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1.
We have determined mineral-melt partition coefficients (D values) for 20 trace elements in garnet-pyroxenite run products, generated in 3 to 7 GPa, 1,425–1,750°C experiments on a high-Fe mantle melt (97SB68) from the Paraná-Etendeka continental-flood-basalt (CFB) province. D values for both garnet (∼Py63Al25Gr12) and clinopyroxene (∼Ca0.2Mg0.6Fe0.2Si2O6) show a large variation with temperature but are less dependent on pressure. At 3 GPa, D cpx/liq values for pyroxenes in garnet-pyroxenite run products are generally lower than those reported from Ca-rich pyroxenes generated in melting experiments on eclogites and basalts (∼Ca0.3–0.5Mg0.3–0.6Fe0.07–0.2Si2O6) but higher than those for Ca-poor pyroxenes from peridotites (∼Ca0.2Mg0.7Fe0.1Si2O6). D grt/liq values for light and heavy rare-earth elements are ≤0.07 and >0.8, respectively, and are similar to those for peridotitic garnets that have comparable grossular but higher pyrope contents (Py70–88All7–20Gr8–14). 97SB68 D LREEgrt/liq values are higher and D HREEgrt/liq values lower than those for eclogitic garnets which generally have higher grossular contents but lower pyrope contents (Py20–70Al10–50Gr10–55). D values agree with those predicted by lattice strain modelling and suggest that equilibrium was closely approached for all of our experimental runs. Correlations of D values with lattice-strain parameters and major-element contents suggest that the wollastonite component and pyrope:grossular ratio exert major controls on 97SB68 clinopyroxene and garnet partitioning, respectively. These are controlled by the prevailing pressure and temperature conditions for a given bulk-composition. The composition of co-existing melt was found to have a relatively minor effect on 97SB68 D values. The variations in D values displayed by different mantle lithologies are subtle and our study confirms previous investigations which have suggested that the modal proportions of garnet and clinopyroxene are by far the most influential factor in determining incompatible trace-element concentrations in mantle melts. The trace-element partition coefficients we have determined may be used to place high-pressure constraints on garnet-pyroxenite melting models.  相似文献   

2.
 Models for estimating the pressure and temperature of igneous rocks from co-existing clino-pyroxene and liquid compositions are calibrated from existing data and from new data obtained from experiments performed on several mafic bulk compositions (from 8–30 kbar and 1100–1475° C). The resulting geothermobarometers involve thermodynamic expressions that relate temperature and pressure to equilibrium constants. Specifically, the jadeite (Jd; NaAlSi2O6)–diopside/hedenbergite (DiHd; Ca(Mg, Fe) Si2O6) exchange equilibrium between clinopyroxene and liquid is temperature sensitive. When compositional corrections are made to the calibrated equilibrium constant the resulting geothermometer is (i) 104 T=6.73−0.26* ln [Jdpx*Caliq*FmliqDiHdpx*Naliq*Alliq] −0.86* ln [MgliqMgliq+Feliq]+0.52*ln [Caliq] an expression which estimates temperature to ±27 K. Compared to (i), the equilibrium constant for jadeite formation is more sensitive to pressure resulting in a thermobarometer (ii) P=−54.3+299* T104+36.4* T104 ln [Jdpx[Siliq]2*Naliq*Alliq] +367*[Naliq*Alliq] which estimates pressure to ± 1.4 kbar. Pressure is in kbar, T is in Kelvin. Quantities such as Naliq represent the cation fraction of the given oxide (NaO0.5) in the liquid and Fm=MgO+FeO. The mole fractions of Jd and diopside+hedenbergite (DiHd) components are calculated from a normative scheme which assigns the lesser of Na or octahedral Al to form Jd; any excess AlVI forms Calcium Tschermak’s component (CaTs; CaAlAlSiO6); Ca remaining after forming CaTs and CaTiAl2O6 is taken as DiHd. Experimental data not included in the regressions were used to test models (i) and (ii). Error on predictions of T using model (i) is ±40 K. A pressure-dependent form of (i) reduces this error to ±30 K. Using model (ii) to predict pressures, the error on mean values of 10 isobaric data sets (0–25 kbar, 118 data) is ±0.3 kbar. Calculating thermodynamic properties from regression coefficients in (ii) gives VJd f of 23.4 ±1.3 cm3/mol, close to the value anticipated from bar molar volume data (23.5 cm3/mol). Applied to clinopyroxene phenocrysts from Mauna Kea, Hawaii lavas, the expressions estimate equilibration depths as great as 40 km. This result indicates that transport was sufficiently rapid that at least some phenocrysts had insufficient time to re-equilibrate at lower pressures. Received: 16 May 1994/Accepted: 15 June 1995  相似文献   

