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1.
An experimental method of melt inclusion synthesis within olivine crystals has been developed to determine the composition of the melt present in a partially molten peridotite assemblage. Trace element doped peridotite was equilibrated with 5 wt% of a C-O-H volatile source at 20 kbar/1175 °C in a piston-cylinder apparatus under buffered oxygen and sulphur fugacity conditions [log(f O2) ∼ IW +1 log unit, log (f S2) ∼ Fe/FeS > +1 log unit]. A single crystal of olivine, which had been cut to a disc shape, was included in the sample capsule. At run conditions the peridotite charge formed olivine, orthopyroxene, clinopyroxene, Fe-Ni sulphide and a volatile-bearing melt. The melt phase is preserved as homogeneous glass inclusions up to 50 μm in size, trapped in situ in the olivine disc. The major element composition of the glass inclusions showed them to be of broadly basaltic character, but with a low Mg/(Mg + ΣFe), which is associated with precipitation of olivine from the melt inclusion onto the walls of the olivine disc during quenching. Thus the equilibrium melt composition has been calculated from the glass inclusion composition by addition of olivine component using the Fe/Mg exchange coefficient of Roeder and Emslie (1970); the desired Mg/(Mg + ΣFe) being determined from the composition of olivine formed at run conditions in the peridotite section of the charge. The melt composition obtained is close to the trend for dry melting established by Falloon and Green (1988), and it is evident that although the reduced volatiles in this case have induced a liquidus depression of some 250 °C, there has been only a small shift in melt composition. Trace element, carbon and hydrogen contents of thirteen melt inclusions have been determined by secondary ion mass spectrometry (SIMS). The trace element signature is consistent with ∼29% melting in equilibrium with a lherzolitic assemblage. The equilibrium melt has a C/H of 0.48 by weight. Carbon solubility in partial melts is thus significant under reducing conditions in the presence of dissolved “water components” and establishes a major melt fluxing role for carbon in the upper mantle. The ubiquitous presence of carbon and hydrogen in basaltic magmas underscores the importance of determining both the position of vapour-present solidi and the composition of melts generated, when developing petrogenetic models. Received: 1 July 1996 / Accepted: 25 June 1997  相似文献   

2.
The heat capacity of synthetic anhydrous Mg and Fe cordierite was measured by differential scanning calorimetry (DSC). Mg cordierite was synthesized from a glass at high temperatures and shows an ordered structural state. Fe cordierite was synthesized hydrothermally and dehydrated under reducing conditions to obtain H2O-free material. IR spectroscopy was used to ascertain the lack of H2O in both phases. The molar volume of both phases was measured using powder X-ray diffraction giving 23.316 (7) J/bar for Mg cordierite and 23.672 (6) J/bar for Fe cordierite. DSC measurements between 300 and 950 K were made following the procedure of Bosenick et al. (1996). The data show a precision of about 1% in the case of Mg cordierite and 1.5% for Fe cordierite. Fitted Cp polynomials in J/mol/K are:
and
for Mg and Fe cordierite, respectively. The Cp values determined for Mg cordierite are slightly larger (1–3%) than those measured by drop calorimetry by Pankratz and Kelley (1963). The Cp data for Fe cordierite permit the calculation of its standard third-law entropy, So 298 K from the reaction 3Fe cordierite=2 almandine + 4 sillimanite + 5 quartz giving 465 J/mol/K, which is in good agreement with recent model estimates. Received: 18 June 1999 / Accepted: 30 August 1999  相似文献   

3.
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   

4.
1 Introduction recognized and accepted by more and more experts engaged in experimental research at high temperature and In-situ laboratory measurement of the electricity of high pressure. This method has been regardedgeological materials at high temperature and high pressure internationally as the most advanced one for the in-situis an important approach to revealing the composition, laboratory measurement of the electric properties ofstructure and properties of materials in the deep interior…  相似文献   

