An Experimental Study of Fe-Al Solubility in the System Corundum-Hematite up to 40 kbar and 1300{degrees}C

The mutual solubility in the system corundum–hematite[-(Al, Fe³⁺)₂O₃] was investigated experimentally using bothsynthetic and natural materials. Mixtures of -Al₂O₃ and -Fe₂O₃(weight ratios of 8:2 and 10:1) were used as starting materialsfor synthesis experiments in air at 800–1300°C withrun times of 7–34 days. Experiments at 8–40 kbarand 490–1100°C were performed in a piston-cylinderapparatus (run times of 0·8–7·4 days) usinga natural diasporite consisting of 60–70 vol. % diasporeand 20–30 vol. % Ti-hematite. During the diasporite–corunditetransformation, the FeTiO₃ component (12–18 mol %) ofTi-hematite only slightly increased, implying that oxygen fugacitywas maintained at high values. Run products were studied byelectron microprobe and X-ray diffraction (Rietveld) techniques.An essentially linear volume of mixing exists in the solid solutionwith a slight positive deviation at the hematite side. Up to1000°C, corundum contains <4 mol % Fe₂O₃ and hematite<10 mol % Al₂O₃; at 1200°C these amounts increase to9·3 and 17·0 mol %, respectively. At 1300°Chematite was no longer stable and coexists with the orthorhombic phase . The present results agree with corundum (solvus) compositions obtained inprevious studies but indicate a larger solubility of Al in hematite.The miscibility gap in the solution can be modelled with anasymmetric Margules equation with interaction parameters (2uncertainties): ; ; ; . Application of the corundum–hematite solution as a solvus geothermometer is limited because of thescarcity of suitable rock compositions. KEY WORDS: corundum; hematite; corundum–hematite miscibility gap; experimental study; Margules model; metabauxite     

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.     

Nepheline--Alkali Feldspar Equilibria: I. Experimental Data and Thermodynamic Calculations

Nepheline-alkali feldspar equilibria with alkali chloride aqueoussolutions have been determined for the temperature range 400to 700 °C at 1000 bars pressure. Nepheline-alkali feldsparequilibria with alkali chloride melts have been determined forthe temperature range 800 to 1100 °C at approximately 6bars pressure. (1) NaAlSiO₄ + KCl(aq) = NaCl(aq) + KAlSiO₄ (2) NaAlSiO₄ + KCl(melt) = NaCl(melt) + KAlSiO₄ (3) NaAlSi₃O₈(high) + KCl(aq) = NaCl(aq) + KAlSi₃O₈(San) (4) NaAlSi₃O₈(low) + KCl(aq) = NaCl(aq) + KAlSi₃O₈(Mic) (5) NaAlSi₃O₈(high) + KCl(melt) = NaCl(melt) + KAlSi₃O₄(San) (6) NaAlSi₃O₈(low) + KCl(melt) = NaCl(melt) + KAlSi₃O₈(Mic) From these, two diagrams of phase relationships were derivedfor the following exchange equilibria: (7) NaAlSiO₄ + KAlSi₃O₈(San) = NaAlSi₃O₈(high) + KAlSiO₄; (8) NaAlSiO₄ + KAlSi₃O₈(Mic) = NaAlSi₃O₈(low) + KAlSiO₄. The effect of pressure on these equilibria has been determinedby comparing the experimental data for 1000 and 5000 bars (t= 500 °C) and thermodynamic calculations. It has also beenshown that the effect of excess silica in nepheline solid solutionon the K—Na distribution between nepheline and alkalifeldspar is substantial and opposite to that of temperature.In the high temperature region an increase in silica contentin nepheline of 2 wt. per cent eliminates the effect on theredistribution of a temperature increase of 100 °C. Thesecation exchange data and unit cell data for the crystal phasesare used to calculate thermodynamic mixing properties of nephelinesolid solution and alkali feldspar solid solution for a widerange of temperature and pressure.     

Melting and Thermal Reconstitution of Pelitic Xenoliths, Wehr Volcano, East Eifel, West Germany

