Melting and subsolidus reactions in the system K2O−CaO−MgO−Al2O3−SiO2−H2O: experiments and petrologic application

Experiments with synthetic starting materials of muscovite, phlogopite, zoisite, kyanite and quartz were performed in the pressure temperature range 10–25 kbar, 640–780° C under water excess conditions. The reaction muscovite+zoisite+quartz+vapor=liquid+kyanite was bracketed at 10.5 kbar/689–700° C, 15.5 kbar/709–731° C and 20 kbar/734–745° C. The equivalent reaction in the Mg-bearing system muscovite_ss +zoisite+quartz+vapor=liquid+kyanite+phlogopite_ss lies at the same temperature around 10 kbar and approximately 10° C higher around 20 kbar, compared with the Mg-free reaction. At slightly higher temperatures formation of melt and tremolite_ss was reversibly observed from the assemblage phlogopite_ss+zoisite +kyanite+quartz around 10.5 kbar/690–710° C, 15.5 kbar/720–750° C and 20.5 kbar/745–760° C. In the subsolidus region, the reaction muscovite_ss+talc_ss+ tremolite_ss=phlogopite_ss+zoisite+quartz+vapor were located in the range 700° C/16.7–19.0 kbar and 740° C/19.7–20.8 kbar. From these data, a wedge shaped stability field of phlogopite_ss+zoisite+quartz appears with a high P, T termination around 21 kbar/755° C. Muscovite+tremolite+talc or kyanite comes in at higher pressures. These phase relations are in qualitative accord with petrographic observations from high pressure metamorphic areas. Formation and crystallization of melts in rocks of a wide compositional range involving zoisite/epidote has been ascribed to relatively high pressures and is consistent with experimentally determined stability fields in the simplified KCMASH system.     

Calculated greenschist facies mineral equilibria in the system CaO−FeO−MgO−Al2O3−SiO2−CO2−H2O

The kinetic problems associated with the experimental determination of reactions among complex solidsolution phases at low temperatures have hindered our understanding of the phase relations in greenschist facies rocks. In the absence of reliable experimental data, we have used the new, expanded internally-consistent thermodynamic dataset of Holland and Powell (1990), to present calculated phase equilibria for the system CaO–FeO–MgO–Al₂O₃–SiO₂–H₂O–CO₂ (CaFMASCH) with quartz in eccess, in the range 400°–500°C at low to intermediate pressures, involving the minerals amphibole, chlorite, anorthite, clinozoisite, dolomite, chloritoid, garnet, margarite, andalusite, and calcite. By solving independent sets of non-linear equations formed from equilibrium relationships, we calculate not only the loci of reactions in pressuretemperature-x(CO₂) space, but also the compositions of coexisting minerals in terms of the substitutions, FeMg_-1 and (Fe,Mg)SiAl_-1Al_-1. Invariant, univariant and divariant equilibria are calculated and discussed in relation to naturally-occurring greenschist facies metabasic and siliceous dolomitic mineral assemblages. We thus avoid the use of activity-corrected curves so commonly presented in the literature as a substitute for genuine univariant phase diagram boundaries.     

Forsterite-diopside-spinel-liquid equilibria in the system CaO−MgO−Al2O3−SiO2 at 20 kbar and petrological applications

