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1.
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   

2.
This study investigates marbles and calcsilicates in Central Dronning Maud Land (CDML), East Antarctica. The paleogeographic positioning of CDML as part of Gondwana is still unclear; however, rock types, mineral assemblages, textures and P–T conditions observed in this study are remarkably similar to the Kerala Khondalite Belt in India. The CDML marbles and calcsilicates experienced a Pan-African granulite facies metamorphism at c. 570 Ma and an amphibolite facies retrogression at c. 520 Ma. The highest grade assemblage in marbles is forsterite+spinel+calcite+dolomite, in calcsilicates the assemblages are diopside+spinel, diopside+garnet, scapolite+wollastonite+clinopyroxene±quartz, scapolite±anorthite±calcite+clinopyroxene+wollastonite. These assemblages constrain the peak metamorphic conditions to 830±20 °C, 6.8±0.5 kbar and X CO2>0.46. During retrogression, highly fluoric humite-group minerals (humite, clinohumite, chondrodite) replaced forsterite, and garnet rims formed at the expense of scapolite during reactions with wollastonite, calcite or clinopyroxene but without involvement of anorthite. Metamorphic conditions were about 650 °C, 4.5±0.7 kbar, 0.2< X CO2fluid<0.36, and the co-existence of garnet, clinopyroxene, wollastonite and quartz constrains fO2 to FMQ-1.5 log units. Mineral textures indicate a very limited influx of H2O-rich fluid during amphibolite facies retrogression and point to significant variations of fluid composition in mm-sized areas of the rock. Gypsum was observed in two samples; it probably replaced metamorphic anhydrite which appears to have formed under amphibolite facies conditions. The observed extensive anorogenic magmatism (anorthosites, A-type granitoids) and the character of metamorphism between 610 and 510 Ma suggest that the crustal thermal structure was characterized by a long-lived (50–100 Ma) rise of the crustal geotherm probably caused by magmatic underplating.  相似文献   

3.
 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   

4.
Solidus temperatures of quartz–alkali feldspar assemblages in the haplogranite system (Qz-Ab-Or) and subsystems in the presence of H2O-H2 fluids have been determined at 1, 2, 5 and 8 kbar vapour pressure to constrain the effects of redox conditions on phase relations in quartzofeldspathic assemblages. The hydrogen fugacity (f H2) in the fluid phase has been controlled using the Shaw membrane technique for moderately reducing conditions (f H2 < 60 bars) at 1 and 2 kbar total pressure. Solid oxygen buffer assemblages in double capsule experiments have been used to obtain more reducing conditions at 1 and 2 kbar and for all investigations at 5 and 8 kbar. The systems Qz-Or-H2O-H2 and Qz-Ab-H2O-H2 have only been investigated at moderately reducing conditions (1 and 5 kbar) and the system Qz-Ab-Or-H2O-H2 has been investigated at redox conditions down to IW (1 to 8 kbar). The results obtained for the water saturated solidi are in good agreement with those of previous studies. At a given pressure, the solidus temperature is found to be constant (within the experimental precision of ± 5°C) in the f H2 range of 0–75 bars. At higher f H2, generated by the oxygen buffers FeO-Fe3O4 (WM) and Fe-FeO (IW), the solidus temperatures increase with increasing H2 content in the vapour phase. The solidus curves obtained at 2 and 5 kbar have similar shapes to those determined for the same quartz - alkali feldspar assemblages with H2O-CO2- or H2O-N2-bearing systems. This suggests that H2 has the behaviour of an inert diluent of the fluid phase and that H2 solubility in aluminosilicate melts is very low. The application of the results to geological relevant conditions [HM (hematite-magnetite) > f O2 > WM] shows that increasing f H2 produces a slight increase of the solidus temperatures (up to 30 °C) of quartz–alkali feldspar assemblages in the presence of H2O-H2 fluids between 1 and 5 kbar total pressure. Received: 4 March 1996 / Accepted: 22 August 1996  相似文献   

