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1.
A thermodynamic solution model is developed for minerals whose compositions lie in the two binary systems Mg2SiO4-Fe2SiO4 and Mg2Si2O6-Fe2Si2O6. The formulation makes explicit provision for nonconvergent ordering of Fe2+ and Mg2+ between M1 and M2 sites in orthopyroxenes and non-zero Gibbs energies of reciprocal ordering reactions in both olivine and orthopyroxene. The calibration is consistent with (1) constraints provided by available experimental and natural data on the Fe-Mg exchange reaction between olivine and orthopyroxene ± quartz, (2) site occupancy data on orthopyroxenes including both crystallographic refinements and Mössbauer spectroscopy, (3) enthalpy of solution data on olivines and orthopyroxenes and enthalpy of disordering data on orthopyroxene, (4) available data on the temperature and ordering dependence of the excess volume of orthopyroxene solid solutions, and (5) direct activity-composition determinations of orthopyroxene and olivine solid solutions at elevated temperatures. Our analysis suggests that the entropies of the exchange [Mg(M2)Fe(M1)Fe(M2)Mg(M1)] and reciprocal ordering reactions [Mg(M2)Mg(M1)+ Fe(M2)Fe(M1)Fe(M2)Mg(M1)+Mg(M2)Fe(M1)] cannot differ significantly (± 1 cal/K) from zero over the temperature range of calibration (400°–1300° C). Consideration of the mixing properties of olivine-orthopyroxene solid solutions places tight constraints on the standard state thermodynamic quantities describing Fe-Mg exchange reactions involving olivine, orthopyroxene, pyralspite garnets, aluminate spinels, ferrite spinels and biotite. These constraints are entirely consistent with the standard state properties for the phases-quartz,-quartz, orthoenstatite, clinoenstatite, protoenstatite, fayalite, ferrosilite and forsterite which were deduced by Berman (1988) from an independent analysis of phase equilibria and calorimetric data. In conjunction with these standard state properties, the solution model presented in this paper provides a means of evaluating an internally consistent set of Gibbs energies of mineral solid solutions in the system Mg2SiO4-Fe2SiO4-SiO2 over the temperature range 0–1300° C and pressure interval 0.001–50 kbars. As a consequence of our analysis, we find that the excess Gibbs energies associated with mixing of Fe and Mg in (Fe, Mg)2SiO4 olivines, (Fe, Mg)3Al2Si3O12 garnets, (Fe, Mg)Al2O4 and (Fe, Mg)Fe2O4 spinels, and K(Mg, Fe)3AlSi3O10(OH)2 biotites may be satisfactory described, on a macroscopic basis, with symmetric regular solution type parameters having values of 4.86±0.12 (olivine), 3.85±0.09 (garnet), 1.96±0.13 (spinel), and 3.21±0.29 kcals/gfw (biotite). Applications of the proposed solution model demonstrate the sensitivity of petrologic modeling to activity-composition relations of olivine-orthopyroxene solutions. We explore the consequences of estimating the activity of silica in melts forming in the mantle and we develop a graphical geothermometer/geobarometer for metamorphic assemblages of olivine+orthopyroxene+quartz. Quantitative evaluation of these results suggests that accurate and realistic estimates of silica activity in melts derived from mantle source regions,P-T paths of metamorphism and other intensive variables of petrologic interest await further refinements involving the addition of trace elements (Al3+ and Fe3+) to the thermodynamic formulation for orthopyroxenes.  相似文献   

2.
We have investigated the effect of Fe on the stabilities of carbonate (carb) in lherzolite assemblages by determining the partitioning of Fe and Mg between silicate (olivine; ol) and carbonates (magnesite, dolomite, magnesian calcite) at high pressures and temperatures. Fe enters olivine preferentially relative to magnesite and ordered dolomite, but Fe and Mg partition almost equally between disordered calcic carbonate and olivine. Measurement of K d (X Fe carb X Mg ol /X Fe ol X Mg carb ) as a function of Fe/ Mg ratio indicates that Fe–Mg carbonates deviate only slightly from ideality. Using the regular solution parameter for olivine W FeMg ol of 3.7±0.8 kJ/mol (Wiser and Wood 1991) we obtain for (FeMg)CO3 a W FeMg carb of 3.05±1.50 kJ/mol. The effect of Ca–Mg–Fe disordering is to raise K d substantially enabling us to calculate W CaMg carb -W CaFe carb of 5.3±2.2 kJ/mol. The activity-composition relationships and partitioning data have been used to calculate the effect of Fe/Mg ratio on mantle decarbonation and exchange reactions. We find that carbonate (dolomite and magnesian calcite) is stable to slightly lower pressures (by 1 kbar) in mantle lherzolitic assemblages than in the CaO–MgO–SiO2(CMS)–CO2 system. The high pressure breakdown of dolomite + orthopyroxene to magnesite + clinopyroxene is displaced to higher pressures (by 2 kbar) in natural compositions relative to CMS. CO2. We also find a stability field of magnesian calcite in lherzolite at 15–25 kbar and 750–1000°C.  相似文献   

