Experimentally derived thermochemical data for pargasite and reinvestigation of its stability with quartz in the system Na2O–CaO–>MgO–Al2O3–SiO2–H2O

 The stability of pargasite in the presence of excess quartz has been determined in the range of 0.5–6.0 kbar and 500–950 °C in the system Na₂O– CaO–MgO–Al₂O₃–SiO₂–H₂O, using synthetic minerals. The experimental results from this study indicate the presence of two distinct mineral assemblage regions: (1) a high temperature supersolidus region containing tremolitic amphibole+melt+quartz; (b) a low temperature subsolidus region consisting of Al-rich amphibole+plagioclase+enstatite+quartz. Compositional reversals have been determined for the following three equilibria: (a) 2 pargasite+9 quartz=tremolite+4 plagioclase (An₅₀)+1.5 enstatite+H₂O, (b) 2 pargasite+10 quartz=tremolite+4 plagioclase (An₅₀)+talc, and (c) pargasite+diopside+5 quartz=tremolite+2 plagioclase (An₅₀). These experiments indicate a continuous change of amphibole composition from pargasite to tremolite with increasing temperature, and an opposite effect with increasing pressure. The third equilibria is used to constrain a site-mixing model for the pargasitic amphiboles, which favor a single-coupled Na^A-Al^T1 site mixing. The thermochemical data for pargasite estimated from the reversal data of the three equilibrium reactions is estimated as for ΔG ⁰ _f ,Pg=−12022.11±5.2 kJ mole^-1, and S ⁰ _Pg=591.7 ±7.9 JK^-1 mole^-1. Received: 31 July 1995/Accepted: 3 June 1996     

Phase relations in the tremolite-pargasite join

The join tremolite (Tr)-pargasite (Pa) has been studied in the temperature range 750 °–1,150 ° C under a water vapor pressure of 1 and 5 kbar. There is a continuous solid solution series between the compositions Tr₈₅Pa₁₅ and Tr_oPa₁₀₀ at 850 ° C and 5 kbar. Tremolite and pargasite are separated by a solvus at 1 kbar and the field of tremolitic amphibole +pargasitic amphibole+vapor is present in the region between Tr₉₀Pa₁₀ and Tr₁₀Pa₉₀ at 800 ° C. The phase assemblages at 850 ° C and 1 kbar change as follows with increasing pargasite component; clinopyroxene +orthopyroxene+quartz+vapor, tremolitic amphibole+vapor, tremolitic amphibole+clinopyroxene +forsterite+plagioclase+vapor, tremolitic amphibole+pargasitic amphibole+vapor, and pargasitic amphibole+vapor. The petrological significance of amphibole pairs in metamorphic rocks is discussed on the basis of the experimental results.     

Melting and subsolidus reactions in the system K2O-CaO-Al2O3-SiO2-H2O

Beginning of melting and subsolidus relationships in the system K₂O-CaO-Al₂O₃-SiO₂-H₂O have been experimentally investigated at pressures up to 20 kbars. The equilibria discussed involve the phases anorthite, sanidine, zoisite, muscovite, quartz, kyanite, gas, and melt and two invariant points: Point [Ky] with the phases An, Or, Zo, Ms, Qz, Vapor, and Melt; point [Or] with An, Zo, Ms, Ky, Qz, Vapor, and Melt.The invariant point [Ky] at 675° C and 8.7 kbars marks the lowest solidus temperature of the system investigated. At pressures above this point the hydrated phases zoisite and muscovite are liquidus phases and the solidus temperatures increase with increasing pressure. At 20 kbars beginning of melting occurs at 740 °C. The solidus temperatures of the quinary system K₂O-CaO-Al₂O₃-SiO₂-H₂O are almost 60° C (at 20 kbars) and 170° C (at 2kbars) below those of the limiting quaternary system CaO-Al₂O₃-SiO₂-H₂O.The maximum water pressure at which anorthite is stable is lowered from 14 to 8.7 kbars in the presence of sanidine. The stability limits of anorthite+ vapor and anorthite+sanidine+vapor at temperatures below 700° C are almost parallel and do not intersect. In the wide temperature — pressure range at pressures above the reaction An+Or+Vapor = Zo+Ms+Qz and temperatures below the melting curve of Zo+Ms+Ky+Qz+Vapor, the feldspar assemblage anorthite+sanidine is replaced by the hydrated phases zoisite and muscovite plus quartz. CaO-Al₂O₃-SiO₂-H₂O. Knowledge of the melting relationships involving the minerals zoisite and muscovite contributes to our understanding of the melting processes occuring in the deeper parts of the crust. Beginning of melting in granites and granodiorites depends on the composition of plagioclase. The solidus temperatures of all granites and granodiorites containing plagioclases of intermediate composition are higher than those of the Ca-free alkali feldspar granite system and below those of the Na-free system discussed in this paper.The investigated system also provides information about the width of the P-T field in which zoisite can be stable together with an Al₂SiO₅ polymorph plus quartz and in which zoisite plus muscovite and quartz can be formed at the expense of anorthite and potassium feldspar. Addition of sodium will shift the boundaries of these fields to higher pressures (at given temperatures), because the pressure stability of albite is almost 10kbars above that of anorthite. Assemblages with zoisite+muscovite or zoisite+kyanite are often considered to be products of secondary or retrograde reactions. The P-T range in which hydration of granitic compositions may occur in nature is of special interest. The present paper documents the highest temperatures at which this hydration can occur in the earth's crust.     

