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1.
Experiments at 750 °C, 200 MPa(H2O), a (H2O)=1, and fO2∼Ni-NiO established that the equilibrium among tourmaline, biotite, cordierite, and melt (± spinel, aluminosilicate, or corundum) occurs with ∼2 wt% B2O3 in strongly peraluminous melt with an aluminosity, measured by the parameter ASI, of >1.2. The experiments demonstrate the relationship of tourmaline stability to the activity product of the tourmaline components boron and aluminum, which are inversely related to one another. Tourmaline is unstable in metaluminous to mildly peraluminous melts (ASI <1.2) at 750 °C regardless of their boron content. For a given aluminosity, addition of components such as F requires a greater boron content of melt at this equilibrium. The stability of tourmaline increases with decreasing temperatures below 750 °C. At the inception of melting, tourmaline breaks down incongruently to assemblages containing crystalline AFM silicates (biotite, cordierite, garnet, sillimanite), aluminates (spinel, corundum), and B-enriched but Fe-Mg-poor melt. Granitic melts are likely to be undersaturated in tourmaline from the start of their crystallization, and their initial boron contents will be limited by the abundance of tourmaline in their source rocks. Quartzofeldspathic (gneissic, metapelitic) rocks that reached conditions of the granulite facies and still contain (prograde) tourmaline are rare, and probably have never yielded a partial melt. Most leucogranitic magmas will initially crystallize biotite, cordierite, or garnet, but not tourmaline. With crystallization, the Fe-Mg content of melt decreases, and the B2O3 content increases until the tourmaline-biotite and/or tourmaline-cordierite (or garnet) equilibria are attained. The B2O3 content of melt is buffered as long as these equilibria continue to operate, but low initial Fe-Mg contents of the magmas limit the quantity of boron that can be consumed by these reactions to <1 wt% B2O3. Normally, leucogranitic magmas contain insufficient Fe and Mg to conserve all boron as tourmaline and thus lose a large fraction of magmatic boron to wallrocks. Leucogranites and pegmatites with tourmaline as an early and only AFM silicate mineral probably contained >2 wt% B2O3 in their bulk magmas. Received: 6 August 1996 / Accepted: 21 July 1997  相似文献   

2.
Reaction textures, fluid inclusions, and metasomatic zoning coupled with thermodynamic calculations have allowed us to estimate the conditions under which a biotite–hornblende gneiss from the Kurunegala district, Sri Lanka [hornblende (NMg=38–42) + biotite (NMg=42–44) + plagioclase + quartz + K-feldspar + ilmenite + magnetite] was transformed into patches of charnockite along shear zones and foliation planes. Primary fluid inclusion data suggest that two immiscible fluids, an alkalic supercritical brine and almost pure CO2, coexisted during the charnockitisation event and subsequent post-peak metamorphic evolution of the charnockite. These metasomatic fluids migrated through the amphibolite gneiss along shear zones and into the wallrock under peak metamorphic conditions of 700–750 °C, 5–6 kbar, and afl H2O=0.52–0.59. This resulted in the formation of charnockite patches containing the assemblage orthopyroxene (NMg=45–48) + K-feldspar (Or70–80) + quartz + plagioclase (An28) in addition to K-feldspar microveins along quartz and plagioclase grain boundaries. Remnants of the CO2-rich fluid were trapped as separate fluid inclusions. The charnockite patches show the following metasomatic zonation patterns: – a transition zone with the assemblage biotite (NMg= 49–51) + hornblende (NMg = 47–50) + plagioclase + quartz + K-feldspar + ilmenite + magnetite; – a KPQ (K-feldspar–plagioclase–quartz) zone with the assemblage K-feldspar + plagioclase + orthopyroxene (NMg=45–48) + quartz + ilmenite + magnetite; – a charnockite core with the assemblage K-feldspar + plagioclase + orthopyroxene (NMg = 39–41) + biotite (NMg=48–52) + quartz + ilmenite + magnetite. Systematic changes in the bulk chemistry and mineralogy across the four zones suggest that along with metasomatic transformation, this process may have been complicated by partial melting in the charnockite core. This melting would have been coeval with metasomatic processes on the periphery of the charnockite patch. There is also good evidence in the charnockitic core that a second mineral assemblage, consisting of orthopyroxene (NMg= 36–42) + biotite (NMg=50–51) + K-feldspar (Or70–80) + quartz + plagioclase (An28–26), could have crystallised from a partial melt during cooling from 720 to 660 °C at decreasing afl H2O from 0.67 to 0.5. Post-magmatic evolution of charnockite at T < 700 °C resulted in fluids being released during the crystallisation of the charnockitic core. These gave rise to the formation of late stage rim myrmekites along K-feldspar grain boundaries as well as late stage biotite, cummingtonite, and carbonates. Received: 15 September 1999 / Accepted: 8 June 2000  相似文献   

