Equilibrium Compositions of Coexisting Garnet and Orthopyroxene: Experimental Determinations in the System FeO-MgO-Al2O3-SiO2, and Applications

We have determined the Fe-Mg fractionation between coexistinggarnet and orthopyroxene at 20–45 kb, 975–1400?C,and the effect of iron on alumina solubility in orthopyroxeneat 25 kb, 1200?C, and 20 kb, 975?C in the FMAS system. The equilibriumcompositions were constrained by experiments with crystallinestarting mixtures of garnet and orthopyroxene of known initialcompositions in graphite capsules. All iron was assumed to beFe²⁺. A mixture of PbO with about 55 mol per cent PbF₂ provedvery effective as a flux. The experimental results do not suggest any significant dependenceof K_D on Fe/Mg ratio at T 1000?C. The lnK_D vs. l/T data havebeen treated in terms of both linear and non-linear thermodynamicfunctional forms, and combined with the garnet mixing modelof Ganguly & Saxena (1984) to develop geothermometric expressionsrelating temperature to K_D and Ca and Mn concentrations in garnet. The effect of Fe is similar to that of Ca and Cr³⁺ in reducingthe alumina solubility in orthopyroxene in equilibrium withgarnet relative to that in the MAS system. Thus, the directapplication of the alumina solubility data in the MAS systemto natural assemblages could lead to significant overestimationof pressure, probably by about 5 kb for the relatively commongarnetlherzolites with about 25 mol per cent Ca+Fe²⁺ in garnetand about 1 wt. per cent Al₂O₃ in orthopyroxene.     

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-Temperature Eclogites and Eclogitic Schists in Mn-rich Metabasites in Ward Creek, California; Mn and Fe Effects on the Transition between Blueschist and Eclogite

In situ eclogitic schist lenses occur in the coherent low-gradeepidote-zone Ward Creek metabasite unit of the Central Franciscanbelt. They contain almandine garnet, clinopyroxene, and rutile.They have slightly higher Mn content (0–5–1–0wt.%) than the coexisting Type III metabasites (0–12–0–25wt%) which contain epidote + glaucophane + actinolite + chlorite+ omphacite + quartz + sphene ? aragonite? lawsonite ? pumpellyite+ albite. The in situ eclogitic schists (130–140 Ma) canbe distinguished from older tectonic eclogites (150–160Ma) in Ward Creek as follows: (1) they are medium grained, whereasType IV tectonic eclogites are coarse grained; (2) they haveunaltered spessartine-rich idioblastic (0–4–10 mm)garnets, whereas Type IV tectonic eclogites have larger xenoblasticto hypidiomorphic spessartine-poor garnets which were corrodedand chloritized along the rim during retrograde metamorphism;(3) clinopyroxenes are chloromelanite in in situ eclogitic schistsbut omphacite in Type IV tectonic eclogites; (4) barroisiticamphiboles occur both as inclusions in garnets and as matrixminerals in Type IV tectonic eclogites but not in in situ eclogiticschists; (5) albite is present in in situ eclogitic schistsbut not in Type IV tectonic eclogites; and (6) the estimatedP-T condition of in situ eclogitic schists is 290 ?C < T<350 ?C, P = 8–9 kb, whereas that of Ward Creek Type IVtectonic eclogites is 500?C< r<540?C, P< 10–11–5kb. Medium-grained eclogites occur as individual blocks in WardCreek; they are different from Type IV tectonic eclogites butare very similar to in situ eclogitic schists. They have unalteredidioblastic garnet with high almandine and spessartine content(Alm₄₇Sp₂3Gr₂₀Py10), and they have chloromel-anitic clinopyroxeneand quartz but no barroisite. Paragonite is also stable in theseeclogites. The blocks formed at 380 ?C< r<400?C, and 9–5kb<P< 14 kb. They are presumably in situ eclogites formedat the highest-temperature part of the Ward Creek metabasiteunit and may be younger than Type IV tectonic eclogites. Such low-temperature occurrences of eclogitic assemblages aredue to the compositional effect on reactions between blueschistand eclogite that are insensitive to pressure and shift towardslower temperatures as bulk-rock MnO content and X_Fe/(Fe+Mg)increase. The Mn/(Mn + Fe) ratio of bulk rock is an importantfactor in controlling the P-T positions of these reactions attemperatures below 450 ?C, whereas the Fe/(Fe + Mg) ratio ofbulk-rock becomes important at temperatures higher than 450?C.     

Eclogites from the Sunndal-Grubse Ultramafic Mass, Almklovdalen, Norway and the T-P History of the Almklovdalen Masses

An orthopyroxene eclogite from the Sunndal-Grubse mass containsclinopyroxenes with lamellae of garnet and orthopyroxene. Differencesin mineral and bulk chemistry distinguish this, and adjacenteclogites, from eclogites in other Almklovdalen ultramafic masses.Analyses are used in conjunction with experimental data to assignthree T-P points in the complex T-P path of the ultramafic masses.Other T-P points are assigned on a basis of petrographic andstructural arguments. The inferred T-P path offers support toearlier suggestions that the masses are tectonically controlledintroductions within the surrounding gneisses. The survivalof eclogite facies assemblages within the ultramafic massesis attributed to a gneissic metamorphism where P_H2O < P_Total.The T-P path also suggests an extended history of subsolidusre-equilibration under mantle conditions possibly complicatedby open system reactions. The eclogites of the Sunndal-Grubsemass are thought to be cumulates and differentiates of relativelyhigh pressure (25–28 kb) melting in ultramafic rocks.The complex T-P path can be explained in terms of convectioncell mechanisms.     