Zoisite- and clinozoisite-segregations in metabasites (Tauern Window, Austria) as evidence for high-pressure fluid–rock interaction

High-pressure zoisite- and clinozoisite-bearing segregations are common in garnet- and albite-bearing amphibolites of the Palaeozoic part of the Lower Schieferhülle, south-central Tauern Window, Austria. The zoisite segregations (primary assemblage: Zo+Qtz+Cal) formed during an early to pre-Hercynian high-pressure event (P≫0.6 GPa, T =500–550 °C) by hydrofracturing as a result of protolith dehydration. Zoisite is growth zoned from Fe³⁺-poor cores (Al₂Fe=9 mol%) to Fe³⁺-rich rims (17 mol%), and has high Sr, Pb and Ga contents and LREE-enriched REE patterns, controlling the trace element budget of the segregations. Hercynian deformation at c. 0.7 GPa/600 °C kinked and cracked primary zoisite and enhanced breakdown into secondary zoisite (13 mol% Al₂Fe), clinozoisite (40–55 mol% Al₂Fe), albite (an_<20), calcite and white mica during an Eoalpine high-pressure event at 0.9–1.2 GPa/400–500 °C. The clinozoisite segregations (primary assemblage: Czo+Qtz+Omp+Ttn+Chl+Cal) are mm- to cm-wide, vein-like bodies, cross-cutting fabric elements of the host garnet amphibolite. They formed during the Eoalpine high-pressure event at 0.9–1.2 GPa/400–500 °C. During Alpine exhumation, omphacite was pseudomorphed by amphibole, albite, quartz and clinozoisite. Oxygen isotope data suggest equilibrium between host metabasite and zoisite segregations and indicate an internal fluid source and fluid buffering by the protolith. Mobility of P, Nb and LREE changed the protolith’s trace element composition in the vicinity of the zoisite segregations: Mobilization of LREE is evidenced by decreasing modal amounts of LREE-rich epidote and decreasing LREE contents in LREE-rich epidote towards the segregations, changing the REE patterns of the host metabasite from LREE-enriched to LREE-depleted. Tectonic discrimination diagrams, based on the trace element content of metabasites, should be applied with extreme caution.     

Upper-pressure stability of synthetic margarite plus quartz

Thermodynamic calculations have shown that the dP/dT slope of the reaction 4 margarite+3 quartz5 kyanite +2 zoisite+3 H₂O as determined by Storre and Nitsch (1974) is too steep. This reaction has been reinvestigated using synthetic margarite, zoisite, kyanite, and natural quartz in the starting mixtures and using infrared spectroscopy to examine the run products. The experimentally determined dP/dT slope ranges between –2.2 and –17 bars/ K, which is in excellent agreement with predictions based on thermodynamics. An internally consistent set of univariant curves could be fitted to the experimental reversals for the above reaction and for the reactions margarite+ quartz anorthite+kyanite+H₂O and 2 zoisite+kyanite +quartz 4 anorthite+H₂O investigated by Nitsch et al. (1981) and Goldsmith (1981), respectively. Addition of up to 40 mol % of the component NaAl₂(Si₃Al) ·O₁₀(OH)₂ (paragonite) to margarite will increase the stability of the margarite solid solution plus quartz by 2–3 kbar without significantly affecting the dP/dT slope, making the paragenesis margarite plus quartz a good geobarometer.     

Phase relations in the greenschist-blueschist-amphibolite-eclogite facies in the system Na2O-CaO-FeO-MgO-Al2O3-SiO2-H2O (NCFMASH), with application to metamorphic rocks from Samos, Greece