5.
P -T paths from anatectic pelites   总被引：2，自引：1，他引：1  
A relatively simple petrogenetic grid for partial melting of pelitic rocks in the NCKFMASH system is presented based on the assumption that the only H2O available for melting is through dehydration reactions. The grid includes both discontinuous and continuous Fe-Mg reactions; contours of Fe/(Fe+Mg) for continuous reactions define P-T vectors along which continuous melting will occur. For biotite-bearing assemblages (garnet+biotite + sillimanite + K-feldspar + liquid and garnet + biotite + cordierite + K-feldspar + liquid), Fe/(Fe+Mg) contours have negative slopes and melting will occur with increasing temperature or pressure. For biotite-absent assemblages (garnet + cordierite + sillimanite + K-feldspar + liquid or garnet + cordierite + orthopyroxene + K-feldspar + liquid) Fe/(Fe + Mg) contours have flat slopes and melting will occur only with increasing pressure. The grid predicts that abundant matrix K-feldspar should only be observed if rocks are heated at P < 3.8 kbar, that abundant retrograde muscovite should only be observed if rocks are cooled at P > 3.8 kbar, and that generation of late biotite + sillimanite replacing garnet, cordierite, or as selvages around leu- cosomes should be common in rocks in which melt is not removed. There is also a predicted field for dehydration melting of staurolite between 5 and 12 kbar. Textures in migmatites from New Hampshire, USA, suggest that prograde dehydration melting reactions are very nearly completely reversible during cooling and crystallization in rocks in which melt is not removed. Therefore, many reaction textures in “low grade” migmatites may represent retrograde rather than prograde reactions. Received: 5 March 1998 / Accepted: 7 August 1998  相似文献   

6.
 Electrical conductivity of lherzolite (65% olivine), measured as a function of time after changes in the oxygen fugacity (f o2) of the surrounding CO2/CO atmosphere, is used to infer the diffusivity of the point defects responsible for conduction in olivine. A total of 63 equilibration runs at temperatures of 900, 1000, 1100, and 1200 ∘C were fit using nonlinear parameter estimation to recover time constants (directly related to diffusivity) and conductivity steps. An observed f o2 dependence in the time constants associated with re-equilibration implies two defect species of fixed diffusivity but with f o2-dependent concentrations. Although the rate-limiting step may not necessarily be associated with a conducting defect, when time constants are converted to diffusivities, the magnitudes and activation energies agree extremely well with the model for magnesium vacancies (the slower species) and small polarons (holes localized on Fe3+) derived by Constable and Roberts (1997). This earlier study used an independent method of simultaneous modeling of thermopower and electrical conductivity as a function of f o2 and temperature, on data from a different type of sample (a dunite). We observe that at high f o2 where polarons dominate over magnesium vacancies in the defect population, re-equilibration is dominated by magnesium vacancy diffusion, and vice versa (at low f o2 magnesium vacancies dominate and re-equilibration proceeds at the faster rate associated with polaron mobility). We interpret this to suggest association between the cation vacancies and polarons, as has been suggested by Tsai and Dieckmann (1997), making the concentration of the minority defect the rate-limiting step in the oxidation/reduction reactions. Received: 18 October 2000 / Accepted: 7 May 2002  相似文献   

7.
Electrical conductivity of orthopyroxene and plagioclase in the lower crust   总被引：4，自引：0，他引：4  
The electrical conductivities of lower crustal orthopyroxene and plagioclase, as well as their dependence on water content, were measured at 6–12 kbar and 300–1,000°C on both natural and pre-annealed samples prepared from fresh mafic xenolith granulites. The complex impedance was determined in an end-loaded piston cylinder apparatus by a Solarton-1260 Impedance/Gain Phase analyzer in the frequency range of 0.1–106 Hz. The spectra usually show an arc over the whole frequency range at low temperature and an arc plus a tail in the high and low frequency range, respectively, at high temperature. The arc is due to conduction in the sample interior, while the tails are probably due to electrode effects. Different conduction mechanisms have been identified under dry and hydrous conditions. For the dry orthopyroxene, the activation enthalpy is ~105 kJ/mol, and the conduction is likely due to small polarons, e.g., electrons hopping between Fe2+ and Fe3+. For the dry plagioclase, the activation enthalpy is ~161 kJ/mol, and the conduction may be related to the mobility of Na+. For the hydrous samples, the activation enthalpy is ~81 kJ/mol for orthopyroxene and ~77 kJ/mol for plagioclase, and the electrical conductivity is markedly enhanced, probably due to proton conduction. For each mineral, the conductivity increases with increasing water content, with an exponent of ~1, and the activation enthalpies are nearly independent of water content. Combining these data with our previous work on the conductivity of lower crustal clinopyroxene, the bulk conductivity of lower crustal granulites is modeled, which is usually >~10−4 S/m in the range of 600–1,000°C. We suggest that the high electrical conductivity in most regions of the lower crust, especially where it consists mostly of granulites, can be explained by the main constitutive minerals, particularly if they contain some water. Contributions from other highly conducting materials such as hydrous fluids, melts, or graphite films are not strictly necessary to explain the observed conductivities.  相似文献   

