The Substitution of Al and F in Titanite at High Pressure and Temperature: Experimental Constraints on Phase Relations and Solid Solution Properties

Experimental studies were carried out to evaluate phase relationsinvolving titanite–F–Al-titanite solid solutionin the system CaSiO₃–Al₂SiO₅–TiO₂–CaF₂. Theexperiments were conducted at 900–1000°C and 1·1–4·0GPa. The average F/Al ratio in titanite solid solution in theexperimental run products is 1·01 ± 0·06,and X_Al ranges from 0·33 ± 0·02 to 0·91± 0·05, consistent with the substitution [TiO²⁺]_–1[AlF²⁺]₁.Analysis of the phase relations indicates that titanite solidsolutions coexisting with rutile are always low in X_Al, whereasthe maximum X_Al of titanite solid solution occurs with fluoriteand either anorthite or Al₂SiO₅. Reaction displacement experimentswere performed by adding fluorite to the assemblage anorthite+ rutile = titanite + kyanite. The reaction shifts from 1·60GPa to 1·15 ± 0·05 GPa at 900°C, from1·79 GPa to 1·375 ± 0·025 GPa at1000°C, and from 1·98 GPa to 1·575 ±0·025 GPa at 1100°C. The data show that the activityof CaTiSiO₄O is very close to the ideal molecular activity model(X_Ti) at 1100°C, but shows a negative deviation at 1000°Cand 900°C. The results constrain     

Calculated Phase Relations in the System NCKFMASH (Na2O-CaO-K2O-FeO-MgO-Al2O3-SiO2-H2O) for High-Pressure Metapelites

Petrogenetic grids in the system NCKFMASH (Na₂O–CaO–K₂O–FeO–MgO–Al₂O₃–SiO₂–H₂O)and the subsystems NCKMASH and NCKFASH calculated with the softwareTHERMOCALC 3.1 are presented for the P–T range 7–30kbar and 450–680°C, for assemblages involving garnet,chloritoid, biotite, carpholite, talc, chlorite, kyanite, staurolite,paragonite, glaucophane, jadeite, omphacite, diopsidic pyroxene,plagioclase, zoisite and lawsonite, with phengite, quartz/coesiteand H₂O in excess. These grids, together with calculated compatibilitydiagrams and P–T and T–X_Ca and P–X_Ca pseudosectionsfor different bulk-rock compositions, show that incorporationof Ca into the NKFMASH system leads to many of the NKFMASH invariantequilibria moving to lower pressure and/or lower temperature,which results, in most cases, in the stability of jadeite andgarnet being enlarged, but in the reduction of stability ofglaucophane, plagioclase and AFM phases. The effect of Ca onthe stability of paragonite is dependent on mineral assemblageat different P–T conditions. The calculated NCKFMASH diagramsare powerful in delineating the phase equilibria and P–Tconditions of natural pelitic assemblages. Moreover, contoursof the calculated phengite Si isopleths in P–T and P–X_Capseudosections confirm that phengite barometry in NCKFMASH isstrongly dependent on mineral assemblage. KEY WORDS: phase relations; metapelites; NCKFMASH; THERMOCALC; phengite geobarometry     

Phase Relations and Stability of Magnetoplumbite- and Crichtonite-Series Phases under Upper-Mantle P-T Conditions: an Experimental Study to 15 GPa with Implications for LILE Metasomatism in the Lithospheric Mantle