3.
Phase relationships in haplogranitic melts containing ferromagnesian minerals were investigated in the temperature range 760–850°C, atP total=2 kbar, =0.25 1.00, and at NNO buffer conditions. The compositions of coexisting biotite, orthopyroxene, magnetite and granitic melt were determined by electron microprobe. Biotite was the only Fe–Mg mineral in the starting material. It disappeared in water-undersaturated melts at temperatures above 830°C and in melts saturated with water above 810°C. Magnetite was present in all runs. Orthopyroxene became stable between 780 and 800°C. The Mg/(Mg+Fe) ratios of biotite (0,63–0,72) and orthopyroxene (0,63–0,71) are similar in water-saturated and undersaturated melts at comparable temperatures and increase slightly with increasing temperature. The solubility of Mg in haplogranitic melts is very low (0,07–0,24 wt% MgO). It increases slightly with temperature and is independent of the prevailing water activity. The solubility of Fe is low (0,91–1,37 wt% FeO); it also increases with increasing temperature, and it is higher in water-saturated than in water-undersaturated melts.  相似文献   

4.
The shoshonitic intrusions of eastern Tibet, which range in age from 33 to 41 Ma and in composition from ultramafic (SiO2 = 42 %) to felsic (SiO2 = 74 %), were produced during the collision of India with Eurasia. The mafic and ultramafic members of the suite are characterized by phenocrysts of phlogopite, olivine and clinopyroxene, low SiO2, high MgO and Mg/Fe ratios, and olivine forsterite contents of Fo87 to Fo93, indicative of equilibrium with mantle olivine and orthopyroxene. Direct melting of the mantle, on the other hand, could not have produced the felsic members. They have a phenocryst assemblage of plagioclase, amphibole and quartz, high SiO2 and low MgO, with Mg/Fe ratios well below the values expected for a melt in equilibrium with the mantle. Furthermore, the lack of decrease in Cr with increasing SiO2 and decreasing MgO from ultramafic to felsic rocks precludes the possibility that the felsic members were derived by fractional crystallization from the mafic members. Similarly, magma mixing, crustal contamination and crystal accumulation can be excluded as important processes. Yet all members of the suite share similar incompatible element and radiogenic isotope ratios, which suggests a common origin and source. We propose that melting for all members of the shoshonite suite was initiated in continental crust that was thrust into the upper mantle at various points along the transpressional Red River-Ailao Shan-Batang-Lijiang fault system. The melt formed by high-degree, fluid-absent melting reactions at high-T and high-P and at the expense of biotite and phengite. The melts acquired their high concentrations of incompatible elements as a consequence of the complete dissolution of pre-existing accessory minerals. The melts produced were quartz-saturated and reacted with the overlying mantle to produce garnet and pyroxene during their ascent. The felsic magmas reacted little with the adjacent mantle and preserved the essential features of their original chemistry, including their high SiO2, low Ni, Cr and MgO contents, and low Mg/Fe ratio, whereas the mafic and ultramafic magmas are the result of extensive reaction with the mantle. Although the mafic magmas preserved the incompatible element and radiogenic isotope ratios of their crustal source, buffering by olivine and orthopyroxene extensively modified their MgO, Ni, Cr, SiO2 contents and Mg/Fe ratio to values dictated by equilibrium with the mantle.  相似文献   

5.
Of great importance in the problem of redox evolution of mantle rocks is the reconstruction of scenarios of alteration of Fe0- or Fe3C-bearing rocks by oxidizing mantle metasomatic agents and the evaluation of stability of these phases under the influence of fluids and melts of different compositions. Original results of high-temperature high-pressure experiments (P = 6.3 GPa, T = 1300–1500°С) in the carbide–oxide–carbonate systems (Fe3C–SiO2–(Mg,Ca)CO3 and Fe3C–SiO2–Al2O3–(Mg,Ca)CO3) are reported. Conditions of formation of mantle silicates with metallic or metal–carbon melt inclusions are determined and their stability in the presence of CO2-fluid representing the potential mantle oxidizing metasomatic agent are estimated. It is established that garnet or orthopyroxene and CO2-fluid are formed in the carbide–oxide–carbonate system through decarbonation, with subsequent redox interaction between CO2 and iron carbide. This results in the formation of assemblage of Fe-rich silicates and graphite. Garnet and orthopyroxene contain inclusions of a Fe–C melt, as well as graphite, fayalite, and ferrosilite. It is experimentally demonstrated that the presence of CO2-fluid in interstices does not affect on the preservation of metallic inclusions, as well as graphite inclusions in silicates. Selective capture of Fe–C melt inclusions by mantle silicates is one of the potential scenarios for the conservation of metallic iron in mantle domains altered by mantle oxidizing metasomatic agents.  相似文献   

