A petrogenetic grid for aluminous granulite facies metapelites in the KFMASH system

Due to the retrograde cation exchange problems experienced by conventional geothermobarometers above their closure temperatures, petrogenetic grids are a potentially powerful alternative to unravelling the P–T evolution of ultrahigh‐T granulite terranes. A new qualitative KFMASH (K₂O–FeO–MgO–Al₂O₃–SiO₂–H₂O) petrogenetic grid for Mg–Al rich metapelites containing K‐feldspar, sillimanite and quartzofeldspathic melt that successfully accounts for the majority of assemblages composed of variations of sapphirine, spinel, garnet, orthopyroxene, cordierite, biotite and quartz is developed. Univariant reactions are predicted utilizing a newly derived ‘melt projection’ and these reactions are entirely consistent with algebraically calculated reaction coefficients obtained using a set of standard phase compositions. Based upon observations of commonly associated mineral assemblages in natural lithologies the [Spr, Spl], [Qtz, Spl], [Bt, Spl], [Opx, Spr], [Opx, Qtz] and [Bt, Opx] invariant points are assumed to be stable, whilst the [Grt, Spr], [Grt, Qtz], [Spr, Qtz] and [Crd, Qtz] are assumed to be metastable. Biotite‐bearing assemblages are confined to the lowest temperatures, and sapphirine + quartz to the highest temperatures. Orthopyroxene + sillimanite ± quartz assemblages are confined to the highest pressures, whilst spinel‐bearing assemblages are stabilized by lower pressures. The alternative choice of invariant point stability leads to significant differences between this grid and previously proposed topologies. Spinel cannot be stable along with the orthopyroxene and sillimanite assemblage as previously proposed. Further, more subtle differences in topology result from the treatment of H₂O in the chemographic projection used to deduce univariant reactions, and projecting from a water‐bearing quartzofeldspathic melt does not yield the same reaction coefficients as projection from H₂O. The new grid allows reinterpretation of previously proposed evolutionary P–T paths for Mg–Al rich granulites from the Napier Complex and Rauer Group, East Antarctica, and In Ouzzal, Algeria.     

Evidence of a Temperature-dependent 'Blueschist' to 'Eclogite' Transformation in High-pressure Metamorphism of Metabasic Rocks

Textures in the blueschist metabasic rocks of the island ofSyros, Greece, indicate a reaction forming omphacite and garnetfrom earlier glaucophane and epidote. A balanced ‘wholerock’ reaction can be written using the phase compositionsand modal mineralogy of the products observed. This reactionis continuous in P-T space if Mg and Fe²⁺ are independent components.The available thermodynamic data suggest that the ‘eclogite’(garnet plus omphacite) assemblage is favoured by higher temperatures. It cannot, however, be conclusively shown that the rocks wentthrough an up-temperature interval of metamorphism. The reactionseen could be promoted by reduced silica, or water activity.The details of the reaction textures and mineral zonation patternsshow furthermore that chemical equilibrium was not maintainedthroughout the rock development. The reaction textures differin detail in different samples. In those samples in which thetextures are most consistent with maintained chemical equilibriumhowever, the mineral zonation patterns do imply up-temperaturemetamorphism.     

Metamorphic Evolution of the Ribeira Belt: Evidence from Outcrops in the Rio de Janeiro Area, Brazil

Migmatitic granulites and arc-related felsic intrusives of Pan-Africanage form the bedrock in the Rio de Janeiro area, SE Brazil.These rocks preserve a partial record of three parageneses.The earliest assemblage (M₁) grew during fabric formation inthe rocks (D₁) and is characterized by the mineral assemblagePl + Bt + Sil + Kfs + Qtz. Peak metamorphic conditions (M₂)are characterized by the assemblage Bt + Crd + Kfs + Pl + Grt+ liq + Qtz and are inferred to have developed during D₂ foldingof the rocks at T = 750–800°C and P = 7 kbar. M₃ reactiontextures overprint the M₂ assemblage and comprise symplectiticintergrowth of cordierite(II) and quartz that formed after garnet,whereas secondary biotite formed as a result of reactions betweengarnet and K-feldspar. By comparing the observed modal abundanceswith modal contours of garnet, cordierite and quartz on therelevant pseudosection a post M₂ P–T vector indicatingcontemporaneous cooling and decompression can be deduced. Theinferred equilibrium assemblage and reaction textures are interpretedto reflect a clockwise P–T path involving heating followedby post-peak decompression and associated cooling. We inferthat metamorphism occurred in response to advective heatingby the abundant syn-collisional (arc-related) I-type granitoidsin the region, consistent with the unusually high peak T/P ratio. KEY WORDS: advective heating; Ribeira belt; granulite; partial melting; P–T pseudosection     