5.
 The melting reaction: albite(solid)+ H2O(fluid) =albite-H2O(melt) has been determined in the presence of H2O–NaCl fluids at 5 and 9.2 kbar, and results compared with those obtained in presence of H2O–CO2 fluids. To a good approximation, albite melts congruently at 9 kbar, indicating that the melting temperature at constant pressure is principally determined by water activity. At 5 kbar, the temperature (T)- mole fraction (X (H2O) ) melting relations in the two systems are almost coincident. By contrast, H2O–NaCl mixing at 9 kbar is quite non-ideal; albite melts ∼70 °C higher in H2O–NaCl brines than in H2O–CO2 fluids for X (H2O) =0.8 and ∼100 °C higher for X (H2O) =0.5. The melting temperature of albite in H2O–NaCl fluids of X (H2O)=0.8 is ∼100 °C higher than in pure water. The P–T curves for albite melting at constant H2O–NaCl show a temperature minimum at about 5 kbar. Water activities in H2O–NaCl fluids calculated from these results, from new experimental data on the dehydration of brucite in presence of H2O–NaCl fluid at 9 kbar, and from previously published experimental data, indicate a large decrease with increasing fluid pressure at pressures up to 10 kbar. Aqueous brines with dissolved chloride salt contents comparable to those of real crustal fluids provide a mechanism for reducing water activities, buffering and limiting crustal melting, and generating anhydrous mineral assemblages during deep crustal metamorphism in the granulite facies and in subduction-related metamorphism. Low water activity in high pressure-temperature metamorphic mineral assemblages is not necessarily a criterion of fluid absence or melting, but may be due to the presence of low a (H2O) brines. Received: 17 March 1995/Accepted: 9 April 1996  相似文献   

6.
Summary Mineral chemistry and petrological data of chromites from chromitite bands in the N–S trending schist belt of Nuggihalli (southern Karnataka, India), belonging to the Dharwar craton of South India, are presented in this paper. Crystal chemical data indicate a komatiitic affinity of the chromitite. P–T calculations of the chromite-hosting peridotites yielded a pressure range of 13 to 28 kbar and temperatures ranging from 775 to 1080 °C; the oxygen fugacity (log fO2) varies from +0.5 to +1.6 above the QFM buffer. The P, T and fO2 data indicate that Nuggihalli chromitites crystallized in an environment akin to the upper mantle. The studied samples also show partial resetting; the lower temperatures ranging from 515 to 680 °C are ascribed to subsequent metamorphism of the area.  相似文献   

7.
The Lherz orogenic lherzolite massif (Eastern French Pyrenees) displays one of the best exposures of subcontinental lithospheric mantle containing veins of amphibole pyroxenites and hornblendites. A reappraisal of the petrogenesis of these rocks has been attempted from a comprehensive study of their mutual structural relationships, their petrography and their mineral compositions. Amphibole pyroxenites comprise clinopyroxene, orthopyroxene and spinel as early cumulus phases, with garnet and late-magmatic K2O-poor pargasite replacing clinopyroxene, and subsolidus exsolution products (olivine, spinel II, garnet II, plagioclase). The original magmatic mineralogy and rock compositions were partly obscured by late-intrusive hornblendites and over a few centimetres by vein–wallrock exchange reactions which continued down to subsolidus temperatures for Mg–Fe. Thermobarometric data and liquidus parageneses indicate that amphibole pyroxenites started to crystallize at P ≥ 13 kbar and recrystallized at P < 12 kbar. The high AlVI/AlIV ratio (>1) of clinopyroxenes, the early precipitation of orthopyroxene and the late-magmatic amphibole are arguments for parental melts richer in silica but poorer in water than alkali basalts. Their modelled major element compositions are similar to transitional alkali basalt with about 1–3 wt% H2O. In contrast to amphibole pyroxenites, hornblendites only show kaersutite as liquidus phase, and phlogopite as intercumulus phase. They are interpreted as crystalline segregates from primary basanitic magmas (mg=0.6; 4–6 wt% H2O). These latter cannot be related to the parental liquids of amphibole pyroxenites by a fractional crystallization process. Rather, basanitic liquids mostly reused pre-existing pyroxenite vein conduits at a higher structural level (P ≤ 10 kbar). A continuous process of redox melting and/or alkali melt/peridotite interaction in a veined lithospheric mantle is proposed to account for the origin of the Lherz hydrous veins. The transitional basalt composition is interpreted in terms of extensive dissolution of olivine and orthopyroxene from wallrock peridotite by alkaline melts produced at the mechanical boundary layer/thermal boundary layer transition (about 45–50 km deep). Continuous fluid ingress allowed remelting of the deeper veined mantle to produce the basanitic, strongly volatiles enriched, melts that precipitated hornblendites. A similar model could be valid for the few orthopyroxene-rich hydrous pyroxenites described in basalt-hosted mantle xenoliths. Received: 15 September 1999 / Accepted: 31 January 2000  相似文献   

