep limb are intensely sheared. It is suggested that the shearing took place in response to plate movements during the break-up of Gondwanaland and that the sheared lherzolites were stress-heated as much as 300°C above their ambient, preshearing temperatures. The point of inflection of the geotherm may mark the top of the low-velocity zone beneath Lesotho in Late Cretaceous time.  相似文献   

10.
 The growth rates of enstatite rims produced by reaction of Fo92 and SiO2 were determined at 250–1500 MPa and 900–1100°C for a wide range of water contents. Growth rates were also determined for forsterite rims between MgO and Mg2Si2O6 and between MgO and SiO2. Rim growth rates are parabolic indicating diffusion-controlled growth of the polycrystalline rims which are composed of ˜ 2 μm diameter grains. Rim growth rates were used to calculate the product of the grain boundary diffusion coefficient (D'A) times the effective grain boundary thickness (δ) assuming in turn that MgO, SiO2, and Mg2Si−1 are the diffusing components (coupled diffusion of a cation and oxygen or interdiffusion of Mg and Si). The values for D'MgOδ, D', and D' for enstatite at 1000°C and 700 MPa confining pressure with about 0.1 wt %  water are about five times larger than the corresponding D'Aδ values for samples initially vacuum dried at 250°C. Most of the increase in D'Aδ occurs with the first 0.1 wt %  water. The activation energy for diffusion through the enstatite rims (1100–950°C) is 162 ± 30 kJ/mole. The diffusion rate through enstatite rims is essentially unchanged for confining pressures from 210–1400 MPa, but the nucleation rate is greatly reduced at low confining pressure (for  ≤ 1.0 wt % water present) and limits the conditions at which rim growth can be measured. The corresponding values for D'Aδ through forsterite rims are essentially identical for the two forsterite-producing reactions when 0.1 wt % water is added and similar to the D'Aδ values for enstatite at the same conditions. The D'Aδ values for forsterite are ˜ 28 times larger for samples starting with 0.1 wt %  water compared to samples that were first vacuum dried. Thus water enhances these grain boundary diffusion rates by a factor of 5–30 depending on the mineralogy, but the total range in D'Aδ is only slightly more than an order of magnitude for as wide a range of water contents as expected for most crustal conditions. Received: 1 July 1995 / Accepted: 1 August 1996  相似文献   

11.
Infrared absorption spectra are presented for four hydrous magnesian silicates which are stable at high pressures and high temperatures characteristic of the earth's mantle: phase A (Mg7Si2O14H6), phase B (approx. Mg23Si8O42H6), chondrodite (Mg5Si2O10H2), clinohumite (Mg9Si4O18H2). The results show that phase B as well as phase A, chondrodite and clinohumite contain hydroxyl groups in their structures. It is also suggested that phase B, in addition to phase A, could be of potential importance in the upper mantle and transition zone as a dense host mineral for hydroxyl ions. Chemical composition of phase A was reexamined by microprobe analysis: it agrees well with Mg7Si2O14H6, estimated by Yamamoto and Akimoto (1974, 1977), but disagrees with a newly proposed formula Mg2SiO5H2 by Benimoff and Sclar (1984).  相似文献   

12.
Kosmochlor (NaCrSi2O6) was synthesized by the flux method from melts along the join Na2O·2 SiO2-Na2O·Cr2O3·4 SiO2 at 1000° C in air, and isolated by dissolving the glassy matrix with hydrofluoric and perchloric acids. The join CaMgSi2O6-NaCrSi2O6 was studied at 1 atmosphere in air by the quenching technique at temperatures between 900° and 1450° C, using mixtures of kosmochlor and diopside crystals or diopside glass as starting materials. The phases are diopside solid solution, kosmochlor, spinel (Mg-chromite), eskolaite (Cr2O3) and glass. The maximum solubility of kosmochlor in diopside is 24 wt percent at 1140° C, while diopside is not soluble at all in kosmochlor, resulting in the existence of a wide range of immiscibility. Petrologic significance of the results is discussed.  相似文献   