Pelitic xenoliths derived from amphibolite grade basement rocksoccur within a Pleistocene, trachytic, pyroclastic unit of theWehr volcano, East Eifel, West Germany: With increasing temperatureand/or prolonged heating at high temperature, quartz-plagioclaseand micaceous layers of the xenoliths have undergone meltingto form buchites and thermal reconstitution by dehydration reactions,melting and crystallization to form restites respectively. Thexenoliths provide detailed evidence of melting, high temperaturedecomposition of minerals, nucleation and growth of new phasesand P-T-f_o2 conditions of contact metamorphism of basement rocksby the Wehr magma. Melting begins at quartz-oligoclase (An_17·3Ab_82·3Or_0·4-An_20·0Ab_78·1Or_1·9)grain boundaries in quartz-plagioclase rich layers and the amountof melting is controlled by H₂O and alkalis released duringdehydroxylation/oxidation of associated micas. Initially, glasscompositions are heterogeneous, but with increasing degreesof melting they become more homogeneous and are similar to S-typegranitic minimum melts with SiO₂ between 71 and 77 wt. per cent;A/(CNK) ratios of 1·2–1·4; Na₂O < 2·95and normative corundum contents of 1·9–4·0per cent. Near micas plagioclase melts by preferential dissolutionof the NaAlSi₃O₈ component accompanied by a simultaneous increasein CaAl²Si²O⁸ (up to 20 mol. per cent An higher than the bulkplagioclase composition) at the melting edge. With increasingtemperature the end product of fractional melting is the formationand persistence of refractory bytownite (An_78–80) in thosexenoliths where extensive melting has taken place. Initial stage decomposition of muscovite involves dehydroxylation(H₂O and alkali loss). At higher temperatures muscovite breaksdown to mullite, sillimanite, corundum, sanidine and a peraluminousmelt. Mullite (40–43 mol. per cent SiO₂) and sillimanite(49 mol. per cent SiO₂) are Fe₂O₃ and TiO₂ rich (up to 6·1–0·84and 3·6–0·24 wt. per cent respectively).Al-rich mullite (up to 77 wt. per cent Al₂O₃) occurs with corundumwhich has high Fe₂O₃ and TiO₂ (up to 6·9 and 2·1wt. per cent respectively). Annealing at high temperatures andreducing conditions results in the exsolution of mullite fromsillimanite and ilmenite from corundum. Glass resulting fromthe melting of muscovite in the presence of quartz is peraluminous(A/(CNK) = 1·3) with SiO² contents of 66–69 percent and normative corundum of 4 per cent. Sanidine (An_1·9Ab_26·0Or_72·1-An_1·3Ab_15·9Or_82·9)crystallized from the melt. Dehydroxylation and oxidation of biotite results in a decreaseof K₂O from 8·6 to less than 1 wt. per cent and oxidetotals (less H₂O + contents) from 96·5 to 88·6,exsolution of Al-magnetite, and a decrease in the Fe/(Fe + Mg)ratio from 0·41 to 0·17. Partial melting of biotitein the presence of quartz/plagioclase to pleonaste, Al-Ti magnetite,sanidine(An_2·0Ab_34·9Or63·1) and melt takesplace at higher temperatures. Glass in the vicinity of meltedbiotite is pale brown and highly peraluminous (A/CNK = 2·1)with up to 6 wt. per cent MgO+FeO_{(total iroq)} and up to 10 percent normative corundum. Near liquidus biotite with higher Al₂O₃and TiO₂ than partially melted biotite crystallized from themelt. Ti-rich biotites (up to 6 wt. per cent TiO₂) occur withinthe restite layers of thermally reconstituted xenoliths. Meltingof Ti-rich biotite and sillimanite in contact with the siliceousmelt of the buchite parts of xenoliths resulted in the formationof cordierite (100 Mg/(Mg+Fe+Mn) = 76·5–69·4),Al-Ti magnetite and sanidine, and development of cordierite/quartzintergrowths into the buchite melt. Growth of sanidine enclosedrelic Ca-plagioclase to form patchy intergrowths in the restitelayers. Cordierite (100 Mg/(Mg+Fe+Mn) = 64–69), quartz,sillimanite, mullite, magnetite and ilmenite, crystallized fromthe peraluminous buchite melt. Green-brown spinels of the pleonaste-magnetite series have awide compositional variation of (mol. per cent) FeAl₂O₄—66·6–45·0;MgAl₂O₄—53·0–18·7; Fe₃O₄—6·9–28·1;MnAl₂O₄—1·2–1·5; Fe₂TiO₄—0·6–6·2.Rims are generally enriched in the Fe₃O₄ component as a resultof oxidation. Compositions of ilmenite and magnetite (single,homogeneous and composite grains) are highly variable and resultfrom varying degrees of high temperature oxidation that is associatedwith dehydroxylation of micas and melting. Oxidation mainlyresults in increasing Fe³⁺, Al and decreasing Ti⁴⁺, Fe²⁺ inilmenite, and increasing Fe²⁺, Ti⁴⁺ and decreasing Fe³⁺ in associatedmagnetite. A higher degree of oxidation is reached with exsolutionof rutile from ilmenite and formation of titanhematite and withexsolution of pleonaste from magnetite. Ti-Al rich magnetite(5·1–7·5 and 8·5–13·5wt. per cent respectively) and ilmenite crystallized from meltsin buchitic parts of the xenoliths. Chemical and mineralogic evidence indicates that even with extensivemelting the primary compositions of individual layers in thexenoliths remained unmodified. Apparently the xenoliths didnot remain long enough at high temperatures for desilicationand enrichment in Al₂O₃, TiO₂, FeO, Fe₂O₃, and MgO that resultsby removal of a ‘granitic’ melt, and/or by interactionwith the magma, to occur. T °C-f_o2 values calculated from unoxidized magnetite/ilmenitegive temperatures ranging from 615–710°C for contactmetamorphism and the beginning of melting, and between 873 and1054°C for the crystallization of oxides and mullite/sillimanitefrom high temperature peraluminous melts. f_o2 values of metamorphismand melting were between the Ni-NiO and Fe₂O₃-Fe₃O₄ buffer curves.The relative abundance of xenolith types, geophysical evidenceand contact metamorphic mineralogy indicates that the xenolithswere derived from depths corresponding to between 2–3kb P_load = P_fluid. The xenoliths were erupted during the latestphreatomagmatic eruption from the Wehr volcano which resultedin vesiculation of melts in partially molten xenoliths causingfragmentation and disorientation of solid restite layers.     