Calculated phase equilibria among the minerals sodic amphibole, calcic amphibole, garnet, chloritoid, talc, chlorite, paragonite, margarite, omphacite, plagioclase, carpholite, zoisite/clinozoisite, lawsonite, pyrophyllite, kyanite, sillimanite, quartz and H₂O are presented for the model system Na₂O-CaO-FeO-MgO-Al₂O₃-SiO₂-H₂O (NCFMASH), which is relevant for many greenschist, blueschist, amphibolite and eclogite facies rocks. Using the activity-composition relationships for multicomponent amphiboles constrained by Will and Powell (1992), equilibria containing coexisting calcic and sodic amphiboles could be determined. The blueschist–greenschist transition reaction in the NCFMASH system, for example, is defined by the univariant reaction sodic amphibole + zoisite = calcic amphibole + chlorite + paragonite + plagioclase (+ quartz + H₂O) occurring between approximately 420 and 450 °C at 9.5 to 10 kbar. The calculated petrogenetic grid is a valuable tool for reconstructing the PT-evolution of metabasic rocks. This is shown for rocks from the island of Samos, Greece. On the basis of mineral and whole rock analyses, PT-pseudosections were calculated and, together with the observed mineral assemblages and reaction textures, are used to reconstruct PT-paths. For rocks from northern Samos, pseudomorphs after lawsonite preserved in garnet, the assemblage sodic amphibole-garnet-paragonite-chlorite-zoisite-quartz and the retrograde appearance of albitic plagioclase and the formation of calcic amphibole around sodic amphibole constrain a clockwise PT-path that reaches its thermal maximum at some 520 °C and 19 kbar. The derived PT-trajectory indicates cooling during exhumation of the rocks and is similar to paths for rocks from the western part of the Attic-Cycladic crystalline complex. Rocks from eastern Samos indicate lower pressures and are probably related to high-pressure rocks from the Menderes Massif in western Turkey. Received: 8 July 1997 / Accepted: 11 February 1998     

The high-pressure stability of zoisite and phase relationships of zoisite-bearing assemblages

The fluid-absent reaction 12 zoisite = 3 lawsonite + 7 grossular + 8 kyanite + 1 coesite was experimentally reversed in the model system CaO-Al₂O₃-SiO₂-H₂O (CASH) using a multi-anvil apparatus. The upper pressure stability limit for zoisite was found to extend to 5.0 GPa at 700 °C and to 6.6 GPa at 950 °C. Additional experiments both in the H₂O-SiO₂-saturated and in the H₂O-Al₂O₃-saturated portions of CASH provide further constraints on high pressure phase relationships of lawsonite, zoisite, grossular, kyanite, coesite, and an aqueous fluid. Consistency of the present experiments with the H₂O-saturated breakdown of lawsonite is demonstrated by thermodynamic analysis using linear programming techniques. Two sets of data consistent with databases of Berman (1988) and Holland and Powell (1990) were retrieved combining experimental phase relationships, calorimetric constraints, and recently measured elastic properties of solid phases. The best fits result in G _{f ,1,298} ^∘,zoisite=−6,499,400 J and S _1,298 ^∘,zoisite=302 J/K, and G _{f ,1,298} ^{∘,lawsonite}=−4,514,600 J and S _1,298 ^{∘,lawsonite}=220 J/K for the dataset of Holland and Powell, and G _{f ,1,298} ^∘,zoisite=−6,492,120 J and S _1,298 ^∘,zoisite=304 J/K, and G _{f ,1,298} ^{∘,lawsonite}=−4,513,000 J and S _1,298 ^{∘,lawsonite}= 218 J/K for the dataset of Berman. Examples of the usage of zoisite as a geohygrometer and as a geobarometer in rocks metamorphosed at eclogite facies conditions are worked, profiting from the thermodynamic properties retrieved here. Received: 23 December 1996 / Accepted: 29 August 1997     

The thermodynamic properties and phase relations of some minerals in the system CaO-AI2O3-SiO2-H2O

The heat capacities of lawsonite, margante, prehnite and zoisite have been measured from 5 to 350 K with an adiabatic-shield calorimeter and from 320 to 999.9 K with a differential-scanning calorimeter. At 298.15 K, their heat capacities, corrected to end-member compositions, are 66.35, 77.30, 79.13 and 83.84 cal K^?1 mol^?1; their entropies are 54.98, 63.01, 69.97 and 70.71 cal K^?1 mol^?1, respectively. Their high-temperature heat capacities are described by the following equations (in calories, K, mol): Lawsonite (298–600 K): Cp° = 66.28 + 55.95 × 10^?3T ? 15.27 × 10⁵T^?2 Margarite (298–1000 K): Cp° = 101.83 + 24.17 × 10^?3T ? 30.24 × 10⁵T^?2 Prehnite (298–800 K): Cp° = 97.04 + 29.99 × 10^?3T ? 25.02 × 10⁵T^?2 Zoisite (298–730 K): Cp° = 98.92 + 36.36 × 10^?3T ? 24.08 × 10⁵T^?2 Calculated Clapeyron slopes for univariant equilibria in the CaO-Al₂O₃-SiO₂-H₂O system compare well with experimental results in most cases. However, the reaction zoisite + quartz = anorthite + grossular + H₂O and some reactions involving prehnite or margarite show disagreements between the experimentally determined and the calculated slopes which may possibly be due to disorder in experimental run products. A phase diagram, calculated from the measured thermodynamic values in conjunction with selected experimental results places strict limits on the stabilities of prehnite and assemblages such as prehnite + aragonite, grossular + lawsonite, grossular + quartz, zoisite + quartz, and zoisite + kyanite + quartz. The presence of this last assemblage in eclogites indicates that they were formed at moderate to high water pressure.     