8.
H2O activities in supercritical fluids in the system KCl-H2O-(MgO) were measured at pressures of 1, 2, 4, 7, 10 and 15  kbar by numerous reversals of vapor compositions in equilibrium with brucite and periclase. Measurements spanned the range 550–900 °C. A change of state of solute KCl occurs as pressures increase above 2 kbar, by which H2O activity becomes very low and, at pressures of 4 kbar and above, nearly coincident with the square of the mole fraction (x H2O). The effect undoubtedly results primarily from ionic dissociation as H2O density (ρH2O) approaches 1 gm/cm3, and is more pronounced than in the NaCl-H2O system at the same P-T-X conditions. Six values of solute KCl activity were yielded by terminal points of the isobaric brucite-periclase T-x H2O curves where sylvite saturation occurs. The H2O mole fraction of the isobaric invariant assemblage brucite-periclase-sylvite-fluid is near 0.52 at all pressures, and the corresponding temperatures span only 100 °C between 1 and 15 kbar. This remarkable convergence of the isobaric equilibrium curves reflects the great influence of pressure on lowering of both KCl and H2O activities. The H2O and KCl activities can be expressed by the formulas: a H2O = γH2O[x H2O+(1 + (1 + α)x KCl)], and a KCL = γKCl[(1 + α)x KCl/(x H2O +(1 + α)x KCl)](1 + α), where α is a degree of dissociation parameter which increases from zero at the lowest pressures to near one at high pressures and the γ's are activity coefficients based on an empirical regular solution parameter W: ln γi = (1 − xi)2W. Least squares fitting of our H2O and KCl activity data evaluates the parameters: α = exp(4.166 −2.709/ρH2O) − 212.1P/T, and W = (−589.6 − 23.10P) /T, with ρH2O in gm/cm3, P in kbar and T in K. The standard deviation from the measured activities is only ± 0.014. The equations define isobaric liquidus curves, which are in perfect agreement with previous DTA liquidus measurements at 0.5–2 kbar, but which depart progressively from their extrapolation to higher pressures because of the pressure-induced dissociation effect. The great similarity of the NaCl-H2O and KCl-H2O systems suggests that H2O activities in the ternary NaCl-KCl-H2O system can be described with reasonable accuracy by assuming proportionality between the binary systems. This assumption was verified by a few reconnaissance measurements at 10 kbar of the brucite-periclase equilibrium with a Na/(Na + K) ratio of 0.5 and of the saturation temperature for Na/(Na + K) of 0.35 and 0.50. At that pressure the brucite-periclase curves reach a lowest x H2O of 0.45 and a temperature of 587 °C before salt saturation occurs, values considerably lower than in either binary. This double-salt eutectic effect may have a significant application to natural polyionic hypersaline solutions in the deep crust and upper mantle in that higher solute concentrations and very low H2O activities may be realized in complex solutions before salt saturation occurs. Concentrated salt solutions seem, from this standpoint, and also because of high mechanical mobility and alkali-exchanging potential, feasible as metasomatic fluids for a variety of deep-crust and upper mantle processes. Received: 9 August 1996 / Accepted: 15 November 1996  相似文献   