Melting of a Hydrous Mantle: I. Phase Relations of Natural Peridotite at High Pressures and Temperatures with Controlled Activities of Water, Carbon Dioxide, and Hydrogen

Four natural peridotite nodules ranging from chemically depletedto Fe-rich, alkaline and calcic (SiO₂ = 43.7–45.7 wt.per cent, A1₂O₃ = 1.6O–8.21 wt. per cent, CaO = 0.70–8.12wt. per cent, alk = 0.10–0.90 wt. per cent and Mg/(Mg+Fe²⁺)= 0.94–0.85) have been investigated in the hypersolidusregion from 800? to 1250?C with variable activities of H₂O,CO₂, and H₂. The vapor-saturated peridotite solidi are 50–200?Cbelow those previously published. The temperature of the beginningof melting of peridotite decreases markedly with decreasingMg/(Mg+SFe) of the starting material at constant CaO/Al₂O₃.Conversely, lowering CaO/Al₂O₃ reduces the temperature at constantMg/(Mg+Fe) of the starting material. Temperature differencesbetween the solidi up to 200?C are observed. All solidi displaya temperature minimum reflecting the appearance of garnet. Thisminimum shifts to lower pressure with decreasing Mg/(Mg + Fe)of the starting material. The temperature of the beginning ofmelting decreases isobarically as approximately a linear functionof the mol fraction of H₂O in the vapor (X_H2O^v). The data alsoshow that some CO₂ may dissolve in silicate melts formed bypartial melting of peridotite. Amphibole (pargasitic hornblende) is a hypersolidus mineralin all compositions, although its P/T stability field dependson bulk rock chemistry. The upper pressure stability of amphiboleis marked by the appearance of garnet. The vapor-saturated (H₂O) liquidus curve for one peridotiteis between 1250? and 1300?C between 10 and 30 kb. Olivine, spinel,and orthopyroxene are either liquidus phases or co-exist immediatelybelow the temperature of the peridotite liquidus. The data suggest considerable mineralogical heterogeneity inthe oceanic upper mantle because the oceanic geotherm passesthrough the P/T band covering the appearance of garnet in variousperidotites. The variable depth to the low-velocity zone is explained byvariable aHjo conditions in the upper mantle and possibly alsoby variations in the composition of the peridotite itself. Itis suggested that komatiite in Precambrian terrane could formby direct melting of hydrous peridotite. Such melting requiresabout 1250?C compared with 1600?C which is required for drymelting. The genesis of kimberlite can be related to partial meltingof peridotite under conditions of X_H2O^v = 0.5–0.25 (X_CO2^v= 0.5–0.75). Such activities of H₂O result in meltingat depths ranging between 125 and 175 km in the mantle. Thisrange is within the minimum depth generally accepted for theformation of kimberlite.     

Calibration and Applications of Spinel Equilibria in the System FeO-Al2O3-SiO2

A new thermobarometer, based on the equilibrium: has been calibrated with experiments carried out in the piston-cylinderapparatus. Reversed equilibria were obtained using well-calibrated2.54 cm NaCl furnace assemblies and Ag₈₀Pd₂₀capsules with f_O2bufferedat or near iron-wustite. The equilibrium is located between5.2–5.4, 6.6–6.8, and 8.6–8.8 kb at 880, 940,and 1020?C, respectively, and at 5.2 and 8.8 kb between 865–880and 1020–1030?C, respectively. X-ray refinement data indicate that the hercynite (a = 8.15546?) has approximately 18 per cent inverse character. M?ssbauerspectra reveal that 4 mol per cent of the Fe is ferric (2 percent magnetite component). Broad Mossbauer lines and a Fe²+energy level splitting of 3.7 kJ mol^–1 calculated fromthe Mossbauer spectra are consistent with the X-ray determineddegree of inversion, although no separate octahedral Fe²⁺ spectraldoublet is resolved. Calibration of this equation allows calculation of the equilibrium: Thermobarometers based on the above equilibria are widely applicablein granulite fades rocks and yield pressure/temperature datathat are consistent with other well-calibrated barometers andthermometers.     

Generation of Palaeocene Adakitic Andesites by Magma Mixing; Yanji Area, NE China