Granulite-Facies Metamorphism at Molodezhnaya Station, East Antarctica

Granulite-facies quartzofeldpathic gneisses metamorphosed 1000m.y. ago are exposed around Molodezhnaya Station (67°40'S,46°E) in East Antarctica. In addition to quartz, K-feldspar,and plagioclase, the fourteen samples studied in detail consistof the assemblages biotite-orthopyroxene-magnetite, biotite-garnet-orthopyroxene-ilmenite±magnetite, biotite-garnet ± ilmenite ± magnetite,biotite-garnet-sillimanite-ilmenite ± rutile, and biotite-garnet-cordierite-ilmenite-(sillimanite-rutile).Garnets are pyrope-almandine (13 to 34 mol per cent pyrope).Biotite (X_Fe = 0.33 to 0.57) is rich in TiO₂ (4 to 6.3 wt percent) and its Al₂O₃ content depends on the mineral assemblage.Orthopyroxene (X_Fe = 0.45 to 0.60) contains 1.5 to 3.0 weightper cent Al₂O₃. By and large, the minerals are chemically homogeneousand compositional variations are systematic, which indicatecrystallization under equilibrium conditions. On the basis ofthe compositions of coexisting garnet-biotite, garnet-cordierite,garnet-plagioclase (with sillimanite), and garnet-plagioclase-orthopyroxene,temperatures and pressures during the granulite-facies metamorphismare estimated to be 700°C ± 30°C and 5.5 ±1 kb. Water pressure apparently was significantly less thantotal pressure. Alteration during events following the granulite-facies metamorphismhas resulted in chemical zoning in garnet, in which grain edgesare more iron-rich than cores, heterogeneous biotite compositions,and anomalous trends involving MnO. Temperatures based on biotiteand garnet-edge compositions range from 410 to 580°C. Differences in the chemical potential (µ) of water andoxygen in the fluid phase can explain compositional variationsamong the three sillimanite-bearing samples and the relativelyiron-rich compositions of garnet and biotite associated withcordierite. Apparently, the water released by the formationof cordierite remained in the rock, forcing µH₂O to increaseas cordierite formed. Buffering of fluid phase composition bythe mineral assemblage suggests that water was not removed fromthe Molodezhnaya rocks by flushing with CO₂-rich fluids duringmetamorphism, a hypothesis evoked to explain ‘dry’mineral assemblages in other granulite-facies terrains.     

An Experimental Investigation of the Influence of Water and Oxygen Fugacity on Differentiation of MORB at 200 MPa

Crystallization experiments were performed at 200 MPa in thetemperature range 1150–950°C at oxygen fugacitiescorresponding to the quartz–fayalite–magnetite (QFM)and MnO–Mn₃O₄ buffers to assess the role of water andf_O2 on phase relations and differentiation trends in mid-oceanridge basalt (MORB) systems. Starting from a primitive (MgO9·8 wt %) and an evolved MORB (MgO 6·49 wt %),crystallization paths with four different water contents (0·35–4·7wt % H₂O) have been investigated. In primitive MORB, olivineis the liquidus phase followed by plagioclase + clinopyroxene.Amphibole is present only at water-saturated conditions below1000°C, but not all fluid-saturated runs contain amphibole.Magnetite and orthopyroxene are not stable at low f_O2 (QFM buffer).Residual liquids obtained at low f_O2 show a tholeiitic differentiationtrend. The crystallization of magnetite at high f_O2 (MnO–Mn₃O₄buffer) results in a decrease of melt FeO^*/MgO ratio, causinga calc-alkaline differentiation trend. Because the magnetitecrystallization temperature is nearly independent of the H₂Ocontent, in contrast to silicate minerals, the calc-alkalinedifferentiation trend is more pronounced at high water contents.Residual melts at 950°C in a primitive MORB system havecompositions approaching those of oceanic plagiogranites interms of SiO₂ and K₂O, but have Ca/Na ratios and FeO^* contentsthat are too high compared with the natural rocks, implyingthat fractionation processes are necessary to reach typicalcompositions of natural oceanic plagiogranites. KEY WORDS: differentiation; MORB; oxygen fugacity; water activity; oceanic plagiogranite     