3.
The Mollendo–Camana Block (MCB) is a 50 × 150 km Precambrian inlier of the Andean belt that outcrops along the Pacific coast of southern Peru. It consists of stromatic migmatites of Paleoproterozoic heritage intensely metamorphosed during the Grenville event (c. 1 Ga; U‐Pb and U‐Th‐Pb ages on zircon and monazite). In the migmatites, aluminous mesosomes (FMAS) and quartzofeldspathic leucosomes (KFMASH), contain various amounts of K‐feldspar (Kfs), orthopyroxene (XMg Opx = 0.86), plagioclase (Pl), sillimanite (Sil; exceptionally kyanite, Ky) ilmenite (Ilm), magnetite (Mag), quartz (Qtz), and minor amounts of garnet (XMg Grt = 0.60), sapphirine (XMg Spr = 0.87), cordierite (XMg Crd = 0.92) and biotite (XMg Bt = 0.83). The ubiquitous peak mineral assemblage is Opx‐Sil‐Kfs‐Qtz‐(± Grt) in most of the MCB, which, together with the high Al content of orthopyroxene (10% Al2O3) and the local coexistence of sapphirine‐quartz, attest to regional UHT metamorphism (> 900 °C) at pressures in excess of 1.0 GPa. Fluid‐absent melting of biotite is responsible for the massive production of orthopyroxene that proceeded until exhaustion of biotite (and most of the garnet) in the southern part of the MCB (Mollendo‐Cocachacra areas). In this area, a first stage of decompression from 1.1–1.2 to 0.8–0.9 GPa at temperatures in excess of 950 °C, is marked by the breakdown of Sil‐Opx to Spr‐Opx‐Crd assemblages according to several bivariant FMAS reactions. High‐T decompression is also shown by Mg‐rich garnet being replaced by Crd‐Spr‐ and Crd‐Opx‐bearing symplectites, and reacting with quartz to produce low‐Al‐Opx‐Sil symplectites in quartz‐rich migmatites. Neither osumilite nor spinel‐quartz assemblages being formed, isobaric cooling at about 0.9 GPa probably followed the initial decompression and proceeded with massive precipitation of melts towards the (Os) invariant point, as demonstrated by Bt‐Qtz‐(± pl) symplectites in quartz‐rich migmatites (melt + Opx + Sil = Bt + Grt + Kfs + Qtz). Finally, Opx rims around secondary biotite attest to late fluid‐absent melting, compatible with a second stage of decompression below 900 °C. The two stages of decompression are interpreted as due to rapid tectonic denudation whereas the regional extent of UHT metamorphism in the area, probably results from large‐scale penetration of hot asthenospheric mantle at the base of an over‐thickened crust.  相似文献   

4.
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   

5.
 Structural parameters and cation ordering are determined for four compositions in the synthetic MgGa2O4-Mg2GeO4 spinel solid solution (0, 8, 15 and 23 mol% Mg2GeO4; 1400 °C, 1 bar) and for spinelloid β-Mg3Ga2GeO8 (1350 °C, 1 bar), by Rietveld refinement of room-temperature neutron diffraction data. Sample chemistry is determined by XRF and EPMA. Addition of Mg2GeO4 causes the cation distribution of the MgGa2O4 component to change from a disordered inverse distribution in end member MgGa2O4, [4]Ga = x = 0.88(3), through the random distribution, toward a normal cation distribution, x = 0.37(3), at 23 mol% Mg2GeO4. An increase in ao with increasing Mg2GeO4 component is correlated with an increase in the amount of Mg on the tetrahedral site, through substitution of 2 Ga3+⇄ Mg2++Ge4+. The spinel exhibits high configurational entropy, reaching 20.2 J mol−1 (four oxygen basis) near the compositional upper limit of the solid solution. This stabilizes the spinel in spite of positive enthalpy of disordering over the solid solution, where ΔH D  = αx + βx 2, α = 22(3), β = −21(3) kJ mol−1. This model for the cation distribution across the join suggests that the empirically determined limit of the spinel solid solution is correlated with the limit of tetrahedral ordering of Mg, after which local charge-balanced substitution is no longer maintained. Spinelloid β-Mg3Ga2GeO8 has cation distribution M1[Mg0.50(2)Ga0.50(2)] M2[Mg0.96(2)Ga0.04(2)] M3[Mg0.77(2) Ga0.23(2)]2 (Ge0.5Ga0.5)2O8 (tetrahedral site occupancies are assumed). Octahedral site size is correlated to Mg distribution, where site volume, site distortion, and Mg content follow the relation M1<M3<M2. The disordered cation distribution provides local electrical neutrality in the structure, and stabilization through increased configurational entropy (27.6 J mol−1; eight oxygen basis). Comparison of the crystal structures of Mg1+ N Ga2−2 N Ge N O4 spinel, β-Mg3Ga2GeO8, and Mg2GeO4 olivine reveals β-Mg3Ga2GeO8 to be a true structural intermediate. Phase transitions across the pseudobinary are necessary to accommodate an increasing divergence of cation size and valence, with addition of Mg2GeO4 component. Octahedral volume increases while tetrahedral volume decreases from spinel to β-Mg3Ga2GeO8 to olivine, with addition of Mg and Ge, respectively. Furthermore, M-M distances increase regularly across the join, suggesting that changes in topology reduce cation-cation repulsion. Received: 9 November 1998 / Revised, accepted: 3 August 1999  相似文献   