Palaeocene (c. 55–58 Ma) adakitic andesites from the Yanjiarea, NE China, are typically clinopyroxene-bearing sodic andesitescontaining 60· 9–62· 2% SiO₂ and 4·02–4· 36% MgO, with high Mg-number [100 Mg/(Mg+ Fe) atomic ratio] from 65· 5 to 70· 1. Whole-rockgeochemical features include high Cr (128–161 ppm) andNi (86–117 ppm) concentrations, extremely high Sr (2013–2282ppm), low Y (10–11 ppm) and heavy rare earth elements(HREE; e.g. Yb = 0· 79–1· 01 ppm), and mid-oceanridge basalt (MORB)-like Sr–Nd–Pb isotopic compositions[e.g. ⁸⁷Sr/ ⁸⁶Sr(i) = 0· 70298–0· 70316,_Nd(t) = +3· 8 to +6· 3 and ²⁰⁶Pb/ ²⁰⁴Pb = 17·98 – 18· 06], analogous to high-Mg adakites occurringin modern subduction zones. However, mineralogical evidencefrom clinopyroxene phenocrysts and microcrystalline plagioclaseclearly points to magma mixing during magma evolution. Iron-richclinopyroxene (augite) cores with low Sr, high Y and heavy REEcontents, slightly fractionated REE patterns and large negativeEu anomalies probably crystallized along with low-Ca plagioclasefrom a lower crustal felsic magma. In contrast, high Mg-numberclinopyroxene (diopside and endiopside) mantles and rims havehigher Sr and lower HREE and Y concentrations, highly fractionatedREE patterns (high La/Yb) and negligible Eu anomalies, similarto those found in adakites from subduction zones. The Yanjiadakitic andesites can be interpreted as a mixture between acrust-derived magma having low Mg-number and Sr, and high Yand HREE, and a mantle-derived high Mg-number adakite havinghigh Sr and low Y and HREE concentrations. During storage and/orascent, the mixed magma experienced further crustal contaminationto capture zircons, of a range of ages, from the wall rocks.The absence of coeval arc magmatism and an extensional tectonicregime in the Yanji area and surrounding regions suggest thatthese Palaeocene adakitic andesites were formed during post-subductionextension that followed the late Cretaceous Izanagi–Farallonridge subduction. Generation of these adakitic andesites doesnot require contemporaneous subduction of a young, hot oceanicridge or delamination of eclogitic lower crust as suggestedby previous models. KEY WORDS: magma mixing; adakitic andesites; Palaeocene; NE China     

Chemistry of Kornerupine and Associated Minerals, a Wet Chemical, Ion Microprobe, and X-Ray Study Emphasizing Li, Be, B and F Contents

Kornerupine and associated minerals in 31 samples of high-graderocks relatively rich in Al and Mg were analysed by wet chemistry,ion microprobe mass analyser, electron microprobe and X-raypowder diffraction. For 11 samples of kornerupine and threesamples of biotite (F only) analysed by both wet chemical andion microprobe methods, the best agreement was obtained forB₂O₃, whereas the ion microprobe Li₂O values were systematicallysomewhat higher than the wet chemical values. The wet chemicalmethods give Li₂O=0–0?19 wt.%; BeO=0–0?032 wt.%;B₂O₃=0–4?01 wt.%; and F=0?07–0?77 wt.% in kornerupine,whereas ion microprobe analyses on other kornerupines give valuesup to 0?35 wt.% Li₂O, O066 wt.% BeO, and 4?72 wt.% B₂O₃. Thesum B+Al+Fe³⁺+Cr is close to 6?9 atoms per 22 (O, OH, F) or21?5 (O) in kornerupine. In general, Li/Fe ratios decrease as follows: kornerupine ?sapphirinebiotite> Crd (Na<0?03 per 18 oxygens)>tourmaline, garnet,orthopyroxene. However, for cordierite with Na>004, Li/Fedecreases as follows: cordierite>kornerupine. Sapphirineand sillimanite are the only associated minerals to incorporatesignificant boron (0?1–0?85 wt.% B₂O₃) and then only whenthe single site for B in kornerupine is approaching capacity.Sillimanite B₂O₃ contents increase regularly with kornerupineF. Fractionation of fluorine increases as follows: kornerupine<biotite<tourmaline,and K^krn-BtD=(F/OH)^Krn/(F/(OH)^Bt (assuming ideal anion composition)increases with biotite Ti. Kornerupine B₂O₃ content is a measureof B₂O₃ activity in associated metamorphic fluid, whereas sillimaniteB₂O₃ content increases with temperature, exceeding 0?4 wt.%whenT=900?C at very low water activities. New data on 11 kornerupines and literature data indicate thatthe unit cell parameters a, c, and V decrease with increasingB content and b, c, and V increase with increasing Fe³⁺ content.In Fe³⁺-poor kornerupines, b increases with Mg and with (Mg+ Fe²⁺) but the effect of Mg on b via the substitution ^VIMg+^IVSi=^VIAl+^IVAloverwhelms the effect of Fe²⁺=Mg substitution.     

Talc-, Magnesite- and Ti-Clinohumite-Bearing Ultrahigh-Pressure Meta-Mafic and Ultramafic Complex in the Dabie Mountains, China

The Bixiling mafic-ultramafic metamorphic complex is a 1•5km² tectonic block within biotite gneiss in the southern Dabieultrahigh-pressure terrane, central China. The complex consistsof banded eclogites that contain thin layers of garnet-bearingcumulate ultramafic rock. Except for common eclogitic phases(garnet, omphacite, kyanite, phengite, zoisite and rutilc),banded eclogites contain additional talc and abundant coesiteinclusions in omphacite, zoisite, kyanite and garnet. Some metaultramaficrocks contain magnesite and Ti-clinohumite. Both eclogites andmeta-ultramafic rocks have undergone multi-stage metamorphism.Eclogite facies metamorphisrn occurred at 610–700C andP>27 kbar, whereas amphibolite facies retrograde metamorphismis characterized by symplectites of plagioclase and hornblendeafter omphacite and replacement of tremolite after talc at P<6–15kbar and T <600C. The meta-ultramafic assemblages such asolivine + enstatite + diopside + garnet and Ti-clinohumite +diopside + enstatite + garnet + magnesite olivine formed at700–800C and 47–67 kbar. Investigation of the phaserelations for the system CaO-MgO-SiO₂-H₂O-CO₂ and the experimentallydetermined stabilities of talc, magnesite and Ti-clinohumiteindicate that (1) UHP talc assemblages are restricted to Mg-Algabbro composition and cannot be an important water-bearingphase in the ultramafic mantle, and (2) Ti-clinohumite and magnesiteare stable H₂O-bearing and CO₂-bearing phases at depths >100km. The mafic-ultramafic cumulates were initially emplaced atcrustal levels, then subducted to great depths during the Triassiccollision of the Sine-Korean and Yangtze cratons. KEY WORDS: eclogite; magnesite; meta-ultramafics; talc; ultrahigh-P metamorphism ^*Corresponding author     

