Low-temperature Compatibility Relations of Cordierite in Haplopelites of the System K2O--MgO--Al2O3--SiO2--H2O

The equilibrium temperatures of the reaction muscovite+chlorite+quartz= cordierite+phlogopite+H₂O (1) in the pure system K₂O—MgO—Al₂O₂—SiO₂—H₂Owere found to be 495±10°C at 1 kb P_H2O; 525±10°Cat 2 kb; 610±15°C at 5 kb; 635±10°C at6 kb. From intersection of this curve with the lower temperaturestability limit of cordierite close to 645°C, 6.5 kb P_H2O,a reaction cordieritc+muscovite = phlogopite+aluminum silicate+quartz+H₂O(2) is generated which has a negative slope and passes throughthe points 645°C, 6.5 kb PH₂O and 700°C, 5 kb PH₂O.On the high-pressure side of this reaction curve cordieriteis restricted to K₂O—poor bulk compositions. Application of the experimentally determined phase relationsto more complex natural pelitic rocks suggests that reaction(1) represents maximum temperatures for the disappearance ofchlorite from pelitic assemblages containing muscovite and quartz,whereas reaction (2) gives maximum water pressures for the disappearanceof cordierite from these rocks.     

Clinoenstatite in a Volcanic Rock from the Cape Vogel Area, Papua

A porphyritic volcanic rock from Cape Vogel, Papua, containsabundant phenocrysts of multiply twinned clinoenstatite, andless common phenocrysts of orthopyroxene, set in a groundmassof pyroxene microlites, glass, and zeolites. The rock contains54% SiO₂, 13–16% MgO, and 6–7% FeO, but only 7–8%Al₂O₃, 45–5% CaO, and 06–08% Na₂O. Microprobeanalyses show that the clinoenstatite phenocrysts range fromEn₉₂ to En₈₂, and have very low Al₂O₃ and extremely low CaOcontents. Their composition differs consistently from that ofthe orthopyroxene phenocrysts, which range from En₈₇ to at leastas Fe-rich as En₇₈. The clinoenstatite phenocrysts are a metastableinversion-product from primary protoenstatite. The crystallizationof protoenstatite as the liquidus phase is attributed directlyto the unique magma composition.     

Experimental Investigation and Optimization of Thermodynamic Properties and Phase Diagrams in the Systems CaO-SiO2, MgO-SiO2, CaMgSi2O6-SiO2 and CaMgSi2O6-Mg2SiO4 to 1{middle dot}0 GPa

Using experimental results at 1·0 GPa for the systemsCaO–SiO₂, MgO–SiO₂, CaMgSi₂O₆–SiO₂ and CaMgSi₂O₆–Mg₂SiO₄,and all the currently available phase equilibria and thermodynamicdata at 1 bar, we have optimized the thermodynamic propertiesof the liquid phase at 1·0 GPa. The new optimized thermodynamicparameters indicate that pressure has little effect on the topologyof the CaO–SiO₂, CaMgSi₂O₆–SiO₂, and CaMgSi₂O₆–Mg₂SiO₄systems but a pronounced one on the MgO–SiO₂ binary. Themost striking change concerns passage of the MgSiO₃ phase fromperitectic melting at 1 bar to eutectic melting at 1·0GPa. This transition is estimated to occur at 0·41 GPa.For the CaMgSi₂O₆–SiO₂ and CaMgSi₂O₆–Mg₂SiO₄ pseudo-binaries,the size of the field clinopyroxene + liquid increases withincreasing pressure. This change is related to the shift ofthe piercing points clinopyroxene + silica + liquid (from 0·375mol fraction SiO₂ at 1 bar to 0·414 at 1·0 GPa)and clinopyroxene + olivine + liquid (from 0·191 molfraction SiO₂ at 1 bar to 0·331 at 1·0 GPa) thatbound the clinopyroxene + liquid field in the CaMgSi₂O₆·SiO₂and CaMgSi₂O₆·Mg₂SiO₄ pseudo-binaries, respectively. KEY WORDS: CaO–SiO₂; CaMgSi₂O₆–Mg₂SiO₄; CaMgSi₂O₆–SiO₂; experiments; MgO–SiO₂     

Immiscible Transition from Carbonate-rich to Silicate-rich Melts in the 3 GPa Melting Interval of Eclogite + CO2 and Genesis of Silica-undersaturated Ocean Island Lavas