6.
Experiments dissolving orthopyroxene (En93) in a variety of Si-undersaturated alkaline melts at 1 atmosphere and variable f O2 demonstrate that orthopyroxene dissolves to form olivine, Si-rich melt and clinopyroxene. These phases form a texturally and chemically distinct boundary layer around the partly dissolved orthopyroxene crystals. The occurrence of clinopyroxene in the boundary layer is due to inward diffusion of Ca from the solvent melt to the boundary layer causing clinopyroxene saturation. Compositional profiles through the solvent and the boundary layer for a number of experiments demonstrate rapid diffusion of cations across the boundary layer – solvent interface. SiO2 diffuses outward from the boundary layer whereas CaO and Al2O3 diffuse toward the Si-enriched boundary layer melt. The rate of Al diffusion is slower under reducing conditions compared to the rates in experiments performed in air. Concentrations of FeO and MgO in the boundary layer and solvent are approximately equal indicating rapid diffusion and attainment of equilibrium despite ongoing crystallisation of clinopyroxene within the boundary layer. The behaviour of Na2O and K2O is strongly affected by f O2. Under reducing conditions Na2O and K2O concentrations are approximately equal in the boundary layer and solvent indicating normal diffusion down the concentration gradient and attainment of equilibrium. Under oxidising conditions, K2O and to a lesser extent Na2O, have compositional profiles indicative of uphill diffusion likely due to their preference for more polymerised Si- and Al-rich melts. Under reduced conditions Al-enrichment in the boundary layer melt is not as extreme and uphill diffusion did not occur. The composition of the solvent melt after the experiments indicates that it was contaminated by the boundary layer by convective mixing due to the onset of hydrodynamic instabilities brought on by density and viscosity contrasts between the two melts. Despite using a wide variety of solvent melt compositions we find that the boundary layer melts converge toward a common composition at high SiO2 contents. The composition of glass generated by orthopyroxene dissolution at 1 atmosphere is similar in many respects to Si-rich glass found in many orthopyroxene-rich mantle xenoliths that have been attributed to high pressure in situ processes including mantle metasomatism. The results of this study suggest that at least some Si-rich melts are likely to have formed by dissolution of xenolith orthopyroxene at low pressure possibly by their Si-undersaturated host magmas. Received: 30 August 1996 / Accepted: 15 April 1998  相似文献   

7.
 We have investigated new samples from the Gees mantle xenolith suite (West Eifel), for which metasomatism by carbonatite melt has been suggested. The major metasomatic change is transformation of harzburgites into phlogopite-rich wehrlites. Silicate glasses are associated with all stages of transformation, and can be resolved into two major groups: a strongly undersaturated alkaline basanite similar to the host magma which infiltrated the xenoliths during ascent, and Si-Al-enriched, variably alkaline glass present exclusively within the xenoliths. Si-Al-rich glasses (up to 72 wt% SiO2 when associated with orthopyroxene (Opx) are usually interpreted in mantle xenoliths as products of decompressional breakdown of hydrous phases like amphibole. In the Gees suite, however, amphibole is not present, nor can the glass be related to phlogopite breakdown. The Si-Al-rich glass is compositionally similar to glasses occurring in many other xenolith suites including those related to carbonatite metasomatism. Petrographically the silicate glass is intimately associated with the metasomatic reactions in Gees, mainly conversion of harzburgite orthopyroxene to olivine + clinopyroxene. Both phases crystallize as microlites from the glass. The chemical composition of the Si-Al-enriched glass shows that it cannot be derived from decompressional melting of the Gees xenoliths, but must have been present prior to their entrainment in the host magma. Simple mass-balance calculations, based on modal analyses, yield a possible composition of the melt prior to ascent of the xenoliths, during which glass + microlite patches were modified by dissolution of olivine, orthopyroxene and spinel. This parental melt is a calc-alkaline andesite (55–60 wt% SiO2), characterized by high Al2O3 (ca. 18 wt%). The obtained composition is very similar to high-alumina, calc-alkaline melts that should form by AFC-type reactions between basalt and harzburgite wall rock according to the model of Kelemen (1990). Thus, we suggest that the Si-Al-enriched glasses of Gees, and possibly of other suites as well, are remnants of upper mantle hybrid melts, and that the Gees suite was metasomatized by silicate and not carbonatite melts. High-Mg, high-Ca composition of metasomatic olivine and clinopyroxene in mantle xenoliths have been explained by carbonatite metasomatism. As these features are also present in the Gees suite, we have calculated the equilibrium Ca contents of olivine and clinopyroxene using the QUI1F thermodynamical model, to show that they are a simple function of silica activity. High-Ca compositions are attained at low a SiO2 and can thus be produced during metasomatism by any melt that is Opx-undersaturated, irrespective of whether it is a carbonatite or a silicate melt. Such low a SiO2 is recorded by the microlites in the Gees Si-Al-rich glasses. Our results imply that xenolith suites cannot confidently be related to carbonatite metasomatism if the significance of silicate glasses, when present, is not investigated. Received: 2 March 1995 / Accepted: 12 June 1995  相似文献   