13.
The enthalpies of solution of several synthetic garnets on the join Mg3Al2Si3O12-Ca3Al2Si3O12 (pyrope-grossular) and of several synthetic clinopyroxenes on the join CaMgSi2O6-CaAl2SiO6 (diopside-Ca-Tschermak's molecule) were measured in a melt of composition 2PbO · B2O3 at 970 K. The determinations were made with sufficient precision so that thermochemical characterizations of the solid solutions could be achieved.The pyrope-grossular solutions show positive enthalpies of mixing. The non-ideality in the range 0–30 mole % grossular is relatively the largest and is in good agreement with the predictions of Ganguly and Kennedy (1974) based largely on cation partitioning of natural high grade metamorphic garnets with biotite, and with the deductions of Hensenet al. (1975) based on measurement of the compositions of synthetic pyrope-rich garnets equilibrated with anorthite, Al2SiO5 and quartz. However, the garnets show smaller excess enthalpies at higher grossular contents. This would lead to an asymmetric solvus with a critical temperature lower than predicted by the symmetrical regular solution model of Ganguly and Kennedy (1974). The composition-dependent non-ideality can be understood by simple ionic size considerations in solid substitution and is analogous to the situations for the calcite-dolomite and enstatite-diopside solvi.The heats of solution of pyropes crystallized in the range 1000–1500°C were all the same, within the precision of measurement, and thus we have found no evidence for temperature-dependent cation disordering as a possible explanation of the high entropy of pyrope, as suggested by Charluet al. (1975). Positional disorder of dodecahedral Mg is a more probable reason.The diopside-CaTs join is also non-ideal, with the larger positive enthalpy deviations near the diopside end. The calorimetric data in the magnesian range are consistemt with the model for completely disordered tetrahedral Si and Al which results from the free energy derivations of wood (1975) based on syntheses of diopside-rich aluminous pyroxenes in the presence of anorthite and quartz. At higher Al concentrations the calorimetric data seem more consistent with the ‘local charge-balance’ model of Wood (1975).No evidence for temperature-dependent disorder was found for either the diopside or CaTs end-members.  相似文献   

14.
The effect of silica concentration on the solubility of Al and Ti in diopsidic pyroxenes has been investigated at one atmosphere in the system diopside-CaTiAl2O6-SiO2 at temperatures between 1150–1420° C. The composition of pyroxene in the system diopside-CaTiAl2O6-SiO2 is influenced by the total SiO2 content. Near the join diopside-CaTiAl2O6, the pyroxene forms a solid solution with the CaTiAl2O6 molecule, and co-exists with perovskite for compositions greater than 11 weight percent CaTiAl2O6. Anorthite is an accompanying phase. With increasing total SiO2 content a series of mineralogical changes involving Ti-bearing phases occur. Sphene solid solution co-exists with diopside solid solution, anorthite, and perovskite in a small compositional range near the diopside-CaTiAl2O6 join. Additional total SiO2 results in the elimination of perovskite and a decrease of solid solution in the pyroxenes. With further increase in SiO2 content, tridymite appears and the pyroxene is approximately pure diopside. Rutile joins diopside, anorthite, sphene solid solution and tridymite over a broad compositional range in the Ti, Si-rich part of the system. These results demonstrate that increased silica concentration decreases the solubility of Al and Ti in diopsidic pyroxenes and controls the stability of co-existing Ti-bearing phases.  相似文献   

15.
An experimental study of Ca-(Fe,Mg) interdiffusion in silicate garnets   总被引：1，自引：0，他引：1  
Ca-(Fe,Mg) interdiffusion experiments between natural single crystals of grossular (Ca2.74Mg0.15 Fe0.23Al1.76Cr0.04Si3.05O12) and almandine (Ca0.21Mg0.40 Fe2.23Mn0.13Al2.00Cr0.08Si2.99O12 or Ca0.43Mg0.36Fe2.11 Al1.95Si3.04O12), were undertaken at 900–1100 °C and 30 kbar, and pressures of 15.0–32.5 kbar at 1000 °C. Samples were buffered by Fe/FeO in most cases. Diffusion profiles were determined by electron microprobe. Across the experimental couples the interdiffusion coefficients (D˜) were almost independent of composition. The diffusion rates in an unbuffered sample were significantly faster than in buffered samples. The temperature dependence of the D˜ (Ca-Fe,Mg) interdiffusion coefficients may be described by
at 30 kbar and 900–1100 °C. This activation energy is marginally higher than previous experimental studies involving Ca-free garnets; the interdiffusion coefficients are higher than previous studies for Fe-Mg and Fe-Mn exchange in garnet. The pressure dependence of D˜ (Ca-Fe,Mg) at 1000 °C yielded an activation volume of 11.2 cm3 mol−1, which is higher than previous results from studies involving garnet and olivine. Comparison with simulation studies suggests a vacancy mechanism for divalent ion migration in garnet, with extrinsic processes being dominant up to very high temperatures. Received: 15 December 1996 / Accepted: 3 November 1998  相似文献   

16.
Solid solubility of Al2O3 in orthorhombic enstatite by the substitution AlAl=MgSi is, in the range studied, mainly a function of temperature and not strongly pressure-dependent. Even at 1 kb up to 9 wt.-% Al2O3 can be substituted at 1200° C. The thermal stability of the orthorhombic pyroxene phase is strongly increased by the incorporation of Al.In crustal rocks the alumina content of orthopyroxene might be used as a geothermometer but not, as sometimes suggested, as a barometer.  相似文献   