8.
 Natural amphiboles with composition close to the binary join cummingtonite–grunerite and crystals of the same samples annealed at 700 °C for 55.5 h, in order to obtain different degrees of non-convergent cation order, have been characterised by means of X-ray single-crystal diffraction and IR spectroscopy. Long-range order parameters describing the non-convergent order of Mg/Fe among the different octahedral sites have been calculated from the site occupancies of the investigated samples. Values of the O6-O5-O6 angles and of the 〈M4-O〉 mean bond distances depend on the C2/m → P21/m phase transition for a given degree of order. In the IR spectra, only two phonon lines dominated by the bending of the tetrahedral chains are sensitive to the displacive phase transition and to the different degree of cation order; all the other wavenumber shifts are correlated with compositional changes only. The local strains arising from the cation substitution, ordering and phase transition have been quantified by means of the autocorrelation function. Very small local heterogeneities are associated with the Mg/Fe substitution and disordering in samples at intermediate composition. The displacive phase transition seems to occur in order to reduce local distortions and the P21/m samples are as homogeneous as orthorhombic anthophyllites. The orthorhombic structure, however, appears less flexible than the monoclinic in accommodating cations larger than Mg at the octahedral sites. Received: 9 February 2000 / Accepted: 30 September 2000  相似文献   

9.
The prograde, high pressure, transition from antigorite serpentinite to enstatite-olivine rock occurs along a tectonically undisturbed profile at Cerro del Almirez, SE Spain. The reactant assemblage is antigorite + olivine with tremolite rimming precursor diopside. The product assemblage of tremolite + chlorite + enstatite + olivine has a spinifex-like texture with arborescent or radiating olivine elongated parallel to [001] and with radially grown enstatite. Product enstatite is very poor in Al2O3. Due to numerous oriented submicroscopic inclusions of chromian magnetite, product olivine has a brownish pleochroism and a bulk chromium content similar to precursor antigorite. Titanian clinohumite with a fluorine content of 0.45–0.50 wt% persisted beyond the breakdown of antigorite. The partitioning of iron and magnesium amongst the silicate phases is almost identical to that at lower pressures. Average Kd values Mn/Mg and Ni/Mg are 0.17 and 0.70 for antigorite-olivine pairs and 1.83 and 0.22 for orthopyroxene-olivine pairs, respectively. These data are useful in discriminating generations of olivine grown on each other. From the field data a phase diagram topology for a portion of the system CaO-MgO-SiO2-H2O is derived. This topology forms the basis for extrapolations into inaccessible P-T regions. Received: 6 February 1998 / Accepted: 24 March 1998  相似文献   

10.
The electrical conduction in synthetic, dry polycrystalline, iron-bearing olivine (Fo90) was investigated as a first-order approach to the electrical conductivity in the upper mantle. This fundamental study is of great importance to better understand the charge-transport mechanisms seen in olivine. Conduction processes in synthetic samples are not influenced by a complex geological history in contrast to conductivity in natural olivine. The experiments show that the apparent activation energy for conductivity for Fo90 is 230 kJ mol−1. In currently accepted defect modeling, natural and synthetic olivine requires a mechanism involving small polaron formation (Fe· Mg and magnesium vacancies (V Mg) as the dominant diffusing species to explain a fO21/6 relation to electrical conduction. Here, Fo90 shows no contribution of small polarons to conductivity at temperatures between 1,000 and 1,200°C and almost no dependence on fO2. Instead, under reducing conditions magnesium vacancies (and electrons) appear to be the major charge carriers.  相似文献   