8.
Whole-rock, major and trace element analyses and microprobe mineral analyses were conducted on serpentinized peridotites recovered from the walls of a MAR (Mid-Atlantic Ridge) 43° N fracture zone. These peridotites are extensively serpentinized; serpentine usually makes up 30–100 vol. percent of the bulk rocks. The relict minerals observed consist mainly of olivine and orthopyroxene with subordinate amounts of clinopyroxene and brown spinel. The range in olivine composition is very limited (Fo91–92). Orthopyroxene forms large, anhedral crystals with clinopyroxene exsolution lamellae and shows undulose extinction with bent cleavages and lamellae. Broad beam microprobe analyses indicate that the composition range of orthopyroxene is also limited (En89.1–87.6Fs8.2-8.0Wo2.7–4.4; Al2O3=1.82–2.64 wt%; Cr2O3=0.63–0.88 wt%). Clinopyroxene tends to fringe large orthopyroxene crystals or fills the interstices between them. The Mg/Fe ratios of clinopyroxene are practically constant; however, the Ca/(Ca + Mg + Fe) ratios range from 0.48 to 0.45. The Cr/(Cr+Al) and Mg/(Mg+ Fe2+) ratios of brown spinel range from 0.57 to 0.36 and 0.69 to 0.56, respectively. The geothermometers utilizing coexisting spinel lherzolite mineral assemblages suggest that the MAR 43° N peridotites attained equilibrium at temperatures from 1100° to 1250° C.Peridotites recovered from the ocean floor are generally considered to have been subjected to partial melting processes and are regarded as residues left after primary magma was removed. Major element chemistry of the MAR 43° N peridotites are compared with those of the ocean-floor ultramafic tectonites reported previously and used together with those published data to demonstrate that the major element abundances of the oceanfloor peridotites define an average trend which is compatible with removal of primary magma from these peridotites at moderate pressures (10–15 kb). Then, the most primitive abyssal tholeiite glasses could be produced by ca. 10% olivine fractionation of such primary magma. Extensive fractionation of olivine and/or orthopyroxene from picritic liquids which are in equilibrium with the lherzolitic or harzburgitic mantle sources at higher pressures (>20 kb) could not yield the majority of the most primitive abyssal tholeiite glasses.  相似文献   

9.
Quaternary volcanism in the Mt. Shasta region has produced primitive magmas [Mg/(Mg+Fe*)>0.7, MgO>8 wt% and Ni>150 ppm] ranging in composition from high-alumina basalt to andesite and these record variable extents ofmelting in their mantle source. Trace and major element chemical variations, petrologic evidence and the results of phase equilibrium studies are consistent with variations in H2O content in the mantle source as the primary control on the differences in extent of melting. High-SiO2, high-MgO (SiO2=52% and MgO=11 wt%) basaltic andesites resemble hydrous melts (H2O=3 to 5 wt%) in equilibrium with a depleted harzburgite residue. These magmas represent depletion of the mantle source by 20 to 30 wt% melting. High-SiO2, high-MgO (SiO2=58% and MgO=9 wt%) andesites are produced by higher degrees of melting and contain evidence for higher H2O contents (H2O=6 wt%). High-alumina basalts (SiO2=48.5% and Al2O3=17 wt%) represent nearly anhydrous low degree partial melts (from 6 to 10% depletion) of a mantle source that has been only slightly enriched by a fluid component derived from the subducted slab. The temperatures and pressures of last equilibration with upper mantle are 1200°C and 1300°C for the basaltic andesite and basaltic magmas, respectively. A model is developed that satisfies the petrologic temperature constraints and involves magma generation whereby a heterogeneous distribution of H2O in the mantle results in the production of a spectrum of mantle melts ranging from wet (calc-alkaline) to dry (tholeiitic).  相似文献   

10.
Garnet pyroxenite from high pressure granulite facies occurs with different mineral assemblages which involve garnet, clinopyroxene, orthopyroxene, plagioclase, amphibole and quartz with spinel developing as symplectite with orthopyroxene and plagioclase in large cracks. Three successive parageneses have been identified. The primary assemblage is characterised by the presence of quartz. The second assemblage involves orthopyroxene–plagioclase–hornblende symplectite, and the third assemblage is characterised by the development of spinel in symplectites with orthopyroxene and plagioclase. Using THERMOCALC (V2.7), a quantitative pseudosection in the system CaO–FeO–MgO–Al2O3–SiO2–H2O has been calculated. The assemblage involving quartz developed at high pressure, while the assemblage involving spinel developed at lower pressure. The peak of metamorphism in Tin Begane was calculated at 860 °C and 13.5 kb with aH2O=0.2. These conditions are followed by a decrease of pressure down to 4.8 kb.  相似文献   