17.
Forty-six reversed determinations of the Al2O3content of enstatite in equilibrium with garnet were made in the P/T range 15–40 kbar/900–1,600° C in the MgO-Al2O3-SiO2 system. Starting materials were mixtures of synthetic pyrope+Al-free enstatite and pyrope+enstatite (5–12% Al2O3). Al2O3 contents in reversal run pairs closely approached common values from both the high- and low-Al sides. Most experiments were done in a piston-cylinder device using a NaCl medium; some runs at very high temperatures were made in pyrex/NaCl or pyrex/talc assemblies. The measured enstatite compositions, expressed as mole fractions of Mg2(MgAl)(AlSi3)O12(X Opy En ) were fitted by a Monte-Carlo method to the equilibrium condition: $$\begin{gathered} \Delta H_{970}^0 - 970\Delta S_{970}^0 \hfill \\ + \mathop \smallint \limits_1^P \Delta V_{970}^0 dP - \mathop \smallint \limits_{970}^T \Delta S_T^0 dT + RT\ln X_{Opy}^{En} = 0 \hfill \\ \end{gathered}$$ where the best fit parameters of ΔH, ΔS and ΔV (1 bar, 970 K) for the reaction pyrope=opy are 2,040 cal/mol, 2.12 eu and 9.55 cc/mol. In addition to the determination of Al2O3 contents of enstatite, the univariant reaction pyrope+forsterite=enstatite+spinel was reversibly located in the range 1,100–1,400°C. A “best-fit” line passes through 22, 22.5 and 25 kbar at 1,040, 1,255 and 1,415°C, respectively. Our results for the univariant reaction are in agreement with previous studies of MacGregor (1974) and Haselton (1979). However, comparison of the experimentally determined curve with thermochemical calculations suggests that there may be a small error in the tabulated ΔH f(970,1) 0 value for enstatite. A value of?8.32 rather than?8.81 kcal/mole (Charlu et al. 1975) is consistent with the present data. Application of garnet-enstatite-spinel-forsterite equilibria to natural materials is fraught with difficulties. The effects of nonternary components are poorly understood, and the low solubilities of Al2O3 in enstatite under most geologically reasonable conditions make barometric or thermometric calculations highly sensitive. More detailed studies, including reversed determinations in low-friction assemblies, are sorely needed before the effects of important diluents such as Fe, Ca and Cr can be fully understood.  相似文献   

18.
Cu-bearing pyroxene, Mg(Cu.56,Mg.44)Si2O6, has been synthesized by a flux method and crystal structure refinement has been performed by single crystal X-ray diffraction. It is found that the crystal structure is orthorhombic (space group Pbca) with unit cell dimensions of a=18.221(4), b=8.890(1), c=5.2260(7)Å and the cell volume of 846.5( )3Å3. In the M2-site one of the M-O bonds(M-O3B) is extremely expanded from 2.444(2) in enstatite to 2.732(2), thus the coordination polyhedron around M2-site is regarded as square pyramidal rather than square planar or octahedral. It is also found that the M1-site in the pyroxene structure is occupied almost exclusively by Mg, while the M2-site is almost evenly occupied by Mg and Cu. The observed extreme site preference shown by Cu2+ is unusual among the divalent cations with similar ionic sizes.  相似文献   

19.
The growth rates of albite and pyroxene (enstatite + diopside + spinel) reaction rims were measured at 1000°C and ˜700 MPa and found to be parabolic indicating diffusion-controlled growth. The parabolic rate constants for the pyroxene (+ spinel) rims in samples with 0.5 wt% H2O added or initially vacuum dried at 25°C and 250°C are 1.68 ± 0.09, 0.54 ± 0.05 and 0.25 ± 0.06 μm2/h, respectively. The values for albite rim growth in samples initially dried at 60°C and with 0.1 wt% H2O added are 0.25 ± 0.04 and 0.33 ± 0.03 μm2/h, respectively. The latter values were used to derive the product of the grain boundary diffusion coefficient D′A, where A = SiO2, NaAlO2, or NaAlSi−1, and the grain boundary thickness δ in albite. The calculated D′SIO2δ in the albite aggregate for the situations of two different water contents are about 9.9 × 10−23 and 1.4 × 10−22 m3 s−1, respectively. Both the rate constants and the calculated D′Aδ demonstrate that the effect of water content on the grain boundary diffusion rate in monomineralic albite and polymineralic pyroxene (+ spinel) aggregates is small, consistent with recent studies of monomineralic enstatite and forsterite rims. Received: 1 July 1995 / Accepted: 1 August 1996  相似文献   

20.
Experimental studies in the Fe3C–SiO2–MgO system (P = 6.3 GPa, T = 1100–1500°C, t = 20–40 h) have been carried out. It has been established that carbide-oxide interaction resulted in the formation of Fe-orthopyroxene, graphite, wustite, and cohenite (1100 and 1200°C), as well as a Fe–C–O melt (1300–1500°C). The main processes occurring in the system at 1100 and 1200°C are the oxidation of cohenite, the extraction of carbon from carbide, and the crystallization of metastable graphite, as well as the formation of ferrosilicates. At T ≥ 1300°C, graphite crystallization and diamond growth occur as a result of the redox interaction of a predominantly metallic melt (Fe–C–O) with oxides and silicates. The carbide–oxide interaction studied can be considered as the basis for modeling a number of carbon-producing processes in the lithospheric mantle at fO2 values near the iron–wustite buffer.  相似文献   

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