3.
Summary ?Hydrothermal experiments to synthesize pumpellyite group minerals of the pumpellyite–okhotskite series and to investigate their stability have been carried out at 200, 300 and 400 MPa P fluid and 250–500 °C by using cold-seal pressure vessels and solid buffers of MnO2–Mn2O3, Cu2O–CuO and Cu2O–Cu buffer assemblages. Okhotskite and pumpellyite rich in the okhotskite component crystallized from an oxide mixture starting material of Ca4MgMn3+ 3Al2Si6O24.5-oxide+excess H2O at P fluid of 200, 300 and 400 MPa and temperatures of 300 and 400 °C. However, a single phase of okhotskite was not produced, and associated piemontite, hausmannite, wollastonite, clinopyroxene, corundum, braunite–neltnerite solid solution and alleghanyite also formed. Mn-pumpellyite of the okhotskite–pumpellyite join occurs as aggregates of needle crystals, rounded grains or flaky crystals. Chemical compositions are variable and range from pumpellyite-(Mn2+) to okhotskite: 31–36 SiO2, 13–21 Al2O3, 12–25 total Mn2O3, 0.6–4 MgO and 20–24 wt.% CaO. Reconnaissance experiments using a starting material of synthetic Ca2Mn3+Al2Si3O12(OH)-piemontite at 300 MPa and temperatures of 250, 300, 400 and 500 °C indicate that Mn-rich pumpellyite can crystallize from piemontite at lower temperatures than the stability field of piemontite. The Mn-rich pumpellyite was accompanied by garnet, wollastonite and alleghanyite. The chemical compositions of the Mn-pumpellyites are 32–36 SiO2, 18–27 Al2O3, 8–18 total Mn2O3 and 20–23 wt.% CaO. This study shows that the stability fields of piemontite, piemontite+Mn-pumpellyite, and Mn-pumpellyite range in this order with decreasing temperature under high fO2 conditions. The maximum stability temperature of Mn-rich pumpellyite lies between 400 and 500 °C at 200–400 MPa in high fO2 conditions. Received March 3, 2000; revised version accepted December 28, 2001  相似文献   

4.
The partitioning of chromium and aluminium between coexisting orthopyroxene and spinel in equilibrium with forsterite in the system MgO–Al2O3–SiO2–Cr2O3 (MAS–Cr) has been experimentally determined as a function of temperature, pressure and Cr/(Cr + Al) ratio. Experiments were conducted at temperatures between 1300 and 1500 °C and at pressures from 5 to 54 kbar. Previous experimental results on the (Al, Cr)2O3 and Mg(Al, Cr)2O4 solid solutions have been combined with the present results plus relevant data from the CMAS system to derive a thermodynamic model for Al–Cr-bearing orthopyroxenes, spinels and corundum–eskolaite solid solutions. The orthopyroxene solid solution can be modelled within the accuracy of all experimental constraints as a ternary solid solution involving the components Mg2Si2O6 ( E), MgAl2SiO6 (M) and MgCr2SiO6 (C), in which the activities are related to composition through the equations: The mole fractions are defined as where n Al and n Cr are the number of Al and Cr cations per orthopyroxene formula unit of six oxygens. These expressions reduce to one-site mixing for Mg2Si2O6–MgAl2SiO6 orthopyroxenes in the Cr-free system, but are equivalent to two-site mixing for the exchange of Al and Cr between orthopyroxene and spinel, as required by the experimental data. We find W opx EM =W opx EC  = 20 kJ mol−1 and W opx MC =0. Received: 9 August 1999 / Accepted: 18 February 2000  相似文献   

5.
 The hydrothermal reaction between grossular and 1 molar manganese chloride solution was studied at 2 kbar and 600 °C at various bulk Ca/(Ca+Mn) compositions: Ca3Al2Si3O12+3Mn2+(aq) ⇔ Mn3Al2Si3O12+3Ca2+(aq) The reaction products are garnets of the spessartine-grossular solid-solution series which discontinuously armour the dissolving grossular grains. The first garnet to crystallize is spessartine rich (X gt Mn≥0.95), reflecting the high Mn content of the solution, but as the reaction proceeds more calcium-rich garnets progressively overgrow the initial products. The armouring product layer is detached from the dissolving grossular, which allows the progressive overgrowth to occur on both its external and internal surfaces and results in the development of a two directional Ca/(Ca+Mn) zoning pattern in the product grains. The compositional changes in the run products are consistent with attainment of heterogeneous equilibrium between the external rims of the spessartine-grossular garnets and the bulk solutions in runs of duration ≥24 hours. Plots of ln KD versus X gt Ca maxima show linear variations that are not consistent with the ideal mixing that has been proposed for spessartine-grossular garnets at temperatures of 900 to 1200 °C. The data rather fit a regular solution model with the parameters ΔG° (600 °C, 2 kbar)=−8.0±0.8 kJ/mol and w gt CaMn=2.6±2.0 kJ/mol. Existing solubility measurements and thermodynamic data from other Ca and Mn silicates support the calculated data. Grossular activities calculated using the w gt CaMn parameter indicate that even in manganese-rich metapelites pressure estimates calculated using the garnet-plagioclase-Al2SiO5-quartz barometer will not be increased by more than 0.2 kbar. Received: 18 January 1995/Accepted: 4 June 1996  相似文献   