11.
Summary Vivianite from Catavi Mine, Llallagua, Bolivia, has a near ideal composition with traces of Mg, Zn and Mn. Total rare-earth elements are < 1,gmg/g. Mössbauer spectroscopy shows FeIII/(FeII + FeIII) is approximately 0.04.a = 10.030Å,b = 13.434Å,c = 4.714Å, = 102.73dg. The middle-infrared powder spectrum shows H2O-related bands at 3490, 3290, 3130 cm–1 (stretch), 1618 cm–1 (bend), 825 cm–1 (rock), and at 665 cm–1 a possible M-OH2 twist. P04 bands occur at 1045-940 cm–1 (stretch) and 570-450 cm–1 (bend). Corresponding laser Raman microprobe bands occur at 1051 (ms), 986 (m), 948 (vs), 867 (mw), 828 (w), 568, 532, 453 (m), 442 (mw). Weak Raman bands at about 342, 303, 270 (w), 235 (ms), 227 (sh, ms), 196 (ms), 187 (sh, m), 162 (mw), and 126 (m) may arise from lattice vibrations. Differential thermal responses include a major endotherm from 115–235°C with a shoulder at 170°C and a maximum at 210°C resulting from loss of structural water combined with oxidation of Fe2+, and two small exotherms with maxima at 605 and 780°C related to structural transformations.
Charakterisierung des Vivianits von Catavi, Llallagua, Bolivien
Zusammenfassung Vivianit von der Catavi Mine, Llallagua, Bolivien zeigt annähernd ideale Zusammensetzung mit Spuren von Mg, Zn und Mn. Der gesamte Gehalt an seltenen EvolElementen ist < 1 ppm. Die Mössbauer Spektroskopie liefert ein Fe3+/(Fe2+ + Fe3+) Verhältnis von ungefähr 0.04.a = 10.030,b = 13.434,c = 4.714 Å, = 102.73°. Das Infrarot-Pulverspektrum zeigt dem H20 zuzuordnende Banden bei 3490, 3290, 3130 cm–1 (Streckschwingungen), 1618 cm–1 (Deformationsschwingung), 825 cm–1 (Schaukelschwingung) und eine mögliche M-OH2 Torsionsschwingung bei 665 cm–1. PO4 Banden liegen bei 1045-940 cm–1 (Streckschwingung) und 570-450 cm–1 (Deformations-schwingung). Entsprechende Banden der Laser Raman Mikrosonde liegen bei 1051 (mst), 986 (m), 948 (sst) 867 (mschw), 828 (schw), 568, 532, 453 (m), 442 (mschw). Raman Banden bei etwa 342, 303, 270 (schw), 235 (mst), 227 (Schulter, mst), 196 (mst), 187 (Schulter, m), 162 (mschw) und 126 (m) können auf Gitterschwingungen zurückgeführt werden. Differential-thermoanalytische Untersuchungen zeigen einen endothermen Bereich von 115–235°C mit einer Schulter bei 170 und einem Maximum bei 210°C, was auf den Verlust von strukturellem Wasser, das an eine Oxidation des Fe2+ gebunden ist, zurückzuführen ist; zwei auf strukturelle Transformationen zurückzuführende exotherme Maxima liegen bei 605 und 780°C.

With 4 Figures  相似文献   

12.
Infrared spectroscopy has been used to study the speciation of CO2 in glasses near the NaAlO2-SiO2 join quenched from melts held at high temperatures and pressures. Absorption bands resulting from the antisymmetric stretches of both molecular CO2 (2,352 cm–1) and CO 3 2– (1,610 cm–1 and 1,375 cm–1) are observed in these glasses. The latter are attributed to distorted Na-carbonate ionic-complexes. Molar absorptivities of 945 liters/mole-cm for the molecular CO2 band, 200 liters/mole-cm for the 1,610 cm–1 band, and 235 liters/mole-cm for the 1,375 cm–1 band have been determined. These molar absorptivities allow the quantitative determination of species concentrations in the glasses with a precision on the order of several percent of the amount present. The accuracy of the method is estimated to be ±15–20% at present.The ratio of molecular CO2 to CO 3 2– in sodium aluminosilicate glasses varies little for each silicate composition over the range of total dissolved CO2 content (0–2%), pressure (15–33 kbar) and temperature (1,400–1,560° C) that we have studied. This ratio is, however, a strong function of silicate composition, increasing both with decreasing Na2O content along the NaAlO2-SiO2 join and with decreasing Na2O content in peraluminous compositions off the join.Infrared spectroscopic measurements of species concentrations in glasses provide insights into the molecular level processes accompanying CO2 solution in melts and can be used to test and constrain thermodynamic models of CO2-bearing melts. CO2 speciation in silicate melts can be modelled by equilibria between molecular CO2, CO 3 2– , and oxygen species in the melts. Consideration of the thermodynamics of such equilibria can account for the observed linear relationship between molecular CO2 and carbonate concentrations in glasses, the proposed linear relationship between total dissolved CO2 content and the activity of CO2 in melts, and observed variations in CO2 solubility in melts.  相似文献   