Equilibrium density and expansivity of silicate melts in the glass transition range

Equilibrium volumes and expansivities of three liquids in the system anorthite (CaAl₂Si₂O₈)–diopside (CaMgSi₂O₆) have been derived from dilatometric measurements of the equilibrium length of samples in the glass transition range. The typical temperature range of 40 K for the measurements is limited at low temperature by the very long times necessary to reach structural equilibrium and at high temperature by the penetration of the rod used to measure sample dilatation. Despite such narrow intervals, the expansivities are determined to better than 3% thanks to the high precision with which length changes are measured. The coefficient of volume thermal expansion (1/V dV/dT) of the fully relaxed liquid just above the glass transition is found to decrease linearly from diopside composition (139 ± 4 × 10⁻⁶ K⁻¹) to anorthite composition (59 ± 2 × 10⁻⁶ K⁻¹). These values are greater than those determined for the same liquids at superliquidus temperatures, demonstrating that expansivities of silicate melts may decrease markedly with increasing temperature. A predictive model based upon partial molar volumes which vary as a linear function of the logarithm of temperature is proposed. Received: 25 February 2000 / Accepted: 29 May 2000     

P–T evolution of kyanite eclogite from the Pirin Mountains (SW Bulgaria): implications for the Rhodope UHP Metamorphic Complex

A new occurrence of kyanite eclogite in the Pirin Mountains of southwestern Bulgaria within the rocks belonging to the Obidim Unit of the Rhodope Metamorphic Complex is presented. This eclogite provides important information about the peak–pressure conditions despite strong thermal overprint at low pressure. Textural relationships, phase equilibrium modelling and conventional geothermobarometry were used to constrain the metamorphic evolution. Garnet porphyroblasts with inclusions of omphacite (up to 43 mol.% Jd), phengite (up to 3.5 Si p.f.u.), kyanite, polycrystalline quartz, pargasitic amphibole, zoisite and rutile in the Mg‐rich cores (X_Mg = 0.44–0.46) record a prograde increase in P–T conditions from ～2.5 GPa and 650 °C to ～3 GPa and 700–750 °C. Maximum pressure values fall within the stability field of coesite. During exhumation, the peak–pressure assemblage garnet + omphacite + phengite + kyanite was variably overprinted by a lower pressure one forming symplectitic textures, such as diopside + plagioclase after omphacite and biotite + plagioclase after phengite. The development of spinel (X_Mg = 0.4–0.45) + corundum + anorthite assemblage in the kyanite‐bearing domains at ～1.1 GPa and 800–850 °C suggests a thermal overprint in the high‐pressure granulite facies stability field. This thermal event was followed by cooling at ～0.8 GPa under amphibolite facies conditions; retrograde kelyphite texture involving plagioclase and amphibole was developed around garnet. Our results add to the already existing evidence for ultra high pressure (UHP) metamorphism in the Upper Allochthon of the Rhodope Metamorphic Complex as in the Kimi Unit and show that it is more widespread than previously known. Published age data and field structural relations suggest that the Obidim Unit represents Variscan continental crust involved into the Alpine nappe edifice of the Rhodopes and that eclogite facies metamorphism was Palaeozoic, in contrast to the Kimi Unit where age determinations suggest a Jurassic or Cretaceous age for UHP metamorphism. This implies that UHP metamorphism in the Upper Allochthon of the Rhodopes may have occurred twice, during Alpine and pre‐Alpine orogenic events, and that two independent HP/UHP provinces of different age overlap in this area.     