High-pressure–high-temperature experiments were performedin the range 7–15 GPa and 1300–1600°C to investigatethe stability and phase relations of the K- and Ba-dominantmembers of the crichtonite and magnetoplumbite series of phasesin simplified bulk compositions in the systems TiO₂–ZrO₂–Cr₂O₃–Fe₂O₃–BaO–K₂Oand TiO₂–Cr₂O₃–Fe₂O₃–BaO–K₂O. Both seriesof phases occur as inclusions in diamond and/or as constituentsof metasomatized peridotite mantle xenoliths sampled by kimberlitesor alkaline lamprophyres. They can accommodate large ion lithophileelements (LILE) and high field strength elements (HFSE) on awt % level and, hence, can critically influence the LILE andHFSE budget of a metasomatized peridotite even if present onlyin trace amounts. The Ba and K end-members of the crichtoniteseries, lindsleyite and mathiasite, are stable to 11 GPa and1500–1600°C. Between 11 and 12 GPa, lindsleyite breaksdown to form two Ba–Cr-titanates of unknown structurethat persist to at least 13 GPa. The high-pressure breakdownproduct of mathiasite is a K–Cr-titanate with an idealizedformula KM₇O₁₂, where M = Ti, Cr, Mg, Fe. This phase possessesspace group P6₃/m with a = 9·175(2) Å, c = 2·879(1)Å, V = 209·9(1) ų. Towards high temperatures,lindsleyite persists to 1600°C, whereas mathiasite breaksdown between 1500 and 1600°C to form a number of complexTi–Cr-oxides. Ba and K end-members of the magnetoplumbiteseries, hawthorneite and yimengite, are stable in runs at 7,10 and 15 GPa between 1300 and 1400°C coexisting with anumber of Ti–Cr-oxides. Molar mixtures (1:1) of lindsleyite–mathiasiteand hawthorneite–yimengite were studied at 7–10GPa and 1300–1400°C, and 9–15 GPa and 1150–1400°C,respectively. In the system lindsleyite–mathiasite, onehomogeneous Ba–K phase is stable, which shows a systematicincrease in the K/(K + Ba) ratio with increasing pressure. Inthe system hawthorneite–yimengite, two coexisting Ba–Kphases appear, which are Ba rich and Ba poor, respectively.The data obtained from this study suggest that Ba- and K-dominantmembers of the crichtonite and magnetoplumbite series of phasesare potentially stable not only throughout the entire subcontinentallithosphere but also under conditions of an average present-daymantle adiabat in the underlying asthenosphere to a depth ofup to 450 km. At still higher pressures, both K and Ba may remainstored in alkali titanates that would also be eminently suitablefor the transport of other ions with large ionic radii. KEY WORDS: crichtonite; magnetoplumbite; high-P–T experiments; phase relations; upper mantle     

Synthesis of Staurolite in Melting Experiments of a Natural Metapelite: Consequences for the Phase Relations in Low-Temperature Pelitic Migmatites

We document experiments on a natural metapelite in the range650–775°C, 6–14 kbar, 10 wt % of added water,and 700–850°C, 4–10 kbar, no added water. Staurolitesystematically formed in the fluid-present melting experimentsabove 675°C, but formed only sporadically in the fluid-absentmelting experiments. The analysis of textures, phase assemblages,and variation of phase composition and Fe–Mg partitioningwith P and T suggests that supersolidus staurolite formed at(near-) equilibrium during fluid-present melting reactions.The experimental results are used to work out the phase relationsin the system K₂O–Na₂O–FeO–MgO–Al₂O₃–SiO₂–H₂Oappropriate for initial melting of metapelites at the upperamphibolite facies. The P–T grid developed predicts theexistence of a stable P–T field for supersolidus staurolitethat should be encountered by aluminous Fe-rich metapelitesduring fluid-present melting at relatively low temperature andintermediate pressures (675–700°C, 6–10 kbarfor X_H2O = 1, in the KNFMASH system), but not during fluid-absentmelting. The implications of these findings for the scarcityof staurolite in migmatites are discussed. KEY WORDS: metapelites; migmatites; partial melting; P–T grid; staurolite     

Melting of Refractory Mantle at 1{middle dot}5, 2 and 2{middle dot}5 GPa under Anhydrous and H2O-undersaturated Conditions: Implications for the Petrogenesis of High-Ca Boninites and the Influence of Subduction Components on Mantle Melting

Boninites are an important ‘end-member’ supra-subductionzone magmatic suite as they have the highest H₂O contents andrequire the most refractory of mantle wedge sources. The pressure–temperatureconditions of boninite origins in the mantle wedge are importantto understanding subduction zone initiation and subsequent evolution.Reaction experiments at 1·5 GPa (1350–1530°C),2 GPa (1400–1600°C) and 2·5 GPa (1450–1530°C)between a model primary high-Ca boninite magma composition anda refractory harzburgite under anhydrous and H₂O-undersaturatedconditions (2–3 wt % H₂O in the melt) have been completed.The boninite composition was modelled on melt inclusions occurringin the most magnesian olivine phenocrysts in high-Ca boninitesfrom the Northern Tongan forearc and the Upper Pillow Lavasof the Troodos ophiolite. Direct melting experiments on a modelrefractory lherzolite and a harzburgite composition at 1·5GPa under anhydrous conditions (1400–1600°C) havealso been completed. Experiments establish a P, T ‘meltinggrid’ for refractory harzburgite at 1·5, 2 and2·5 GPa and in the presence of 2–3 wt % H₂O. Theeffect of 2–3 wt % dissolved H₂O produces a liquidus depressionin primary boninite of     