13.
Ab-initio interionic potentials for Mg2+, Si4+, and O2– have been used in molecular dynamics (MD) simulations to investigate diffusivity changes, pressure-induced structural transitions, and temperature effects on polymerization in MgSiO3 and Mg2SiO4 melts and glasses. The potential gives reasonable agreement with the 0.1 MPa radial distribution function of MgSiO3 glass. Maxima in the diffusion coefficients of Si4+ and O2– occur as pressure is increased on the MgSiO3 melt. The controlling structural mechanism for this behavior is the Q1 species of SiO4 tetrahedra. Mg2+ diffusion coefficients decrease monotonically with pressure in both melt compositions. Increasing Mg2+ coordination number and population of 3- and 4-membered SiO4 rings with pressure combine to hinder translation of the Mg2+ ions. The dominant changes in structure with pressure are a decrease in the intertetrahedral (Si-O--Si) angle up to approximately 4 g/cm3 and coordination changes of the ions above this density. Temperature effects on viscosity in these simulated melts are indirectly studied by analyzing polymerization changes with temperature. Polymerization and coordination numbers increase with decreasing temperature and a small quench rate effect is observed. Fair agreement is found between the MD simulations and experimental equation of state for Mg2SiO4, but the equation of state predictions for MgSiO3 melts are much less accurate. The zero pressure volume, V 0, is significantly higher and K 0 is lower in the simulations than empirical values. The inadequacies reflect error in using the ionic approximation for polymerized systems and a need to collect more data for a variety of molecular configurations in the development of ab-initio potentials.  相似文献   

14.
The Tin Zebane gabbro–anorthosite layered mafic intrusion represented by plagioclase-rich cumulates forms a set of small lenticular to round-shaped mainly undeformed bodies intruding the Pan-African high-pressure metamorphic rocks from western Hoggar (Tuareg shield, southwest Algeria). The coarse-grained anorthosites are mainly made of slightly zoned bytownite (An86–74) with the higher anorthite content at the cores. Anorthosites are interlayered with leucogabbros and gabbros that show preserved magmatic structures and with olivine gabbros characterised by coronitic textures. The primary assemblage in gabbros includes plagioclase (An93–70), olivine (Fo77–70), zoned clinopyroxene (En43–48Fs05–13Wo41–49 with Al2O3 up to 4.3 wt.%) and rare orthopyroxene (En73–78). Pyroxenes and olivine are commonly surrounded by Ca-amphibole. The olivine–plagioclase contact is usually marked by a fine orthopyroxene–Cr-spinel–amphibole symplectite. A magnesian pigeonite (En70–75Fs19–20Wo6–10) is also involved in corona. The coronitic minerals have equilibrated with the primary mineral rims at P–T–aH2O conditions of 797 ± 42 °C for aH2O=0.5 and 808 ± 44 °C for aH2O=0.6 at 6.2 ± 1.4 kbar. The Tin Zebane gabbroic rocks are depleted in REE with a positive Eu anomaly, high Sr (>10 * chondrite) and Al2O3 concentrations (17–33%) that support plagioclase accumulation with the extreme case represented by the anorthosites. The REE patterns can be modelised using plagioclase, clinopyroxene and orthopyroxene REE signature, without any role played by accessory minerals. High MgO content points to olivine as a major cumulate phase. Anorthositic gabbros Sr and Nd isotopic initial ratios are typical of a depleted mantle source (Sri=0.70257–0.70278; Nd=+5.9 to +7.8). This isotopic signature is identical to that of the 10-km wide 592 Ma old dyke complex composed of alkaline to peralkaline granites and tholeiitic gabbros and one single bimodal complex can be inferred. The source of the Tin Zebane basic rocks corresponds to the prevalent mantle (PREMA). The Tin Zebane complex was emplaced along the mega-shear zone bounding to the west the Archaean In Ouzzal metacraton. The model proposed suggests a linear lithospheric delamination along this rigid and cold terrane due to post-collisional transtensional movements. This allowed the asthenosphere to rise rapidly and to melt by adiabatic pressure release. Transtension along a rigid body allowed these mantle melts to reach the surface rapidly without any crustal contamination.  相似文献   