9.
Water-saturated and water-undersaturated experiments (a H2 O = 1.0 and 0.5) were performed in the temperature range 780–1040°C at 2 and 5 kbar in order to determine the upper thermal stability of phlogopite in granitic melts. Starting compositions were: (A) subaluminous mixtures of 20 wt % synthetic phlogopite and 80 wt % synthetic anhydrous haplogranitic glass; (B) peraluminous mixtures (normative corundum  = 4 %) of 20 wt % synthetic phlogopite and 80 wt % synthetic anhydrous peraluminous haplogranitic glass. The molar quartz: albite: orthoclase ratio of the glasses of the 2␣kbar runs was 35:39:26 and that of the 5 kbar runs 30:42:28. In the subaluminous system, phlogopite is stable up to 820°C at a H2 O = 1.0 and up to 780°C at a H2 O = 0.5. At higher temperatures, it is replaced by enstatite. In the peraluminous system phlogopite has a remarkably higher thermal stability (up to 1000°C at 5 kbar and a H2 O = 1.0) and there is a temperature interval of 80°C at a H2 O = 1.0, and 90–100°C at a H2 O = 0.5 between the first appearance of enstatite and the disappearance of phlogopite. In the peraluminous system, phlogopite is a solid solution (ss) of phlogopite, muscovite, talc and eastonite components. The crystalline product of the phlogopitess breakdown reaction is an aluminous enstatite. The MgO-content of the melt depends on the normative corundum content of the starting material and the run temperature. It is independent of pressure. In the subaluminous system, the MgO-content ranges between 0.05 and 0.3 wt % in the temperature interval 780–880°C at both investigated water activities. The MgO-content of the peraluminous melts at a H2 O = 1.0 ranges between 0.4 and 1.7 wt % and at a H2 O = 0.5 between 0.2 and 1.4 wt % in the temperature range 780–980°C. Received: 28 August 1995 / Accepted: 6 August 1996  相似文献   