Liquidus phase relationships in the CaAlAl–SiO₆–Mg₂SiO₄–CaMgSi₂O₆–CaAlSi₂O₈ portion of the simplified basalt tetrahedron in the CaO–MgO–SiO₂–Al₂O₃ system have been experimentally determined at 20 kbar pressure. The fo+di _ss+sp+li univariant curve, that pierces the fo-di-an join and meets the fo+di _ss+ en_ss+sp+li invariant point in the basalt tetrahedron, extends all the way to and pierces the di-fo-CaTs join, the limit of the simplified basalt tetrahedron toward the silica undersaturated portion.An algebraic method, relying on compositions of two successive liquids on a univariant curve and those of the crystalline phases in equilibrium with the respective liquids, is developed to identify the type of reaction that takes place along an isobarically univariant curve and to detect whether there is a temperature maximum on that curve. Use of this method for the di _ss+fo+sp+li univariant equilibria shows that a temperature maximum exists on this curve at the composition Fo₁₁Di₅₆An₃CaTs₃₀, very close to and slighthly to the SiO₂-rich side of the fo-di-CaTs join. The temperature along the univariant curve continuously decreases from the temperature maximum (1500°C) to the invariant point (1475°C) where the univariant curve is terminated by the appearance of e _ss as a member of the equilibrium assemblage. Along this part of the curve, a reaction relationship occurs according to the equation fo+li=di _ss+ sp. Compositions of di _ss in equilibrium with the liquids from the temperature maximum to the fo+di _ss+en_ss+ sp+li invariant point range from Di₆₆En₉CaTs₂₅ to Di₃₆En₄₀CaTs₂₄. Because of the reaction relationship of forsterite with liquid, fractional crystallization of a model alkalic basaltic liquid would cause liquids to move off the fo-di _ss-sp-li univariant curve onto the sp-di _ss divariant surface. Crystallization of di _ss and sp would then lead to silica enrichment of residual liquids. Thus at pressures below 30 kbar, at which pressure the Al₂O₃–CaSiO₃–MgSiO₃ plane becomes a new thermal divide cutting through both the tholeiitic and alkalic volumes, alkalic liquids will fractionate toward tholeiitic compositions without crossing a thermal divide. This relationship would be expected to persist at pressures down to about 4 kbar where a maximum on the fo-di-an-li boundary line causes a thermal divide near the fo-di-an plane. Strongly SiO₂-undersaturated liquids (e.g. nephelinites, basanites), on the other hand, cannot be derived from SiO₂-undersaturated basalts (e.g. alkali olivine basalt) by fractional crystallization at 20 kbar. We also found that no gt primary phase volume cuts the wo-en-Al₂O₃ join at 20 kbar pressure. The wehrlite, the olivine clinopyroxenite, and the Al-augite group lherzolite xenoliths, containing highly aluminous clinopyroxenes (enriched in Ca-Tschermak), can be interpreted as crystal cumulates from alkalic basalts in the light of this experimental study. This is consistent with the mode of origin of these xenoliths proposed from petrographic, mineralogic, and geochemical studies.Abbreviations and notations di CaMgSi₂O₆ - fo Mg₂SiO₄ - an CaAl₂Si₂O₈ - CaTs CaAlAlSiO₆ - sp MgAl₂O₄ - en MgSiO₃ - wo CaSiO₃ - gt Ca₃Al₂Si₃O₁₂–Mg₃Al₂Si₃O₁₂ - qz SiO₂ - li Liquid - gl glass - ss Solid Solution - A An mxn matrix - X A column vector - kbar kilobar     

High pressure fluids in the system MgO–SiO2–H2O under upper mantle conditions

Fluids and melts have been trapped and analysed in high pressure experiments in the model mantle system MgO-SiO₂-H₂O at 6 to 10.5 GPa and 900 to 1,200 °C. The fluid/melt traps consisted of a diamond layer that was added to the experimental charge and was separate from the silicate phases. The recovered diamond traps were analysed by laser ablation - ICP - MS. Starting materials were synthetic mixtures of brucite, talc and silica with variable Mg/Si containing 11-31 wt% H₂O. Experiments on a serpentine starting composition [Mg₃Si₂O₅(OH)₄] result in MgO/SiO₂ weight ratios in the subsolidus fluids close to 1 at 6 GPa and close to 2 at 9 GPa. Melt compositions at 6 and 9 GPa have MgO/SiO₂ ratios close to that of forsterite. At a single pressure the amount of dissolved silicate in the fluid increases steadily with increasing temperature up to 1,150 °C, where a sudden increase of both SiO₂ and MgO is observed. This discrete step marks the solidus, which is more clearly developed at 6 than at 9 GPa. Thus, hydrous melts within the model mantle subsystem Mg₂SiO₄-Mg₂Si₂O₆-H₂O are chemically distinct from aqueous fluids up to at least 9 GPa, corresponding to 300 km depth. Extrapolation of the current data set implies that total convergence between fluid and melt along the solidus probably occurs at 12-13 GPa (~400 km), i.e. close to the Earth's mantle transition zone. Beneath cratons, interactions of hydrous fluids with upper mantle lithologies cause relative silica depletion (olivine enrichment) at depths greater than 200 km and silica (orthopyroxene) enrichment at shallower depths.     