6.
Summary Previous petrogenetic grids for very low grade metamorphism do not apply to garnet-bearing prehnite-pumpellyite facies rocks. Garnet-bearing metabasites with Act – absent of prehnite-pumpellyite facies have been found in the Darbut-Sartuohai ophiolite, Xinjiang, China. Results of thermodynamic calculation in the CMASH system using the internally consistent mineral thermodynamic database of Berman (1988) show that equilibria reactions among the end-member species in mineral paragenesis of Pmp-Prh-Grs-Zo-Chl-Qtz intersect at a pressure of 4.75 kbar and temperature of 350 °C. The association of grossular-rich garnet and pumpellyite occurs at pressures and temperatures similar to the Pmp-Act facies. Based on the petrogenetic grid derived in this study, peak metamorphic conditions for metabasites from the Darbut-Sartuohai ophiolite are 310 to 330 °C, and 3.0 to 4.0 kbar, which are affected by the substitution of Fe3+Al−1. This study shows that grossular-rich garnet can appear in metabasites of the prehnite-pumpellyite facies, but it depends on the substitution between Fe3+ and Al in the CMASH+Fe3+ system.
Zusammenfassung Phasenbeziehungen in Grandit-führenden Metabasiten (Prehnit-Pumpelleyit Fazies) vom Darbut-Sartuohai Ophiolit, westliches Junggar (Xinjiang, China) Bereits existierende petrogenetische Netze für niedrig-gradige Metamorphose k?nnen nicht auf Grandit-führende Metabasite angewendet werden. Solche Metabasite der Prehnit-Pumpellyit Fazies wurden in Darbut-Sartuohai Ophiolit gefunden. Thermodynamische Berechnungen mit dem Datensatz von Berman (1988) zeigen, dass die Endglieder der Mineralparagenese Pmp-Prh-Grs-Zo-Chl-Qtz einen invarianten Punkt bei 4.75 kbar und 350 °C bilden. Daher kommen Grossular-reicher Grandit und Pumpellyit unter ?hnlichen PT-Bedingungen der Pmp-Act Fazies vor. Anhand des petrogenetischen Netzes, das in der hier vorliegenden Arbeit berechet worden ist, konnten die Peak-metamorphen Bedingungen für den Darbut-Sartuohai Ophiolit mit 310–330 °C und 3.0–4.0 kbar ermittelt werden. Diese Bedingungen sind vom Fe3+Al−1 Austausch abh?ngig. Diese Arbeit zeigt, dass Grossular-reiche Granate im CAMSH-System in der Prehnit-Pumpellyit Fazies selbst bei Anwesenheit von Chlorit stabil sind.

Received September 25, 1999; revised version accepted July 3, 2000  相似文献   

7.
 The structures of Ca2CoSi2O7, Ca2MgSi2O7, and Ca2(Mg0.55Fe0.45)Si2O7 have been determined in the temperature range between 297 and 773 K with arbitrary intervals. The structures of the incommensurate phase of the three compounds are characterized by the presence of the six-, seven-, and eight-coordinated Ca–O polyhedra and of the bundles along the c-axes consisting of four arrays of the six-coordinated Ca–O polyhedra and an array of T1O4 (T1: Co, Mg, or Mg–Fe) tetrahedra in the structures. The number of bundles in each material decreases at elevated temperatures. The incommensurate phase undergoes a phase transition into the normal phase at 493 K in Ca2CoSi2O7, at 360 K in Ca2MgSi2O7, and at 510 K in Ca2(Mg0.55Fe0.45)Si2O7. The features of the structures of the normal phase are almost the same as those found in the basic structures (the averaged structures of the incommensurate structures), and this fact implies that the characteristics of the structures, such as the six-coordinated Ca–O polyhedra or fragments of the bundles, should be partially preserved at higher temperatures both in the incommensurate structures and also in the structures of the normal phase. Analyses of anisotropic displacement parameters clarified that disorder of the modulation waves is developed in the structures at higher temperatures. The evolution of a disorder in the structures was ascertained by observation of the circular diffuse streaks in the vicinity of the transition temperature between the incommensurate and normal phases. Received: 3 July 2000 / Accepted: 26 October 2000  相似文献   