Melting of a Hydrous Mantle: I. Phase Relations of Natural Peridotite at High Pressures and Temperatures with Controlled Activities of Water, Carbon Dioxide, and Hydrogen

Four natural peridotite nodules ranging from chemically depletedto Fe-rich, alkaline and calcic (SiO₂=43?7–45?7 wt. percent, Al₂O3=1?6O–8?21 wt. per cent, CaO=0?70–8?12wt. per cent,alk=0?10–0?90 wt. per cent and Mg/(Mg+Fe²⁺)=0?94–0?85)have been investigated in the hypersolidus region from 800?to 1250?C with variable activities of H₂O, CO₂, and H₂. Thevapor-saturated peridotite solidi are 50–200?C below thosepreviously published. The temperature of the beginning of meltingof peridotite decreases markedly with decreasing Mg/(Mg+Fe)of the starting material at constant CaO/Al₂O₃. Conversely,lowering CaO/Al₂O₃ reduces the temperature at constant Mg/(Mg+Fe)of the starting material. Temperature differences between thesolidi up to 200?C are observed. All solidi display a temperatureminimum reflecting the appearance of garnet. This minimum shiftsto lower pressure with decreasing Mg/(Mg+Fe) of the startingmaterial. The temperature of the beginning of melting decreasesisobarically as approximately a linear function of the mol fractionof H₂O in the vapor (X_H2O). The data also show that some CO₂may dissolve in silicate melts formed by partial melting ofperidotite. Amphibole (pargasitic hornblende) is a hypersolidus mineralin all compositions, although its P/T stability field dependson bulk rock chemistry. The upper pressure stability of amphiboleis marked by the appearance of garnet. The vapor-saturated (H₂O) liquidus curve for one peridotiteis between 1250? and 1300?C between 10 and 30 kb. Olivine, spinel,and orthopyroxene are either liquidus phases or coexist immediatelybelow the temperature of the peridotite liquidus. The data suggest considerable mineralogical heterogeneity inthe oceanic upper mantle because the oceanic geotherm passesthrough the P/T band covering the appearance of garnet in variousperidotites. The variable depth to the low-velocity zone is explained byvariable a_H2O conditions in the upper mantle and possibly alsoby variations in the composition of the peridotite itself. It is suggested that komatiite in Precambrian terrane couldform by direct melting of hydrous peridotite. Such melting requiresabout 1250?C compared with 1600?C which is required for drymelting. The genesis of kimberlite can be related to partial meltingof peridotite under conditions of (). Such activities of H₂Oresult in melting at depths ranging between 125 and 175 km inthe mantle. This range is within the minimum depth generallyaccepted for the formation of kimberlite.     

Water-Saturated and -Undersaturated Melting of Metaluminous and Peraluminous Crustal Compositions at 10 kb: Evidence for the Origin of Silicic Magmas in the Taupo Volcanic Zone, New Zealand, and Other Occurrences