Calculated mineral equilibria in the greenschist-blueschist-eclogite facies in Na2O−FeO−MgO−Al2O3−SiO2−H2O

The new, greatly expanded internally-consistent dataset of Holland and Powell includes thermodynamic data for a wide range of mineral end-members in common rock-forming minerals, in particular, including FeMg_-1 substitutions in glaucophane, garnet, chloritoid and carpholite, and FeMg_-1 and MgSiAl_-1Al_-1 substitutions in talc and chlorite. Moreover, we have the uncertainties and correlations for these data. With the data, we have calculated the full pressure-temperature phase diagram for the system Na₂O–FeO–MgO–Al₂O₃–SiO₂–H₂O (NFMASH) for quartz (or coesite) and H₂O in excess, in the range 300°–800°C and 5–50 kbars. By solving the set of non-linear equations formed by the equilibrium relationships for an independent set of equations between the end-members in an assemblage in NFMASH, the compositions of the minerals (and PT) can be calculated. Thus the changes in MgSiAl_-1Al_-1 along NMASH reactions, and FeSiAl_-1Al_-1 along NFASH reactions, are calculated, and the changes in FeMg_-1 and MgSiAl_-1Al_-1 along NFMASH reactions are calculated. From this information it is straightforward to generate PT diagrams for specific rock compositions. Mineral assemblages and mineral compositional changes in the phase diagram are discussed in relation to greenschist, blueschist and eclogite facies assemblages in metapelitic rocks. It is found that the correspondence between the predictions of the phase diagrams and the observations on rocks is remarkably good. When semiquantitative extensions of the phase diagram to include Ca(MgFe)_-1, NaSiCa_-1Al_-1, Fe³⁺Al_-1 and KNa_-1 substitutions are taken into account the agreement is essentially complete.     

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     

Experimental investigation of zoisite–clinozoisite phase equilibria in the system CaO–Fe2O3–Al2O3–SiO2–H2O

The system Ca₂Al₃Si₃O₁₁(O/OH)-Ca₂Al₂FeSi₃O₁₁(O/OH), with emphasis on the Al-rich portion, was investigated by synthesis experiments at 0.5 and 2.0 GPa, 500-800 °C, using the technique of producing overgrowths on natural seed crystals. Electron microprobe analyses of overgrowths up to >100 µm wide have located the phase transition from clinozoisite to zoisite as a function of P-T-X_ps and a miscibility gap in the clinozoisite solid solution. The experiments confirm a narrow, steep zoisite-clinozoisite two-phase loop in T-X_ps section. Maximum and minimum iron contents in coexisting zoisite and clinozoisite are given by X_ps^zo (max) = 1.9*10 ^{- 4} T+ 3.1*10 ^{- 2} P - 5.36*10 ^{- 2}{\rm X}_{{\rm ps}}^{{\rm zo}} {\rm (max) = 1}{\rm .9*10}^{ - 4} T{\rm + 3}{\rm .1*10}^{ - 2} P - {\rm 5}{\rm .36*10}^{ - 2} and X_ps^czo (min) = (4.6 * 10 ^{- 4} - 4 * 10 ^{- 5} P)T + 3.82 * 10 ^{- 2} P - 8.76 * 10 ^{- 2}{\rm X}_{{\rm ps}}^{{\rm czo}} {\rm (min)} = {\rm (4}{\rm .6} * {\rm 10}^{ - {\rm 4}} - 4 * {\rm 10}^{ - {\rm 5}} P{\rm )}T + {\rm 3}{\rm .82} * {\rm 10}^{ - {\rm 2}} P - {\rm 8}{\rm .76} * {\rm 10}^{ - {\rm 2}} (P in GPa, T in °C). The iron-free end member reaction clinozoisite = zoisite has equilibrium temperatures of 185ᇆ °C at 0.5 GPa and 0ᇆ °C at 2.0 GPa, with (H_r⁰=2.8ǃ.3 kJ/mol and (S_r⁰=4.5ǃ.4 J/mol2K. At 0.5 GPa, two clinozoisite modifications exist, which have compositions of clinozoisite I ~0.15 to 0.25 X_ps and clinozoisite II >0.55 X_ps. The upper thermal stability of clinozoisite I at 0.5 GPa lies slightly above 600 °C, whereas Fe-rich clinozoisite II is stable at 650 °C. The schematic phase relations between epidote minerals, grossular-andradite solid solutions and other phases in the system CaO-Al₂O₃-Fe₂O₃-SiO₂-H₂O are shown.     