We explore the partial melting behavior of a carbonated silica-deficienteclogite (SLEC1; 5 wt % CO₂) from experiments at 3 GPa and comparethe compositions of partial melts with those of alkalic andhighly alkalic oceanic island basalts (OIBs). The solidus islocated at 1050–1075 °C and the liquidus at 1415 °C.The sub-solidus assemblage consists of clinopyroxene, garnet,ilmenite, and calcio-dolomitic solid solution and the near solidusmelt is carbonatitic (<2 wt % SiO₂, <1 wt % Al₂O₃, and<0·1 wt % TiO₂). Beginning at 1225 °C, a stronglysilica-undersaturated silicate melt (34–43 wt % SiO₂)with high TiO₂ (up to 19 wt %) coexists with carbonate-richmelt (<5 wt % SiO₂). The first appearance of carbonated silicatemelt is 100 °C cooler than the expected solidus of CO₂-freeeclogite. In contrast to the continuous transition from carbonateto silicate melts observed experimentally in peridotite + CO₂systems, carbonate and silicate melt coexist over a wide temperatureinterval for partial melting of SLEC1 carbonated eclogite at3 GPa. Silicate melts generated from SLEC1, especially at highmelt fraction (>20 wt %), may be plausible sources or contributingcomponents to melilitites and melilititic nephelinites fromoceanic provinces, as they have strong compositional similaritiesincluding their SiO₂, FeO^*, MgO, CaO, TiO₂ and Na₂O contents,and CaO/Al₂O₃ ratios. Carbonated silicate partial melts fromeclogite may also contribute to less extreme alkalic OIB, asthese lavas have a number of compositional attributes, suchas high TiO₂ and FeO^* and low Al₂O₃, that have not been observedfrom partial melting of peridotite ± CO₂. In upwellingmantle, formation of carbonatite and silicate melts from eclogiteand peridotite source lithologies occurs over a wide range ofdepths, producing significant opportunities for metasomatictransfer and implantation of melts. KEY WORDS: carbonated eclogite; experimental phase equilibria; partial melting; liquid immiscibility; ocean island basalts     

Liquidus Equilibria in the System K2O-Na2O-Al2O3-SiO2-F2O-1-H2O to 100 MPa: I. Silicate-Fluoride Liquid Immiscibility in Anhydrous Systems

Liquidus relations in the four-component system Na₂O–Al₂O₃–SiO₂–F₂O_–1were studied at 0· 1 and 100 MPa to define the locationof fluoride–silicate liquid immiscibility and outlinedifferentiation paths of fluorine-bearing silicic magmas. Thefluoride–silicate liquid immiscibility spans the silica–albite–cryoliteand silica–topaz–cryolite ternaries and the haplogranite-cryolitebinary at greater than 960°C and 0· 1–100 MPa.With increasing Al₂O₃ in the system and increasing aluminum/alkalication ratio, the two-liquid gap contracts and migrates fromthe silica liquidus to the cryolite liquidus. The gap does notextend to subaluminous and peraluminous melt compositions. Forall alkali feldspar–quartz-bearing systems, the miscibilitygap remains located on the cryolite liquidus and is thus inaccessibleto differentiating granitic and rhyolitic melts. In peralkalinesystems, the magmatic differentiation is terminated at the albite–quartz–cryoliteeutectic at 770°C, 100 MPa, 5 wt % F and cation Al/Na =0· 75. The addition of topaz, however, significantlylowers melting temperatures and allows strong fluorine enrichmentin subaluminous compositions. At 100 MPa, the binary topaz–cryoliteeutectic is located at 770°C, 39 wt % F, cation Al/Na 0·95, and the ternary quartz–topaz–cryolite eutecticis found at 740°C, 32 wt % F, 30 wt % SiO₂ and cation Al/Na 0· 95. Such location of both eutectics enables fractionationpaths of subaluminous quartz-saturated systems to produce fluorine-rich,SiO₂-depleted and nepheline-normative residual liquids. KEY WORDS: silicate melt; granite; rhyolite; fluorine; liquid immiscibility     

Subsolidus and Partial Melting Reactions in the Quartz-excess CaO+MgO+Al2O3+SiO2+H2O System under Water-excess and Water-deficient Conditions to 10 kb: Some Implications for the Origin of Peraluminous Melts from Mafic Rocks