Beginning of melting in the granite system Qz-Or-Ab-An-H2O

The beginning of melting in the system Qz-Or-Ab-An-H₂ O was experimentally reversed in the pressure range kbar using starting materials made up of mixtures of quartz and synthetic feldspars. With increasing pressure the melting temperature decreases from 690° C at 2 kbar to 630° C at 17 kbar in the An-free alkalifeldspar granite system Qz-Or-Ab-H₂O. In the granite system Qz-Or-Ab-An-H₂O the increase of the solidus temperature with increasing An-content is only very small. In comparison to the alkalifeldspar granite system the solidus temperature increases by 3° C (7° C) if albite is replaced by plagioclase An 20 (An 40). The difference between the solidus temperatures of the alkalifeldspar granite system and of quartz — anorthite — sanidine assemblages (system Qz-Or-An-H₂O) is approximately 50° C. With increasing water pressures plagioclase and plagioclase-alkalifeldspar assemblages become unstable and are replaced by zoisite+kyanite+quartz and zoisite+muscovite-paragonite_ss +quartz, respectively. The pressure stability limits of these assemblages are found to lie between 6 and 16 kbar at 600° C. At high water pressures (10–18 kbar) zoisite — muscovite — quartz assemblages are stable up to 700 and 720° C. The solidus curve of this assemblage is 10–20° C above the beginning of melting of sanidine — zoisite — muscovite — quartz mixtures. The amount of water necessary to produce sufficient amounts of melt to change a metamorphic rock into a magmatic looking one is only small. In case of layered migmatites it is shown that 1 % of water (or even less) is sufficient to transform portions of a gneiss into (magmatic looking) leucosomes. High grade metamorphic rocks were probably relatively dry, and anatectic magmas of granitic or granodioritic composition are usually not saturated with water.     

Relics of eclogite facies metamorphism in the Austroalpine basement,Hochgrössen (Speik complex), Austria

Summary Retrograde eclogites and serpentinites from the Hochgr?ssen massif, Styria, are parts of the Speik complex in the Austroalpine basement nappes of the Eastern Alps. They are in tectonic contact with pre-Alpine gneisses, amphibolites, and Permo-Triassic quartz phyllites (Rannach Series). The eclogites are derived from ocean-floor basalts with affinities to mid-ocean ridge and back-arc basin basalts. Fresh eclogites are rare and contain omphacite with a maximum of 39 mol% jadeite content, garnet (Py_15–19) and amphibole. Retrograde eclogites consist of amphibole and symplectites of Na-poor clinopyroxene (5–8 mol% Jd) + albite ± amphibole. Amphiboles are classified as edenite, pargasite, tschermakite, magnesiohornblende and actinolite. In relatively fresh eclogite, edenite is a common amphibole and texturally coexists with omphacite and garnet. An average temperature of 700 °C was obtained for eclogite facies metamorphism using garnet-pyroxene thermometry. A minimum pressure of 1.5 GPa is indicated by the maximum jadeite content in omphacite. Thermobarometric calculations using the TWEEQ program for amphibole in textural equilibrium with omphacite and garnet give pressures of 1.8–2.2 GPa at 700 °C. The equilibrium assemblage of Na-poor clinopyroxene, albite, amphibole and zoisite in the symplectites gives a pressure of about 0.6–0.8 GPa at 590–640 °C. ⁴⁰Ar/³⁹Ar radiometric dating of edenitic amphibole in textural equilibrium with omphacite gave a plateau age of 397.3 ± 7.8 Ma, and probably indicates retrograde cooling through the closure temperature for amphibole (∼500 °C). The age of the high-pressure metamorphism thus must be pre-Variscan and points to one of the earliest metamorphic events in the Austroalpine nappes known to date. Received June 11, 2000; revised version accepted January 2, 2001     

Zur Stabilität von Margarit im System CaO-Al2O3-SiO2-H2O

An increasing number of occurrences of margarite have been reported in the last years. However, previous experimental investigations in the system CaO-Al₂O₃-SiO₂-H₂O are limited to the synthesis of margarite and to the upper stability limit according to the reaction (1) 1 margarite?1 anorthite +1 corundum +1 H₂O (Chatterjee, 1971; Velde, 1971). Since margarite often occurs together with quartz, the upper stability limit of margarite in the presence of quartz is of special interest. Therefore, the reactions (5) 1 margarite +1 quartz ?1anorthite +1 kyanite/andalusite +1 H₂O and (6) 4 margarite+3 quartz ? 2 zoisite+5 kyanite+3 H₂O were investigated experimentally using mixtures of natural margarite (from Chester, Mass., USA), quartz, kyanite, andalusite, zoisite, and synthetic anorthite. The indicated equilibrium temperatures at water pressures equal to total pressure are: 515± 25°C at 4 kb, 545 ±15°C at 5 kb, 590±10°C at 7 kb, and 650±10°C at 9 kb for reaction (5), and 651±11°C at 10 kb, 648 ± 8°C at 12.5kb, and 643±13°C at 15kb for reaction (6), respectively. Besides this, additional brackets for equilibrium temperatures were determined for the above cited reaction (1): 520±10°C at 3 kb, 580±10°C at 5 kb, and 640± 20°C at 7 kb. On the basis of these experimentally determined reactions (1), (5), and (6) and of the reactions (3) 2 zoisite +1 kyanite? 4 anorthite +1 corundum +1 H₂O (7) 2 zoisite +1 kyanite +1 quartz ? 4 anorthite +1 H₂O and (10) 1 pyrophyllite ? 1 andalusite/kyanite+3 quartz+1 H₂O for which experimental or, in the case of reaction (3), calculated data were already available, a pressure-temperature diagram with 3 invariant points and 11 univariant reactions was developed using the method of Schreinemakers. This diagram, summarizing both experimental and phase relation studies, allows conclusions about the conditions under which margarite has been formed in nature. Margarite is limited to low grade metamorphism at water pressures up to approximately 3.5 kb; in the presence of quartz, margarite is even limited to low grade metamorphism at water pressures up to 5.5 kb. Only at water pressures higher than the values stated before margarite, and margarite+quartz, respectively, can occur in medium grade metamorphism (as defined by Winkler, 1970 and 1973). For the combined occurrence of margarite+quartz and staurolite as reported by Harder (1956) and Frey (personal communication, 1973) it may be estimated that water pressure has been greater than approximately 5.5 kb, wheras temperature has been in the range from 550 to 650°C. Furthermore, the present study shows that the assemblage zoisite+kyanite (+ H₂O) is an indicator of both pressure [P _{H 2 O}> approximately 9kb]and temperature [T> approximately 640 to 650° Cat water Pressures up to 15 kb].     