8.
 Amphiboles were synthesized from bulk compositions prepared along the join Ca1.8Mg5.2Si8O22(OH)2–Ca1.8Mg3Ga4Si6O22(OH)2 hydrothermally at 750–850 °C and 1.0–1.8 GPa, and along the join Ca2Mg5Si8O22F2–Ca2Mg3Ga4Si6O22F2, anhydrously at 1000 °C and 0.7 GPa to document how closely the tschermak-type substitution is obeyed in these analogues of aluminous amphiboles. Electron-microprobe analyses and Rietveld X-ray diffraction structure refinements were performed to determine cation site occupancies. The extent of Ga substitution was found to be limited in both joins, but with the fluorine series having about twice the Ga content (0.6 atoms per formula unit, apfu) of the hydroxyl-series amphiboles (0.3 apfu). The tschermak-type substitution was followed very closely in the hydroxyl series with essentially equal partitioning of Ga between tetrahedral and octahedral sites. The fluorine-series amphiboles deviated significantly from the tschermak-type substitution and, instead, appeared to follow a substitution that is close to a Ca-pargasite substitution of the type: [6]Ga3++2[4]Ga3++1/2[A] Ca2+ = [6]Mg2++2[4]Si4++1/2[A]□. Infrared spectroscopy revealed an inverse correlation between the intensity of the OH-stretching bands and the Ga content for the hydroxyl- and fluorine-series amphiboles. The direct correlation between the Ga and F content and inverse relationship between the Ga and OH content may be a general phenomenon present in other minerals and suggests, for example, that high F contents in titanite are controlled by the Al content of the host rock and that there may be similar direct Al–F correlations in tschermakitic amphiboles. Evidence for the possibility that Al (Ga) might substitute onto only a subset of the tetrahedral sites in tschermakitic amphiboles was sought but not observed in this study. Received: 5 March 2001 / Accepted: 31 July 2001  相似文献   

9.
The exchange equilibrium
was studied by reversal experiments as a function of temperature (650 ≤ T ≤ 1000 °C), pressure (10 ≤ P ≤ 20 kbar), and chemical composition. Experiments were performed in a piston-cylinder apparatus using starting mixtures consisting of 95% garnet and 5% ilmenite. At the lower temperatures, 3–5% PbO flux was added to the reactants. The PbO was reduced to metallic lead by the graphite of the capsules. The EMP analysis shows that ilmenite is essentially a solid solution of FeTiO3 and MnTiO3 with up to 4.5 mol% Fe2O3 (for Fe-rich compositions). Garnet is compositionally close to (Fe,Mn)3 Al2Si3O12 but apparently contains up to 1.0 wt% TiO2. As garnet was usually analyzed within 5–15 μm distance from ilmenite grains, the Ti measured in garnet appears to be largely an analytical artifact (due to secondary fluorescence). This was confirmed by analyzing profiles across a couple constructed from ilmenite and Ti-free garnet. The more than 100 exchange runs indicate that the distribution coefficient KD [=(X Mn gnt·X Fe ilm)/(X Fe gnt·X Mn ilm)] is essentially independent of P and decreases with T. With a few exceptions at Mn-rich compositions, the present results are consistent with previous studies on the Fe-Mn partitioning between garnet and ilmenite. Contrary to previous studies, however, the narrow experimental brackets obtained during the present calibration constrain that, at constant T, KD is larger for Mn-rich compositions than for Fe-rich ones. This compositional dependence of KD will complicate garnet-ilmenite geothermometry. Mutually consistent activity models for Fe-Mn garnet and ilmenite, based on a thermodynamic analysis of the present results and other phase equilibria studies in the system Fe-MnO-Al2O3-TiO2-SiO2-O2, will be presented in a following contribution (M. Engi and A. Feenstra, in preparation). Received: 12 September 1996 / Accepted: 11 December 1997  相似文献   

10.
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   

11.
Phase transformations in a natural sample of hedenbergite ((Ca0.93Fe0.61Mn0.34Mg0.08Na0.01Zn0.02Al0.003)Si2O6) have been studied by X-ray diffraction up to 40 GPa at ∼ 1200°C in a diamond anvil cell interfaced with a laser heating system. The starting hedenbergite phase decomposed into a garnet plus γ-spinel and stishovite at ∼ 14 GPa; then into garnet plus stishovite and wüstite at ∼ 18 GPa; and finally into perovskite plus stishovite and wüstite at pressures higher than ∼ 24 GPa. On decompression to 0.1 MPa, all the high pressure phases are retained except for the cubic perovskite, which reverts back into the ɛ-CaSiO3 phase, in accordance with previous reports. Energy-dispersive SEM analyses show that the garnet is present as a calcium-rich ABO 3-type phase. As no garnet phase has been previously observed either in pure CaSiO3 or in pure CaMgSi2O6, it appears that the observed calcium-rich garnet phase has been stabilized by the presence of other cations such as the Na+, Zn2+, Mn2+, Fe2+, Mn3+, Fe3+ and Al3+.  相似文献   