Cordierite microstructure and texture in a moldanubian gneiss

The microstructure and texture in cordierites of a moldanubian gneiss from the Bohemian Massif has been analysed by transmission electron microscopy (TEM) and universal stage in order to get information on the deformation mechanisms and textural development of this rock-forming mineral. Deformation may have taken place at temperatures between about 500° C and 630° C and pressures smaller than about 3 kb. The elongated cordierite xenoblasts show a typical dislocation creep microstructure consisting of subgrain boundaries and free dislocations. The dislocations have [001], [010] and 1/2<110> Burgers vectors. [001] dislocations often have pure screw and edge character the latter type being climb-dissociated on (001). Among the dislocations reactions are common. The main subgrain boundaries observed are (010)[001], {110}[001] and (001)[010] tilt boundaries. Burgers vectors and dislocation line directions reveal (100)[001], (010)[001], (100)[010], {110} 1/2<110> and (001)1/2<110> as activated slip systems. The crystallographic preferred orientation (here referred to as texture) consists of a [001] maximum in the foliation parallel to the mineral lineation. [100] and [010] maxima are perpendicular to it within and normal to the foliation, respectively, with a girdle tendency normal to the lineation. The texture may be explained by simple shear deformation on the {hkO}[001] slip systems with preference of (010)[001].     

燕山地区褶皱冲断带和盆地中的晚侏罗世土城子组/后城组形成分析（英文）

高级变质-深熔作用中伴随有熔体的形成,在缺失流体的不一致熔融条件下,如果熔体的萃取不完全,原地结晶熔体与残留体之间可发生特殊的退变反应———逆(熔)反应,这种反应与进变质脱水熔融恰好相反。逆(熔)反应的最佳判断标志就是在浅色体和早期深熔过程中形成的不一致熔融相之间含水矿物组合的生长。逆(熔)反应形成的退变组合是深熔作用过程的一部分,而不是另外期次的变质事件叠加。逆(熔)反应的地质意义在于它可能会影响到熔体和流体组成、流体-岩石的相互作用以及对质量平衡的研究,尤其是对p-T路径恢复的影响,从而影响到构造和热流模型的推断。     

Metamorphism of metapelites: calculations of equilibrium assemblages and numerical simulations of the crystallization of garnet