The melting relations of two proposed crustal source compositionsfor rhyolitic magmas of the Taupo Volcanic Zone (TVZ), New Zealand,have been studied in a piston-cylinder apparatus at 10 kb totalpressure and a range of water activities generated by H₂O-CO₂vapour. Starting materials were glasses of intermediate composition(65 wt.% Si0₂ representing a metaluminous ‘I-type’dacite and a peraluminous ‘S-type’ greywacke. Crystallizationexperiments were carried out over the temperature range 675to 975?C, with aH₂O values of approximately 1?0, 0?75, 0?5,and 0?25. Talc-pyrex furnace assemblies imposed oxygen fugacitiesclose to quartz-fayalite-magnetite buffer conditions. Assemblages in both compositions remain saturated with quartzand plagioclase through 675–700?C at high aH₂O, 725–750?Cat aH₂O0?5, and 800–875?C at aH₂O0?25, corresponding to<60–70% melting. Concentrations of refractory mineralcomponents (Fe, Mg, Mn, P, Ti) in liquids increase throughoutthis melting interval with increasing temperature and decreasingaH₂O. Biotite and hornblende are the only mafic phases presentnear the solidus in the dacite, compared with biotite, garnet,gedritic orthoamphibole, and tschermakitic clinoamphibole inthe greywacke. Near-solidus melting reactions are of the type:biotite + quartz + plagioclase = amphibole ? garnet, potentiallyreleasing H₂O for dehydration melting in the greywacke, butproducing larger amounts of hornblende and releasing littleH₂O in the dacite. At aH₂O0?25 and temperatures 825–850?C,amphibole dehydration produces anhydrous mineral phases typicalof granulite fades assemblages (clinopyroxene, orthopyroxene,plagioclase?quartz in the dacite; garnet, orthopyroxene, plagioclase?quartzin the greywacke) coexisting with melt proportions as low as40%. Hornblendce-saturated liquids in the dacite are weaklyperaluminous (0?3–1?6 wt.% normative C—within therange of peraluminous TVZ rhyolites), whereas, at aH₂O0?25 andtemperatures 925?C, metaluminous partial melt compositions (upto 1?8 wt.% normative Di) coexist with plagioclase, orthopyroxene,and clinopyroxene. At all water activities, partial melts ofthe greywacke are uniformly more peraluminous (1?5–2?6wt.% normative C), reflecting their saturation in the componentsof more aluminous mafic minerals, particularly garnet and Al-richorthopyroxene. A metaluminous source for the predominantly Di-normativeTVZ rhyolites is therefore indicated. With decreasing aH₂O the stability fields of plagioclase andquartz expand, whereas that of biotite contracts. These changesare reflected in the proportions of normative salic componentsin partial melts of both the dacite and greywacke. At high aH₂O,partial melts are rich in An and Ab and poor in Or (trondhjemitic-tonalitic);with decreasing aH₂O they become notably poorer in An and richerin Or (granodioritic-granitic). These systematic variationsin salic components observed in experimental metaluminous tostrongly peraluminous melts demonstrate that a wide varietyof granitoid magmas may be produced from similar source rocksdepending upon P-T-aH₂O conditions attending partial melting.Some peraluminous granitoids, notably trondhjemitic leucosomesin migmatites, and sodic granodiorites and granites emplacedat deep crustal levels, have bulk compositions similar to nearsolidus melt compositions in both the dacite and greywacke,indicating possible derivation by anatexis without the involvementof a significant restite component.     

The Mineral Chemistry of Ultramafic Xenoliths of Eastern China: Implications for Upper Mantle Composition and the Paleogeotherms

Ultramafic xenoliths of garnet lherzolite (?rare spinel), spinellherzolites, spinel harzburgites, clinopyroxenites, and clinopyroxenemegacrysts were collected from Cenozoic basalts in all partsof eastern China. From their modal composition and mineral chemistryall the xenoliths may be placed into three types representing:a fertile or more primitive mantle (garnet lherzolite and spinellherzolite), a refractory or more depleted mantle (spinel harzburgiteand dunite), and inclusions cognate with the host alkali basaltsat mantle pressures (pyroxenite and megacrysts). There are systematicdifferences between the mineral compositions of each type. Spinelshows a wide compositional range and the spinel cr-number [100Cr/(Cr + Al)] is a significant indicator of the xenolithtype. Spinel cr-number and Al₂O₃ of coexisting minerals (spinel,clinopyroxene, and orthopyroxene) are useful as refractory indicatorsfor spinel peridotite in that the cr-number increases and thepercentage of Al₂O₃ decreases with increasing degrees of melting.In garnet peridotite, however, the same functions vary withpressure, not degree of melting. According to P–T estimates,the various xenoliths were derived from a large range of depthsin the upper mantle: spinel peridotite from approximately 11to 22 kb (37–66 km), spinel/garnet lherzolite from 19to 24 kb (62–80 km), and garnet lherzolite from 24 to25 kb (79–83 km). We conclude that the uppermost mantlebeneath eastern China is heterogeneous, with a north-northeastzone of more depleted mantle lying beneath the continental marginand a more primitive mantle occurring towards the continentalinterior.     

Pumpellyite-Actinolite Facies Schists of the Taveyanne Formation near Lo?che, Valais, Switzerland