6.
Five new biotite reference materials were calibrated at the SwissSIMS laboratory (University of Lausanne) for oxygen isotope determination by secondary ion mass spectrometry (SIMS) and are available to the scientific community. The oxygen isotope composition of the biotites, UNIL_B1 to B5, was determined by laser‐heating fluorination to be 11.4 ± 0.11‰, 8.6 ± 0.15‰, 6.1 ± 0.04‰, 7.1 ± 0.05‰ and 7.6 ± 0.04‰, respectively. SIMS analyses on spots smaller than 20 μm gave a measurement repeatability of 0.3‰ (2 standard deviation, 2s). The matrix effect due to solid solution in natural biotite could be expressed as a linear function of XMg and XF for biotite. No effect was found for different crystallographic orientations. SIMS analysis allows the oxygen isotope composition of biotite to be measured with a measurement uncertainty of 0.3–0.4‰ (2s) for biotites with similar major element compositions. A measurement uncertainty of 0.5‰ (2s) is realistic when F poor biotites (lower than 0.2% m/m oxides) within the compositional range of XMg of 0.3–0.9 were compared from different sessions. The linear correlation with F content offers a reasonable working curve for F‐rich biotites, but additional reference materials are needed to confirm the model.  相似文献   

7.
Meta-sedimentary rocks including marbles and calcsilicates in Central Dronning Maud Land (CDML) in East Antarctica experienced a Pan-African granulite facies metamorphism with peak metamorphic conditions around 830 ± 20 °C at 6.8 ± 0.5 kbar which was accompanied by the post-kinematic intrusion of huge amounts of syenitic (charnockitic) magmas at 4.5 ± 0.7 kbar. The marbles and calcsilicates may represent meta-evaporites as indicated by the occurrence of metamorphic gypsum/anhydrite and Cl-rich scapolite that formed in the presence of saline fluids with X NaCl in the range 0.15–0.27. The marbles and calcsilicates bear biotite, tremolite and/or hornblende and humite group minerals (clinohumite, chondrodite and humite) which are inferred to have crystallized at about 650 °C and 4.5 kbar. The syenitic intrusives contain late-magmatic biotite and amphibole (formed between 750 and 800 °C) as well as relictic magmatic fayalite, orthopyroxene and clinopyroxene. Two syenite and two calcsilicate samples contain fluorite. Corona textures in the marbles and calcsilicates suggest very low fluid-rock ratios during the formation of the retrograde (650 °C) assemblages. Biotite in all but two syenite samples crystallized at log(f H 2 O/f HF) ratios of 2.9 ± 0.4, while in the calcsilicates, both biotite and humite group minerals indicate generally higher log(f H 2 O/f HF) values of up to 5.2. A few samples, though, overlap with the syenite values. Log(f H 2 O/f HCl) derived from biotite covers the range 0.5–2.6 in all rock types. Within a single sample, the calculated values for both parameters vary typically by 0.1 to 0.8 log units. Water and halogen acid fugacities calculated from biotite-olivine/orthopyroxene-feldspar-quartz equilibria and the above fugacity ratios are 1510–2790 bars for H2O, 1.3–5.3 bars for HF and 7–600 bars for HCl. The results are interpreted to reflect the reaction of relatively homogeneous magmatic fluids [in terms of log(f H 2 O /f HF)] derived from the late-magmatic stages of the syenites with both earlier crystallized, still hotter parts of the syenites and with adjacent country rocks during down-temperature fluid flow. Fluorine is successively removed from the fluid and incorporated into F-bearing minerals (close to the syenite into metamorphic fluorite). In the course of this process log(f H 2 O /f HF) increases significantly. Chlorine preferably partitions into the fluid and hence log(f H 2 O /f HCl) does not change markedly during fluid-rock interaction. Received: 28 November 1997 / Accepted: 27 April 1998  相似文献   