10.
Summary In the Odenwald Crystalline Complex, calc-silicate rocks are concentrated at the margins of the marble layer of Auerbach. They were presumably formed by metasomatic exchange between the calcite marble and the neighbouring granodioritic and quartz-dioritic intrusives. The investigated samples contain the characteristic mineral assemblages: garnet + clinopyroxene + epidote/clinozoisite + calcite + quartz ± titanite (1) and wollastonite + clinopyroxene + garnet + calcite ± quartz ± epidote/clinozoisite ± titanite (2). Microprobe analyses revealed the following compositional ranges: garnet grs40–98adr2–55alm<5.5sps<5.5pyp<1; clinopyroxene di46–88hed9–47joh0–5cats0–6; epidote/clinozoisite ps20–80. Different phase diagrams were calculated in the system CaO-MgO-Al2O3-TiO2-SiO2-CO2-H2O (CMATSCH) to decipher the P-T-XCO2 parameters of metamorphism: isobaric T-XCO2 sections and a P-T projection with mixed volatiles. The phase diagrams illustrate that the observed assemblages can only form in the presence of an H2O-rich volatile phase. The assemblages are stable over a large range of temperatures, from 580 °C to < 400 °C (at 4 kbar) and at XCO2 values of less than 0.055 (at 4 kbar). Higher temperatures can be inferred from reaction textures which indicate that garnet + plagioclase (T > 580 °C, at 4 kbar) and wollastonite + plagioclase (T > 660 °C, at 4 kbar) coexisted during an early metamorphic stage. A minimum pressure of 3.5 kbar can be inferred for the early high-temperature stage. Furthermore, on the basis of the calculated phase diagrams, combined with modal abundances in thin sections, it is possible to evaluate fluid behaviour; in the investigated specimens, infiltration of fluids from an external reservoir occurred. A minimum fluid:rock ratio of 3.6:1 can be estimated.
Zusammenfassung Phasenbeziehungen in Kalksilikat-Paragenesen des Marmorzuges von Auerbach, Odenwald-Kristallin-Komplex, Deutschland Im kristallinen Odenwald konzentrieren sich kalksilikatische Gesteine in den Randbereichen des Marmorzuges von Auerbach. Die kalksilikatischen Partien wurden vermutlich duch metasomatischen Austausch zwischen dem Calcit-Marmor und benachbarten Granodioriten und Quarzdioriten gebildet. Die untersuchten Proben enthalten die charakteristischen Mineralparagenesen: Granat + Klinopyroxen + Epidot/Klinozoisit + Calcit + Quarz + Titanit (1) und Wollastonit + Klinopyroxen + Granat + Calcit ± Quarz ± Epidot/Klinozoisit ± Titanit (2). Mikrosondenanalysen ergaben folgendes Zusammensetzungsspektrum: Granat grs40–98adr2–55alm<5.5sps<5.5pyp<1; Klinopyroxen di46–88hed9–47joh0–5cats0–6s; Epidot/Klinozoisit ps20–80. Verschiedene Phasendiagramme wurden für das Modellsystem CaO-MgO-Al2O3-TiO2-SiO2-CO2-H2O (CMATSCH) berechnet, um die P-T-XCO2-Parameter der Metamorphose einzugrenzen: Isobare T-XCO2-Schnitte und eine P-T-Projektion mit einer Fluid-Mischphase. Die Phasendiagramme verdeutlichen, da? die beobachteten Paragenesen nur in Anwesenheit eines H2O-reichen Fluids gebildet werden k?nnen. Die Paragenesen sind über einen gro?en Temperaturbereich hinweg stabil, von 580 °C bis < 400 °C (bei 4 kbar) und bei XCO2-Gehalten von < 0.055 (bei 4 kbar). Ursprünglich h?here Temperaturen k?nnen anhand von Reaktions-Texturen rekonstruiert werden, die zeigen, da? Granat + Plagioklas (T > 580 °C, bei 4 kbar) und Wollastonit + Plagioklas (T > 660 °C, bei 4 kbar) w?hrend eines früheren Metamorphosestadiums koexistierten. Ein Minimaldruck von 3.5 kbar kann für dieses frühe Hochtemperatur-Stadium abgeleitet werden. Mit Hilfe der berechneten Phasendiagramme, in Kombination mit beobachteten Modalgehalten, ist es m?glich, das Verhalten der fluiden Phase abzusch?tzen. Die untersuchten Gesteine implizieren Fluidinfiltration, wobei ein minimales Verh?ltnis Fluid:Gestein von 3.6:1 abgesch?tzt werden kann.

Received July 29, 1999; accepted March 28, 2000  相似文献   

11.
Petrographic, electron microprobe, and bulk-rock geochemical analyses indicate that the distribution and composition of ferromagnesian silicates (biotite, garnet, and staurolite) in and adjacent to the metamorphosed Bleikvassli Zn–Pb–(Cu) volcanogenic massive sulfide deposit, Norway, are dependent upon the competing effects of f O2–f S2 and host-rock composition. The enrichment in magnesium content of these silicates within the orebody and at distances of as much as 5–10 m away is due to the increased f O2 and f S2 conditions imposed on the silicates in zones subject to minor hydrothermal alteration during regional metamorphism. Alternatively, within pelitic country rocks at distances >5–10 m from ore, the host-rock chemistry controls the composition of metamorphic silicate minerals. Also, country rocks within a few meters of ore are distinguished by the common presence of zinc-bearing staurolite (up to 9 wt% ZnO) coexisting with biotite ± garnet. Rocks in the Bleikvassli deposit were hydrothermally enriched in zinc and fluorine prior to metamorphism. The fluorine resides mainly in biotite, which is an additional contributing factor to the magnesium enrichment of that mineral due to Fe2+–F avoidance. Our inference that the sulfidation–oxidation halo around the Bleikvassli ore deposit is only meters in width contrasts with the view of Maiga (1983), who proposed the effects of sulfidation could be identified at distances >159 m from ore. It is evident that the delineation of a sulfidation–oxidation halo bordering a metamorphosed massive sulfide deposit must be done carefully in order to discriminate between the effects due to variations in primary rock composition versus those resulting from a sulfur and oxygen fugacity gradient between the massive sulfides and the sulfur-poor country rocks. Received: 1 March 1998 / Accepted: 3 May 2000  相似文献   