Electron microprobe analyses are presented for new-formed mineralsfrom a small exposure of semi-schistose Taveyanne Formationof the pumpellyite-actinolite facies near Lo?che, Valais. Comparisonsare drawn with minerals of other low-grade metamorphic areas,especially in southern New Zealand. Sphene shows considerablesubstitution of Ca(Al,Fe)SiO₄(OH) for CaTiSiO₅. Epidotes aresharply divided into early pistacitic (Ps = 0.28–0.37)and later clinozoisitic varieties (Ps = 0.11–0.19). Pumpellyitesrange from pumpellyite-(Fe) to pumpellyite-(Al) and are generallyless Fe-rich than those of zeolite and prehnite-pumpellyitefacies. Pumpellyite inclusions in albitized plagioclase areparticularly low in Mg. Actinolites are low in A1₂O₃, TiO₂,and Na₂O, essentially identical compositions being nucleatedon detrital augite, hornblende, and in the matrix. Phengitesare also extremely low in Na₂O and TiO₂. Chlorites are ripidolites.Albitized clastic plagioclase has the composition An0.7–1.6and albite in clinozoisite-calcite-albite-phengite-chloriteveins An2.1–2.3. Calcites carry minor Mn > Fe ? Mg.New-formed iron oxides are absent, whereas pyrrhotite and minorpyrite occur in one rock, buffering fs₂ and indicating low fo₂. Ratios Mg: Fe^* (Fe^* = total Fe) in coexisting chlorites andA1, Na-poor actinolites vary sympathetically both in the Lo?cheand southern New Zealand rocks here considered, giving K_D =(Mg/Fe^*) _actlnolIte/(Mg/Fe^*)_chlorle = 1.72. Mg/Fe^* ratios inpumpellyites tend to vary sympathetically with those of coexistingchlorites and actinolites but are more variable. Substitutionof (Fe, Mg)Si for A1₂ in phengitic micas and chlorites variessympathetically in the same suites between mafic volcanic andmore pelitic extremes. Various minor elements also behave ina consistent fashion, indicating an encouraging tendency towardsequilibrium. Variable (though small) A1₂O₃ contents of actinolite,Fe: Al ratios in epidotes and pumpellyites, and Mg: Fe^* ratiosin phengites, even within a single grain, are evidence of short-rangedisequilibrium; metamorphic equilibration is evidently easierbetween some crystal structures and structural sites than betweenothers. In phase rule analysis of assemblages in such rocks it is commonlynecessary to treat Fe²O₃, FeO, and MgO as separate componentsand it may also be necessary to regard CO² as an inert componentand/or to interpret observed assemblages as of low variance.The presence of the Ca-Al silicates and sphene indicates verylow X_co2 in the metamorphic fluids in all rocks examined exceptan albite-chlorite-calcite-quartz-anatase assemblage. But higherAn in albites than in isofacial and in greenschist facies rocksof southern New Zealand can be ascribed to significantly higherXco₂ at Lo?che, especially in the veins, than in New Zealand. Pumpellyite and epidotes of the pumpellyite-actinolite faciestend to be lower in Fe and richer in Al than those of lowergrade facies. Important reactions include those of the formpumpellyite-(Fe³⁺)+chlorite+quartz+H₂=pumpellyite-(Al)+actinolite,and pumpellyite+chlorite+quartz- ‘epidote’+actinolite+water.Careful selection of pumpellyite and chlorite compositions isrequired for experimental and chemographic analysis of pumpellyitestability. In the absence of critical data, temperatures ofabout 250–350? and pressures of several kilobars are provisionallysuggested for the Lo?che metamorphism.     

Melting Behaviour of Model Lherzolite in the System CaO-MgO-Al2O3-SiO2-FeO at 0{middle dot}7-2{middle dot}8 GPa

Fe–Mg exchange is the most important solid solution involvedin partial melting of spinel lherzolite, and the system CaO–MgO–Al₂O₃–SiO₂–FeO(CMASF) is ideally suited to explore this type of exchange duringmantle melting. Also, if primary mid-ocean ridge basalts arelargely generated in the spinel lherzolite stability field bynear-fractional fusion, then Na and other highly incompatibleelements will early on become depleted in the source, and themelting behaviour of mantle lherzolite should resemble the meltingbehaviour of simplified lherzolite in the CMASF system. We havedetermined the isobarically univariant melting relations ofthe lherzolite phase assemblage in the CMASF system in the 0·7–2·8GPa pressure range. Isobarically, for every 1 wt % increasein the FeO content of the melt in equilibrium with the lherzolitephase assemblage, the equilibrium temperature is lower by about3–5°C. Relative to the solidus of model lherzolitein the CaO–MgO–Al₂O₃–SiO₂ system, melt compositionsin the CMASF system are displaced slightly towards the alkalicside of the basalt tetrahedron. The transition on the solidusfrom spinel to plagioclase lherzolite has a positive Clapeyronslope with the spinel lherzolite assemblage on the high-temperatureside, and has an almost identical position in P–T spaceto the comparable transition in the CaO–MgO–Al₂O₃–SiO₂–Na₂O(CMASN) system. When the compositions of all phases are describedmathematically and used to model the generation of primary basalts,temperature and melt composition changes are small as percentmelting increases. More specifically, 10% melting takes placeover 1·5–2°C, melt compositions are relativelyinsensitive to the degree of melting and bulk composition, andequilibrium and near-fractional melting yield similar melt compositions.FeO and MgO are the oxides that exhibit the greatest changein the melt with degree of melting and bulk composition. Theamount of FeO decreases with increasing degree of melting, whereasthe amount of MgO increases. The coefficients for Fe–Mgexchange between the coexisting crystalline phases and melt,K_dFe–Mg^xl–liq, show a relatively simple and predictablebehaviour with pressure and temperature: the coefficients forolivine and spinel do not show significant dependence on temperature,whereas the coefficients for orthopyroxene and clinopyroxeneincrease with pressure and temperature. When melting of lherzoliteis modeled in the CMASF system, a strong linear correlationis observed between the mg-number of the lherzolite and themg-number of the near-solidus melts. Comparison with meltingin the CMASN system indicates that Na₂O has a strong effecton lherzolite melting behaviour only at small degrees of melting. KEY WORDS: CMASF; lherzolite solidus; mantle melting     

Diffusion Gradients in an Eclogite Xenolith from the Roberts Victor Kimberlite Pipe: 1. Mechanism and Evolution of Garnet Exsolution in Al2O3-rich Clinopyroxene