12.
Al-containing MgSiO3 perovskites of four different compositions were synthesized at 27 GPa and 1,873 K using a Kawai-type high-pressure apparatus: stoichiometric compositions of Mg0.975Si0.975Al0.05O3 and Mg0.95Si0.95Al0.10O3 considering only coupled substitution Mg2+ + Si4+ = 2Al3+, and nonstoichiometric compositions of Mg0.99Si0.96Al0.05O2.985 and Mg0.97Si0.93Al0.10O2.98 taking account of not only the coupled substitution but also oxygen vacancy substitution 2Si4+ = 2Al3+ + VO¨. Using the X-ray diffraction profiles, Rietveld analyses were performed, and the results were compared between the stoichiometric and nonstoichiometric perovskites. Lattice parameter–composition relations, in space group Pbnm, were obtained as follows. The a parameters of both of the stoichiometric and nonstoichiometric perovskites are almost constant in the X Al range of 0–0.05, where X Al is Al number on the basis of total cation of two (X Al = 2Al/(Mg + Si + Al)), and decrease with further increasing X Al. The b and c parameters of the stoichiometric perovskites increase linearly with increasing Al content. The change in the b parameter of the nonstoichiometric perovskites with Al content is the same as that of the stoichiometric perovskites within the uncertainties. The c parameter of the nonstoichiometric perovskites is slightly smaller than that of the stoichiometric perovskites at X Al of 0.10, though they are the same as each other at X Al of 0.05. The Si(Al)–O1 distance, Si(Al)–O1–Si(Al) angle and minimum Mg(Al)–O distance of the nonstoichiometric perovskites keep almost constant up to X Al of 0.05, and then the Si(Al)–O1 increases and both of the Si(Al)–O1–Si(Al) angle and minimum Mg(Al)–O decrease with further Al substitution. These results suggest that the oxygen vacancy substitution may be superior to the coupled substitution up to X Al of about 0.05 and that more Al could be substituted only by the coupled substitution at 27 GPa. The Si(Al)–O1 distance and one of two independent Si(Al)–O2 distances in Si(Al)O6 octahedra in the nonstoichiometric perovskites are always shorter than those in the stoichiometric perovskite at the same Al content. These results imply that oxygen defects may exist in the nonstoichiometric perovskites and distribute randomly.  相似文献   

13.
Summary. ?Ca-tourmaline has been synthesized hydrothermally in the presence of Ca(OH)2 and CaCl2-bearing solutions of different concentration at T = 300–700 °C at a constant fluid pressure of 200 MPa in the system CaO-MgO-Al2O3-SiO2-B2O3-H2O-HCl. Synthesis of tourmaline was possible at 400 °C, but only above 500 °C considerable amounts of tourmaline formed. Electron microprobe analysis and X-ray powder data indicate that the synthetic tourmalines are essentially solid solutions between oxy-uvite, CaMg3- Al6(Si6O18)(BO3)3(OH)3O, and oxy-Mg-foitite, □(MgAl2)Al6(Si6O18)(BO3)3(OH)3O. The amount of Ca ranges from 0.36 to 0.88 Ca pfu and increases with synthesis temperature as well as with bulk Ca-concentration in the starting mixture. No hydroxy-uvite, CaMg3(MgAl5)(Si6O18)(BO3)3(OH)3(OH), could be synthesized. All tourmalines have < 3 Mg and > 6 Al pfu. The Al/(Al + Mg)-ratio decreases from 0.80 to 0.70 with increasing Ca content. Al is coupled with Mg and Ca via the substitutions Al2□Mg−2Ca−1 and AlMg−1H−1. No single phase tourmaline could be synthesized. Anorthite ( + quartz in most runs) has been found coexisting with tourmaline. Other phases are chlorite, tremolite, enstatite or cordierite. Between solid and fluid, Ca is strongly fractionated into tourmaline ( + anorthite). The concentration ratio D = Ca(fluid)/Ca(tur) increases from 0.20 at 500 °C up to 0.31 at 700 °C. For the assemblage turmaline + anorthite + quartz + chlorite or tremolite or cordierite, the relationship between Ca content in tourmaline and in fluid with temperature can be described by the equation (whereby T = temperature in °C, Ca(tur) = amount of Ca on the X-site in tourmaline, Ca( fluid) = concentration of Ca2+ in the fluid in mol/l). The investigations may serve as a first guideline to evaluate the possibility to use tourmaline as an indicator for the fluid composition.
Zusammenfassung. ?Synthese von Ca-Turmelin im System CaO-MgO-Al 2 O 3 -SiO 2 -B 2 O 3 -H 2 O-HCl Im System CaO-MgO-Al2O3-SiO2-B2O3-H2O-HCl wurde Ca-Turmalin hydrothermal aus Ca(OH)2 and CaCl2-haltigen L?sungen bei T = 300–700 °C und einem konstanten Fluiddruck von 200 MPa synthetisiert. Die Synthese von Turmalin war m?glich ab 400 °C, aber nur oberhalb von 500 °C bildeten sich deutliche Mengen an Turmalin. Elektronenstrahl-Mikrosondenanalysen und R?ntgenpulveraufnahmen zeigen, da? Mischkristalle der Reihe Oxy-Uvit, CaMg3Al6(Si6O18)(BO3)3(OH)3O, und Oxy-Mg-Foitit, □(MgAl2)Al6(Si6O18)(BO3)3(OH)3O gebildet wurden. Der Anteil an Ca variiert zwischen 0.36 und 0.88 Ca pfu und nimmt mit zunehmender Synthesetemperatur und zunehmender Ca-Konzentration im System zu. Hydroxy-Uvit, CaMg3(MgAl5) (Si6O18)(BO3)3(OH)3(OH), konnte nicht synthetisiert werden. Alle Turmaline haben < 3 Mg und > 6 Al pfu. Dabei nimmt das Al/(Al + Mg)- Verh?ltnis mit zunehmendem Ca-Gehalt von 0.80 auf 0.70 ab. Al ist gekoppelt mit Mg und Ca über die Substitutionen Al2□Mg−2Ca−1 und AlMg−1H−1. Einphasiger Turmalin konnte nicht synthetisiert werden. Anorthit (+ Quarz in den meisten F?llen) koexistiert mit Turmalin. Andere Phasen sind Chlorit, Tremolit, Enstatit oder Cordierit. Ca zeigt eine deutliche Fraktionierung in den Festk?rpern Turmalin (+ Anorthit). Das Konzentrationsverh?ltnis D = Ca(fluid)/Ca(tur) nimmt von 0.20 bei 500 °C auf 0.31 bei 700 °C zu. Für die Paragenese Turmalin + Anorthit + Quarz mit Chlorit oder Tremolit oder Cordierit gilt folgende Beziehung zwischen Ca-Gehalt in Turmalin und Fluid und der Temperatur: (wobei T = Temperatur in °C, Ca(tur) = Anteil an Ca auf der X-Position in Turmalin, Ca(fluid) = Konzentration von Ca2+ im Fluid in mol/l). Die Untersuchungen dienen zur ersten Absch?tzung, ob Turmalin als Fluidindikator petrologisch nutzbar ist.