Fluid infiltration during contact metamorphism of interbedded marble and calc-silicate hornfels, Twin Lakes area, central Sierra Nevada, California

Abstract In the Twin Lakes area, central Sierra Nevada, California, most contact metamorphosed marbles contain calcite + dolomite + forsterite ± diopside ± phlogopite ± tremolite, and most calc-silicate hornfelses contain calcite + diopside + wollastonite + quartz ± anorthite ± K-feldspar ± grossular ± titanite. Mineral-fluid equilibria involving calcite + dolomite + tremolite + diopside + forsterite in two marble samples and wollastonite + anorthite + quartz + grossular in three hornfels samples record P± 3 kbar and T± 630° C. Various isobaric univariant assemblages record CO₂-H₂O fluid compositions of χCO₂= 0.61–0.74 in the marbles and χCO₂= 0.11 in the hornfelses. Assuming a siliceous dolomitic limestone protolith consisting of dolomite + quartz ° Calcite ± K-feldspar ± muscovite ± rutile, all plausible prograde reaction pathways were deduced for marble and hornfels on isobaric T-XCO₂ diagrams in the model system K₂O-CaO-MgO-Al₂O₃-SiO₂-H₂O-CO₂. Progress of the prograde reactions was estimated from measured modes and mass-balance calculations. Time-integrated fluxes of reactive fluid which infiltrated samples were computed for a temperature gradient of 150 °C/km along the fluid flow path, calculated fluid compositions, and estimated reaction progress using the mass-continuity equation. Marbles and hornfelses record values in the range 0.1–3.6 × 10⁴ cm³/cm² and 4.8–12.9 × 10⁴ cm³/cm², respectively. For an estimated duration of metamorphism of 10⁵ years, average in situ metamorphic rock permeabilities, calculated from Darcy's Law, are 0.1–8 × 10^?6 D in the marbles and 10–27 × 10^?6 D in the hornfelses. Reactive metamorphic fluids flowed up-temperature, and were preferentially channellized in hornfelses relative to the marbles. These results appear to give a general characterization of hydrothermal activity during contact metamorphism of small pendants and screens (dimensions ± 1 km or less) associated with emplacement of the Sierra Nevada batholith.     

Experimental studies on the formation of inclusions in plagioclases from metatonalites,Hohe Tauern,Austria (lower temperature stability limit of the paragenesis anorthite plus potash feldspar)

New experimental data are presented at stability conditions of paragenesis in the system K₂O-CaO-Al₂O₃-SiO₂-H₂O. These results are used to estimate the pressure temperature conditions under which minute inclusions, mostly consisting of zoisite/clinozoisite and muscovite, have crystallized in calcic plagioclases from metatonalites and metadiorites (Hohe Tauern, Austria). In the pressure region 1.5–8 kb the following reactions were observed: zoisite+muscovite+quartz=anorthite+potash feldspar+water (1) grossularite+muscovite+quartz=anorthite+potash feldspar+water (2) zoisite+quartz=anorthite+grossularite+water (3) natural plagioclase with its inclusions (zoisite/clinozoisite and muscovite) (4) =more basic plagioclase without inclusions.In order to determine the curves of reaction (1), (2) and (3), runs were made in hydrothermal bombs using synthetic phases crystallized from gels as starting materials. The reaction curves (1), (2) and (3) intersect at an invariant point at 7.25±0.5 kb and 685±20° C. In runs to define the reaction (4), it could be demonstrated that the inclusion minerals zoisite/ clinozoisite and muscovite became instable at slightly lower temperatures than those occurring in reaction (1). These facts illustrate that the reaction curve (1), found in the pure system, gives possible information about the pressure temperature conditions during the formation of the inclusions.     