Xenolith JJG41 is from the Roberts Victor kimberlite and isa bimineralic eclogite which is striking for its Al- and Ca-richclinopyroxene crystals showing garnet exsolution lamellae. Thedevelopment of the exsolution has been interpreted as a resultof a slow cooling at depth from near-solidus conditions (c.1400?C) towards normal mantle lithosphere temperatures (Harte& Gurney, 1975). The clinopyroxene retains marked compositionalgradients adjacent to the garnet lamellae and the present paperis concerned with the generation and preservation of these diffusiongradients within a rock from the Earth's mantle In order to understand the mechanism of exsolution reactiona re-examination has been made of the microtexture and chemistryof the garnet lamellae in relation to the compositional gradientsin adjacent clinopyroxene. Three sets of garnet lamellae, whichappear to have crystallized in sequence, may be recognised:type A, large lamellae, nucleated first and closest to the transformationtemperature; type B of intermediate size and age; and type C,small lamellae, nucleated last and with the greatest overstepof the transformation temperature. The major compositional zoning in JJG41 clinopyroxene, a decreaseof Al as Si and Mg increase, is consistent with the garnet growthreaction 2Diop+Al₂Si^–1Mg^–1=2Gros, 1Py.Ca, unlikemost of the elements, shows very flat composition profiles,but with a higher concentration than the initial Ca contentof the unexsolved clinopyroxene. Garnet lamellae are individuallyhomogeneous, but Ca contents vary between lamellae as a functionof lamellae size. In contrast the Fe/Mg distribution coefficientsat interfaces between garnet and clinopyroxene are relativelyconstant irrespective of garnet size. The redistribution of the principal cations—Ca, Fe, Mg,Al, Si—between and within the clinopyrox ene and garnet,during garnet exsolution and cooling, obviously proceeded differentlyfor different elements. Two principal stages in the coolinghistory may be identified: (1) The growth of the sets of garnetlamellae controlled by Al₂Mg^–1Si^–1 redistributionin clinopyroxene. This redistribution was both part of the nettransfer reaction creating garnet, and an exchange reactionin clinopyroxene essential for the diffusional transport ofAl to the growing garnet. Al diffusion in clinopyroxene wasprobably the rate-limiting step, and all other cations, Ca andFe as well as Mg and Si, were mobile during this stage. (2)The occurrence, after the cessation of garnet growth, of diffusionof Fe, Mg and Ca in garnet and interdiffusion of Fe-Mg in clinopyroxene.This resulted in the setting of the KD Fe-Mg at the Cpx-Gt interfacesto a roughly constant value equivalent to approximately 1000?C,which is taken to be the final (‘freezing-in’) temperaturefor redistribution of any elements. During this post garnet-growthstage Ca also became homogenized within individual garnet lamellae,but there is no evidence of Ca equilibration with the clinopyroxene.Under the P-T conditions operating, the initial clinopyroxenecomposition probably resulted in a maximum (M2 site fully occupied)Ca content in clinopyroxene during the stage of garnet growth,and this was maintained during the post-growth stage.     

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     

Petrology and Petrogenesis of Clinopyroxene-Rich Tholeiitic Lavas, Merelava Volcano, Vanuatu

The mineralogy, petrography and geochemistry of a suite of clinopyroxene-richolivine tholenite lavas from Merelava island, Vanuatu are described.Located at the southern end of the Northern Trough back-arcbasin, this suite displays all the characteristics of primitiveisland arc lavas: flat REE patterns, depleted HFSE, enrichmentin K-group elements relative to LREE, highly calcic plagioclase(to An_{9 3} and Cr-rich spinels (cr-number80) Analysis of groundmasscompositions demonstrates that the variation in MgO within thelava suite (from 13?7 to 4?3% MgO) represents only a small departurefrom a liquid line of descent. Some of the more primitive lavas contain low-Al₂O₃ clinopyroxenemegacrysts (mg-number = 100Mg/(Mg+Fe^{2 +} and ultramafic xenoliths,the latter ranging from fine-grained, tectonite wehrlites andchnopyroxene-bearing harzburgites, to coarse-grained cumulatewehrlites. The cumulate nodules, megacrysts and phenocrysts are shown tobe co-magmatic, and an empirical compositional relationshipis demonstrated for equilibrium olivine-clinopyroxene pairs,covering the observed fractionation range (mg-number_Cpx=0?6375mg-number_O1 + 35?3). On the basis that the most primitive olivine(mg-number _{91 7}) is close to the liquidus composition, thiscompositional relationship demonstrates that clinopyroxene (mg-number=94,and containing no Fe³⁺) was also a liquidus phase. Clinopyroxeneswith mg-number>94 are the product of local oxidation duringmixing of primitive, relatively reduced magmas, and more evolved,oxidized magmas. This mixing also gave rise to relatively narrow,reversely zoned, internal rims on many clinopyroxene and olivinephenocrysts, cumulus crystals, and clinopyroxene megacrysts. Fractionation modelling demonstrates that the most differentiatedsample with 19 wt.% Al₂O₃ can be derived from the most primitivesample with 10?3% Al₂O₃ by removal of 48% crystals of clinopyroxeneand olivine in the proportions 73:27 Plagioclase is a late crystallizingphase and has an insignificant role in the fractionation process. The parent melt composition (mg-number=77) is deduced from themost primitive olivine composition and the liquid line of descent,and is shown to contain equal amounts of MgO and CaO (137 wt.%),a high CaO/Al₂O₃ ratio of 1?3 and an unusually low Ni contentof 137 ppm. Data from published high pressure (8–20 kb)experiments on melting of peridotite and pyrolite do not providean explanati in for the large normative diopside component inthis parent melt (38 mol.%), and a hypothesis is proposed wherebyhigh degrees of melting of refractory Iherzolite or harzburgite+acomponent of lower crustal pyroxenite and/or wehrlite takesplace at the base of the crust (5–55 kb). At this depth,and initially under hydrous conditions, high degrees of meltingwould progressively eliminate orthopyroxene and then clinopyroxeneto produce a dunite residue. The liquid produced near the pointof clinopyroxene elimination would be compatible with the highCaO and Sc contents, and high Sc/Ni, Cr/Ni and D1/Hy ratiosof the lavas, and the refractory nature of the phenocrysts.     