11.
Diffusion couples made from homogeneous gem quality natural pyrope and almandine garnets were annealed within graphite capsules under anhydrous conditions at 22–40 kbar, 1057–1400 °C in a piston-cylinder apparatus. The concentration profiles that developed in each couple were modeled to retrieve the self diffusion coefficients [D(I)] of the divalent cations Fe, Mg, Mn and Ca. Because of their usually low concentrations and lack of sufficient compositional change across the interface of the diffusion couples, only a few reliable data can be obtained for D(Ca) and D(Mn) from these experiments. However, nine sets of D(Fe) and D(Mg) data were retrieved in the above P-T range, and cast in the form of Arrhenian relation, D=D 0exp{−[Q(1 bar)+PΔV +]/RT}. The values of the activation energy (Q) and activation volume (ΔV +) depend on whether f O2 is constrained by graphite in the system C-O or held constant. For the first case, we have for Fe:Q(1 bar)=65,532±10,111 cal/mol, D 0=3.50 (±2.30)×10−5 cm2/s, ΔV +=5.6(±2.9) cm3/mol, and for Mg:Q(1 bar)=60,760±8,257 cal/mol, D 0=4.66 (±2.48)×10−5 cm2/s, ΔV +=5.3(±3.0) cm3/mol. Here the ΔV + values have been taken from Chakraborty and Ganguly (1992). For the condition of constant f O2, the Q values are ∼9 kcal lower and ΔV + values are ∼4.9 cm3/mol larger than the above values. Lower temperature extrapolation of the Arrhenian relation for D(Mg) is in good agreement with the Mg tracer diffusion data (D * Mg) of Chakraborty and Rubie (1996) and Cygan and Lasaga (1985) at 1 bar, 750–900 °C, when all data are normalized to the same pressure and to f O2 defined by graphite in the system C-O. The D * Mg data of Schwandt et al. (1995), on the other hand, are lower by more than an order of magnitude than the low temperature extrapolation of the present data, when all data are normalized to the same pressure and to f O2 defined by the graphite buffer. Comparison of the D(Fe), D(Mg) and D(Mn) data in the pyrope-almandine diffusion couple with those in the spessartine-almandine diffusion couple of Chakraborty and Ganguly (1992) shows that the self diffusion of Fe and Mn are significantly enhanced with the increase in Mn/Mg ratio; the enhancement effect on D(Mg) is, however, relatively small. Proper application of the self diffusion data to calculate interdiffusion coefficient or D matrix elements for the purpose of modeling of diffusion processes in natural garnets must take into account these compositional effects on D(I) along with the effects of thermodynamic nonideality, f O2, and pressure. Received: 8 May 1997 / Accepted: 2 October 1997  相似文献   