Synthesis and Stability Relations of Mg--Al Pumpellyite, Ca4Al5MgSi6O21(OH)7

Hydrothermal synthesis and investigations of stability relationsof Mg—Al pumpellyite were conducted using high-pressurecold-seal apparatus over the temperature range 250–600°C and 2–8 kb P_fluid. Mg—Al pumpellyite Ca₄Al₅MgSi₆O₂₁(OH)₇was synthesized from partially crystalline gel mixtures of stoichiometriccomposition at 275–410 °C, 6–9 kb P_fluid, andruns of 7–90 days. Pure monomineralic synthetic Mg—Alpumpellyite has refractive index n_ß = 1.624 (2) andcell dimensions = 8.825 (8) Á, b = 5.875 (5) Á,c = 19.10 (1) Á, and ß = 97.39 (7)°. The high temperature assemblage of the equivalent bulk compositionconsists of clinozoisite, hydrogrossular/grossular, aluminousseptechlorite/chlorite, quartz, and H₂O. Hydrogrossular wassynthesized in the presence of quartz at 8 kb from 400–500°C, and hydrogrossular + quartz are unstable with respectto grossular + H₂O at 400 °C and 8 kb P_fluid. At 8 kb P_fluid,aluminous septechlorite forms at temperatures below 500 °Cwhereas aluminous 14 Á chlorite crystallizes at 500–600°C. The equilibrium relations of Mg—Al pumpellyite were determinedusing subequal mixtures of synthetic Mg—Al pumpellyiteand its high temperature assemblage. The reaction 9 Mg—Alpumpellyite = 9 clinozoisite + 6 grossular + 2 chlorite + 4quartz + 19 H₂O occurs at temperatures of 390 °C at 8 kb,368 °C at 5 kb, and near 325 °C at 2 kb P_fluid. Thereversal data yield an approximate value of –3141 joules/mole°K for the standard entropy of formation for the syntheticMg—Al pumpellyite. The Schreinemakers' relations for pumpellyite, prehnite, clinozoisite,tremolite, grossular, and amesite in the presence of excessquartz and fluid were constructed in the pseudo-ternary systemCaO–Al₂O₃–MgO(SiO₂–H₂O). The results, togetherwith reconnaissance experiments on the reaction 4 Mg—Alpumpellyite + 2 quartz = 8 prehnite + aluminous septechlorite+ 2 H₂O, locate the invariant point [TR] at approximately 5.7kb P_fluid and 375 °C. The results of the present study arenot compatible with previous experimental data on the invariantpoint [GR]. The P–T oriented phase relations are used to interpretsome natural parageneses developed in low-grade metabasalticrocks recrystallized under conditions of low _co2. The high-temperaturestability relations of Mg—Al pumpellyite are useful todenote the onset of greenschist facies metamorphism in rocksof basaltic composition.     

Fractionation and Assimilation Processes in the Alkaline Augite Syenite Unit of the Ilimaussaq Intrusion, South Greenland, as Deduced from Phase Equilibria

The early augite syenite unit in the 1·13-Ga-old Ilímaussaqintrusive complex, South Greenland, consists of a magmatic assemblageof ternary alkali feldspar + fayalitic olivine + augite + titanomagnetite+ apatite + baddeleyite ± nepheline ± quartz ±ilmenite ± zircon. Feldspar, nepheline and QUILF thermometryyield T = 1000–700°C, at P = 1 kbar, which is derivedfrom fluid inclusion data from other parts of the complex. Ternaryfeldspar was the first major liquidus phase. It crystallizedat temperatures between 950 and 1000°C from a homogeneousmagma with a_SiO2 = 0·8 and f_O2 about 1·5–2log units below the fayalite–magnetite–quartz (FMQ)buffer. Later, closed system fractionation produced nepheline-bearingassemblages with a_SiO2 = 0·4 and log f_O2 = FMQ –3 to FMQ – 5. Assimilation of wall rocks produced localvariations of melt composition. Four traverses through the unitwere sampled parallel to the assumed direction of crystallization.They exhibit significant differences in their mineral assemblagesand compositions. The chemical zoning and calculated intensiveparameters of four sample suites reflect both closed systemfractional crystallization and local assimilation of wall rocks. KEY WORDS: alkaline magmatism; assimilation; fractionation; redox equilibria; QUILF     

Variations in Melt Productivity and Melting Conditions along SWIR (70{degrees}E-49{degrees}E): Evidence from Olivine-hosted and Plagioclase-hosted Melt Inclusions

Melt inclusion and host glass compositions from the easternend of the Southwest Indian Ridge show a progressive depletionin light rare earth elements (LREE), Na₈ and (La/Sm)_n, but anincrease in Fe₈, from the NE (64°E) towards the SW (49°E).These changes indicate an increase in the degree of mantle meltingtowards the SW and correlate with a shallowing of the ridgeaxial depth and increase in crustal thickness. In addition,LREE enrichment in both melt inclusions and host glasses fromthe NE end of the ridge are compatible with re-fertilizationof a depleted mantle source. The large compositional variations(e.g. P₂O₅ and K₂O) of the melt inclusions from the NE end ofthe ridge (64°E), coupled with low Fe₈ values, suggest thatmelts from the NE correspond to a variety of different batchesof melts generated at shallow levels in the mantle melting column.In contrast, the progressively more depleted compositions andhigher Fe₈ values of the olivine- and plagioclase-hosted meltinclusions at the SW end of the studied region (49°E), suggestthat these melt inclusions represent batches of melt generatedby higher degrees of melting at greater mean depths in the mantlemelting column. Systematic differences in Fe₈ values betweenthe plagioclase- and the olivine-hosted melt inclusions in theSW end (49°E) of the studied ridge area, suggest that theplagioclase-hosted melt inclusions represent final batches ofmelt generated at the top of the mantle melting column, whereasthe olivine-hosted melt inclusions correspond to melts generatedfrom less depleted, more fertile mantle at greater depths. KEY WORDS: basalt; melt inclusions; olivine; plagioclase; Southwest Indian Ridge     

The Phase Relations of Aluminous Iron Biotites in the System KAISi3O8-KAISiO4-AI2O3-Fe-O-H