12.
 The equilibrium water content of cordierite has been measured for 31 samples synthesized at pressures of 1000 and 2000 bars and temperatures from 600 to 750° C using the cold-seal hydrothermal technique. Ten data points are presented for pure magnesian cordierite, 11 data points for intermediate iron/magnesium ratios from 0.25 to 0.65 and 10 data points for pure iron cordierite. By representing the contribution of H2O to the heat capacity of cordierite as steam at the same temperature and pressure, it is possible to calculate a standard enthalpy and entropy of reaction at 298.18° K and 1 bar for, (Mg,Fe)2Al4Si5O18+H2O ⇄ (Fe,Mg)2Al4Si5O18.H2O Combining the 31 new data points with 89 previously published experimental measurements gives: ΔH ° r =–37141±3520 J and ΔS °  r =–99.2±4 J/degree. This enthalpy of reaction is within experimental uncertainty of calorimetric data. The enthalpy and entropy of hydration derived separately for magnesian cordierite (–34400±3016 J, –96.5±3.4 J/degree) and iron cordierite (–39613±2475, –99.5±2.5 J/degree) cannot be distinguished within the present experimental uncertainty. The water content as a function of temperature, T(K), and water fugacity, f(bars), is given by n H2O=1/[1+1/(K ⋅ f H2O)] where the equilibrium constant for the hydration reaction as written above is, ln K=4466.4/T–11.906 with the standard state for H2O as the gas at 1 bar and T, and for cordierite components, the hydrous and anhydrous endmembers at P and T. Received: 2 August 1994/Accepted: 7 February 1996  相似文献   

13.
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   

14.
Liquidus phase relations have been experimentally determined in the systems Qz-Ab-Or-(H2O), Qz-Ab-(H2O) and Qz-Or-(H2O) at H2O-undersaturated conditions (a H2O = 0.07) and P = 5 kbar. Starting materials were homogeneous synthetic glasses containing 1 wt% H2O. The liquidus temperatures were bracketed by crystallization and dissolution experiments. The results of kinetic studies showed that crushed glasses are the best starting materials to overcome undercooling and to minimize the temperature difference between the lowest temperature of complete dissolution (melting) and the highest temperature at which crystallization can be observed. At P = 5 kbar and a H2O = 0.07, the Qz-Ab eutectic composition is Qz32Ab68 at 1095 °C (±10 °C) and the Qz-Or eutectic is Qz38Or62 at 1030 °C (±10 °C). The minimum temperature of the ternary system Qz-Ab-Or is 990 °C (±10 °C) and the minimum composition is Qz32Ab35‐ Or33. The Qz content of the minimum composition in the system Qz-Ab-Or-H2O remains constant with changing a H2O. The normative Or content, however, increases by approximately 10 wt% with decreasing a H2O from 1 to 0.07. Such an increase has already been observed in the system Qz-Ab-Or-H2O-CO2 at high a H2O and it is concluded that the use of CO2 to reduce water activities does not influence the composition of the minima in quartz-feldspar systems. The determined liquidus temperature in melts with 1 wt% H2O is very similar to that obtained in previous nominally “dry” experiments. This discrepancy is interpreted to be due to problems in obtaining absolutely dry conditions. Thus, the hitherto published solidus and liquidus temperatures for “dry” conditions are probably underestimated. Received: 27 March 1997 / Accepted: 1 October 1997  相似文献   