12.
Summary The stability of members of the lazulite-scorzalite solid-solution series, (Mg,Fe)Al2 (OH)2(PO4)2, was investigated as a function of T (505 to 675 °C), P (0.1 to 0.3 GPa) and Fe/Mg ratio in hydrothermal synthesis experiments. The oxygen fugacity was controlled by means of the Ni/NiO buffer. It was found that starting from end-member lazulite the stability of the solid-solution members strongly decreases with increasing content of scorzalite component. At 0.2 GPa pure lazulite decomposes at about 660 °C whereas at the same pressure a solid-solution with 80% of lazulite component is only stable up to 590 °C under the oxygen fugacity of the Ni/NiO buffer. The members of the lazulite-scorzalite solid-solution series with limiting composition coexist with an Fe-richer member of the (Mg,Fe)Al(PO4)O series and berlinite. The mixing behaviour of both the lazulite-scorzalite and the (Mg,Fe)Al(PO4)O solid-solution series disregarding small amounts of Fe3+ is interpreted in terms of a model on the basis of a simple mixture for the lazulite-scorzalite system and of an ideal mixture for the (Mg,Fe)Al(PO4)O series. With this model the interaction parameter which expresses the non-ideality of the lazulite-scorzalite solid-solution series amounts to . Zusammenfassung P-T Stabilit?t von Lazulith-Scorzalith Mischkristallen Die Stabilit?t der Glieder der Lazulith-Scorzalith Mischkristallreihe, (Mg, Fe)Al2(OH)2(PO4)2 wurde als Funktion der Temperatur (505 bis 675 °C), des Druckes (0.1 bis 0.3 GPa) und des Fe/Mg-Verh?ltnisses in hydrothermalen Syntheseversuchen untersucht. Die Sauerstoffugazit?t wurde mittels eines Ni/NiO-Puffer kontrolliert. Es konnte festgestellt werden, da? ausgehend vom Lazulith-Endglied die Stabilit?t der Mischkristalle mit zunehmendem Scorzalith-Gehalt stark abnimmt. Reiner Lazulith, MgAl2(OH)2(PO4)2 zerf?llt unter 0.2 GPa bei 660 °C, w?hrend ein Mischkristall mit 80 mol% Gehalt an Lazulith-Komponente nur bis 590 °C unter der Sauerstoffugazit?t des Ni/NiO-Puffers stabil ist. Hierbei koexistieren die Lazulith-Scorzalith Mischkristalle mit Grenzzusammensetzung mit eisenreicheren Mischphasen des Systems (Mg,Fe)Al(PO4)2O und Berlinit. Das Mischungsverhalten sowohl der Lazulith-Scorzalith- als auch der (Mg,Fe)Al(PO4)2O-Reihe wurde mit Hilfe eines quantitativen Modelles auf der Basis einer symmetrischen Mischung für Lazulith-Scorzalith und einer idealen Mischung für das System (Mg,Fe)Al(PO4)2O interpretiert. Mit Hilfe dieses Modelles wurde der Wechelwirkungsparameter , der die Nichtidealit?t der Lazulith-Scorzalith Mischreihe ausdrückt zu bestimmt. Received August 26, 1998; revised version accepted July 30, 1999  相似文献   

13.
Summary Garnet occurs as a significant mineral constituent of felsic garnet-biotite granite in the southern edge of the Třebíč pluton. Two textural groups of garnet were recognized on the basis of their shape and relationship to biotite. Group I garnets are 1.5–2.5 mm, euhedral grains which have no reaction relationship with biotite. They are zoned having high XMn at the rims and are considered as magmatic. Group II garnets form grain aggregates up to 2.5 cm in size, with anhedral shape of individual grains. The individual garnet II grains are usually rimmed by biotite and have no compositional zoning. The core of group I garnets and group II garnets contains 67–80 mol% of almandine, 5–19 mol% of pyrope, 7–17 mol% of spessartine and 2–4 mol% of grossular. Biotite occurs in two generations; both are magnesian siderophyllites with Fe/(Fe + Mg) = 0.50–0.69. The matrix biotite in granites (biotite I) has high Ti content (0.09–0.31 apfu) and Fe/(Fe + Mg) ratio between 0.50 and 0.59. Biotite II forms reaction rims around garnet, is poor in Ti (0.00–0.06 apfu) and has a Fe/(Fe + Mg) ratio between 0.61 and 0.69. The textural relationship between biotite and garnet indicates that garnet reacted with granitic melt to form Ti-poor biotite and a new granitic melt, depleted in Ti and Mg and enriched in Fe and Al. In contrast to the host durbachites (hornblende-biotite melagranites), which originated by mixing of crustal melts and upper mantle melts, the origin of garnet-bearing granites is related to partial melting of the aluminium-rich metamorphic series of the Moldanubian Zone.  相似文献   