Experimental results up to 10 kb pressure are presented on thestability of amphibole in the quartz-excess CaO+MgO+Al₂O₃ (CMASH)system under H₂O)-excess and H₂O deficient conditions. Amphiboleis stable above the solidus under H₂O-excess conditions whereasunder H₂O-deficient conditions dehydration melting of amphibole-bearingassemblages defines the solidus. The successive appearance ofamphibole, talc, and zoisite with increasing pressure considerablymodifies the plagioclase-pyroxene-garnet-kyanite reactions documentedexperimentally in the CaO+MgO+Al₂O₃+SiO₂ system for gabbro-granulite-eclogitetransitions. Although both clino pyroxene and cordierite (withanorthite+orthopyroxene+quartz) may melt eutectically at oneatmosphere to form diopside-normative and corundum-normativemelts respectively, at higher pressures under H₂O-excess conditionsthe peritectic melting of mafic rock compositions produces corundum-normativeliquids together with either clinopyroxene or amphibole. Dehydrationmelting produces melts which are not corundum-normative. Thesedata are used to discuss the origins and evolution of contrastingbasalt-andesite-dacite-rhyolite volcanic suites and graniticplutons, many of whose silicic variants are corundum-normativein character, such as the Toba luff ignimbrites, Indonesia (Beddoc-Stephenset al., 1983) and I-type granite minimum melts (White &Chappell, 1977). In contrast, it is proposed that for the Cascadesbasalt-andesite-dacite-rhyolite suite the ortho pyroxene-plagioclase-quartzthermal divide was maintained up to rhyolite compositions, therebyprohibiting the derivation of corundum-normative rocks fromdiopside-normative parent magmas. The deduced reaction relations between pyroxenes, amphibole,plagioclase, quartz, and liquid are used to explain the absenceor extreme scarcity of hydrous phases in some hydrous magmas.These phase relations can also explain the development of laterplagioclase overgrowths on resorbed plagioclase cores in graniticintrusives, and the general absence of resorption and overgrowthsin chemically equivalent extrusive rocks. A theoretical analysis of the partial melting of forsterite-bearingassemblages in the CaO+MgO+Al₂O₃+SiO₂+H₂O system shows thatunder H₂O-excess conditions partial melting may generate corundum-normative(but low SiO₂) melts from a peridotite source at shallow depths.     

The Stability of Hercynite and Hercynite-Gahnite Spinels in Corundum- or Quartz-Bearing Assemblages

The equilibrium 3FeAl₂O₄ + 3Al₂SiO₃ = 5 Al₂O₃ (1) has been calibrated in the piston-cylinder apparatus. Experimentswere carried out using well-calibrated NaCl furnace assembliesand Ag₈₀Pd₂₀ capsules with oxygen fugacity buffered at or neariron–w?stite. The equilibrium is located at less than7?2 kb at 85O?C and between 8?0 and 8?2, 10?0 and 10?5, and12?0 and 12?2 kb at 900, 1000, and 1100?C, respectively. Experimentshave also been conducted to determine the effect of gahnite(ZnAl₂O₄) component in spinel on equilibrium (1). Graphite capsuleswere used with oxygen fugacity buffered at or near graphite-CO-CO₂.The addition of zinc displaces the reaction to higher pressures.For hercyniteg₈₆-gahnite₁₄, the equilibrium is located between9?4 and 9?6 and 12?7 and 13?0kb at 900 and 1050?C, respectively.For hercynite₇₀-gahnite₃₀, the equilibrium is located between10?8 and 11?0 and 15?4 and 15?6 kb at 900 and 1050?C, respectively.The results indicate that hercynite-gahnite solutions are somewhatnon-ideal (W_G = +6?54 kJ/mol at 900?Q assuming a symmetric regularsolution model. A thermobarometer based on equilibrium (1) is applicable inhigh-grade metapelitic rocks. Pressure/temperature estimatesusing this equilibrium agree with other well-calibrated thermometersand barometers. Failure of equilibrium (1) to intersect the equilibrium 3 FeAl₂O₄ + 5 SiO₂ = Fe₃Al₂Si₃O₁₂ + 2 Al₂SiO₅ (2) indicates that the equilibrium corundum + quartz = sillimaniteis metastable at all pressures and temperatures. This impliesthat co-occurrences of corundum and quartz in granulites aremetastable.     

Mineral Chemistry and Metasomatic Growth of Aluminous Enclaves in Gedrite--Cordierite-Gneiss from Southwestern New Hampshire, USA