Received July 24, 1998;/revised version accepted October 21, 1999  相似文献   

14.
 We have performed atomistic computer simulations on trace element incorporation into the divalent dodecahedral X-sites of pyrope (Py — Mg3Al2Si3O12) – grossular (Gr — Ca3Al2Si3O12) solid solutions. An ionic model and the Mott–Littleton two-region approach to defect energies were used to calculate the energetics of substitution by a range of divalent trace-elements and of charge-balanced substitution by trivalent ions in the static limit. Results are compared with experimental high-temperature, high-pressure garnet-melt trace element partitioning data obtained for the same garnet solid solution to refine our understanding of the factors controlling element partitioning into solid solutions. Defect energies (U def,f), relaxation (lattice strain) energies (U rel), and solution energies (U sol) were derived using two different approaches. One approach assumes the presence of one type of hybrid X-site with properties intermediate between pure Mg and Ca sites, and the other assumes discrete Mg and Ca X-sites, and thus two distinct cation sublattices. The hybrid model is shown to be inadequate, since it averages out local distortions in the garnet structure. The discrete model results suggest trace elements are more soluble in Py50Gy50 than in either end-member compound. Physically this is due to small changes in size of the X-sites and the removal of unfavourable interactions between third nearest neighbours of the same size. Surprisingly, depending on the local order, large trace element cations may substitute for Mg2+ and small trace elements for Ca2+ in Py50Gr50. These solubilities provide an explanation for the anomalous trace-element partitioning behaviour along the pyrope–grossular join observed experimentally. Received: 27 January 2000 / Accepted: 14 February 2003  相似文献   

15.
 Melting relations on the enstatite−diopside (En, Mg2Si2O6−Di, CaMgSi2O6) join, including the compositions of crystalline phases and melts coexisting along the solidi, were experimentally determined in the pressure range 70–224 kbar with a split-sphere anvil apparatus (USSA-2000). Melting is peritectic in enstatite-rich compositions at 70–124 kbar (1840–2100° C) and eutectic at higher pressures, while the diopside-rich clinopyroxene melts azeotropically at 70–165 kbar and up to 300° C lower temperatures than the eutectic. Orthopyroxene is replaced with enstatite-rich clinopyroxene at 120 kbar and 2090°C. First garnet with 17 mol% Di forms on the solidus at 158 kbar and 2100° C. Two garnets coexist on the solidus at 165–183 kbar and 2100° C, garnet coexists with CaSiO3 perovskite at 183–224 kbar (2100–2230° C) and two coexisting perovskites are stable at higher pressures. The melting curve of diopside was determined at 80–170 kbar; the slope becomes negative at 140 kbar and 2155° C. At 170 kbar and 2100° C, diopside with 96% Di breaks down to garnet with 89% Di and CaSiO3 perovskite. The new data were used to calculate an improved temperature-pressure phase diagram for the CMAS system, which can be useful for estimating the mineralogy of the Earth's upper mantle. Received: 15 October 1994 / Accepted: 15 October 1995  相似文献   