The experimental work on biotites has primarily involved compositionsalong the annite-phlogopite join, but most natural biotitescontain significantly larger amounts of aluminum. At the sametime, the aluminum content of natural biotites varies considerably.The available evidence indicates that these variations in thealuminum content of biotite depend on the conditions of formationand the whole rock chemistry. Experiments on the phase relations of aluminous iron biotitesin the silica deficient system KAlSiO₄-KAlSi₃O₈-Al₂O₃-Fe-O-H(pfluid = 2 kb) indicate that compositions up to Ann₇₅ can besynthesized on the join annite [K₂Fe₆Al₂Si₆O₂₀(OH)₄]-aluminumbiotite [K₂Al₆Al₂Al₆O₂₀(OH)₄]. The aluminous biotites are stableto higher temperatures than annite. An isobaric divariant equilibrium,Bio_ss-Mt_ss-Sa-Lc-V, extends to higher oxygen fugacities fromthe Ann-Mt-Sa-Lc-V curve of Eugster & Wones (1962). Compositioncontours on this surface indicate that both the magnetite andbiotite become more aluminous with increasing temperature and/oroxygen fugacity. The Bio_ss-Mt_ss-Sa-Lc-V reaction surface isterminated by equilibria involving the additional phases muscovite,corundum, and hercynite respectively as the conditions becomemore reducing. At 2 kb fluid pressure; aluminum-rich iron biotiteis stable to 555 °C on the HM buffer, 763 °C on theMt-Hc-Cor buffer, 820 °C on NNO, and about 860 °C onQFM. The data obtained can be applied to a number of biotitesyenites and appears to explain why iron-rich aluminum biotitesoccur in these rocks.     

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     

Calculation of Garnet Fractionation in Metamorphic Rocks, with Application to a Flat-Top, Y-rich Garnet Population from the Ruhla Crystalline Complex, Central Germany

A mathematical approach is presented for the calculation ofthe major and trace element fractionation that is caused bygrowth of zoned garnet in metamorphic rocks. This approach isbased on textural and compositional parameters directly obtainedfrom natural examples. It takes into account the mode and compositionof all unzoned minerals, as well as the mode, crystal size distributionand zonation patterns of garnet grains of different sizes withina certain rock volume. These parameters can be used to fit functionsfrom which the amount of garnet fractionation at each step ofa garnet growth history can be calculated. The approach is testedfor two compositionally distinct domains within a single garnet–biotitegneiss sample from the Ruhla Crystalline Complex. This samplecontains unusual flat-top garnet grains with Y₂O₃-rich cores.It is shown that MnO, FeO and Y₂O₃ are extremely fractionatedduring garnet growth, but in different ways, and that MnO fractionationdoes not obey a Rayleigh function. To demonstrate the influenceof garnet fractionation on P–T path estimates, quantitativephase diagrams in the model system Na₂O–K₂O–CaO–MnO–FeO–MgO–Al₂O₃–TiO₂–SiO₂–H₂Oare constructed by means of the computer software THERMOCALC.The good agreement between calculated and observed mineral assemblagesand garnet compositions for all fractionation steps indicatesthat the new approach can be used to infer detailed P–Tpaths, even for rocks that contain complexly zoned garnet grains.The results indicate that garnet growth in the metapelite underinvestigation occurred along a linear P–T path from 470°Cand 2·7 kbar to 580°C and 8·5 kbar. The resultsalso show that garnet cores with high Y₂O₃ contents of about1 wt % nucleated over a temperature interval of c. 90°C,indicating that Y in garnet is relatively insensitive to temperaturechanges. KEY WORDS: garnet; fractionation; pseudosection; yttrium; THERMOCALC     

Experimentally Determined Phase Relations in Hydrous Peridotites to 6{middle dot}5 GPa and their Consequences on the Dynamics of Subduction Zones

Fluid-saturated subsolidus experiments from 2·0 to 6·5GPa, and from 680 to 800°C have been performed on threemodel peridotites in the system Na₂O–CaO–FeO–MgO–Al₂O₃–SiO₂–H₂O(NCFMASH). Amphibole and chlorite coexist up to 2·4 GPa,700°C. Chlorite persists to 4·2 GPa at 680°C.Starting from 4·8 GPa, 680°C a 10 Å phase structurereplaces chlorite in all compositions. The 10 Å phasestructure contains significant Al₂O₃ (up to 10·53 wt%) deviating from the MgO–SiO₂–H₂O 10 Å phase(MSH 10 Å phase). A mixed layered structure (chlorite–MSH10 Å phase) is proposed to account for aluminium observed.In the Tinaquillo lherzolite amphibole breakdown occurs viathe reaction Thermal stabilityof chlorite (chlorite + orthopyroxene = forsterite + garnet+ H₂O) is shifted towards lower temperatures, compared withthe system MASH. Furthermore, the chlorite thermal breakdownis also related to the degenerate reaction Chlorite and the Al-10 Å phase structurecontribute significantly to the water budget in subduction zonesin the depth range relevant for arc magmatism, whereas amphibole-relatedfluid release is restricted to the forearc region. Chloriteand Al-10 Å phase breakdowns might explain the occurrenceof a double seismic zone by dehydration embrittlement. KEY WORDS: amphibole; chlorite; high pressure; peridotites; subduction zones     