The aluminous enclaves occur in gedrite-cordierite-gneissesof the Middle Ordovician Ammonoosuc Volcanics, and are composedof combinations of the aluminous minerals sillimanite (Sill),kyanite, corundum (Cor), staurolite (St), sapphirine (Sa), andspinel (Sp), which are set in a matrix of cordierite (Crd) orplagioclase (Plag). Generally, where plagioclase is present,both it and the aluminous minerals are separated from gedrite(Ged) and rare hornblende (Hbl) by cordierite. The enclavesarc interpreted to have formed near the peak of Acadian (Devonian)metamorphism at sillimanite-staurolite-muscovite grade by reactionsthat were encountered during the pressure decrease which accompaniedthe rise of gneiss domes in the region. The enclaves are divided into two main types: (1) enclaves ofcordierite surrounding aluminous minerals; and (2) enclavesof cordierite and plagioclase surrounding aluminuous minerals.Sapphirine grains contain between 9?2 and 9?3 Al atoms per formulacalculated to 14 cations. Staurolites from the enclaves areMg-rich and have (Fe²⁺+ Mn)/(Fe²⁺+Mn+Mg) ratios of 0-59–0?64. The textures and mineralogy of the enclaves suggest that theserocks originally consisted of Ged+Sill?Qz?Hbl?Sp?Plag. Theseminerals reacted to form Crd+Aluminous Minerals?Plag. The mineralogyof both main types of enclaves can be explained by two analogoussets of continuous Fe-Mg reactions:The structure of the enclavessuggests that the mineral growth by the above reactions wasdiffusion controlled, which would have resulted from oversteppingthe above reactions (i.e. the P change exceeded the reactionrate). Therefore, chemical potential gradients (relative mobilityof diffusing components) between gedrite and sillimanite controlledthe location of mineral growth. The Fe-Mg ratio of the bulkcomposition and the proportions of non-Fe-Mg minerals (quartzand sillimanite) appear to determine which continuous Fe-Mgreactions were encountered. Examples of mineral sequences in the cordierite enclaves are:Sill (core)/St+Crd/Ged (matrix); Cor+Crd (core)/Ged (matrix),and Sill (core)/St+Crd/Sa+Crd/Ged (matrix). Examples of themineral sequences in the cordierite-plagioclase enclaves are:Sill (core)/St+Plag/Plag+Crd/Hbl+Ged (matrix); Cor+Plag (core)/St+Plag/Sa+Plag/Ged+ Hbl (matrix); and St+Plag (core)/Plag+Crd/Ged+Hbl (matrix). P–µ_FeMg–1 diagrams proved to be an importanttool for understanding and illustrating the development of theenclaves. These diagrams allow one to view simultaneously allthe discontinuous and continuous Fe-Mg reactions along a P–µ_H2O(or T) rock path. With this information it is possible to determinequalitatively which reactions and what sequence of reactionsmight be encountered by bulk compositions with variable Fe-Mgratios and modal proportions of phases.     

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     

Stability and Phase Relations of Trioctahedral Calcium Brittle Micas (Clintonite Group)

On the pseudobinary join CaO:3MgO:Al₂O₃:2SiO₂:_xH2O–CaO:1.25MgO:2.75 Al₂O₃: 0.25SiO₂:_xH₂O clintonite mixed crystals Ca(Mg_{1+ x}Al_{2 – x}) (Al_{4 – x}Si_xO₁₀)(OH)₂ with x rangingfrom 0.6 to 1.4 occur in the temperature range 600–830?C, 2 kb fluid pressure. On the MgSirich side clintonites coexistwith chlorite, forsterite, diopside, and calcite (due to smallamounts of CO₂ in the gas phase) and, at lower temperatures,also with idocrase, hydrogrossularite, and aluminous serpentine.Decomposition of clintonite over a divariant temperature rangeoccurs above 830 ?C, 2 kb; clintonite-free subsolidus assemblagescomprising three or four solid phases are formed in the temperatureranges 890 ?–1120 ?C. The subsolidus assemblages can berepresented in a polyhedron defined by the corners forsterite,diopside, melilite, spinel, anorthite, corundum, and calciumdialuminate. Above 1120 ?C partial melting occurs. The upper thermal stability limits of three selected compositionshave been reversed in the P-T range 0.5–20 kb and 730–1050 ?C, respectively. Below some 4 kb breakdown is dueto the divariant reactions: (1)Ca(Mg_2.25Al_0.75)(Al_2.75)(Si_1.25O₁₀)(OH)₂ spinel+diopside_ss+forsterite+clintonite_ss+vapor, (2)Ca(Mg₂Al)(Al₃SiO₁₀)(OH)₂ spinelx002B;melilite_ss+anorthite+clintonite_ss+vapor, (3)Ca(Mg_1.75Al_1.25)(Al_3.25)(Si_0.75O₁₀)(OH)₂ spinel+melilite_ss+corundum+clintonite_ss+vapor, At the terminations of the divariant temperature ranges (1)melilite_ss, (2) diopside_ss, and (3) anorthite enter those assemblagesand clintonitess disappears completely. The reactions can berepresented by the following equations (1)log,_H2O = 10.2879–8113/T+0.0856(P–1)/T, (2)log = 9.5852–7325/T+0.0794(P–1)/T, (3)log = 7.8358–5250/T+0.077(P–1)/T, with P expressed in bars and Tin ?K. Above 4 kb the upper thermalstability limit of clintonite is defined by incongruent melting,with grossularite participating at pressures above 9 kb. Thesecurves exhibit a very steep, probably even negative slope inthe P-T diagram. There is a close correspondence between natural clintonite-bearingassemblages and thosefound experimentally. The rarity of clintonitein nature is not due to special conditions of pressure and temperaturebut rather due to special bulk compositions of the rocks.     