Continuous Gradations among Primary Carbonatitic, Kimberlitic, Melilititic, Basaltic, Picritic, and Komatiitic Melts in Equilibrium with Garnet Lherzolite at 3-8 GPa

Multianvil melting experiments in the system CaO–MgO–Al₂O₃–SiO₂–CO₂(CMAS–CO₂) at 3–8 GPa, 1340–1800°C, involvingthe garnet lherzolite phase assemblage in equilibrium with CO₂-bearingmelts, yield continuous gradations in melt composition betweencarbonatite, kimberlite, melilitite, komatiite, picrite, andbasalt melts. The phase relations encompass a divariant surfacein P–T space. Comparison of the carbonatitic melts producedat the low-temperature side of this surface with naturally occurringcarbonatites indicates that natural magnesiocarbonatites couldbe generated over a wide range of pressures >2·5 GPa.Melts analogous to kimberlites form at higher temperatures alongthe divariant surface, which suggests that kimberlite genesisrequires more elevated geotherms. However, the amount of waterfound in some kimberlites has the potential to lower temperaturesfor the generation of kimberlitic melts by up to 150°C,provided no hydrous phases are present. Compositions resemblinggroup IB and IA kimberlites are produced at pressures around5–6 GPa and 10 GPa, respectively, whereas the compositionsof some other kimberlites suggest generation at higher pressuresstill. At pressures <4 GPa, an elevated geotherm producesmelilitite-like melt in the CMAS–CO₂ system rather thankimberlite. Even when a relatively CO₂-rich mantle compositioncontaining 0·15 wt % CO₂ is assumed, kimberlites andmelilitites are produced by <1% melting and carbonatitesare generated by even smaller degrees of melting of <0·5%. KEY WORDS: carbonatite; CO₂; kimberlite; melilitite; melt generation     

Polymetamorphism in the NE Shackleton Range, Antarctica: Constraints from Petrology and U-Pb, Sm-Nd, Rb-Sr TIMS and in situ U-Pb LA-PIMMS Dating

Metapelitic rock samples from the NE Shackleton Range, Antarctica,include garnet with contrasting zonation patterns and two agespectra. Garnet porphyroblasts in K-rich kyanite–sillimanite–staurolite–garnet–muscovite–biotite schistsfrom Lord Nunatak show prograde growth zonation, and give Sm–Ndgarnet, U–Pb monazite and Rb–Sr muscovite ages of518 ± 5, 514 ± 1 and 499 ± 12 Ma, respectively.Geothermobarometry and P–T pseudo-section calculationsin the model system CaO–Na₂O–K₂O– TiO₂–MnO–FeO–MgO–Al₂O₃–SiO₂–H₂Oare consistent with garnet growth during prograde heating from540°C/7 kbar to 650°C/7·5 kbar, and partial resorptionduring a subsequent P–T decrease to <650°C at <6kbar. All data indicate that rocks from Lord Nunatak were affectedby a single orogenic cycle. In contrast, garnet porphyroblastsin K-poor kyanite–sillimanite– staurolite–garnet–cordierite–biotite-schistsfrom Meade Nunatak show two growth stages and diffusion-controlledzonation. Two distinct age groups were obtained. Laser ablationplasma ionization multicollector mass spectrometry in situ analysesof monazite, completely enclosed by a first garnet generation,yield ages of c. 1700 Ma, whereas monazite grains in open garnetfractures and in most matrix domains give c. 500 Ma. Both agegroups are also obtained by U–Pb thermal ionization massspectrometry analyses of matrix monazite and zircon, which fallon a discordia with lower and upper intercepts at 502 ±1 and 1686 ± 2 Ma, respectively. Sm–Nd garnet datingyields an age of 1571 ± 40 Ma and Rb–Sr biotiteanalyses give an age of 504 ± 1 Ma. Integrated geochronologicaland petrological data provide evidence that rocks from MeadeNunatak underwent a polymetamorphic Barrovian-type metamorphism:(1) garnet 1 growth and subsequent diffusive garnet annealingbetween 1700 and 1570 Ma; (2) garnet 2 growth during the RossOrogeny at c. 500 Ma. During the final orogenic event the rocksexperienced peak P–T conditions of about 650°C/7·0kbar and a retrograde stage at c. 575°C/4·0 kbar. KEY WORDS: garnet microtexture; P–T pseudosection; geochronology; polymetamorphism; Shackleton Range; Antarctica     