16.
The polymorphic relations for Mg3(PO4)2 and Mg2PO4OH have been determined by reversed experiments in the temperature-pressure (T-P) range 500–1100 °C, 2–30 kbar. The phase transition between the low-pressure phase farringtonite and Mg3(PO4)2-II, the Mg analogue of sarcopside, is very pressure dependent and was tightly bracketed between 625 °C, 7 kbar and 850 °C, 9 kbar. The high-temperature, high-pressure polymorph, Mg3(PO4)2-III, is stable above 1050 °C at 10 kbar and above 900 °C at 30 kbar. The low-pressure stability of farringtonite is in keeping with its occurrence in meteorites. The presence of iron stabilizes the sarcopside-type phase towards lower P. From the five Mg2PO4OH polymorphs only althausite, holtedahlite, β-Mg2PO4OH (the hydroxyl analogue of wagnerite) and ɛ-Mg2PO4OH were encountered. Relatively speaking, holtedahlite is the low-temperature phase (<600 °C), ɛ-Mg2PO4OH the high-temperature, low-pressure phase and β-Mg2PO4OH the high-temperature, high-pressure phase, with an intervening stability field for althausite which extends from about 3 kbar at 500 °C to about 12 kbar at 800 °C. Althausite and holtedahlite are to be expected in F-free natural systems under most geological conditions; however, wagnerite is the most common Mg-phosphate mineral, implying that fluorine has a major effect in stabilizing the wagnerite structure. Coexisting althausite and holtedahlite from Modum, S. Norway, show that minor fluorine is strongly partitioned into althausite (KD F/OH≈ 4) and that holtedahlite may incorporate up to 4 wt% SiO2. Synthetic phosphoellenbergerite has a composition close to (Mg0.9□0.1)2Mg12P8O38H8.4. It is a high-pressure phase, which breaks down to Mg2PO4OH + Mg3(PO4)2 + H2O below 8.5 kbar at 650 °C, 22.5 kbar at 900 °C and 30 kbar at 975 °C. The stability field of the phosphate end-member of the ellenbergerite series extends therefore to much lower P and higher T than that of the silicate end-members (stable above 27 kbar and below ca. 725 °C). Thus the Si/P ratio of intermediate members of the series has a great barometric potential, especially in the Si-buffering assemblage with clinochlore + talc + kyanite + rutile + H2O. Application to zoned ellenbergerite crystals included in the Dora-Maira pyrope megablasts, western Alps, reveals that growth zoning is preserved at T as high as 700–725 °C. However, the record of attainment of the highest T and/or of decreasing P through P-rich rims (1 to 2 Si pfu) is only possible in the presence of an additional phosphate phase (OH-bearing or even OH-dominant wagnerite in these rocks), otherwise the trace amounts of P in the system remain sequestered in the core of Si-rich crystals (5 to 8 Si pfu) and can no longer react. Received: 7 April 1995 / Accepted: 12 November 1997  相似文献   

17.
 The crystal chemical response of basalt clinopyroxene to increasing pressure was investigated by means of crystal-structure simulation (a procedure that enables modeling of the structural parameters of a clinopyroxene of known chemistry without requiring direct X-ray diffraction analysis) using available experimental chemical data. Pressure proved the main physical variable governing clinopyroxene behavior in a magmatic environment. The general internal consistency of the simulation data permitted construction of an empirical geobarometer based on the relationship of cell volume (Vc) vs M1-site volume (VM1). The straightforward geobarometric formulation in the absence of direct X-ray analysis is: P(kbar)=698.443+4.985⋅AlT−26.826⋅Fe2+ M1−3.764⋅Fe3+ +53.989⋅AlM1+3.948⋅Ti+14.651⋅Cr −700.431⋅Ca−666.629⋅Na−682.848⋅MgM2−691.138⋅Fe2+ M2−688.384⋅Mn−6.267⋅(MgM2)2−4.144⋅(Fe2+ M2 where: (Fe2+ M1⋅MgM2)/(Fe2+ M2⋅MgM1)=e**(0.238⋅R3++0.289⋅CNM−2.315), CNM=Ca+Na+Mn, and R3+=AlM1+Fe3++Ti+Cr, with cations in atoms per formula unit. The geobarometer reproduces experimental pressures within ±2 kbar (=1σ; max. dev. ≤5 kbar; N=29) in the range 0–24 kbar and is applicable to near-liquidus C2/c clinopyroxenes crystallized from basaltic melts in the absence of garnet (excepting high-Al2O3 basalts). It is therefore suitable for many natural clinopyroxenes occurring as mega- or phenocrysts or forming well-preserved cumulate pyroxenites. If the above restrictions are not wholly satisfied, the Vc vs VM1 plot can also be used qualitatively to deduce the relative pressure conditions of clinopyroxenes forming from similar batches of magma. The structural simulation of experimental data also provided insight into the influence of minor chemical changes of the parental magma on the crystal chemistry of clinopyroxene at high pressure. Within the considered compositional space at given P-T, a CaO and a SiO2 in the melt have opposite effects on M2- and T-site cation populations. As a result, under similar physical conditions, clinopyroxenes from higher-CaO or more undersaturated basalts have higher VM2, VT and Vc and lower VM1. For basalts with normal contents of Al2O3 (<18 wt %), variations of major elements in the melt do not reduce the accuracy of the geobarometer. Received: 3 April 1994 / Accepted: 23 December 1995  相似文献   