8.
This study of La Gloria pluton in the Chilean Andes evaluates what information about magmatic conditions can be extracted from minerals in a granitic pluton, despite lower-temperature re-equilibration. The pluton is zoned vertically from granodiorite/quartz monzodiorite to quartz monzonite at the roof, with the uppermost 1500 m showing the strongest modal and compositional trends. This mimics the pattern frequently inferred from zoning in voluminous ignimbrites: a strongly zoned cap overlying a more homogeneous main␣body. The presence of large, euhedral amphibole ± biotite at the chamber margins and roof indicate that water was concentrated there. Biotite and amphibole compositions indicate a roofward increase in magmatic f HF, f HCl and F/Cl ratio, analogous to pre-eruptive volatile gradients recorded in zoned ignimbrites. Hornblende that crystallized directly from the melt in the volatile-rich wall and roof zones yields total-Al solidification pressures of ˜1 kbar, consistent with the estimated 4000 m of cover at the time of emplacement. In the core of the pluton, actinolitic amphibole formed by reaction of melt with early-crystallized clinopyroxene. Plag-cpx cumulate clots in the lower level are interpreted as early crystallizing phases entrained in rising granitic magma. Cores of amphibole phenocrysts in mafic enclaves suggest initial crystallization at pressures of 2–3 kbar. Lower Ti and Al contents of rims and acicular groundmass amphibole, overlapping the composition of amphibole in the host granitoid, indicate that the enclaves equilibrated with the host at the present exposure level in the presence of interstitial melt. A roofward relative increase in fO2 of the magma is recorded by an increasing proportion of Fe-Ti oxides as a fraction of the mafic phases, greater Mn content of ilmenite, and constant or higher Mg/(Mg+Fe) in hornblende and biotite despite declining whole-rock MgO contents. Association␣of subhedral biotite and magnetite with actinolitic amphibole in clots implies a reaction: K-Ti-hb + O2(gas) = bi + mt + actinolitic amph + titanite. Magnetite coexisting with biotite with Fe/(Fe+Mg) = 0.34– 0.40 implies temperatures of equilibration no lower than about 720–750 °C, i.e., late-magmatic rather than subsolidus. Saturation with respect to a water-rich vapor and subsequent diffusive loss of hydrogen may have caused this oxidation trend, which resulted in the most magnesian mafic phases occurring in the most compositionally evolved rocks, opposite to trends in most zoned ignimbrites, which presumably record conditions nearer the liquidus and prior to exsolution of a water-rich vapor. Two-feldspar and Fe-Ti-oxide geothermometers record subsolidus conditions in the pluton and yield higher temperatures for samples from the roof zone, suggesting that slower cooling at deeper levels allowed these minerals to continue to equilibrate to lower temperatures. Individual minerals span wide ranges in composition at any given level of the pluton, from those appropriate for phenocrysts, to those that record conditions well below the solidus. We suggest that the shallow level and isolated position of the pluton led to rapid escape of magmatic volatiles and rapid cooling, thereby preventing development of a long-lived hydrothermal system. Resulting small water/rock ratios may account for why late-magmatic and subsolidus re-equilibration were not pervasive. Received: 23 August 1996 / Accepted: 18 October 1996  相似文献   

9.
The Bleikvassli massive sulfide ore deposit is hosted by Proterozoic pelitic, quartzofeldspathic, and amphibolitic rocks of the Uppermost Allochthon of the Scandinavian Caledonides. Staurolite-garnet-biotite and kyanite-staurolite-biotite assemblages indicate that metamorphism reached the kyanite zone of the amphibolite facies. Geothermobarometry was conducted on rocks in and around the deposit using a variety of silicate and sulfide calibrations. Temperature determinations are most reliant on the garnet-biotite exchange reaction, with analyses obtained from 259 garnet rims and adjacent biotite. Results from nine calibrations of the garnet-biotite geothermometer are considered, but compositional limitations of many calibrations involving high Ca and Mn contents in garnet and AlVI and Ti in biotite make many of the coexisting mineral pairs unsuitable. Average temperatures calculated from the two calibrations that most closely address the garnet-biotite compositions observed at Bleikvassli are 584 °C ± 49 °C and 570 °C ± 40 °C. The application of two calibrations of the garnet-staurolite geothermometer on a limited number of samples yields 581 °C ± 2 °C and 589 °C ± 12 °C, assuming a H2O=0.84, based upon calculations of the modal proportions of gaseous species. Pressure determinations are less constrained. Phengite and plagioclase-biotite-garnet-muscovite geobarometers give average pressures of approximately 5.0 kbar and 8.5 ± 1.2 kbar, respectively. Pressures obtained from the sphalerite-hexagonal pyrrhotite-pyrite barometer average 7.7 ± 1.0 kbar. In consideration of these results, the peak metamorphic conditions at the Bleikvassli deposit are estimated to be 580 °C and 8 kbar. Received: 18 June 1997 / Accepted: 14 May 1998  相似文献   