Calculated Phase Relations in High-Pressure Metapelites in the System NKFMASH (Na2O-K2O-FeO-MgO-Al2O3-SiO2-H2O)

Using an internally consistent thermodynamic dataset and updatedmodels of activity–composition relation for solid solutions,petrogenetic grids in the system NKFMASH (Na₂O–K₂O–FeO–MgO–Al₂O₃–SiO₂–H₂O)and the subsystems NKMASH and NKFASH have been calculated withthe software THERMOCALC 3.1 in the P–T range 5–36kbar and 400–810°C, involving garnet, chloritoid,biotite, carpholite, talc, chlorite, kyanite/sillimanite, staurolite,phengite, paragonite, albite, glaucophane, jadeite, with quartz/coesiteand H₂O in excess. These grids, together with calculated AFMcompatibility diagrams and P–T pseudosections, are shownto be powerful tools for delineating the phase equilibria andP–T conditions of Na-bearing pelitic assemblages for avariety of bulk compositions from high-P terranes around theworld. These calculated equilibria are in good agreement withpetrological studies. Moreover, contours of the calculated phengiteSi isopleths in P–T pseudosections for different bulkcompositions confirm that phengite barometry is highly dependenton mineral assemblage. KEY WORDS: phase relations; HP metapelite; NKFMASH; THERMOCALC; phengite geobarometry     

The Effect of Reaction Overstep on Garnet Microtextures in Metapelitic Rocks of the Ilesha Schist Belt, SW Nigeria

Garnet-bearing assemblages of K-rich and K-poor metapelitesfrom the Ilesha Schist belt, SW Nigeria, are investigated. K-richsamples contain the assemblages (A) garnet–staurolite–muscovite–chlorite–magnetite,(B) andalusite–garnet–staurolite–muscovite–chlorite–magnetiteand (C) sillimanite–andalusite–garnet–muscovite–chlorite–magnetite.K-poor samples contain the assemblages (D) garnet–staurolite–cordierite–chloriteand (E) garnet–cordierite–chlorite ± staurolite.All assemblages contain quartz, plagioclase, biotite and ilmenite.P–T pseudosections calculated in the system CaO–Na₂O–K₂O–TiO₂–MnO–FeO–MgO–Al₂O₃–SiO₂ –H₂O ± O₂ suggest peak metamorphismat 590 ± 20°C at 5 ± 0·5 kbar, followedby retrogression to 550°C at 3·0 kbar, in agreementwith field evidence, domain assemblages, mineral compositions,modes and geothermobarometry. The absence of compositional zonationshows that garnet in all investigated rocks nucleated and grewat constant P–T–X in equilibrium with associatedminerals on the thin-section scale. However, the garnet-in reactiondid not begin until the establishment of a significant temperatureoverstep of     

Zoisite--Anorthite--Calcite Stability Relations in H2O--CO2 Fluids at 5000 Bars: An Experimental and SEM Study

The reaction 2 zoisite + CO₂ = 3 anorthite + calcite + H₂O hasbeen reversed experimentally in cold-seal pressure vessels usingnatural phases and H2O–C02 fluids generated by water-silveroxalate mixtures. Equilibrium has been determined at 5000 50bars, 599 9 °C and 0–075 ± 0–010 X_{CO2.Extrapolation using the MRK equation of Kerrick & Jacobs(1981) gives an equilibrium curve of negative T–X slopeconsistent with bracketing runs at 500, 550 and 650 °C.The curve agrees only with a new bracket of Nitsch (in Hoschek,1980), and is at higher XCo2} than all other experimental determinationsand at lower XCO₂ than those calculated from the thermodynamicdata of Helgeson et al. (1978). Discrepancies are attributedto differences in starting materials and small errors in thethermodynamic properties of the phases. Reaction direction and equilibrium have been determined by observingsurface textures of run products by SEM. Growth and solutiontextures are non-equivalent, permitting unequivocal determinationof reaction direction even where the extent of reaction is small,an advantage over conventional and insensitive XRD methods whichmeasure bulk changes in the charge. Dissolution features ofanorthite and zoisite are defect-related indicating controlby surface reaction, whereas calcite dissolves by both surfacereaction and diffusion controlled processes. Margarite forms in most runs below 585 °C. Textural features,its restriction to the margarite stability field and comparisonwith feldspar solubility data demonstrate it is an equilibriumphase formed by incongruent solubility of anorthite and zoisitein H₂O-CO₂ fluids. Quench phases formed from the solute areconsequently silica-rich, with implications for metasomaticprocesses in feldspar–epidote–bearing rock and fluidsystems. Absence of margarite from runs with anorthite, zoisiteand calcite in the zoisite stability field is apparently dueto the fast growth rate of zoisite. The full equilibrium assemblageis zoisite–anorthite–calcite–margarite atthese temperatures, and the degeneracy of the model system isunobtainable in experiments, and presumably, in nature.     