Petro-tectonic Imprints in the Sapphirine Granulites from Anantagiri, Eastern Ghats Mobile Belt, India

Sapphirine granulite occurring as lenses in charnockite at Anantagiri,Eastern Ghat, India, displays an array of minerals which developedunder different P-T-X conditions. Reaction textures in conjunctionwith mineral chemical data attest to several Fe-Mg continuousreactions, such as

1. spinel+rutile+quartz+MgFe_–1=sapphirine+ilmenite
2. cordierite=sapphirine+quartz+MgFe_–1
3. sapphirine+quartz=orthopyroxene+sillimanite+MgFe_–1
4. orthopyroxene+sapphirine+quartz=garnet+MgFe_–1
5. orthopyroxene+sillimanite=garnet+quartz+MgFe_–1
6. orthopyroxene+sillimanite+quartz+MgFe_–1=cordierite.

Calculated positions of the reaction curves in P-T space, togetherwith discrete P-T points obtained through geothermobarometryin sapphirine granulite and the closely associated charnockiteand mafic granulite, define an anticlockwise P-T trajectory.This comprises a high-T/P prograde metamorphic path which culminatedin a pressure regime of 8?3 kb above 950?C, a nearly isobariccooling (IBC) path (from 950?C, 8?3 kb, to 675?C, 7?5kb) anda terminal decompressive path (from 7?5 to 4?5 kb). Spinel,quartz, high-Mg cordierite, and sapphirine were stabilized duringthe prograde high-T/P metamorphism, followed by the developmentof orthopyroxene, sillimanite, and garnet during the IBC. Retrogradelow-Mg cordierite appeared as a consequence of decompressionin the sapphirine granulite. Deformational structures, reportedfrom the Eastern Ghat granulites, and the available geochronologicaldata indicate that prograde metamorphism could have occurredat 30001?00 and 2500?100 Ma during a compressive orogeny thatwas associated with high heat influx through mafic magmatism. IBC ensued from P_max and was thus a direct consequence of progrademetamorphism. However, in the absence of sufficient study onthe spatial variation in P-T paths and the strain historiesin relation to time, the linkage between IBC and isothermaldecompression (ITD) has remained obscure. A prolonged IBC followedby ITD could be the consequence of one extensional mechanismwhich had an insufficient acceleration at the early stage, orITD separately could be caused by an unrelated extensional tectonism.The complex cooled nearly isobarically from 2500 Ma. It sufferedrapid decompression accompanied by anorthosite and alkalinemagmatism at 1400–1000 Ma.     

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.     

Phase Equilibria in the Pyroxene Quadrilateral

Experimental phase equilibrium data on compositions of coexistingpyroxenes in the quadrilateral enstatite-diopside-ferrosilite-hedenbergitehave been used to model pyroxene solid solutions and to formulatepyroxene geothermometers. Each pyroxene is treated as a solidsolution of four quad-components using the Kohler formulation where G_ij^* is the excess free energy of mixing in a binary solutioncalculated with binary mole fractions (e.g. X_i^o = X_i/(X_i+X_j))and X_i is the mole fraction in a multicomponent solution. Thefit to the experimental data is achieved by minimizing the totalGibbs free energy of the assemblage. The following set of thermochemicaldata and simple mixture parameters (W_ij) are found to be bestsuited. Standard (T = 298?15 K) enthalpy and entropy of formationfrom elements for fictive orthohedenbergite are –1416?8kJ and 84?88 J K^–1 mol ^–1 respectively. The heatcapacity is given by 114?67+17?09E-3T–31?40E5T^–2.The W_ij data are: Opx: W₁₂ = W₂₁ = 25 W₁₃ = (13?1–0-015T),W₃₁ = (3?37–0?005T), W₂₃ = 20, W₃₂ = 16, W₂₄ = 5, W₄₂= 7, W₃₄ = 15, W₄₃ = 15; Cpx: W₁₂ = (25?484+0?0812P), W₂₁ =(31?216–0?0061P),W₃₁ = W₁₃ = 0W₁₄ = (93?3–0?045T), W₄₁ = (–20?0+0?028T),W₂₃ = 24, W₃₂ = 15, W₂₄ = 12, W₄₂ = 12, W₃₄ = (16?941+0?00592P),W₄₃ = (20?697–0?00235P). Coexisting pyroxene compositionshave been computed in the temperature range of 700 to 1400?C. Two geothermometers have been constructed, one based on atomicfraction of iron (Fe/(Fe + Mg)) in orthopyroxene and the Fe-Mgdistribution coefficient and the other, based on wollastonitecontent of clinopyroxene. The two scales yield different temperatureswhen applied to the same rock. In igneous pyroxenes, the Catransfer ceased at 150 to 200?C above the closure temperatureof the Fe-Mg ion-exchange. In metamorphic rocks an oppositeeffect seems to have prevailed.