Experimental studies to 10 kb of the bulk composition tremolite50-tschermakite50+excess H2O

Phase relations for the magnesio-hornblende bulk composition, 2 CaO·4 MgO·Al₂O₃·7 SiO₂+ excess H₂O, have been investigated to 10 kb employing hydrothermal and piston-cylinder techniques. The low-temperature limit of amphibole in this system lies at 519° C, 1,000 bars, 541° C, 2,000 bars, and 718° C, 10 kb. The low-T assemblage consists of an+chl+di+tc(+f), and is related to the adjacent high-T equilibrium assemblage, amph+an+chl+f, by the solid-solid reaction (A): 2 di+tc=tr. Small amounts of aluminum, hypothesized to be preferentially dissolved in the cpx (and in the tc) relative to amph, may account for the broad P-T stability range of the di+tc assemblage in the synthetic work relative to systems involving stoichiometric tr, Ca₂Mg₅Si₈O₂₂(OH)₂, such as are common in natural, Al-poor calc-silicate parageneses. Alternatively, the low-temperature assemblage produced in the experiments may be metastable. For the investigated bulk composition, synthetic tremolitic-cummingtonitic amphibole contains relatively modest amounts of ts, Ca₂Mg₃Al₂ ^IVSi₆-Al₂ ^IVO₂₂(OH)₂; at pressures of 1,000–3,000 bars, solid solution extends from near tremolite only to about cu₁₁tr₆₉ts₂₀, analogous to most analyzed natural magnesio-hornblendic specimens. At 10 kb fluid pressure, the solid solution reaches approximately cu₀₆tr₅₃ts₄₁ for the investigated bulk composition, and appears to be virtually independent of temperature. Amphibole and 14 Å chl react within the amphibole stability field, along curve (B), at about 704° C and 2,000 bars, to produce an, en, fo and f (H=40.9 kcal/ mole); at pressures greater than approximately 7kb, due to the incompatibility of an and fo, the higher temperature assemblage consists of amph, an, en, sp and f. Above P _fluid– T curve (B), the amphibole coexists with an+en+fo+f at low pressures; at higher pressures, the amphibole, which is in equilibrium with an+en+sp+f, is relatively more aluminous. The high-T stability limit of aluminous tr+fo lies approximately 20–25° C below the dehydration curve for stoichiometric tremolite on its own bulk composition. Reaction (C), tr+fo=2 di+5 en+f (H = 39.4 kcal/mole), produces an+di+en+f, the highest temperature subsolidus assemblage investigated for the tr₅₀ts₅₀ bulk composition. Hydrous melt is encountered at temperatures at least as low as 900° C at 10 kb, and at that fluid pressure coexists with amphibole over an interval of more than 60° C. Limited solid solution observed between tr and ts in nature (tr_100-70) is accounted for by the restricted range of amphibole compositions produced in the present study. Such amphiboles, moreover, appear to have both high- and low-temperature stability limits, as demonstrated by the experimental results.Institute of Geophysics and Planetary Physics Publication No. 2811     