Partial Melting of Metapelitic Rocks Beneath the Bushveld Complex, South Africa

Metapelitic rocks in the aureole beneath the Bushveld Complexpreserve evidence for both high- and low-a_H2O anatexis. Theaureole is characterized by an inverted thermal structure inwhich suprasolidus rocks potentially interacted with an H₂O-richvolatile phase derived from underlying, dehydrating rocks. Atlower grade (T < 700°C) the rocks contain fibrolite matsand seams that record local redistribution of volatiles. Incongruentreactions consuming biotite produced small quantities (<1mol %) of liquid and peritectic cordierite that remained trappedwithin the mesosome. Larger volumes of melt (3–4%), preservedas coarse-grained discordant leucosomes, were produced by congruentmelting following a structurally focused influx of H₂O. Subhorizontalvolatile-phase flow was concentrated within thin (     

The Stability of Andradite, Hedenbergite, and Related Minerals in the System Ca--Fe--Si--O--H

Phase relations for the bulk compositions 3CaO·2FeO_x·3SiO₂+excessH₂O and CaO·FeO_x·2SiO₂+excess H₂O were determinedusing conventional hydrothermal techniques with solid phaseoxygen buffers to control fO₂. Andradite, Ca₃Fe³⁺₂Si₃O₁₂, synthesized above 550 °C hasan average unit cell edge, a_o, of 12.055±0.001 Å,and an index of refraction, n, of 1.887±0.003. Belowthis temperature, a_o increases whereas n decreases, indicatingthe formation of a member of the andradite-hydroandradite solidsolution. At 2000 bars P_fluid andradite is stable above an f_O2of 10¹⁵ bar at 800 °C and 10-³² bar at 400 °C. At lowerf_O2 andradite+fluid gives way at successively lower temperaturesto the condensed assemblages magnetite+wollastonite, kirschsteinite(CaFe²⁺SiO₄)+ wollastonite and kirschsteinite+xonotlite (Ca₆Si₆O₁₇(OH)₂). Synthetic hedenbergite, CaFe²⁺Si₂O₆, has average unit cell dimensionsof a_o = 9.857± 0.004 Å, b_o = 9.033±0.002Å, c_o = 5.254±0.002 Å and ß = 104.82°±0.03°,and refractive indices of n = 1.731±0.003 and n = 1.755±0.005.At 2000 bars P_fiuid, hedenbergite is stable below an f_O2 of10-¹³ bar at 800 °C and 10-²⁸ bar at 400 °C. Above thesef_O2 values, hedenbergite+O₂ breaks down to andradite+magnetite+quartz. The mineral pair andradite +hedenbergite thus limit the f_O2range possible for their joint formation under equilibrium conditions. The hydration of wollastonite to xonotlite occurs at much lowertemperatures than previous experimental work indicated. A tentativehigh temperature limit for this reaction is set at 185°±15°C and 5000±25 bars and 210°±15 °Cand 2000±20 bars. Inasmuch as the growth of xonotlitefrom wollastonite + H₂O was never accomplished, this high temperaturelimit does not represent an equilibrium univariant curve. Nine phases were encountered in the study of andradite and hedenbergite.They are andradite, hedenbergite, magnetite, wollastonite, kirschsteinite,xonotlite, quartz, ilvaite, and vapor (fluid). An invariantpoint analysis using the method of Schreinemakers shows thetopologic relations of the reactions involved. The resultinggrid can be used to interpret natural occurrences.     

Phase Relations of Basalts in their Melting Range at PH2O = 5 kb as a Function of Oxygen Fugacity: Part I. Mafic Phases

The phase relations of three basalts, the Picture Gorge tholeiite,the 1921 Kilauea olivine tholeiite, and the 1801 Hualalai alkalibasalt, were studied at 5 kb water pressure, 680–1000°C,at the oxygen fugacities of the quartz-fayalite-magnetite (QFM)and hematite-magnetite (HM) buffers. In the range 680–850 °C, the crystalline assemblageon the QFM buffer is dominantly hornblende+ plagioclase, ±ilmenite, magnetite, sphene, fayalitic olivine, and phlogopiticmica. From 875 to 1000 °C the crystalline assemblage ishornblende+ olivine± augite+ ilmenite± magnetite.A melt phase is present from 700 to 1000 °C; a vapor phasewas present in all charges. The hornblendes formed on the QFM buffer range in compositionfrom common green hornblendes at low temperatures to kaersutitichornblendes at 1000 °C. A1(IV) and Ti increase temperature.AI(VI) passes through a maximum near 825 °C, decreasingboth above and below this temperature. AI(IV) is proportionalto the sum A1(VI)+2Ti. There is a positive linear correlationof approximately 3 : 1 between AI(IV) and the number of cationsin the A-site. The most likely explanation for this correlationat present is that the substitution of AI(VI) or Ti⁺⁴for a divalentcation creates local charge imbalances in the amphibole structurewhich can be compensated only by further A-site substitution.There also appears to be a correlation between the a-cell dimensionof hornblende and the A-site occupancy. Above a thresh holdvalue of approxmately 0.5 cations in A, a increases as A-siteoccupancy increases. Phase relations on the hematite-magnetite buffer are considerablysimpler. The hornblendes show relatively little change in compositionas temperature increases, and in the tholelitic compositionsbreak down at or below 970 °C 35–60 °C above thefirst appearance of augite±olivine. The melting of hornblendeis incongruent in all cases. The Fe-Ti oxides are pseudo-brookiteand titanohematite; at 1000 °C these oxides make up 10 percent by weight of the assemblage and contain most of the Tio₂and FeO in the charge. The patterns of hornblende variation observed in this studycompare closely with those reported in a wide range of experimentaland field data. The appearance of high-TiO₂ kaersutitic hornblendesin the tholeities at 1000° C, P_H2O= 5 kb on the QFM bufferimplies that the restricted occurence of kaersutite in nature(where it is associated only with mafic to intermediate alkalicrocks) is controlled by volatile content (H₂O_,F₂)rather thanby differences in condensed bulk composition.     