Thermal expansion of gehlenite, Ca2Al[AlSiO7], and the related aluminates LnCaAl[Al2O7] with Ln = Tb, Sm

The thermal expansion of gehlenite, Ca₂Al[AlSiO₇], (up to T=830 K), TbCaAl[Al₂O₇] (up to T=1100 K) and SmCaAl[Al₂O₇] (up to T=1024 K) has been determined. All compounds are of the melilite structure type with space group Thermal expansion data were obtained from in situ X-ray powder diffraction experiments in-house and at HASYLAB at the Deutsches Elektronen Synchrotron (DESY) in Hamburg (Germany). The thermal expansion coefficients for gehlenite were found to be: α₁=7.2(4)×10⁻⁶×K⁻¹+3.6(7)×10⁻⁹ΔT×K⁻² and α₃=15.0(1)×10⁻⁶×K⁻¹. For TbCaAl[Al₂O₇] the respective values are: α₁=7.0(2)×10⁻⁶×K⁻¹+2.0(2)×10⁻⁹ΔT×K⁻² and α₃=8.5(2)×10⁻⁶×K⁻¹+2.0(3)×10⁻⁹ΔT×K⁻², and the thermal expansion coefficients for SmCaAl[Al₂O₇] are: α₁=6.9(2)×10⁻⁶×K⁻¹+1.7(2)×10⁻⁹ΔT×K⁻² and α₃=9.344(5)×10⁻⁶×K⁻¹. The expansion mechanisms of the three compounds are explained in terms of structural trends obtained from Rietveld refinements of the crystal structures of the compounds against the powder diffraction patterns. No structural phase transitions have been observed. While gehlenite behaves like a ‘proper’ layer structure, the aluminates show increased framework structure behavior. This is most probably explained by stronger coulombic interactions between the tetrahedral conformation and the layer-bridging cations due to the coupled substitution (Ca²⁺+Si⁴⁺)–(Ln ³⁺+Al³⁺) in the melilite-type structure. This article has been mistakenly published twice. The first and original version of it is available at .     

Phase relations and chemistry of Ti-rich K-richterite-bearing mantle assemblages: an experimental study to 8.0 GPa in a Ti-KNCMASH system

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

Thermal expansion of gehlenite, Ca2Al[AlSiO7], and the related aluminates LnCaAl[Al2O7] with Ln=Tb, Sm

The thermal expansion of gehlenite, Ca₂Al[AlSiO₇], (up to T=830 K), TbCaAl[Al₂O₇] (up to T=1,100 K) and SmCaAl[Al₂O₇] (up to T=1,024 K) has been determined. All compounds are of the melilite structure type with space group Thermal expansion data was obtained from in situ X-ray powder diffraction experiments in-house and at HASYLAB at the Deutsches Elektronen Synchrotron (DESY) in Hamburg (Germany). The thermal expansion coefficients for gehlenite were found to be: α₁=7.2(4)×10⁻⁶ K⁻¹+3.6(7)×10⁻⁹ΔT K⁻² and α₃=15.0(1)×10⁻⁶ K⁻¹. For TbCaAl[Al₂O₇] the respective values are: α₁=7.0(2)×10⁻⁶ K⁻¹+2.0(2)×10⁻⁹ΔT K⁻² and α₃=8.5(2)×10⁻⁶ K⁻¹+2.0(3)×10⁻⁹ΔT K⁻², and the thermal expansion coefficients for SmCaAl[Al₂O₇] are: α₁=6.9(2)× 10⁻⁶ K⁻¹+1.7(2)×10⁻⁹ΔT K⁻² and α₃=9.344(5)×10⁻⁶ K⁻¹. The expansion-mechanisms of the three compounds are explained in terms of structural trends obtained from Rietveld refinements of the crystal structures of the compounds against the powder diffraction patterns. No structural phase transitions have been observed. While gehlenite behaves like a ’proper’ layer structure, the aluminates show increased framework structure behaviour. This is most probably explained by stronger coulombic interactions between the tetrahedral conformation and the layer-bridging cations due to the coupled substitution (Ca²⁺+Si⁴⁺)-(Ln ³⁺+Al³⁺) in the melilite-type structure. Electronic Supplementary Material Supplementary material is available for this article at     

Ultra high temperature metamorphism of mafic granulites from South Altyn Orogen,West China: A result from the rapid exhumation of deeply subducted continental crust