The stability of sapphirine-quartz and hypersthene-sillimanite-quartz assemblages: an experimental investigation in the system FeO−MgO−Al2O3−SiO2 under H2O and CO2 conditions

Phase relations and mineral chemistry involving the phases garnet (Gt), spinel (Sp), hypersthene (Hy), sapphirine (Sa), cordierite (Cd), sillimanite (Sil) and quartz (Qz) have been experimentally determined in the system FMAS (FeO−MgO−Al₂O₂−SiO₂) under low fO₂ and for various H₂O/CO₂ conditions. Several compositions were studied with 100 (Mg/Mg+Fe) ratio ranging from 64 to 87 with excess quartz and sillimanite. Our data do not show any differences in Gt−Cd stability and composition as a function of H₂O, CO₂ and H₂O−CO₂ (±CH₄) content, in good agreement with a previous experimental study at lower temperature (Aranovich and Podlesskii 1983). At 1,000° C and 11 kbar, under CO₂-saturated conditions, cordierite grew from a crystalline mix unseeded with cordierite. Thus, under water-absent conditions, cordierite will have a high-P stability field in the presence of CO₂. If water has a pressure stabilizing effect on cordierite, then our results would indicate that the effects of H₂O and CO₂ are of the same magnitude at high temperature. Our data support the theoretical P-T grid proposed by Hensen (1986) for high-T metapelites and are largely consistent with the high-temperature experimental data of Hensen and Green (1973). The univariant boundary Gt+Cd=Hy+Sil+Qz, which marks the disappearance of Hy−Sil−Qz assemblages, has a negative dP/dT slope above 1,000° C and a positive one below this temperature. Extrapolation of our data to iron-free systems shows that the high-P breakdown limit of Mg-cordierite has a negative slope in the range 1,025–1,300° C and probably positive below 1,000° C. This indicates a maximum of stability for Mg-cordierite at around 1,000° C and 13 kbar. Because of the curvature of the univariant reactions En+Sil=Py+Qz, Mg−Cd=En+Sil+Qz and Gt+Cd=Hy+Sil+Qz, the iron-free invariant point involving the phases Py, En, Cd, Sil and Qz probably does not exist. Sapphirine—Qz-bearing assemblages are stable only at temperatures above 1,050° C. At 1,075° C, the joint Gt−Sa is stable up to 11 kbar. At higher pressure, garnet, sapphirine and quartz react according to the reaction Gt+Sa+Qz=Hy+Sil. Reequilibrated sapphirines are more aluminous than the theoretical endmember Mg₂Al₄SiO₁₀ due to AlAl=MgSi substitutions [100(Al₂O₃/Al₂O₃+FeO+MgO) in experimental sapphirines ranges from 50.5 to 52.2]. Sapphirine in the assemblage Sa−Cd−Sil−Qz shows a decrease in Al content with decreasing temperature and pressure, such that the alumina isopleths for sapphirine have a slight negative dP/dT slope. A similar decrease in Al content of sapphirine with temperature is also observed in Sa−Sil−Qz assemblages.     

Thermodynamic data of lawsonite and zoisite in the system CaO–Al2O3–SiO2–H2O based on experimental phase equilibria and calorimetric work