The Effect of Cr2O3 on the Partial Melting of Spinel Lherzolite in the System CaO-MgO-Al2O3-SiO2-Cr2O3 at 1{middle dot}1 GPa

Chromium as Cr³⁺ substitutes for octahedrally coordinated Alin upper-mantle minerals, thereby reducing the activity of Al₂O₃in the system and hence the concentration of Al₂O₃ in partialmelts. The effect of Cr₂O₃ on melt compositions multiply saturatedwith the spinel lherzolite phase assemblage has been quantifiedin the system CaO–MgO–Al₂O₃–SiO₂–Cr₂O₃at 1·1 GPa as a function of 100 Cr/(Cr + Al) in the spinel(Cr#_sp). The decrease of Al₂O₃ in the melt with increasing Cr#_spis accompanied by increasing MgO and SiO₂, whereas CaO remainsalmost constant. Consequently, the CaO/Al₂O₃ ratio of the meltincreases with Cr#_sp, and the melt becomes richer in normativediopside, hypersthene and quartz. The effect may explain certainmantle melts with unusually high CaO/Al₂O₃ ratios. The concentrationof Cr₂O₃ in the melt remains low even at high Cr#_sp, which meansthat the strong effect of Cr₂O₃ on partial melting equilibriais not readily apparent from its concentration in the melt itself.The existence of a highly refractory major component such asCr₂O₃ nullifies simplified conclusions from the ‘inverseapproach’ in the experimental study of basalt petrogenesis,as there is insufficient information in the composition of thepartial melt to reconstruct the conditions of melting. KEY WORDS: basalt petrogenesis; partial melting; reversal experiment; spinel lherzolite; system CMAS–Cr₂O₃; CaO/Al₂O₃ of melt; effect of Cr₂O₃     

Liquidus Equilibria in the System K2O-Na2O-Al2O3-SiO2-F2O-1-H2O to 100 MPa: II. Differentiation Paths of Fluorosilicic Magmas in Hydrous Systems

We investigated phase equilibria in the six-component systemNa₂O–K₂O–Al₂O₃–SiO₂–F₂O_–1–H₂Oat 100 MPa to characterize differentiation paths of naturalfluorine-bearing granitic and rhyolitic magmas. Topaz and cryoliteare stable saturating solid phases in calcium-poor systems.At 100 MPa the maximum solidus depression and fluorine solubilityin evolving silicic melts are controlled by the eutectics haplogranite–cryolite–H₂Oat 640°C and 4 wt % F, and haplogranite–topaz–H₂Oat 640°C and 2 wt % F. Topaz and cryolite form a binaryperalkaline eutectic at 660°C, 100 MPa and fluid saturation.The low-temperature nature of this invariant point causes displacementof multiphase eutectics with quartz and alkali feldspar towardsthe topaz–cryolite join and enables the silicate liquidusand cotectic surfaces to extend to very high fluorine concentrations(more than 30 wt % F) for weakly peraluminous and subaluminouscompositions. The differentiation of fluorine-bearing magmasfollows two distinct paths of fluorine behavior, depending onwhether additional minerals buffer the alkali/alumina ratioin the melt. In systems with micas or aluminosilicates thatbuffer the activity of alumina, magmatic crystallization willreach either topaz or cryolite saturation and the system solidifiesat low fluorine concentration. In leucogranitic suites precipitatingquartz and feldspar only, the liquid line of descent will reachtopaz or cryolite but fluorine will continue to increase untilthe quaternary eutectic with two fluorine-bearing solid phasesis reached at 540°C, 100 MPa and aqueous-fluid saturation.The maximum water solubility in the haplogranitic melts increaseswith the fluorine content and reaches 12· 5 ±0· 5 wt % H₂O at the quartz–cryolite–topazeutectic composition. A continuous transition between hydrousfluorosilicate melts and solute-rich aqueous fluids is not documentedby this study. Our experimental results are applicable to leucocraticfluorosilicic magmas. In multicomponent systems, however, thepresence of calcium may severely limit enrichment of fluorineby crystallization of fluorite. KEY WORDS: granite; rhyolite; topaz; cryolite; magmatic differentiation     

The System Na2O-Al2O3-Fc2O3-SiO2 at 1 Atmosphere, and the Petrogenesis of Alkaline Rocks