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

11.
Dense isotropic polycrystalline specimens of majorite-rich garnets (Py100, Py62Mj38, Py50Mj50, Py21Mj79 and Mj100) along the pyrope (Mg3Al2Si3O12 = Py100)-majorite (MgSiO3 = Mj100) join were fabricated in a 2000-ton uniaxial split-sphere anvil apparatus (USSA-2000) at pressures from 10 to 18.5 GPa and temperatures from 1200 to 1850 °C, within their stability fields in runs of 2–4-h duration, using hot-pressing techniques developed by Gwanmesia et al. (1993). These specimens are single-phased, fine-grained (≤5 mm), free of microcracks, and have bulk densities greater than 99% of the corresponding single-crystal X-ray density. Elastic compressional (P) and shear (S) wave velocities were determined at room pressure and temperature for these polycrystalline garnet specimens by phase comparison ultrasonic interferometry. For Mj100, the P and S wave velocities are within 1% of the Hashin-Shtrikman averages calculated from the single crystal elastic moduli measured by Brillouin spectroscopy. Both the elastic bulk modulus (K) and the shear modulus (G) decrease continuously with increasing majorite content from pyrope garnet (Py100) to pure majorite garnet (Mj100). The compositional dependence of K and G are given by K = 172.3 (40) − 0.085X, and G = 91.6 (10) − 0.038X, where X = mol% majorite), respectively, indicating that substitution of Si for Mg and Al decreases both K and G by about 5% along the solid solution series. Received: 25 March 1999 / Accepted: 12 July 1999  相似文献   

12.
Experimental studies of the element distribution between carbonatite melts and hydrous fluids are hampered by the fact that neither the fluid nor the melt can be isochemically quenched in conventional high-pressure vessels. In order to overcome this problem, we used a double-capsule technique to separate immiscible fluid and melt phases during and after the runs. The inner platinum capsules were charged with carbonate mixtures (CaCO3, MgCO3 and Na2CO3) and placed inside the outer capsules charged with distilled water and diamond powder. The latter was used as an inert trap for solids precipitating from the fluid on quenching. Carbonate melt and hydrous fluid equilibrated through a small hole left in the upper end of the inner capsule. The runs were performed in rapid-quench cold-seal pressure vessels at 0.1–0.2 GPa and 700–900 °C in the two-phase (fluid + melt) stability region. Both quenched melt and quenched fluid were dissolved in dilute HCl and analysed by inductively coupled plasma atomic emission spectroscopy. The results show that under all conditions investigated, fluid/melt partition coefficients for Ca and Mg are similar and several times smaller than those for Na. At 0.1 GPa and a water/carbonatite ratio of 1 (by weight), the partition coefficients are DNa = 0.35 ± 0.02, DCa = 0.09 ± 0.02, and DMg = 0.13 ± 0.01. Between 700 and 900 °C, the effect of temperature on partitioning is negligible. However, DNa increases significantly with decreasing water/carbonatite ratio in the system. Our data show that the release of a hydrous fluid enriched in sodium and simultaneous crystallisation of calcite can transform an alkaline, vapour-saturated carbonatite melt into a body of pure calcite surrounded by zones of sodium metasomatism. Thus, it is quite possible that carbonate magmas with substantial amounts of alkalies were common parental liquids of plutonic carbonatites. Received: 6 May 1999 / Accepted: 31 August 1999  相似文献   

13.
 Mg-Fe partitioning experiments between (Mg,Fe)2SiO4 spinel and (Mg,Fe)O magnesiowüstite were carried out at pressures of 17–21.3 GPa at temperatures of 1400 and 1600 °C, using a multi-anvil apparatus, in order to determine interaction parameters of spinel and magnesiowüstite solid solutions and also to constrain the equilibrium boundaries of the postspinel transition in the Fe-rich side in the system Mg2SiO4-Fe2SiO4. The obtained values of the interaction parameters were 3.4 ± 1.5 and 13.9 ± 1.4 kJ mol−1, respectively, for spinel and magnesiowüstite solid solutions at 19 GPa and 1600 °C. The partitioning data in the system Mg2SiO4-Fe2SiO4 at 1400 and 1600 °C showed that the transition boundary between spinel and the mixture of magnesiowüstite and stishovite has a negative dP/dT slope. Using the above interaction parameters and available thermodynamic data of the Mg2SiO4 and Fe2SiO4 end members, the transition boundaries of spinel to the mixture of magnesiowüstite and stishovite were calculated. Within the uncertainties of the data used, the calculated boundaries are in good agreement with the boundaries at 1400 and 1600 °C experimentally determined in this study. The dissociation boundary of Fe2SiO4 spinel to wüstite and stishovite, calculated from the thermodynamic data, has a negative slope of −1.5 ± 0.6 MPa K−1. Received: 18 February 1998 / Revised, accepted: 18 October 1999  相似文献   