The enthalpy of drop-solution in molten 2PbO·B₂O₃ of synthetic and natural lawsonite, CaAl₂(Si₂O₇)(OH)₂·H₂O, was measured by high-temperature oxide melt calorimetry. The enthalpy of formation determined for the synthetic material is (_fH^Oxides=-168.7Dž.4 kJ mol^-1, or (_fH⁰₂₉₈=-4,872.5dž.0 kJ mol^-1. These values are in reasonable agreement with previously published data, although previous calorimetric work yielded slightly more exothermic data and optimisation methods resulted in slightly less exothermic values. The equilibrium conditions for the dehydration of lawsonite to zoisite, kyanite and quartz/coesite at pressures and temperatures up to 5 GPa and 850 °C were determined by piston cylinder experiments. These results, other recent phase equilibrium data, and new calorimetric and thermophysical data for lawsonite and zoisite, Ca₂Al₃(SiO₄)(Si₂O₇)O(OH), were used to constrain a mathematical programming analysis of the thermodynamic data for these two minerals in the chemical system CaO-Al₂O₃-SiO₂-H₂O (CASH). The following data for lawsonite and zoisite were obtained: (_fH⁰₂₉₈ (lawsonite)=-4,865.68 kJ mol^-1 , S⁰₂₉₈ (lawsonite)=229.27 J K^-1 mol^-1 , (_fH⁰₂₉₈ (zoisite)=-6,888.99 kJ mol^-1 , S⁰₂₉₈ (zoisite)=297.71 J K^-1 mol^-1 . Additionally, a recalculation of the bulk modulus of lawsonite yielded K=120.7 GPa, which is in good agreement with recent experimental work.     

The restricted stability of osumilite under hydrous conditions in the system K2O-MgO–Al2O3–SiO2–H2O

Osumilite_ss was synthesized as a single phase product in the model system K₂O-MgO-Al₂O₃-SiO₂ at 800° C/ 0.5 Kbar water pressure and at 800° to 840° C/1.0 Kbar total pressure with 0.3 in the gas phase. The experimentally determined solid solubility range of synthetic osumilites can be expressed by the formula KMg₂(Al_3-xMg_x) (Al_2–xSi_10+x)O₃₀ with 0x0.4. A survey of sixteen chemical analyses of natural osumilites from eleven occurrences shows a solid solubility characterized by 0x0.6. Reversed stability experiments for the synthetic osumilite KMg₂(Al_2.75Mg_0.25)(Al_1.75Si_10.25)O₃₀ determined at water pressure equal to total pressure demonstrate its restriction to water pressures below 0.8 Kbar (at 0.5 Kbar, the stability range is between 765° and 800° C). At the lower thermal stability limit osumilite+H₂O vapor break down to cordierite+K feldspar+phlogopite_ss+quartz, at the higher one to cordierite+K feldspar+phlogopite+liquid. Reduction of water fugacity will expand the stability field largely by shifting the lower and higher thermal stability limits to lower and higher temperatures, respectively. The dependence of osumilite stability on water fugacity makes osumilite a sensitive indicator mineral for dry conditions in rocks formed at total pressures higher than about 0.8 Kbar.     

Phase relations in high-pressure metapelites in the system KFMASH (K2O–FeO–MgO–Al2O3–SiO2–H2O) with application to natural rocks

Using a previously published, internally consistent thermodynamic dataset and updated models of activity–composition relations for solid solutions, petrogenetic grids in the model system KFMASH (K₂O–FeO–MgO–Al₂O₃–SiO₂–H₂O) and the subsystems KMASH and KFASH have been calculated with the software THERMOCALC 3.1 in the P–T range 5–36 kbar and 400–810 °C, involving garnet, chloritoid, biotite, carpholite, talc, chlorite, staurolite and kyanite/sillimanite with phengite, quartz/coesite and H₂O in excess. These grids, together with calculated AFM compatibility diagrams and pseudosections, are shown to be powerful tools for delineating the phase equilibria and P–T conditions of pelitic high-P assemblages for a variety of bulk compositions. The calculated equilibria and mineral compositions are in good agreement with petrological observation. The calculation indicates that the typical whiteschist assemblage kyanite–talc is restricted to the rocks with extremely high X_Mg values, decreasing X_Mg in a bulk composition favoring the stability of chloritoid and garnet. Also, the chloritoid–talc paragenesis is stable over 19–20 kbar in a temperature range of ca. 520–620 °C, being more petrologically important than the previously highlighted assemblage talc–phengite. Moreover, contours of the calculated Si isopleths in phengite in P–T and P–X pseudosections for different bulk compositions extend the experimentally derived phengite geobarometers to various KFMASH assemblages.     