The Mineralogy and Geochemistry of the Metamorphosed Basic and Ultrabasic Rocks of the Jijal Complex, Kohistan, NW Pakistan

The Jijal complex, covering more than 150 sq. km in the extremenorth of Pakistan, is a tectonic wedge of garnet granulitesintruded in the south by a 10 x 4 km slab of ultramafic rocks.The granulites are divisible into plagioclase-bearing (basicto intermediate) and plagioclase-free (ultrabasic to basic)types, the two types reflecting differences in bulk chemistry.Garnet + plagioclase + clinopyroxene + quartz + rutile ±hornblende ± epidote is the most common assemblage. Theplagioclase-free rocks are composed mainly of two or three ofthe minerals garnet, amphibole, clinopyroxene and epidote. Orthopyroxeneoccurs in websteritic rocks devoid of epidote. Much of the amphiboleand some epidote appear to be prograde products. Although variationdiagrams do not reveal a genetic link between the two typesof granulite, it is considered that they are comagmatic ratherthan the products of two or more unrelated magmas. The compositions of garnet (Py_28–46 Alm _27–43Gro_16–28),clinopyroxene (Mg_44–34Fe_5–17Ca_51–49, Al₂O₃3·0–9·9 per cent), orthopyroxene (with upto 5·5 per cent Al₂O₃), amphibole (with up to 16·3per cent Al₂O₃ and high Al^vi/Al^iv), and the abundance of garnetsuggest a high-pressure origin for the granulites. The rocksappear to have differentiated from a tholeiitic magma of oceanicaffinity or they may be genetically related to the pyroxenegranulites of Swat considered to have originally crystallizedfrom a calc-alkaline magma of island arc or continental marginaffinity. They probably crystallized in the ancient Tethyancrust/upper mantle (or less likely in a continental margin),later to be metamorphosed to granulites (670–790 °C,12–14 kb) during the collision of the Indian-Asian landmasses,and carried upwards during later Himalayan orogenic episodes. The ultramafic rocks are alpine-type in nature and devoid ofgarnet. They are dominated by diopsidites; dunites, peridotites,and harzburgites together form <50 per cent of the area ofoutcrop. The chemistry of the rocks, and their olivines (Fo_92–89)and clinopyroxenes (Mg_49.5–48Fe_2.8–5.2Ca_47.4–46.8)are similar to those of alpine complexes of the harzburgitesubtype. It is not clear whether they represent a faulted slabof suboceanic crust/upper mantle, mantle diapirs in deep orogenicroots, or dismembered ultramafic rocks differentiated from abasaltic magma. They seem to have a complex history; their presentmineralogy is suggestive of high grade metamorphism (800–850°C, 8–12 kb). They are magmatically unrelated to thegarnet granulites and were probably intruded into the latteras plastic crystalline material after both had been independentlymetamorphosed, but before the entire complex was carried tectonicallyinto its present surroundings. The abundances of the diopsiditesis in marked contrast to other alpine-type complexes and thepossibility of Ca and Si metasomatism during or before theirmetamorphism should not be totally ruled out.     

The Stability of Sodalite in a Synthetic Syenite plus Aqueous Chloride Fluid System

Natural feldspathoidal syenites may be approximated by assemblagescontaining some or all of the phases sodalite, nepheline, oneor two alkali feldspars, and aqueous chloride fluid in the systemNaAISi₃O₈-KAISi₃O₈-NaAISiO₄-KAISiO₄-NaCI-KCI-H₂O. The stabilityof sodalite in these assemblages was studied in the range 500–700°C and 600–2000 bars fluid pressure. Sodalite appears to be a stable phase on the vapor-saturatedliquidus in this system over a wide range of pressure. At or near the vapor-saturated liquidus minimum in this system,three distinct types of sodalite-bearing syenite can crystallize.Nepheline-sodalite-one alkali feldspar rocks, nepheline-sodalite-twoalkali feldspars rocks and sodalite-analcime-bearing rocks crystallizebelow 1600 bars, between 1600 and 2750 bars and above 2750 barsfluid pressure, respectively. The effects of closed-system cooling on the assemblage sodalite-nepheline-twoalkali feldspars-aqueous fluid are different and distinguishablefrom the effects of metasomatism. Closed-system cooling resultsin replacement of K-feldspar by albite, feldspathoids remainingnearly unchanged, while metasomatism generally results in sismultaneousenrichment or impoverishment in sodalite plus K-feldspar.     