Equilibria involving acmite, albite, nepheline, quartz, anda liquid phase constitute the petrologically important partof the system Na₂O–Al₂O₃–Fe₂O₂–SiO₂, and theunivariant and invariant relations provide useful analogiesfor a wide variety of alkaline igneous rocks. These relationsare dominated by the incongruent melting behaviour of acmite,which does not appear on the liquidus of the join acmite-nepheline-silica;instead, a broad field of hematite is present and acmite crystallizesonly from liquids containing potential sodium silicate. Consequently,the oversaturated and undersaturated eutectics, correspondingto granitic and nepheline syenitic liquids, are rich in sodiumsilicate and distinct from those found in Petrogeny's Residuasystem: the temperatures of the eutectics are 7285C and 7155C, respectively. Survival of peralkaline granite in the aluminouscontinental crust can be explained by the strongly peralkalinecomposition of the oversaturated eutectic. Magma of this typemay be the primitive granite of the non-orogenic zones. Theubiquitous alkali metasomatism around alkaline complexes canalso be interpreted in terms of residual liquids enriched inalkali silicates. Transition from undersaturated to oversaturatedliquids is possible by fractionation of hematite and a new processfor achieving the reverse transition has been found. This dependson the substitution of Fe³ for Al³ in feldspar and suggestsa more important role for syenite in any scheme of petrogenesis. Each of the two eutectics is linked to a corresponding peritecticat which hematite reacts to give acmite. The liquid at the undersaturated,quaternary reaction point is of ijolitic type, providing thefirst intimation that ijolite may represent a low-melting fractionin nature. The system Na₂O–Al₂O₃–Fe₂O₃–SiO₂thus constitutes the peralkaline residua system and on thisbasis a coherent picture of stable continental magmatism canbe constructed. Ijolite is seen as the low-melting fractionfrom a range of peralkaline compositions and from rocks suchas melilite basalt, while the frequently associated carbonatiteis considered to be the volatile-rich, fugitive material fromthe mantle. Such a relationship is consistent with the dualassociation of carbonatite with either ijolite or kimberliteunder different tectonic conditions. The more common syenite,nepheline syenite, and alkaline granite of the non-orogenicregions are regarded as low-melting fractions from basalticmaterials in the deep crust. Most of this activity, involvingmagmas of residual type, could thus be explained in terms ofpartial melting in the deep crust and upper mantle. A possiblemechanism for this would be arching of the rigid continentalcrust, the consequent relief of lithostatic load giving riseto melting, and the concentration of fugitive constituents,in the underlying zones.     

Stability of Yoderite in the Absence and in the Presence of Quartz: an Experimental Study in the System MgO-Al2O3-Fe2O3-SiO2-H2O

The water-pressure temperature stability field of yoderite,ideally Mg₂Al_5.6Fe^{3 +} _0.4Si₄O₁₈(OH)₂, was determined at highoxygen fugacities by high-pressure bracketing runs on eightpossible breakdown reactions involving the phases chlorite,kyanite, talc, staurolite, pyrope, enstatite, boron-free kornerupine,cordierite, quartz, and invariably an excess of hematite. Yoderitewas found to be stable over the surprisingly large PT rangefrom 6 to 25 kbar water pressure and 590 to 795 C. It is thusa high-pressure mineral covering the upper amphibolite and portionsof the eclogite facies. In the presence of quartz its upperpressure stability is reduced to some 15 kbar, and its uppertemperature stability to 715 C. Two of the yoderite-producingreactions are anomalous as they show dehydration in the directiontowards lower temperatures. Importantly, this is also true forthe reaction kyanite + talc + hematite+H₂O=yoderite+quartz whichis responsible for the only yoderite occurrence in nature atMautia Hill, Tanzania. Preliminary thermodynamic calculationsindicate that—owing to this unusual dehydration behavior—thestability field for the assemblage yoderite+quartz disappearsfor water activities lower than 0.5. The rarity of yoderitein natural rocks, which is in contrast to its large PT stabilityfield, must be explained on chemical rather than on physicalgrounds. Yoderite can only occur in whiteschist-type bulk compositionsrich in MgO, Al₂O₃, SiO₂, and containing some iron, but poorin alkalis and CaO. Oxygen fugacities must be unusually highto keep Fe trivalent, and—at least for rocks with excessquartz—the water activity must be high as well. In anenvironment of this kind, yoderite formation in the Mautia Hillwhiteschist may have occurred even at constant total pressureand temperature simply by an influx of hydrous fluid duringthe late stages of metamorphism under amphibolite facies conditions.     

Solid-Fluid Equilibria in the System KAlSi3O8-NaAlSi3O8-Al2SiO5-SiO2-H2O-HCl

Activity diagrams in the system KAlSi₃O₈-NaAlSi₃O₈-Al₂SiO₅-SiO₂-H₂O-HClhave been calculated in terms of a_K+/a_H+ and a_N+/a_H+ from existingexperimental data. They show the effect of temperature, pressure,and a_H2O on the stability fields of the alkali feldspars, micas,and aluminium silicate. These activity diagrams are useful in revealing the bufferingcapacity of mineral assemblages and the chemical potential gradientsestablished by changes in T, P, a_H2O, and mineral assemblage.An analysis of mineral paragenesis in terms of these diagramssuggests that mosaic equilibrium, allowing limited metasomatismand internal buffering of chemical potentials, best describemetamorphic systems. Thus the dehydration reaction: muscovite+quartz=K-feldspar+Al₂SiO₅+H₂O which is most important in closed systems, probably fails todescribe in detail the mechanism of natural muscovite decomposition.Rather the decomposition of muscovite is more likely representedby ionic reactions. The replacement of muscovite by feldspar: muscovite+6 SiO₂+2 K⁺=3 K-feldspar+2 H⁺ muscovite+6 SiO₂+3 Na⁺=3 Albite+K⁺+2 H⁺ is favored at high temperature and low pressure, and may accountfor the crystallization of some feldspars in metamorphic rocks.The reaction involving aluminium silicate replacement of muscovite: 2 muscovite+2 H⁺=3 Al₂SiO₅+3 SiO₂+3 H₂O+2 K⁺ is favored at high temperature and pressure and low a_H2O, andcould contribute to the development of the aluminium silicates.It is concluded that both activity diagrams and AKNa projectionsshould be used together to more completely evaluate mineralparagenesis in terms of mosaic equilibria.     