Lawsonite-Omphacite-Bearing Metabasites of the Pam Peninsula, NE New Caledonia: Evidence for Disrupted Blueschist- to Eclogite-Facies Conditions

The Diahot terrane of NE New Caledonia contains an interbeddedsequence of Cretaceous to Eocene metasediments, felsic and maficmetavolcanics that experienced c. 40 Ma high-P/T metamorphism.Metabasaltic assemblages define two prograde events (M₁ andM₂) and a tectonically disrupted crustal profile that extendsfrom lawsonite–blueschist conditions in the SW to paragonite–eclogiteconditions in the NE. Weakly deformed metabasalts from lowest-gradeparts of the Diahot terrane contain M₁ omphacite, chlorite,lawsonite and glaucophane-bearing assemblages that partiallypseudomorph igneous plagioclase and augite, and reflect P =0·7–1·0 GPa and T = 350–400°C.M₁ assemblages are enveloped by a steeply SW-dipping S₂ foliationthat becomes progressively more intense towards the NE overa distance of c. 15 km. S₂ assemblages are divided into fourzones: (1) lawsonite–omphacite; (2) lawsonite–clinozoisite–spessartine;(3) clinozoisite–hornblende–almandine; (4) almandine–omphacite.S₂ assemblages reflect a P–T gradient that spans the exposed15 km of the Diahot terrane from P = 0·8–1·0GPa and T = 350–400°C (Zone 1) to P = 1·6–1·7GPa and T = 550–600°C (Zone 4). The systematic mineralogicalchanges reflect parts of a P–T array between 1·0and 1·7 GPa that was extensively disrupted by tectonicthinning during exhumation. KEY WORDS: blueschist; eclogite; New Caledonia; CNFMASH; pseudosection     

Calculation of Phase Relations Involving Haplogranitic Melts Using an Internally Consistent Thermodynamic Dataset

A simple thermodynamic model is developed for silicate meltsin the system CaO–Na₂O–K₂O–Al₂O₃–SiO₂–H₂O(CNKASH). The Holland & Powell (Journal of Metamorphic Geology,16, 289–302, 1998) internally consistent thermodynamicdataset is extended via the incorporation of the experimentallydetermined melting relationships in unary and binary subsystemsof CNKASH. The predictive capability of the model is evaluatedvia the experimental data in ternary and quaternary subsystems.The resulting dataset, with the software THERMOCALC, is thenused to calculate melting relationships for haplogranitic compositions.Predictions of the P–T stabilities of assemblages in water-saturatedand -undersaturated bulk compositions are illustrated. It isnow possible to make useful calculations of the melting behaviourof appropriate composition rocks under crustal conditions. KEY WORDS: thermodynamics; melts; granite; dataset     

Phase Relations in Peridotitic and Pyroxenitic Rocks in the Model Systems CMASH and NCMASH

Alpine-type peridotites and associated pyroxenites are foundas lenses in the continental crust in many different orogens.The reconstruction of the pressure–temperature (P–T)evolution of these rocks is, however, difficult or even impossible.With geothermobarometry, usually one point on the overall P–Tpath can be obtained. To use the different mineral assemblagesobserved in ultramafic rocks as P–T indicators, quantitativeP–T phase diagrams are required. This study presents newcalculated phase diagrams for peridotitic and pyroxenitic rocksin the model systems CaO–MgO–Al₂O₃–SiO₂–H₂O(CMASH) and Na₂O–CaO–MgO–Al₂O₃–SiO₂–H₂O(NCMASH), which include the respective solid solutions as continuousexchange vectors. These phase diagrams represent applicablepetrogenetic grids for peridotite and pyroxenite. On the basisof these general petrogenetic grids, phase diagrams for particularperidotite and pyroxenite bulk compositions are constructed.In an example of pyroxenite from the Shackleton Range, Antarctica,the different observed mineral assemblages are reflected bythe phase diagrams. For these rocks, a high-pressure metamorphicstage around 18 kbar and an anticlockwise P–T evolution,not recognized previously, can be inferred. KEY WORDS: Antarctic; high-pressure metamorphism; peridotite; phase diagrams; pyroxenite     