14.
 Fe–K edge XAFS spectra (pre-edge, XANES and EXAFS) were collected for eight grandidierites from Madagascar and Zimbabwe, as well as for Fe(II) and Fe(III) model compounds (staurolite, siderite, enstatite, berlinite, yoderite, acmite, and andradite). The pre-edge spectra for these samples are consistent with dominantly 5-coordinated ferrous iron. The analysis of the XANES and EXAFS spectra confirms that Fe(II) substitutes for Mg(II) in grandidierite, with a slight expansion of the local structure around Mg by ∼2%. In addition, ferric iron was also detected in some samples [5–10 mol% of the total Fe or 500–1100 ppm Fe(III)]. Based on theoretical calculations of the EXAFS region, Fe(III) appears to be located in the 5-coordinated sites of Mg(II) or in the most distorted 6-coordinated sites of Al (depending on the sample studied). Special attention is therefore required when using grandidierite as a model for ferrous iron in C3v geometry, because of the possible presence of an extra contribution related to Fe(III). This additional contribution enhances significantly the Fe–K pre-edge integrated area [+40% for 1000 ppm Fe(III)]. Therefore, only a few grandidierite samples can be used as a robust structural model for the study of the Fe(II) coordination in glasses and melts. Received: 26 June 2000 / Accepted: 19 February 2001  相似文献   

15.
 The partitioning of Mg and Fe between magnesiowüstite and ringwoodite solid solutions has been measured between 15 and 23 GPa and 1200–1600 ∘C using both Fe and Re capsule materials to vary the oxidation conditions. The partitioning results show a clear dependence on the capsule material used due to the variation in Fe3+ concentrations as a consequence of the different oxidation environments. Using results from experiments performed in Fe capsules, where metallic Fe was also added to the starting materials, the difference in the interaction parameters for the two solid solutions (W FeMg mw−W FeMg ring) is calculated to be 8.5±1 kJ mol−1. Similar experiments performed in Re metal capsules result in a value for W FeMg mw−W FeMg ring that is apparently 4 kJ higher, if all Fe is assumed to be FeO. Electron energy-loss near-edge structure (ELNES) spectroscopic analyses, however, show Fe3+ concentrations to be approximately three times higher in magnesiowüstite produced in Re capsules than in Fe capsules and that Fe3+ partitions preferentially into magnesiowüstite, with K D Fe3+ ring/mw estimated between 0.1 and 0.6. Using an existing activity composition model for magnesiowüstite, a least–squares fit to the partitioning data collected in Fe capsules results in a value for the ringwoodite interaction parameter (W FeMg ring) of 3.5±1 kJ mol−1. The equivalent regular interaction parameter for magnesiowüstite (W FeMg mw) is 12.1±1.8 kJ mol. These determinations take into account the Fe3+ concentrations that occur in both phases in the presence of metallic Fe. The free energy change in J mol−1 for the Fe exchange reaction can be described, over the range of experimental conditions, by 912 + 4.15 (T−298)+18.9P with T in K, P in kbar. The estimated volume change for this reaction is smaller than that predicted using current compilations of equation of state data and is much closer to the volume change at ambient conditions. These results are therefore a useful test of high pressure and temperature equation of state data. Using thermodynamic data consistent with this study the reaction of ringwoodite to form magnesiowüstite and stishovite is calculated from the data collected using Fe capsules. Comparison of these results with previous studies shows that the presence of Fe3+ in phases produced in multianvil experiments using Re capsules can have a marked effect on apparent phase relations and determined thermodynamic properties. Received: 13 September 2000 / Accepted: 25 March 2001  相似文献   