Geobarometry for Peridotites: Experiments in Simple and Natural Systems from 6 to 10 GPa

Experiments with peridotite minerals in simple (MgO–Al₂O₃–SiO₂,CaO–MgO–SiO₂ and CaO–MgO–Al₂O₃–SiO₂)and natural systems were conducted at 1300–1500°Cand 6–10 GPa using a multi-anvil apparatus. The experimentsin simple systems demonstrated consistency with previous lowerpressure experiments in belt and piston–cylinder set-ups.The analysis of spatial variations in pyroxene compositionswithin experimental samples was used to demonstrate that pressureand temperature variations within the samples were less than0·4 GPa and 50°C. Olivine capsules were used in natural-systemexperiments with two mineral mixtures: SC1 (olivine + high-Alorthopyroxene + high-Al clinopyroxene + spinel) and J4 (olivine+ low-Al orthopyroxene + low-Al clinopyroxene + garnet). Theexperiments produced olivine + orthopyroxene + garnet ±clinopyroxene assemblages, occasionally with magnesite and carbonate-richmelt. Equilibrium compositions were derived by the analysisof grain rims and evaluation of mineral zoning. They were comparedwith our previous experiments with the same starting mixturesat 2·8–6·0 GPa and the results from simplesystems. The compositions of minerals from experiments withnatural mixtures show smooth pressure and temperature dependencesup to a pressure of 8 GPa. The experiments at 9 and 10 GPa producedandradite-rich garnets and pyroxene compositions deviating fromthe trends defined by the lower pressure experiments (e.g. higherAl in orthopyroxene and Ca in clinopyroxene). This discrepancyis attributed to a higher degree of oxidation in the high-pressureexperiments and an orthopyroxene–high-P clinopyroxenephase transition at 9 GPa. Based on new and previous resultsin simple and natural systems, a new version of the Al-in-orthopyroxenebarometer is presented. The new barometer adequately reproducesexperimental pressures up to 8 GPa. KEY WORDS: garnet; mineral equilibrium; multi-anvil apparatus; orthopyroxene; geobarometry     

P--T Stabilities of Laumontite, Wairakite, Lawsonite, and Related Minerals in the System CaAl2Si2O8-SiO2-H2O

Hydrothermal investigation of the bulk composition CaO.Al₂O₃.4SiO₂+excessH₂O has been conducted using conventional techniques over thetemperature ranges 200–450 °C and 500–6000 barsP_fluid. A number of reactions have been studied by employingmineral mixtures consisting of reactants and products in about9: 1 and 1: 9 ratios. The phase relations were deduced fromrelatively long experiments by observing which seeded assemblagedisappeared or decreased markedly in one of the paired run charges. Laumontite was synthesized in the laboratory, probably for thefirst time. Laumontite was grown from seeded wairakite to over99 per cent using a weak NaCl solution. The refractive indicesof the synthetic material are about = 1.504 and = 1.514. Theaverage unit cell dimensions are a₀ = 14.761±0.005 Å;b₀ = 13.077±0.005 Å; c₀ = 7.561±0.003 Å;and ß = 112.02°±0.04°. Within the errorof measurement, the optical properties and cell parameters arein good agreement with those of natural laumontite. The equilibriumdehydration of laumontite involves two reactions: (1) laumontite= wairakite+2H₂O, passing through about 230 °C at 0.5 kb,255±5 °C at 1 kb, 282±5 °C at 2 kb, 297±5°C at 3 kb and 325±5 °C at 6 kb; and (2) laumontite= lawsonite+2 quartz+2H₂O, taking place at about 210 °Cat 3 kb and 275 °C at 3.2 kb. Above 300 °C, the equilibriumcurve for the solid-solid reaction (3) lawsonite+2 quartz =wairakite passes through 305 °C, 3.4 kb and 390 °C,4.4 kb. Equilibrium has been demonstrated unambiguously forthe above three reactions. The hydrothermal decomposition ofnatural laumontite above its own stability limit appears tobe a very slow process. Combined with previously published equilibria determined hydrothermallyfor wairakite, the phase relations are further investigatedby chemographic analysis interrelating the phases, laumontite,wairakite, lawsonite, anorthite, prehnite+kaolinite, and 2 pumpellyite+kaolinitein the system CaAl₂Si₂O₈-SiO₂-H₂O. This synthesis allowed theconstruction of a semiquantitative petrogenetic grid applicableto natural parageneses and the delineation of the physical conditionsfor the various low-grade metamorphic facies in low µCO₂environments. The similar stratigraphic zonations, consistentlyfound in a variety of environments, are recognized to be a functionof burial depth, geothermal gradient, and mineralogical andchemical composition of the parental rocks. Departures fromthe normal sequences are believed to be due to the combinationsof mineralogical variations, availability of H₂O, differencesin the ratio µCO₂/µH₂O, and the rate of reaction.The possible P-T boundaries for diagenesis, the zeolite facies,the lawsonite-albite facies, the prehnite-pumpellyite facies,and the adjacent metamorphic facies are illustrated diagrammatically.