Liquidus Phase Relations in the System CaO-MgO-Al2O3-SiO2 at 2{middle dot}0 GPa: Applications to Basalt Fractionation, Eclogites, and Igneous Sapphirine

To model magmatic crystallization processes for mafic to intermediatecompositions at high pressure, liquidus phase relations in theforsterite–anorthite–diopside–silica (FADS)tetrahedron within the CaO–MgO–Al₂O₃–SiO₂system have been determined at 2·0 GPa. Compositionsof five liquidus invariant points have been determined and theapproximate compositions of five others have been inferred.These involve primary phase volumes for forsterite (fo), enstatite(en), diopside (di), high quartz (qz), spinel (sp), sapphirine(sa), garnet (gt), anorthite (an), and corundum (cor). The determined(with wt % coefficients) and inferred reactions (without coefficients)that define each isobaric invariant point are as follows: 23 en + 68 di + 9 sp = 84 liq + 16 fo 37 di + 63 sa = 47 liq + 40 sp + 13 en 100 gt = 21 liq + 27 sa + 55 en + 18 di 1 di + 59 en + 41 an = 43 liq + 57 gt 18 di + 21 qz + 15 en + 47 an = 100 liq di + an + gt = liq + sa an + gt = liq + sa + en sa + an + di = liq + sp sa + an = liq + cor + sp di + cor = liq + an + sp. These phase relations provide a diverse range of constraintson igneous processes at pressures near 2 GPa. They show thatfractional crystallization of a model basalt gives a residualliquid strongly enriched in SiO₂, strongly depleted in MgO,and mildly enriched in Al₂O₃. Such a trend is consistent withthe calc-alkaline fractionation trend observed at subductionzones, but is in disagreement with suggestions that fractionationof tholeiitic basalt in this pressure range yields an alkalicbasalt. Both trends may occur for natural basalts dependingon the Na₂O content of the parental magma. Also, the data showthat the minimum pressure for the formation of cumulate eclogitesand garnet pyroxenites is about 1·8–1·9GPa. The lower limit of pressure at which sapphirine can crystallizefrom a liquid in the FADS tetrahedron is estimated to be 1·1–1·5GPa and the upper limit is >3 GPa. Sapphirine crystallizesfrom magmas intermediate in composition between basalt and andesite.Probable igneous sapphirine in mafic associations is rare, butit occurs as part of a pyroxenite xenolith from Delegate, Australia,that we suggest is a cumulate assemblage and in a sapphirinenorite at Wilson Lake, Labrador, Canada. KEY WORDS: basalt; eclogite; sapphirine; fractional crystallization     

Progressive Low-Grade Metamorphism of a Black Shale Formation, Central Swiss Alps, with Special Reference to Pyrophyllite and Margarite Bearing Assemblages

The unmetamorphosed equivalents of the regionally metamorphosedclays and marls that make up the Alpine Liassic black shaleformation consist of illite, irregular mixed-layer illite/montmorillonite,chlorite, kaolinite, quartz, calcite, and dolomite, with accessoryfeldspars and organic material. At higher grade, in the anchizonalslates, pyrophyllite is present and is thought to have formedat the expense of kaolinite; paragonite and a mixed-layer paragonite/muscovitepresumably formed from the mixed-layer illite/montmorillonite.Anchimetamorphic illite is poorer in Fe and Mg than at the diageneticstage, having lost these elements during the formation of chlorite.Detrital feldspar has disappeared. In epimetamorphic phyllites, chloritoid and margarite appearby the reactions pyrophyllite + chlorite = chloritoid + quartz+ H₂O and pyrophyllite + calcite ± paragonite = margarite+ quartz + H₂O + CO₂, respectively. At the epi-mesozone transition,paragonite and chloritoid seem to become incompatible in thepresence of carbonates and yield the following breakdown products:plagioclase, margarite, clinozoisite (and minor zoisite), andbiotite. The maximum distribution of margarite is at the epizone-mesozoneboundary; at higher metamorphic grade margarite is consumedby a continuous reaction producing plagioclase. Most of the observed assemblages in the anchi-and epizone canbe treated in the two subsystems MgO (or FeO)-Na₂O–CaO–Al₂O₃–(KAl₃O₅–SiO₂–H₂O–CO₂).Chemographic analyses show that the variance of assemblagesdecreases with increasing metamorphic grade. Physical conditions are estimated from calibrated mineral reactionsand other petrographic data. The composition of the fluid phasewas low in X_CO2 throughout the metamorphic profile, whereasX_CH4 was very high, particularly in the anchizone where a_H2Owas probably as low as 0.2. P-T conditions along the metamorphicprofile are 1–2 kb/200–300 °C in the anchizone(Glarus Alps), and 5 kb/500–550 °C at the epi-mesozonetransition (Lukmanier area). Calculated geothermal gradientsdecrease from 50 °C/km in the anchimetamorphic Glarus Alpsto 30 °C/km at the epi-mesozone transition of the Lukmanierarea.     