16.
Experiments have been conducted in a peralkaline Ti-KNCMASH system representative of MARID-type bulk compositions to delimit the stability field of K-richterite in a Ti-rich hydrous mantle assemblage, to assess the compositional variation of amphibole and coexisting phases as a function of P and T, and to characterise the composition of partial melts derived from the hydrous assemblage. K-richterite is stable in experiments from 0.5 to 8.0 GPa coexisting with phlogopite, clinopyroxene and a Ti-phase (titanite, rutile or rutile + perovskite). At 8.0 GPa, garnet appears as an additional phase. The upper T stability limit of K-richterite is 1200–1250 °C at 4.0 GPa and 1300–1400 °C at 8.0 GPa. In the presence of phlogopite, K-richterite shows a systematic increase in K with increasing P to 1.03 pfu (per formula unit) at 8.0 GPa/1100 °C. In the absence of phlogopite, K-richterite attains a maximum of 1.14 K pfu at 8.0 GPa/1200 °C. Titanium in both amphibole and mica decreases continuously towards high P with a nearly constant partitioning while Ti in clinopyroxene remains more or less constant. In all experiments below 6.0 GPa ΣSi + Al in K-richterite is less than 8.0 when normalised to 23 oxygens+stoichiometric OH. Rutiles in the Ti-KNCMASH system are characterised by minor Al and Mg contents that show a systematic variation in concentration with P(T) and the coexisting assemblage. Partial melts produced in the Ti-KNCMASH system are extremely peralkaline [(K2O+Na2O)/Al2O3 = 1.7–3.7], Si-poor (40–45 wt% SiO2), and Ti-rich (5.6–9.2 wt% TiO2) and are very similar to certain Ti-rich lamproite glasses. At 4.0 GPa, the solidus is thought to coincide with the K-richterite-out reaction, the first melt is saturated in a phlogopite-rutile-lherzolite assemblage. Both phlogopite and rutile disappear ca. 150 °C above the solidus. At 8.0 GPa, the solidus must be located at T≤1400 °C. At this temperature, a melt is in equilibrium with a garnet- rutile-lherzolite assemblage. As opposed to 4.0 GPa, phlogopite does not buffer the melt composition at 8.0 GPa. The experimental results suggest that partial melting of MARID-type assemblages at pressures ≥4.0 GPa can generate Si-poor and partly ultrapotassic melts similar in composition to that of olivine lamproites. Received: 23 December 1996 / Accepted: 20 March 1997  相似文献   

17.
 Interactions between several silicate and metallic phases are studied by applying a self consistent thermodynamic approach and using recent thermodynamic data. We compute proportions and compositions of oxidized silicates and of reduced metallic phase in equilibrium at various temperatures and oxygen fugacities. The empirically observed activity-composition relationships for ternary metallic alloys are used and their applications to a general thermodynamic expression for a non-regular ternary system is explicitly discussed. We show that the stability limits of olivines and pyroxenes with respect to precipitation of metallic phases under reducing conditions are directly related to the presence of nickel impurities. We precisely evaluate the modifications of the stability limits as a function of nickel content. For typical mantle olivines [Fe/(Fe+Mg) = 0.1] the stability limits are given for values of x Ni= Ni/(Ni+Fe+Mg) ranging from 10 ppm to 1% by: ln f O2=−39.83+ 7.86 ln x Ni, ln f O2=−14.68+6.21 ln x Ni, at 900 K and 1600 K, respectively. Received: 17 November 1999 / Accepted: 14 May 2000  相似文献   

18.
The in situ electrical conductivity of hydrous garnet samples (Py20Alm76Grs4–Py73Alm14Grs13) was determined at pressures of 1.0–4.0 GPa and temperatures of 873–1273 K in the YJ-3000t apparatus using a Solartron-1260 impedance/gain-phase analyzer for various chemical compositions and oxygen fugacities. The oxygen fugacity was controlled by five solid-state oxygen buffers (Fe2O3 + Fe3O4, Ni + NiO, Fe + Fe3O4, Fe + FeO, and Mo + MoO2). Experimental results indicate that within a frequency range from 10−2 to 106 Hz, electrical conductivity is strongly dependent on signal frequency. Electrical conductivity shows an Arrhenius increase with temperature. At 2.0 GPa, the electrical conductivity of anhydrous garnet single crystals with various chemical compositions (Py20Alm76Grs4, Py30Alm67Grs3, Py56Alm43Grs1, and Py73Alm14Grs13) decreases with increasing pyrope component (Py). With increasing oxygen fugacity, the electrical conductivity of dry Py73Alm14Grs13 garnet single crystal shows an increase, whereas that of a hydrous sample with 465 ppm water shows a decrease, both following a power law (exponents of 0.061 and −0.071, respectively). With increasing pressure, the electrical conductivity of this hydrous garnet increases, along with the pre-exponential factors, and the activation energy and activation volume of hydrous samples are 0.7731 ± 0.0041 eV and −1.4 ± 0.15 cm3/mol, respectively. The results show that small hopping polarons ( \textFe\textMg · ) \left( {{\text{Fe}}_{\text{Mg}}^{ \cdot } } \right) and protons ( \textH · {\text{H}}^{ \cdot } ) are the dominant conduction mechanisms for dry and wet garnet single crystals, respectively. Based on these results and the effective medium theory, we established the electrical conductivity of an eclogite model with different mineral contents at high temperatures and high pressures, thereby providing constraints on the inversion of field magnetotelluric sounding results in future studies.  相似文献   