15.
A large body of recent work has linked the origin of Si-Al-rich alkaline glass inclusions to metasomatic processes in the upper mantle. This study examines one possible origin for these glass inclusions, i.e., the dissolution of orthopyroxene in Si-poor alkaline (basanitic) melt. Equilibrium dissolution experiments between 0.4 and 2 GPa show that secondary glass compositions are only slightly Si enriched and are alkali poor relative to natural glass inclusions. However, disequilibrium experiments designed to examine dissolution of orthopyroxene by a basanitic melt under anhydrous, hydrous and CO2-bearing conditions show complex reaction zones consisting of olivine, ± clinopyroxene and Si-rich alkaline glass similar in composition to that seen in mantle xenoliths. Dissolution rates are rapid and dependent on volatile content. Experiments using an anhydrous solvent show time dependent dissolution rates that are related to variable diffusion rates caused by the saturation of clinopyroxene in experiments longer than 10 minutes. The reaction zone glass shows a close compositional correspondence with natural Si-rich alkaline glass in mantle-derived xenoliths. The most Si-and alkali-rich melts are restricted to pressures of 1 GPa and below under anhydrous and CO2-bearing conditions. At 2 GPa glass in hydrous experiments is still Si-␣and alkali-rich whereas glass in the anhydrous and CO2-bearing experiments is only slightly enriched in SiO2 and alkalis compared with the original solvent. In the low pressure region, anhydrous and hydrous solvent melts yield glass of similar composition whereas the glass from CO2-bearing experiments is less SiO2 rich. The mechanism of dissolution of orthopyroxene is complex involving rapid incongruent breakdown of the orthopyroxene, combined with olivine saturation in the reaction zone forming up to 60% olivine. Inward diffusion of CaO causes clinopyroxene saturation and uphill diffusion of Na and K give the glasses their strongly alkaline characteristics. Addition of Na and K also causes minor SiO2 enrichment of the reaction glass by increasing the phase volume of olivine. Olivine and clinopyroxene are transiently stable phases within the reaction zone. Clinopyroxene is precipitated from the reaction zone melt near the orthopyroxene crystal and redissolved in the outer part of the reaction zone. Olivine defines the thickness of the reaction zone and is progressively dissolved in the solvent as the orthopyroxene continues to dissolve. Although there are compelling reasons for supporting the hypothesis that Si-rich alkaline melts are produced in the mantle by orthopyroxene – melt reaction in the mantle, there are several complications particularly regarding quenching in of disequilibrium reaction zone compositions and the mobility of highly polymerized melts in the upper mantle. It is considered likely that formation of veins and pools of Si-rich alkaline glass by orthopyroxene – melt reaction is a common process during the ascent of xenoliths. However, reaction in situ within the mantle will lead to equilibration and therefore secondary melts will be only moderately siliceous and alkali poor. Received: 24 August 1998 / Accepted: 2 December 1998  相似文献   

16.
The solubility and incorporation mechanisms of water in synthetic and natural MgAl2O4 spinel have been investigated in a series of high-pressure/temperature annealing experiments. In contrast to most other nominally anhydrous minerals, natural spinel appears to be completely anhydrous. On the other hand, non-stoichiometric Al-rich synthetic (defect) spinel can accommodate several hundred ppm water in the form of structurally-incorporated hydrogen. Infrared (IR) spectra of hydrated defect spinel contain one main O-H stretching band at 3343-3352 cm−1 and a doublet consisting of two distinct O-H bands at 3505-3517 cm−1 and 3557-3566 cm−1. IR spectra and structural refinements based on single-crystal X-ray data are consistent with hydrogen incorporation in defect spinel onto both octahedral and tetrahedral O-O edges. Fine structure of O-H bands in IR spectra can be explained by partial coupling of interstitial hydrogen with cation vacancies, or by the effects of Mg-Al disorder on the tetrahedral site. The concentration of cation vacancies in defect spinel is a major control on hydrogen affinity. The commercial availability of large single crystals of defect spinel coupled with high water solubility and similarities in water incorporation mechanisms between hydrous defect spinel and hydrous ringwoodite (Mg2SiO4) suggests that synthetic defect spinel may be a useful low-pressure analogue material for investigating the causes and consequences of water incorporation in the lower part of Earth’s mantle transition zone.  相似文献   

17.
The influence of water on melting of mantle peridotite   总被引：47，自引：8，他引：39  
This experimental study examines the effects of variable concentrations of dissolved H2O on the compositions of silicate melts and their coexisting mineral assemblage of olivine + orthopyroxene ± clinopyroxene ± spinel ± garnet. Experiments were performed at pressures of 1.2 to 2.0 GPa and temperatures of 1100 to 1345 °C, with up to ∼12 wt% H2O dissolved in the liquid. The effects of increasing the concentration of dissolved H2O on the major element compositions of melts in equilibrium with a spinel lherzolite mineral assemblage are to decrease the concentrations of SiO2, FeO, MgO, and CaO. The concentration of Al2O3 is unaffected. The lower SiO2 contents of the hydrous melts result from an increase in the activity coefficient for SiO2 with increasing dissolved H2O. The lower concentrations of FeO and MgO result from the lower temperatures at which H2O-bearing melts coexist with mantle minerals as compared to anhydrous melts. These compositional changes produce an elevated SiO2/(MgO + FeO) ratio in hydrous peridotite partial melts, making them relatively SiO2 rich when compared to anhydrous melts on a volatile-free basis. Hydrous peridotite melting reactions are affected primarily by the lowered mantle solidus. Temperature-induced compositional variations in coexisting pyroxenes lower the proportion of clinopyroxene entering the melt relative to orthopyroxene. Isobaric batch melting calculations indicate that fluid-undersaturated peridotite melting is characterized by significantly lower melt productivity than anhydrous peridotite melting, and that the peridotite melting process in subduction zones is strongly influenced by the composition of the H2O-rich component introduced into the mantle wedge from the subducted slab. Received: 7 April 1997 / Accepted: 9 January 1998  相似文献   