Calculated Phase Relations in the System Na2O-CaO-K2O-FeO-MgO-Al2O3-SiO2-H2O with Applications to UHP Eclogites and Whiteschists

Pressure–temperature grids in the system Na₂O–CaO–K₂O–FeO–MgO–Al₂O₃–SiO₂–H₂O and its subsystems have been calculatedin the range 15–45 kbar and 550–900°C, usingan internally consistent thermodynamic dataset and new thermodynamicmodels for amphibole, white mica, and clinopyroxene, with thesoftware THERMOCALC. Minerals considered for the grids includegarnet, omphacite, diopside, jadeite, hornblende, actinolite,glaucophane, zoisite, lawsonite, kyanite, coesite, quartz, talc,muscovite, paragonite, biotite, chlorite, and plagioclase. Compatibilitydiagrams are used to illustrate the phase relationships in thegrids. Coesite-bearing eclogites and a whiteschist from Chinaare used to demonstrate the ability of pseudosections to modelphase relationships in natural ultrahigh-pressure metamorphicrocks. Under water-saturated conditions, chlorite-bearing assemblagesin Mg- and Al-rich eclogites are stable at lower temperaturesthan in Fe-rich eclogites. The relative temperature stabilityof the three amphiboles is hornblende > actinolite > glaucophane(amphibole names used sensu lato). Talc-bearing assemblagesare stable only at low temperature and high pressure in Mg-and Al-rich eclogites. For most eclogite compositions, talccoexists with lawsonite, but not zoisite, in the stability fieldof coesite. Water content contouring of pressure–temperaturepseudosections, along with appropriate geotherms, provides newconstraints concerning dehydration of such rocks in subductingslabs. Chlorite and lawsonite are two important H₂O-carriersin subducting slabs. Depending on bulk composition and pressure–temperaturepath, amphibole may or may not be a major H₂O-carrier to depth.In most cases, dehydration to make ultrahigh-pressure eclogitestakes place gradually, with H₂O content controlled by divariantor higher variance assemblages. Therefore, fluid fluxes in subductionzones are likely to be continuous, with the rate of dehydrationchanging with changing pressure and temperature. Further, eclogitesof different bulk compositions dehydrate differently. Dehydrationof Fe-rich eclogite is nearly complete at relatively shallowdepth, whereas Mg- and Al-rich eclogites dehydrate continuouslydown to greater depth. KEY WORDS: dehydration; eclogites; phase relations; THERMOCALC; UHP metamorphism; whiteschists     

Solubility of Anhydrite, CaSO4, in NaCl-H2O Solutions at High Pressures and Temperatures: Applications to Fluid-Rock Interaction

Anhydrite solubility in H₂O–NaCl solutions was measuredat 6–14 kbar, 600–800°C and NaCl mole fractions(X_NaCl) of 0–0·3 in piston–cylinder apparatus.Solubilities were determined by weight changes of natural anhydritein perforated Pt envelopes confined with fluid in larger Ptcapsules. In initially pure H₂O at 10 kbar and 800°C, CaSO₄concentration is low (0·03 molal), though much largerthan at the same temperature and 1 kbar. Hematite-buffered experimentsshowed slightly lower solubilities than unbuffered runs. CaSO₄solubility increases enormously with NaCl activity: at 800°Cand 10 kbar and X_NaCl of 0·3, CaSO₄ molality is 200 timeshigher than with pure H₂O. Whereas CaSO₄ solubility in pureH₂O decreases with rising T at low T and P, the high-P resultsshow that anhydrite solubility increases with T at constantP at all X_NaCl investigated. The effects of salinity and temperatureare so great at 10 kbar that critical mixing between sulfate-richhydrosaline melts and aqueous salt solutions is probable at900°C at X_NaCl 0·3. Recent experimental evidencethat volatile-laden magmas crystallizing in the deep crust mayevolve concentrated salt solutions could, in light of the presentwork, have important implications regarding such diverse processesas Mount Pinatubo-type S-rich volcanism, high-f O₂ regionalmetamorphism, and emplacement of porphyry Cu–Mo ore bodies,where anhydrite–hematite alteration and fluid inclusionsreveal the action of very oxidized saline solutions rich insulfur. KEY WORDS: anhydrite; sulfur; solubility; metamorphic brines; granulites     