19.
 Using a combination of dielectric spectroscopy and atomistic computer simulation techniques, the dynamical behaviour of the loosely bound (Na+ and K+) channel ions in nepheline has been investigated. The low-frequency dielectric properties of a natural Bancroft nepheline have been studied from room temperature to 1100 K. At each temperature, the dielectric constant, conductivity and dielectric loss were determined over a range of frequencies from 100 Hz to 10 MHz. At high temperatures a distinct Debye-type relaxation in the dielectric loss spectrum was observed; the activation energy for this process was determined to be 1.38 ± 0.02 eV. Atomistic simulation techniques were used to elucidate the mechanism and energetics of cation migration. A mechanism involving the hopping of Na+ ions between oval sites and partially occupied hexagonal (K+) sites, via a bottleneck consisting of a distorted sixfold ring of (Al,Si)O4 tetrahedra, was found to give a calculated energy barrier in very good agreement with the experimentally determined activation energy. These results confirm the nature of the process responsible for the observed dielectric behaviour. Overall, this study demonstrates the intrinsic, microscopic control of cation diffusion processes in rock-forming minerals. Identifying specific energy barriers and preferred diffusion pathways is fundamental to the prediction of diffusion energetics. Received: 8 May 2000 / Accepted: 21 July 2000  相似文献   

20.
Summary ?The Yunlong tin deposit is located in the northern part of the Lancangjiang metamorphic zone of the Sanjiang Tethys orogen series in western Yunan province of China. It consists of vein-type cassiterite ores, which are mainly hosted in migmatites of Caledonian age. Abundant tourmaline is associated with the ores, quartz–tourmaline veins and barren migmatized gneiss and migmatites. A detailed electron microprobe study has been carried out to document the chemical compositions of tourmaline from this deposit. The results exhibit a systematic compositional change that might be used as tracer for ore genesis and in prospecting for tin mineralization. Tourmalines from the ore bodies are dravite with Fe/(Fe + Mg) ratios of 0.09 ∼ 0.31 and Ca/(Ca + Na) ratios of 0.03 ∼ 0.40. These tourmalines are also rich in chromium (up to 0.74 wt% Cr2O3) and tin (up to 0.42 wt% Sn). In contrast, tourmalines from the barren migmatites are mostly schorl with Fe/(Fe + Mg) ratios of 0.38 ∼ 0.94 and Ca/(Ca + Na) ratios of 0.00 ∼ 0.14. Tourmalines from quartz–tourmaline veins that occur between ore bodies and the migmatites show intermediate compositions, i.e., Fe/(Fe + Mg) = 0.09 ∼ 0.59, Ca/(Ca + Na) = 0.01 ∼ 0.22. It is suggested that the Mg-rich nature of the tourmaline can be used as an exploration tool in this region to target tin mineralization, because the tourmalines show increasing Mg contents and are more dravitic when approaching the ore bodies. It is likely that the formation of the Yunlong tin deposit was related to migmatitic-hydrothermal processes. The high Mg and Cr contents in tourmalines from the ore bodies were probably derived from the local meta-sedimentary and meta-volcanic rocks of the Precambian Chongshan Group rather than from the granites in the region. Received December 28, 2000; revised version accepted January 25, 2002  相似文献   

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