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     

Petrology of Biotite-Cordierite-Garnet Gneiss of the McCullough Range, Nevada I. Evidence for Proterozoic Low-Pressure Fluid-Absent Granulite Grade Metamorphism in the Southern Cordillera

Proterozoic migmatitic paragneisses exposed in the McCulloughRange, southern Nevada, consist of cordierite+almanditic garnet+biotite+sillimanite+plagioclase+K-feldspar+quartz+ilmenite+hercynite.This assemblage is indicative of a low-pressure fades seriesat hornblende-granulite grade. Textures record a single metamorphicevent involving crystallization of cordierite at the expenseof biotite and sillimanite. Thermobarometry utilizing cation exchange between garnet, biotite,cordierite, hercynite, and plagioclase yields a preferred temperaturerange of 590–750?C and a pressure range of 3–4 kb.Equilibrium among biotite, sillimanite, quartz, garnet, andK-feldspar records a_H2O between 0?03 and 0?26. The low a_H2Otogetherwith low f_O2 (QFM) and optical properties of cordierite indicatemetamorphism under fluid-absent conditions. Preserved mineralcompositions are not consistent with equilibrium with a meltphase. Earlier limited partial melting was apparently extensiveenough to cause desiccation of the pelitic assemblage. The relatively low pressures attending high-grade metamorphismof the McCullough Range paragneisses allies this terrane withbiotite-cordierite-garnet granulites in other orogenic belts.aosure pressures and temperatures require a transient apparentthermal gradient ofat least 50?C/km during part of this Proterozoicevent in the southern Cordillera. ^*Present address: Institute of Geophysics and Planetary Physics, University of California, Los Angeles, CA 90024-1567     

The Solubility of Alumina in Orthopyroxene Coexisting with Garnet in FeO-MgO--Al2O3--SiO2 and CaO--FeO--MgO--Al2O3--SiO2

The pressure-temperature-compositional (P-T-X) dependence ofthe solubility of Al₂O₃ in orthopyroxene coexisting with garnethas been experimentally determined in the P-T range 5–30kilobars and 800–1200 ?C in the system FeO—MgO—Al₂O₃—SiO₂(FMAS). These results have been extended into the CaO—FeO—MgO—Al₂O₃—SiO₂(CFMAS) system in a further set of experiments designed to determinethe effect of the calcium content of garnet on the Al₂O₃ contentsof coexisting orthopyroxene at near-constant Mg/(Mg + Fe). Startingmaterials were mainly glasses of differing Mg/(Mg + Fe) or Ca/(Ca+ Mg + Fe) values, seeded with garnet and orthopyroxene of knowncomposition, but mineral mixes were also used to demonstratereversible equilibrium. Experiments were performed in a piston-cylinderapparatus using a talc/pyrex medium. Measured orthopyroxene and corrected garnet compositions werefitted by multiple and stepwise regression techniques to anequilibrium relation in the FMAS system, yielding best-fit,model-dependent parameters G^o_y= –5436 + 2.45T cal mol^–1,and W^M1_FeA1= –920 cal mol^–1. The volume change ofreaction, V^o, the entropy change, S^o₉₇₀ and the enthalpy changeH^o_1,970, were calculated from the MAS system data of Perkinset al. (1981) and available heat capacity data for the phases.Data from CFMAS experiments were fitted to an expanded equilibriumrelation to give an estimate of the term W^ga_CaMg = 1900 ? 400cal/mole cation, using the other parametric values already obtainedin FMAS. The experimental data allow the development of a arnet-orthopyroxenegeobarometer applicable in FMAS and CFMAS: where This geobarometer is applicable to both pelitic and metabasicgranulites containing garnet orthopyroxene, and to garnet peridoditeand garnet pyroxenite assemblages found as xenoliths in diatremesor in peridotite massifs. It is limited, however, by the necessityof an independent temperature estimate, by errors associatedwith analysis of low Al₂O₃ contents in orthopyroxenes in high-pressureor low-temperature parageneses, and by uncertainties in thecomposition of garnet in equilibrium with orthopyroxene. Ananalysis of errors associated with this formulation of the geobarometersuggests that it is subject to great uncertainty at low pressuresand for Fe-rich compositions. The results of application ofthis geobarometer to natural assemblages are presented in acompanion paper.     