The South Altyn orogen in West China contains ultra high pressure (UHP) terranes formed by ultra‐deep (>150–300 km) subduction of continental crust. Mafic granulites which together with ultramafic interlayers occur as blocks in massive felsic granulites in the Bashiwake UHP terrane, are mainly composed of garnet, clinopyroxene, plagioclase, amphibole, rutile/ilmenite, and quartz with or without kyanite and sapphirine. The kyanite/sapphirine‐bearing granulites are interpreted to have experienced decompression‐dominated evolution from eclogite facies conditions with peak pressures of 4–7 GPa to high pressure (HP)–ultra high temperature (UHT) granulite facies conditions and further to low pressure (LP)–UHT facies conditions based on petrographic observations, phase equilibria modelling, and thermobarometry. The HP–UHT granulite facies conditions are constrained to be 2.3–1.6 GPa/1,000–1,070°C based on the observed mineral assemblages of garnet+clinopyroxene+rutile+plagioclase+amphibole±quartz and measured mineral compositions including the core–rim increasing anorthite in plagioclase (X_An = 0.52–0.58), core–rim decreasing jadeite in clinopyroxene (X_Jd = 0.20–0.15), and TiO₂ in amphibole (Ti^M2/2 = 0.14–0.18). The LP–UHT granulite facies conditions are identified from the symplectites of sapphirine+plagioclase+spinel, formed by the metastable reaction between garnet and kyanite at <0.6–0.7 GPa/940–1,030°C based on the calculated stability of the symplectite assemblages and sapphirine–spinel thermometer results. The common granulites without kyanite/sapphirine are identified to record a similar decompression evolution, including eclogite, HP–UHT granulite, and LP–UHT granulite facies conditions, and a subsequent isobaric cooling stage. The decompression under HP–UHT granulite facies is estimated to be from 2.3 to 1.3 GPa at ~1,040°C on the basis of textural records, anorthite content in plagioclase (X_An = 0.25–0.32), and grossular content in garnet (X_Grs = 0.22–0.19). The further decompression to LP–UHT facies is defined to be >0.2–0.3 GPa based on the calculated stability for hematite‐bearing ilmenite. The isobaric cooling evolution is inferred mainly from the amphibole (Ti^M2/2 = 0.14–0.08) growth due to the crystallization of residual melts, consistent with a temperature decrease from >1,000°C to ~800°C at ~0.4 GPa. Zircon U–Pb dating for the two types of mafic granulite yields similar protolith and metamorphic ages of c. 900 Ma and c. 500 Ma respectively. However, the metamorphic age is interpreted to represent the HP–UHT granulite stage for the kyanite/sapphirine‐bearing granulites, but the isobaric cooling stage for the common granulites on the basis of phase equilibria modelling results. The two types of mafic granulite should share the same metamorphic evolution, but show contrasting features in petrography, details of metamorphic reactions in each stage, thermobarometric results, and also the meaning of zircon ages as a result of their different bulk‐rock compositions. Moreover, the UHT metamorphism in UHP terranes is revealed to represent the lower pressure overprinting over early UHP assemblages during the rapid exhumation of ultra‐deep subducted continental slabs, in contrast to the cause of traditional UHT metamorphism by voluminous heat addition from the mantle.     

Mode of formation of hibonite (CaAl12O19) within the U-Th skarns from the granulites of S-E Madagascar

 In Madagascar, hibonite occurs as a rather frequent mineral within thorianite-bearing skarns which are widespread in the Pan African granulitic formations constituting the S-E part of the Island (Tranomaro area). In these skarns, leucocratic segregations made up of CO₃-scapolite to meionite (An_equivalent=89–95% which implies T≥850° C), spinel and corundum were formed at stage 1 of metasomatism in a titanite-bearing matrix consisting of scapolite (An_eq=77–88) and aluminous diopside. During stage 2 of metasomatism, scapolite from the lenses were altered to anorthite+calcite while the less calcic scapolite remained stable which indicates T≈800° C. Hibonite crystallized at the expense of corundum and spinel. Expressed as mol% of the CaAl₁₂O₁₉/Ca(Al₁₀TiR²⁺)O₁₉/REE(Al₁₁R²⁺)O₁₉ [+Th (Al₁₀R²⁺ ₂)O₁₉] end-members (R ²⁺=Mg, Fe²⁺, Zn²⁺; Al=Al, Fe³⁺; Ti=Ti, Si), its composition varies from 26/72/2 to 50/23/27. The ideal activity of the CaAl₁₂O₁₉ component is about 0.25. Fluid inclusions in corundum, hibonite and anorthite are composed of nearly pure CO₂. In corundum, the isochores for primary inclusions are in agreement with the P-T estimates for regional metamorphism and stage 1 metasomatism (T≈850° C, P≈5 kbar). Inclusions with the highest density in hibonite and anorthite constrain P to about 3–3.5 kbar for T=800° C. Thermodynamic calculations indicate that, in addition to a low activity of CaAl₁₂O₁₉, stability of hibonite in equilibrium with anorthite and calcite implies an extremely low activity of silica (below the zircon-baddeleyite buffer). By contrast the activity of CO₂ may be high, in agreement with the observed fluid compositions. These results are corroborated by a short comparison with the other granulite occurrences of hibonite in Tanzania and South India. Received: 18 August 1994 / Accepted: 12 October 1995