15.
  The diffusivity of water has been investigated for a haplogranitic melt of anhydrous composition Qz28Ab38Or34 (in wt %) at temperatures of 800–1200°C and at pressures of 0.5–5.0 kbar using the diffusion couple technique. Water contents of the starting glass pairs varied between 0 and 9 wt %. Concentration-distance profiles for the different water species (molecular water and hydroxyl groups) were determined by near-infrared microspectroscopy. Because the water speciation of the melt is not quenchable (Nowak 1995; Nowak and Behrens 1995; Shen and Keppler 1995), the diffusivities of the individual species can not be evaluated directly from these profiles. Therefore, apparent chemical diffusion coefficients of water (D water) were determined from the total water profiles using a modified Boltzmann-Matano analysis. The diffusivity of water increases linearly with water content <3 wt % but exponentially at higher water contents. The activation energy decreases from 64 ± 10 kJ/mole for 0.5 wt % water to 46 ± 5 kJ/mole for 4 wt % water but remains constant at higher water contents. A small but systematic decrease of D water with pressure indicates an average activation volume of about 9 cm3/mole. The diffusivity (in cm2/s) can be calculated for given water content (in wt %), T (in K) and P (in kbar) by
in the ranges 1073 K ≤ T ≤ 1473 K; 0.5 kbar ≤ P≤ 5␣kbar; 0.5 wt % ≤ C water ≤ 6 wt %. The absence of alkali concentration gradients in the glasses after the experiments shows that interdiffusion of alkali and H+ or H3O+ gives no contribution to the transport of water in aluminosilicate melts. The H/D interdiffusion coefficients obtained at 800°C and 5 kbar using glass pieces with almost the same molar content of either water or deuterium oxide are almost identical to the chemical diffusivities of water. This indicates that protons are transported by the neutral component H2O under these conditions. Received: 26 March 1996 / Accepted: 23 August 1996  相似文献   

16.
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   

17.
Summary Pyroclastites erupted from the Upper Pollara magma chamber (13 ka, Salina Island, Aeolian Archipelago) resulted from mingling and mixing of rhyolitic and andesitic magmas. An experimental study has been conducted on the rhyolitic end-member to constrain the pre-eruptive conditions of the magma. In order to check for the role of mixing on the equilibrium phase assemblage, three different starting compositions, corresponding to three different mixing degrees, have been used. The crystallization experiments were conducted at two different oxygen fugacities and at variable temperature and fluid contents. The results indicate that the natural mineralogical assemblage can only be reproduced from a composition showing a certain degree of mixing. Assuming a pressure of 200 MPa (generally accepted for the Aeolian Islands), the pre-eruptive temperature of the magmas is estimated between 755 and 800 °C and the water content of the melt was higher than 4–4.5 wt.%. The Upper Pollara magma crystallized at relatively high fO2 (ΔlogfO2 = Ni–NiO + 1 log unit), compared to rhyolitic magmas from Lipari and Vulcano. As this difference has not been observed for the most primitive magmas the difference in fO2 could be related to different degassing processes operating in Salina and Lipari – Vulcano magmas.  相似文献   