Low-Pressure Phase Relationships in the System Na2O--CaO--FeO--MgO--Al2O3--SiO2 at 1100C, with Implications for the Differentiation of Basaltic Magmas

Experiments were performed on the system Na₂O–CaO–FeO–MgO–Al₂O₃–SiO₂at 1100C, with the interest focused on the assemblage Liq+Aug+Pl+Oland its boundaries. Glass synthesized in a very reducing atmospherewas used as starting material. To avoid sodium loss during theexperiment, the starting material was loaded into iron capsules,and the experiments were carried out in evacuated silica glasstubes. All phases in the products were identified and analysedwith an electron microprobe. The probe analyses indicate thatthe assemblage Liq+Aug+Pl+Ol is stable over a wide range ofcompositions, and is bounded by the appearance of pigeonitein the silica-rich compositions. In the silica-poor compositions,the assemblage is successively bounded by the appearance ofkirschsteinite, melilite, and nepheline with increasing sodiumcontent. Owing to the isothermal and ‘isobaric’divariant nature of the assemblage Liq+Aug+Pl+Ol in the studiedsystem, a numerical method has been used to describe the phasecompositions with Si and Na contents in the liquid as two arbitrarilychosen independent variables. This procedure results in quantitativecharacterization of the assemblage Liq+Aug+Pl+Ol over a rangeof compositions. ^*Present address: Geochemistry Group, Geology Dept., Beijing University, Beijing, 100871, P.R. China.     

Reaction Textures in a Suite of Spinel Granulites from the Eastern Ghats Belt, India: Evidence for Polymetamorphism, a Partial Petrogenetic Grid in the System KFMASH and the Roles of ZnO and Fe2O3

Spinel granulites, with or without sapphirine, occur as lensesin garnetiferous quartzofeldspathic gneisses (leptynites) nearGokavaram in the Eastern Ghats Belt, India. Spinel granulitesare mineralogically heterogeneous and six mineral associationsoccur in closely spaced domains. These are (I) spinel–quartz–cordierite,(II) spinel–quartz–cordierite–garnet–orthopyroxene–sillimanite,(III) spinel–cordierite–orthopyroxene–sillimanite,(IV) spinel–quartz–sapphirine–sillimanite–garnet,(V) spinel–quartz-sapphirine–garnet and (IV) rhombohedral(Fe–Ti) oxide–cordierite–orthopyroxene–sillimanite.Common to all the associations are a porphyroblastic garnet(containing an internal schistosify defined by biotite, sillimaniteand quartz), perthite and plagioclase. Spinel contains variableamounts of exsolved magnetite and is distinctly Zn rich in thesapphirine-absent associations. X_Mg in the coexisting phasesdecreases in the order cordierite–biotite–sapphirine–orthopyroxene–spinel–garnet–(Fe–Ti)oxides. Textural criteria and compositional characteristicsof the phases document several retrograde mineral reactionswhich occurred subsequent to prograde dehydration melting reactionsinvolving biotite, sillimanite, quartz, plagioclase and spinel.The following retrograde mineral reactions are deduced: (1)spinel + quartz cordierite, (2) spinel + quartz garnet + sillimanite,(3) garnet + quartz cordierite + orthopyroxene, (4) garnet+ quartz + sillimanite cordierite, (5) spinel + cordierite orthopyroxene + sillimanite, (6) spinel + sillimanite + quartz sapphirine, (7) spinel + sapphirine + quartz garnet + sillimanite,and (8) spinel + quartz sapphirine + garnet. A partial petrogeneticgrid for the system FeO–MgO–Al₂O₃–SiO₂–K₂O–H₂Oat high fo₂, has been constructed and the effects of ZnO andFe₂O₃ on this grid have been explored Combining available experimentaland natural occurrence data, the high fo₂ invariant points inthe partial grid have been located in P–T space. Geothermobarometricdata and consideration of the deduced mineral reactions in thepetrogenetic grid show that the spinel granulites evolved throughan anticlockwise P–T trajectory reaching peak metamorphicconditions >9 kbar and 950C, followed by near-isobaric cooling(dT/dP = 150C/kbar). This was superimposed by an event of near-isothermaldecompression (dT/dP = 15C/kbar). The studied spinel granulites,therefore, preserve relic prograde mineral associations andreaction textures despite being metamorphosed at very high temperatures,and bear evidence of polymetamorphism. KEY WORDS: spinel granulite; Eastern Ghats; India; polymetamorphism; geothermometry; geobarometry Corresponding author