Petrogenesis of the Eastern Bushveld Complex: Crystallization of the Middle Critical Zone

The bronzite—chromite-anorthite assemblage of the F—unit(Cameron & Emerson, 1959) from the Critical Zone of theBushveld Igneous Complex, was examined with the aid of an electrolyticcell designed after Sato (1971). The resultant fO₂-T data reveala last equilibration at an fO₂ value of 10^{11·82 ±·40} atm and at a temperature of 1091 ± 35 °C.These fO₂-T data when compared with: (1) a one atmosphere quenching—technique solidus determinationof 1110 ± 5 °C, (2) the Bushveld plagioclase compositional trends (Cameron,1970), (3) Bushveld petrofabric examinations (Cameron, 1969) (4) phase equilibria in the system CaO–MgO–FeO–CaAl₂Si₂O₈–SiO₂(Roeder & Osborn, 1966), (5) phase equilibria in the system CaAl₂Si₂O₈–NaAlSi₃O₈–SiO₂–MgO–Fe–O₂–H₂O–CO₂(Eggler, 1974), all support the idea that the Eastern Bushveld magma was notappreciably differentiating in the middle Critical Zone betweenF and the L Horizons, an accumulation of nearly 220 meters.     

An Experimentally Constrained Petrogenetic Grid in the Silica-Saturated Portion of the System KFMASH at High Temperatures and Pressures

Experiments in the quartz-saturated part of the system KFMASHunder fO₂ conditions of the haematite–magnetite bufferand using bulk compositions with X_Mg of 0·81, 0·72,0·53 define the stability limits of several mineral assemblageswithin the P–T field 9–12 kbar, 850–1100°C.The stability limits of the mineral assemblages orthopyroxene+ spinel + cordierite ± sapphirine, orthopyroxene + garnet+ sapphirine, sapphirine + cordierite + orthopyroxene and garnet+ orthopyroxene + spinel have been delineated on the basis ofP–T and T–X pseudosections. Sapphirine did not appearin the bulk composition of X_Mg = 0·53. A partial petrogeneticgrid applicable to high Mg–Al granulites metamorphosedat high fO₂, developed in our earlier work, was extended tohigher pressures. The experimental results were successfullyapplied to several high-grade terranes to estimate P–Tconditions and retrograde P–T trajectories. KEY WORDS: KFMASH equilibria; experimental petrogenetic grid at high fO₂     

Origin of Grandite Garnet in Calc-Silicate Granulites: Mineral-Fluid Equilibria and Petrogenetic Grids

The role of clinopyroxene in producing grandite garnet is evaluatedusing data from an ultrahigh-temperature metamorphosed calc-silicategranulite occurrence in the Eastern Ghats Belt, India. ‘Peak’pressure–temperature conditions of metamorphism were previouslyconstrained from associated high Mg–Al granulites as c.0·9 GPa, >950°C, and the rocks were near-isobaricallycooled to c. 750°C. Grandite garnet of variable compositionwas produced by a number of reactions involving phases suchas clinopyroxene, scapolite, plagioclase, wollastonite and calcite,in closely spaced domains. Compositional heterogeneity is preservedeven on a microscale. This precludes pervasive fluid fluxingduring either the peak or the retrograde stage of metamorphism,and is further corroborated by computation of fluid–rockratios. With the help of detailed textural and mineral compositionalstudies leading to formulation of balanced reactions, and usingan internally consistent thermodynamic dataset and relevantactivity–composition relationships, new petrogenetic gridsare developed involving clinopyroxene in the system CaO–Al₂O₃–FeO–SiO₂–CO₂–O₂in T–aCO₂–fO₂ space to demonstrate the importanceof these factors in the formation of grandite garnet. Two singularcompositions in garnet-producing reactions in this system arededuced, which explain apparently anomalous textural relations.The possible role of an esseneite component in clinopyroxenein the production of grandite garnet is evaluated. It is concludedthat temperature and fO₂ are the most crucial variables controllinggarnet composition in calc-silicate granulites. fO₂, however,behaves as a dependent variable of CO₂ in the fluid phase. Externalfluid fluxing of any composition is not necessary to producechemical heterogeneity of garnet solid solution. KEY WORDS: grandite garnet; role of clinopyroxene; internal buffering; oxidation–decarbonation equilibria