18.
Fluid inclusions in granite quartz and three generations of veins indicate that three fluids have affected the Caledonian Galway Granite. These fluids were examined by petrography, microthermometry, chlorite thermometry, fluid chemistry and stable isotope studies. The earliest fluid was a H2O-CO2-NaCl fluid of moderate salinity (4–10 wt% NaCl eq.) that deposited late-magmatic molybdenite mineralised quartz veins (V1) and formed the earliest secondary inclusions in granite quartz. This fluid is more abundant in the west of the batholith, corresponding to a decrease in emplacement depth. Within veins, and to the east, this fluid was trapped homogeneously, but in granite quartz in the west it unmixed at 305–390 °C and 0.7–1.8 kbar. Homogeneous quartz δ18O across the batholith (9.5 ± 0.4‰n = 12) suggests V1 precipitation at high temperatures (perhaps 600 °C) and pressures (1–3 kbar) from magmatic fluids. Microthermometric data for V1 indicate lower temperatures, suggesting inclusion volumes re-equilibrated during cooling. The second fluid was a H2O-NaCl-KCl, low-moderate salinity (0–10 wt% NaCl eq.), moderate temperature (270–340 °C), high δD (−18 ± 2‰), low δ18O (0.5–2.0‰) fluid of meteoric origin. This fluid penetrated the batholith via quartz veins (V2) which infill faults active during post-consolidation uplift of the batholith. It forms the most common inclusion type in granite quartz throughout the batholith and is responsible for widespread retrograde alteration involving chloritization of biotite and hornblende, sericitization and saussuritization of plagioclase, and reddening of K-feldspar. The salinity was generated by fluid-rock interactions within the granite. Within granite quartz this fluid was trapped at 0.5–2.3 kbar, having become overpressured. This fluid probably infiltrated the Granite in a meteoric-convection system during cooling after intrusion, but a later age cannot be ruled out. The final fluid to enter the Granite and its host rocks was a H2O-NaCl-CaCl2-KCl fluid with variable salinity (8–28 wt% NaCl eq.), temperature (125–205 °C), δD (−17 to −45‰), δ18O (−3 to + 1.2‰), δ13CCO2 (−19 to 0‰) and δ34Ssulphate (13–23‰) that deposited veins containing quartz, fluorite, calcite, barite, galena, chalcopyrite sphalerite and pyrite (V3). Correlations of salinity, temperature, δD and δ18O are interpreted as the result of mixing of two fluid end-members, one a high-δD (−17 to −8‰), moderate-δ18O (1.2–2.5‰), high-δ13CCO2 (> −4‰), low-δ34Ssulphate (13‰), high-temperature (205–230 °C), moderate-salinity (8–12 wt% NaCl eq.) fluid, the other a low-δD (−61 to −45‰), low-δ18O (−5.4 to −3‰), low-δ13C (<−10‰), high-δ34Ssulphate (20–23‰) low-temperature (80–125 °C), high-salinity (21–28 wt% NaCl eq.) fluid. Geochronological evidence suggests V3 veins are late Triassic; the high-δD end-member is interpreted as a contemporaneous surface fluid, probably mixed meteoric water and evaporated seawater and/or dissolved evaporites, whereas the low-δD end-member is interpreted as a basinal brine derived from the adjacent Carboniferous sequence. This study demonstrates that the Galway Granite was a locus for repeated fluid events for a variety of reasons; from expulsion of magmatic fluids during the final stages of crystallisation, through a meteoric convection system, probably driven by waning magmatic heat, to much later mineralisation, concentrated in its vicinity due to thermal, tectonic and compositional properties of granite batholiths which encourage mineralisation long after magmatic heat has abated. Received: 3 April 1996 / Accepted: 5 May 1997  相似文献   

19.
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   

20.
The water solubility in haplogranitic melts (normative composition Ab39Or32Qz29) coexisting with H2O-H2 fluids at 800 and 950 °C and 1, 2 and 3 kbar vapour pressure has been determined using IR spectroscopy. The experiments were performed in internally heated pressure vessels and the hydrogen fugacity (f H2) was controlled using the double capsule technique and oxygen buffer assemblages (WM and IW). Due to the limited lifetimes of these oxygen buffers the water solubility was determined from diffusion profiles (concentration-distance profiles) measured with IR spectroscopy in the quenched glasses. The reliability of the experimental strategy was demonstrated by comparing the results of short- and long-duration experiments performed with pure H2O fluids. The water solubility in Ab39Or32Qz29 melts equilibrated with H2O-H2 fluids decreases progressively with decreasing f H2O, as f H2 (or X H2) increases in the fluid phase. The effect of H2 on the evolution of the water solubility is similar to that of CO2 or another volatile with a low solubility in the melt and can be calculated in a first approximation with the Burnham water solubility model. Recalculation of high temperature water speciation for AOQ melts coexisting with H2O-H2 fluids at 800 °C, 2 kbar suggests that the concentrations of molecular H2O are proportional to f H2O (calculated using available mixing models), indicating Henrian behaviour for the solubility of molecular H2O in haplogranitic melts. Received: 29 June 1998 / Accepted: 10 March 1999  相似文献   

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