14.
In order to develop models simulating the crystallization of Fe-Ti oxides in natural lavas, we have processed published experimental data on magnetite-melt and ilmenite-melt equilibria. These data include 62 Mt-melt and 75 Ilm-melt pairs at temperatures 1040–1150 °C, oxygen fugacities from IW to NNO+2, and bulk compositions ranging from ferrobasalts to andesites and dacites. Five major cations (Fe3+, Fe2+, Ti4+, Mg2+ and Al3+) were considered for the purpose of describing Fe-Ti oxide saturation as a function of melt composition, temperature and oxygen fugacity at 1 atmosphere pressure. The empirically calibrated mineral-melt expression based on multiple linear regressions is: ln D i  = a/T + blog f O2 + c + d 1 X Na + d 2 X K + d 3 X P, where D i represents molar distribution coefficients of the given cations between Mt/Ilm and melt; X Na, X K, and X P are the molar fractions of Na, K, and P in the melt. The empirically calibrated Mt-melt and Ilm-melt equilibria equations allowed us to develop two models for calculating crystallization temperatures of the Fe-Ti oxides in the melts with an accuracy of 10–15 °C, and compositions with an accuracy of 0.5–2 mol%. These models have been integrated into the COMAGMAT-3.5 program, improving our ability to study numerically the effects of temperature and oxygen fugacity on the stability and phase equilibria of Fe-Ti oxides. Application of this approach to the tholeiitic series of Chazhma Sill from Eastern Kamchatka (Russia) indicates oxygen fugacity conditions near NNO + 0.5. Numerical simulation of fractional crystallization of an iron-enriched basaltic andesite parent at these oxidizing conditions accurately reproduces the FeO-SiO2 relations observed in the Chazhma suite. Received: 3 March 1998 / Accepted: 7 August 1998  相似文献   

15.
Phase relations of three samples of the Laacher See Tephra (LST) have been determined experimentally as a function of temperature (760 to 880 °C), pressure (200, 300 and 400 MPa), water content of the melt and oxygen fugacity (ƒO2). The crystallization experiments were carried out at ƒO2=NNO buffer and at NNO=+ 2.3 log units. The melt water contents varied between 6 and more than 8 wt% H2O, corresponding to water-undersaturated and water saturated conditions respectively. The synthetic products are compared to the natural phases to constrain pre-eruptive conditions in the Laacher See magma chamber. The major phases occurring in the LST have been reproduced. The stability of hauyne is favoured at high ƒO2 (≈NNO + 2.3). The CaO contents in melt and plagioclase synthesized under water-saturated conditions are significantly higher than in the natural phases, implying that most of the differentiation of the phonolites took place under water-undersaturated conditions. However, this does not exclude the presence of a S-, Cl- and CO2-rich fluid phase in the upper parts of the magma chamber. The phase relationships and the TiO2 contents of melts show that the temperature was lower than 760 °C in the upper part of the magma column (probably down to 720 °C in the most differentiated levels) and that temperatures above 840–860 °C prevailed in the lower part. The variation of the X Mg of ferromagnesian minerals observed in both natural and experimental phases reflects the strong variations in ƒO2 in the lower magma chamber just prior to eruption (probably variation of about 2 log units). The most probable explanation for these ƒO2 variations is the injection of an oxidized alkali-rich magma, containing Mg-rich phenocrysts, at the base of a chemically zoned and more reduced magma column prior to eruption. Although the amount of injected magma may not have been very important, it was sufficient to change the ƒO2 conditions locally, explaining the heterogeneous X Mg of ferromagnesian minerals and the formation of hauyne at the base of the chamber. Received: 30 May 2000 / Accepted: 12 August 2000  相似文献   