18.
The incorporation and site preference of minor amounts (about 1 wt%) of Yb3+ in synthetic pyrope (Mg3Al2Si3O12) and grossular (Ca3Al2Si3O12) garnet were studied by X-ray Absorption Fine-Structure (XAFS) Spectroscopy. The measurements, performed in the temperature range 77–343 K at both Yb LI- and LIII-edges, demonstrate that Yb3+ enters the garnet structure and is located in the dodecahedral site in both samples. The coordination environment of Yb3+ in the two samples was compared to that of the X-site cation in end-member synthetic pyrope and grossular and in Yb3Al5O12 as determined by single-crystal X-ray diffraction. The local geometry around Yb3+ is different from that of Mg and Ca in the bulk of the garnet, and also from that of Yb3+ in Yb3Al5O12. Τhe XAFS results indicate that, (1) structural relaxation occurs around Yb3+ in the garnet structure; (2) the host garnet matrix exerts a major structural control on the incorporation of Yb3+, and (3) minor amounts of Yb3+ in garnet are located in structural sites and not in ill-defined defects. Received: 15 January 1998/ Revised, accepted: 21 July 1998  相似文献   

19.
Experiments ranging from 2 to 3 GPa and 800 to 1300 °C and at 0.15 GPa and 770 °C were performed to investigate the stability and mutual solubility of the K2ZrSi3O9 (wadeite) and K2TiSi3O9 cyclosilicates under upper mantle conditions. The K2ZrSi3O9–K2TiSi3O9 join exhibits complete miscibility in the P–T interval investigated. With increasing degree of melting the solid solution becomes progressively enriched in Zr, indicating that K2ZrSi3O9 is the more refractory end member. At 2 GPa, in the more complex K2ZrSi3O9–K2TiSi3O9–K2Mg6Al2Si6O20(OH)4 system, the presence of phlogopite clearly limits the extent of solid solution of the cyclosilicate to more Zr-rich compositions [Zr/(Zr + Ti) > 0.85], comparable to wadeite found in nature, with TiO2 partitioning strongly into the coexisting mica and/or liquid. However, at 1200 °C, with increasing pressure from 2 to 3 GPa, the partitioning behaviour of TiO2 changes in favour of the cyclosilicate, with Zr/(Zr + Ti) of the K2(Zr,Ti)Si3O9 phase decreasing from ∼0.9 to ∼0.6. The variation in the Ti content of the coexisting phlogopite is related to its degree of melting to forsterite and liquid, following the major substitution VITi+VI□=2VIMg. Received: 26 January 1999 / Accepted: 10 January 2000  相似文献   

20.
Summary The mineral chemistry of a Variscan lamprophyre (kersantite) from the Frankenwald, Germany, has been investigated by electron microprobe. This potassic, Si-saturated, mafic rock contains an assemblage of different generations of titanite and allanite-(Ce), Th-rich zircon, and metamict REE–Ti–Zr–Th silicates. The primary ferroan-ceroan titanite contains unusually high contents of REE2O3 (max. (ΣLa to Sm)+Y = 36.8 oxide wt.%), ZrO2 (max. 5.4 wt.%), and ThO2 (max. 3.1 wt.%). Its empirical formula averages to (Ca0.31 La0.17 Ce0.30 Pr0.03 Nd0.08 Sm0.01 Y0.01 Fe2+0.06 Th0.02 Mn0.01)Σ1.00 (Ti0.60 Fe2+0.22 Al0.06 Zr0.07 Mg0.04 Nb0.01)Σ1.00 O1.00(Si0.93 Al0.07)Σ1.00 O4. Element correlations reveal operation of the complex substitution Ca2++Ti4++Th4+ ⇔ REE3++Al3++Zr4+. In comparison to allanite-(Ce), ferroan-ceroan titanite preferentially incorporated the LREE and Th. This finding is inconsistent with previous experimental studies and suggests that both minerals are not cogenetic. High Zr contents in titanite, usually known only from Si-undersaturated alkaline rocks, and the predominance of Fe2+ suggest that the ferroan-ceroan titanite crystallized from an alkali-rich, low-fO2 residual melt.  相似文献   

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