Cookeite LiAl4(Si3Al)O10(OH)8: Experimental study and thermodynamical analysis of its compatibility relations in the Li2O−Al2O3−SiO2−H2O system

Three reactions limiting the stability field of the di-trioctahedral chlorite cookeite in the presence of quartz, in the system Li₂O−Al₂O₃−SiO₂−H₂O (LASH) have been reversed in the range 290–480°C, 0.8–14 kbar, using natural material close to the end member composition. Combining our results with known and estimated thermodynamic properties of the other minerals belonging to the LASH system, the enthalpy (-8512200 J/mol) and the entropy (504.8 J/mol^*K) of cookeite are calculated by a feasible solution space approach. The knowledge of these values allowed us to draw the first P−T phase diagram involving both the hydrated Li-aluminosilicates cookeite and bikitaite, which is applicable to a large variety of natural rock systems. The low thermal extent of the stability field of cookeite+quartz (260–480°C) makes cookeite a valuable indicator of low temperature conditions within a wide range of pressure (1–14 kbar).     

Modelling phase–assemblage diagrams for magnesian metapelites in the system K2O–FeO–MgO–Al2O3–SiO2–H2O: geodynamic consequences for the Monte Rosa nappe, Western Alps

Magnesian metamorphic rocks with metapelitic mineral assemblage and composition are of great interest in metamorphic petrology for their ability to constrain P–T conditions in terranes where metamorphism is not easily visible. Phase–assemblage diagrams for natural and model magnesian metapelites in the system KFMASH are presented to document how phase relationships respond to water activity, bulk composition, pressure and temperature. The phase assemblages displayed on these phase diagrams are consistent with natural mineral assemblages occurring in magnesian metapelites. It is shown that the equilibrium assemblages at high pressure conditions are very sensitive to a(H₂O). Specifically, the appearance of the characteristic HP assemblage chloritoid–talc–phengite–quartz (with excess H₂O) in the magnesian metapelites of the Monte Rosa nappe (Western Alps) is due to the reduction of a(H₂O). Furthermore, the mineral assemblages are determined by the whole-rock FeO/(FeO+MgO) ratio and effective Al content X _A as well as P and T. The predicted mineral associations for the low- and high-X _A model bulk compositions of magnesian metapelites at high pressure are not dependent on the X _A variations as they show a similar sequence of mineral assemblages. Above 20 kbar, the prograde sequence of assemblages associated with phengite (with excess SiO₂ and H₂O) for low- and high-X _A bulk compositions of magnesian metapelites is: carpholite–chlorite → chlorite–chloritoid → chloritoid–talc → chloritoid–talc–kyanite → talc–garnet–kyanite → garnet–kyanite ± biotite. At low to medium P–T conditions, a low-X _A stabilises the phengite-bearing assemblages associated with chlorite, chlorite + K-feldspar and chlorite + biotite while a high-X _A results in the chlorite–phengite bearing assemblages associated with pyrophyllite, andalusite, kyanite and carpholite. A high-X _A magnesian metapelite with nearly iron-free content stabilises the talc–kyanite–phengite assemblage at moderate to high P–T conditions. Taking into account the effective bulk composition and a(H₂O) involved in the metamorphic history, the phase–assemblage diagrams presented here may be applied to all magnesian metapelites that have compositions within the system KFMASH and therefore may contribute to gaining insights into the metamorphic evolution of terranes. As an example, the magnesian metapelites of the Monte Rosa nappe have been investigated, and an exhumation path with P–T conditions for the western roof of the Monte Rosa nappe has been derived for the first time. The exhumation shows first a near-isothermal decompression from the Alpine eclogite peak conditions around 24 kbar and 505°C down to approximately 8 kbar and 475°C followed by a second decompression with concomitant cooling.M. Frey: deceased