16.
The chemical compositions of rock-forming minerals have been determined for both altered and least-altered igneous rocks spatially associated with numerous mineralized zones (Nucleus Au–Bi–Cu–As deposit, Revenue Au ± Cu and Stoddart Cu–Mo ± W mineral occurrences, and Laforma Au–Ag deposit) across the Freegold Mountain area, Yukon, Canada. Within the study area, K-feldspar has a narrow compositional range (89.4–91% Or), whereas plagioclase spans a wide range (4.4–70.07% An). In all of the investigated samples, T Ab = T An = T Or, suggesting that magmatic equilibrium between the coexisting plagioclase and K-feldspar was maintained. Igneous amphibole phenocrysts from hypabyssal dikes are typically calcic, whereas the Stoddart Cu–Mo ± W, Laforma Au–Ag, and Goldy Au mineralization are associated with Mg-enriched primary amphibole of edenite composition, and Au–Bi–Cu–As mineralization from Nucleus is related to Al-enriched primary amphibole of ferropargasite composition. Primary biotite phenocrysts across the Freegold Mountain area re-equilibrated with oxidized magma (f(O2) values between 10–13 and 10–11.5 bars, lying between the Ni/NiO and the magnetite/haematite buffers). However, biotite and amphibole phenocrysts from Stoddart, Goldy, Laforma, and the Highway zones crystallized from a more oxidized magma, as indicated by their elevated X Mg up to 0.65, relative to biotite and hornblende from Nucleus and Revenue characterized by a lower X Mg (typically < 0.50). This suggests that various sources and (or) rapid emplacement were involved in magma genesis, as further supported by the considerable variation of pressure (1.8–7.3 kb) of amphibole crystallization and of the total Al content in least-altered biotite (2.6–2.9 afu) within the Freegold Mountain area. Biotite and apatite equilibrated within the T range of 520–780°C, consistent with temperatures of equilibration between ilmenite and magnetite, and their compositions indicate that they formed from an oxidized I-type magma. Magma differentiated by fractional crystallization (indicated by the presence of normally zoned plagioclase with Ca-rich cores and Na-enriched outer rims) and multiple magma mixing (supported by the presence of reversed zoned plagioclase and coexistence of normally and reversely zoned plagioclase). Lower X Mg biotite associated with the mineralized (Cu–Mo ± W) potassic alteration incorporated more F and Cl relative to least-altered biotite with higher X Mg. In both Nucleus and Revenue Au–Cu mineralizations, secondary biotite composition varies with respect to the associated alteration mineral assemblages. Although secondary biotite in the skarn re-equilibrated with F-poor fluids, secondary biotite from the pervasive biotitization is related to F- and Cl-enriched fluids, and secondary biotite from the phyllitic zone is related to F-, Cl-, and Mg-depleted fluids, thus consistent with a change in mineralizing fluid composition during mineralization.  相似文献   

17.
 Calorimetric and P–V–T data for the high-pressure phase Mg5Al5Si6O21(OH)7 (Mg-sursassite) have been obtained. The enthalpy of drop solution of three different samples was measured by high-temperature oxide melt calorimetry in two laboratories (UC Davis, California, and Ruhr University Bochum, Germany) using lead borate (2PbO·B2O3) at T=700 ∘C as solvent. The resulting values were used to calculate the enthalpy of formation from different thermodynamic datasets; they range from −221.1 to −259.4 kJ mol−1 (formation from the oxides) respectively −13892.2 to −13927.9 kJ mol−1 (formation from the elements). The heat capacity of Mg5Al5Si6O21(OH)7 has been measured from T=50 ∘C to T=500 ∘C by differential scanning calorimetry in step-scanning mode. A Berman and Brown (1985)-type four-term equation represents the heat capacity over the entire temperature range to within the experimental uncertainty: C P (Mg-sursassite) =(1571.104 −10560.89×T −0.5−26217890.0 ×T −2+1798861000.0×T −3) J K−1 mol−1 (T in K). The P V T behaviour of Mg-sursassite has been determined under high pressures and high temperatures up to 8 GPa and 800 ∘C using a MAX 80 cubic anvil high-pressure apparatus. The samples were mixed with Vaseline to ensure hydrostatic pressure-transmitting conditions, NaCl served as an internal standard for pressure calibration. By fitting a Birch-Murnaghan EOS to the data, the bulk modulus was determined as 116.0±1.3 GPa, (K ′=4), V T,0 =446.49 3 exp[∫(0.33±0.05) × 10−4 + (0.65±0.85)×10−8 T dT], (K T/T) P  = −0.011± 0.004 GPa K−1. The thermodynamic data obtained for Mg-sursassite are consistent with phase equilibrium data reported recently (Fockenberg 1998); the best agreement was obtained with Δf H 0 298 (Mg-sursassite) = −13901.33 kJ mol−1, and S 0 298 (Mg-sursassite) = 614.61 J K−1 mol−1. Received: 21 September 2000 / Accepted: 26 February 2001  相似文献   