18.
The phase relations in the system grossular-spessartine-H2O were investigated at 2.0 Kb aqueous fluid pressure and at subsolidus temperatures down to 420 ° C. Despite metastable persistence of a compositional gap found in some intermediate members, a complete solid solution between grossular and spessartine exists.Linear relations between the unit cell edge, a 0, and composition were readily observed down to 620 ° C with a 0=11.849(2) Å and 11.613(2) Å for grossular and spessartine, respectively. Hydrated garnets began to appear at higher temperature for the Ca-rich members. Grossular and spessartine formed at 420 ° C have a 0=11.901(2) Å and 11.632(2) Å, indicating the presence of 0.6 and 0.2 mol H2O, respectively. Intermediate members show varying degrees of hydration. Infrared spectra of the more hydrated members show a major and minor absorption bands at 3,620 cm–1 and 3,660 cm–1, respectively, in addition to a broad band around 3,430 cm–1. All the hydrogarnets formed at 420 ° C were proven to be metastable.The rare occurrence of the intermediate grossular-spessartine garnets may be attributed to the lack of appropriate bulk chemistry of the rock rather than to the P-T conditions to which the rock is subjected. There may be a stability field for hydrogrossular below 420 ° C at 2 Kb, but not for hydrospessartine. Any occurrence of hydrogarnet may be used as a temperature indicator setting the maximum of formation for the hydrogarnet-bearing assemblage below 420 ° C at 2 Kb.  相似文献   

19.
The influence on the structure of Fe2+ Mg substitution was studied in synthetic single crystals belonging to the MgCr2O4–FeCr2O4 series produced by flux growth at 900–1200 °C in controlled atmosphere. Samples were analyzed by single-crystal X-ray diffraction, electron microprobe analyses, optical absorption-, infrared- and Mössbauer spectroscopy. The Mössbauer data show that iron occurs almost exclusively as IVFe2+. Only minor Fe3+ (<0.005 apfu) was observed in samples with very low total Fe. Optical absorption spectra show that chromium with few exceptions is present as a trivalent cation at the octahedral site. Additional absorption bands attributable to Cr2+ and Cr3+ at the tetrahedral site are evident in spectra of end-member magnesiochromite and solid-solution crystals with low ferrous contents. Structural parameters a0, u and T–O increase with chromite content, while the M–O bond distance remains nearly constant, with an average value equal to 1.995(1) Å corresponding to the Cr3+ octahedral bond distance. The ideal trend between cell parameter, T–O bond length and Fe2+ content (apfu) is described by the following linear relations: a0=8.3325(5) + 0.0443(8)Fe2+ (Å) and T–O=1.9645(6) + 0.033(1)Fe2+ (Å) Consequently, Fe2+ and Mg tetrahedral bond lengths are equal to 1.998(1) Å and 1.965(1) Å, respectively.  相似文献   

20.
The variation of silica activity with temperature and pressure for a variety of silica buffers (mineral pairs) allows P total to be calculated for a wide range of igneous rocks. The method also depends on evaluating ( log a SiO 2/P)T and ( log a SiO 2/ T)p; the former is equivalent to the partial molar volume of silica in silicate liquids, while the latter is estimated from published experiments on natural melts. Results for calc-alkaline rhyolites with phenocrysts of quartz, olivine or orthopyroxene, and iron-titanium oxides, range from 3.45 to 9.58 kilobars; a pantellerite is intermediate at 7.53 kilobars. At 1327° C, the silicate inclusions in diamond equilibrated at 63.5 kilobars, and the kimberlite crystallisation path intersected the baddeleyite-zircon reaction at 55.7 kilobars. Two trachybasalts would equilibrate with their lherzolite xenoliths at 17.0 and 21.0 kilobars at surface quenching temperatures. Potassic lavas such as orendites and ugandites at 1300° C would be in equilibrium with mantle olivine-orthropyroxene at 35.1 and 69.0 kilobars respectively. Basalts and basaltic-andesites could equilibrate (at 1100° C) with quartz at between 24.9 and 26.8 kilobars; quartz can therefore be considered a possible high pressure xenocryst in lavas with low Sr87/Sr86 ratios. Andesites will equilibrate at 1300° C with the mantle at a depth of 75 kilometres; at greater depths andesite will have a basaltic precursor. In general, lavas with low silica activity will equilibrate at greater depths in the mantle than those with higher silica activities.The Apollo 11 basalts contain minerals which suggest equilibration at 37 kilobars; the calculated quenching temperature is 1009° C, from which logf O 2 can be derived (–15.2) which in turn indicates approximately 0.10% Fe2O3 in these lavas.  相似文献   

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