18.
 Olivine and augite minette powders have been equilibrated from one bar to nearly 2.0 kbar (water-saturated), and from 900 to 1300° C, and then quenched rapidly, at oxygen fugacities controlled between the nickel-nickel oxide (NNO) and hematite-magnetite (HM) oxygen buffers. The liquidus of both samples is suppressed ∼100° C at water-saturated conditions and 1500 bar. Both lavas contained between 3 and 4 wt% water at the stage of phenocryst precipitation. The partitioning of ferric and ferrous iron between phlogopite and liquid has been determined on eight samples across 3 log f O2 units; when these determinations are combined with previous studies, Fe2O3/(Σ FeO total) of Mg-rich biotite can be calculated knowing log f O2, T, and X Fe. Thermodynamic modelling of biotite-liquid equilibria results in two expressions for calculating activity coefficients (γ) for annite and phlogopite in natural biotites. Based on the partitioning of BaO and TiO2 between biotite and liquid, we have formulated a thermometer and barometer. Over the range of 400° C, TiO2 partitioning between phlogopite and liquid is a function of temperature (±50° C), and is insensitive to pressure and H2O and O2 activities. BaO partitioning between phlogopite and liquid is a function of both temperature and pressure (±4 kbar), the latter being most important. Applying the TiO2 and BaO partitioning expressions to lamprophyre and lamproite suites shows that Mexican minettes equilibrated at low pressures (5 to 15 kbar;±4 kbar) and temperatures (1090 to 1160° C; ±50° C), while Australian lamproites equilibrated at higher P (up to 30 kbar; ±4 kbar) and T (1125 to 1400° C; ±50° C). Experimental glass compositions and phenocryst fractionation calculations, together with the BaO- and TiO2- based pressure calculations indicate that felsic minettes from the Mexican suite of lavas can be generated by simple fractionation of a more mafic parent minette at mid to lower crustal pressures. Received: 1 August 1994/Accepted: 30 June 1995  相似文献   

19.
The Archean Shawmere anorthosite lies within the granulite facies portion of the Kapuskasing Structural Zone (KSZ), Ontario, and is crosscut by numerous linear alteration veins containing calcite + quartz ± dolomite ± zoisite ± clinozoisite ± margarite ±paragonite ± chlorite. These veins roughly parallel the trend of the Ivanhoe Lake Cataclastic Zone. Equilibria involving clinozoisite + margarite + quartz ± calcite ± plagioclase show that the vein minerals were stable at T < 600 °C, XCO2 < 0.4 at P ≈ 6 kbar. The stabilities of margarite and paragonite in equilibrium with quartz are also consistent with T < 600 °C and XCO2 < 0.4 at 6 kbar. Additional assemblages consisting of calcite + clinochlore + quartz + talc + margarite indicate T < 500 °C with XCO2 > 0.9. Thus, vein formation, while clearly retrograde, spanned a range of temperatures, and fluid compositions evolved from H2O-rich to CO2-rich. The calcite in the retrograde veins has δ18O values that range from 8.4 to 11.2‰ (average = +9.7 ± 0.9‰) and δ13C values that range from −3.9 to −1.6‰ (average = −3.1 ± 0.6‰). These values indicate that the fluids from which calcite precipitated underwent extensive exchange with the anorthosite and other crustal lithologies. The fluids may have been initially derived either from devolatilization of metamorphic rocks or crystallization of igneous rocks in the adjacent Abitibi subprovince. Vein quartz contains CO2-rich fluid inclusions (final melting T = −57.0 to −58.7 °C) that range in size from 5 to 17 μm. Measured homogenization temperatures (T h) range from −44.0 to 14.5 °C, however for most inclusions (46 of S1), T h = −44.0 to −21.1 °C (ρCO2 ≈ 1.13 to 1.05 g/cm3). At 400 to 600 °C, these densities correspond to pressures of 3.5 to 7 kbar, which is the best estimate of pressures of vein formation. It has been argued that some high density CO2-rich fluid inclusions found in the KSZ were formed during peak metamorphism and thus document the presence of a CO2-rich fluid during peak granulite facies metamorphism (Rudnick et al. 1984). The association of high density CO2-rich fluid inclusions with clearly retrograde veins documents the formation of similar composition and density inclusions after the peak of metamorphism. Thus, the coincidence of entrapment pressures calculated from fluid inclusion density measurements with peak metamorphic pressures alone should not be considered strong evidence for peak metamorphic inclusion entrapment. All fluid inclusion results are consistent with an initially semi-isobaric retrograde P–T path. Received: 2 April 1996 / Accepted: 15 November 1996  相似文献   

20.
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   

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