Abstract This work uses a simplified model of equilibrium to predict the assemblage sequence and compositional zoning in garnet that should result from prograde metamorphism of common bulk compositions of pelitic rocks. An internally-consistent set of model thermodynamic data are derived for natural mineral compositions from natural assemblages. Equilibrium assemblages can be calculated for pelitic compositions with excess quartz and either muscovite or K-feldspar at any pressure and water pressure. The compositions and abundances of phases in equilibrium assemblages can be calculated where the elements Mg, Fe and Mn are exchanged among phases. The prograde metamorphic assemblage sequences and the effects of pressure on assemblages, predicted by the simulation method presented here, are similar enough to natural observations to suggest that the simulations can be used to analyse natural equilibrium and growth processes. The calculated phase diagrams at moderate and high crustal pressures explain the mineral assemblage sequence produced by prograde metamorphism in common pelitic compositions. Garnet appears by continuous reaction of biotite and chlorite as the garnet-biotite-chlorite divariant field migrates toward higher Mg/Fe ratios over the bulk composition. Staurolite appears in common bulk compositions when garnet and chlorite become incompatible. An aluminum silicate phase can appear when staurolite and chlorite react. Staurolite breaks down at an extremum point to produce garnet. Continuous reaction of biotite and sillimanite causes growth of abundant garnet. The reaction sequence involving garnet, staurolite and aluminum silicates is probably different at low pressure, but the main reason that staurolite and garnet are rare is the restricted compositional range over which their assemblages exist. Andalusite appears by the divariant reaction of chlorite and cordierite appears at low temperature in low pressure assemblages for common bulk compositions by the extremumpoint breakdown reaction of chlorite. Compositional zoning of garnet and the systematic variation of biotite composition in metamorphic sequences indicate that garnet is probably fractionated during growth. Fractionation of garnet causes garnet-consuming, univariant reactions to become multivariant. The metastable persistence of garnet should reduce the abundance and stability range of staurolite. Fractionation of even small quantities of garnet should deplete the equilibrating bulk composition of Mn, but have little effect otherwise. The simulations show that the prograde assemblage sequence in pelitic rocks can be complex in detail, with some assemblages lasting over temperature intervals of only a few degrees. The major prograde reactions that release water are the breakdown of chlorite to form garnet at low grade and the breakdown of muscovite at high grade. The volume of water released by formation of garnet at high grade is also important. These reactions have the capacity to buffer water pressure. The density of anhydrous pelitic rock increases markedly when chlorite breaks down and by the continuous reaction forming garnet at high grade. The heat content is controlled principally by heat capacity and continuous reactions. Discontinuous reactions have little thermal buffering capacity. Simulations of garnet fractionation show that commonly-observed garnet zoning profiles can be formed by garnet growth in the assemblage garnet-biotite-chlorite in common bulk compositions. A reversal of Fe-zoning in garnet can occur when garnet resumes growth above staurolite grade in the assemblage garnetbiotite-sillimanite. Discontinuities in zoning profiles can be caused only by disequilibrium. The disequilibrium can be due to either metastable persistence during a hiatus in growth or to growth by irreversible reaction. Because the appearance of garnet is controlled by a continuous rather than a discontinuous reaction, the appearance of garnet is very sensitive to bulk composition. The early development of garnet is also sensitive to the pressure and water pressure of metamorphism. As a consequence the first garnet isograd is of limited thermometric value. Metastable persistence of kyanite and manite at high grades could reduce the abundance of garnet and allow biotite to persist. Metastable persistence would also limit the of cordierite formation.     

Cadomian Lower-Crustal Contributions to Variscan Granite Petrogenesis (South Bohemian Pluton, Austria): Constraints from Zircon Typology and Geochronology, Whole-Rock, and Feldspar Pb-Sr Isotope Systematics

A hybrid pyroxene-bearing Weinsberg type granitoid of the SouthBohemian batholith (Austria) consists of two independent mineralassemblages that were formed during two different magmatic events.The older, inherited assemblage forms unevenly distributed millimetre-sizedmulti-grain patches of quartz + mesoperthitic alkali feldspar+ andesine/bytownite + clinopyroxene (X_Mg = 0·50–0·54)+ orthopyroxene (X_Mg = 0·35–0·42) ±ilmenite ± accessories. It is interpreted to representremnants of a mangeritic igneous rock with a superimposed granulite-faciesre-equilibration texture characterized by unzoned pyroxenesand plagioclase. The enclosing younger assemblage with alkalifeldspar + oligoclase/andesine + quartz + biotite ± accessoriescrystallized from a biotite-bearing granitic melt with feldsparsexhibiting typical magmatic zoning. Coexisting with the inheritedassemblage are zircons with a characteristic typology (S23 toD, mean J4). Zircons belonging to the granitic assemblage, onthe other hand, show a distinctly different typology (L2 toS5, mean L4) or are anhedral. A Cambrian age of formation andsubsequent re-equilibration of the inherited assemblage is inferredfrom a mean U/Pb and ²⁰⁷Pb/²⁰⁶Pb evaporation age of 523 ±5 Ma for the J4 zircons. Granitic L4 zircons show a mean ²⁰⁷Pb/²⁰⁶Pbevaporation age of 355 ± 9 Ma, interpreted as the ageof zircon growth during a Carboniferous partial melting eventin the lower crust. Granite emplacement at 345 ± 5 Mais inferred from U/Pb analysis of the anhedral zircon population.The comparably low radiogenic common Pb isotope compositionof megacrystic alkali feldspars suggests that at least somedomains of these crystals are inherited from the older, pyroxene-bearingmineral assemblage. Rb/Sr whole-rock dating is thus severelyjeopardized by the presence of the inherited alkali feldsparcrystals, leading to widely scattering data points and errorchronages of no geological significance. KEY WORDS: Austria; Bohemian Massif; geochronology; granites; Pb–Sr isotopes     

A Natural Example of Metastable Reactions Involving Garnet and Sillimanite

The broad objective of this work is to develop models of reactionthat can be used to understand dynamic processes. The kineticsof reactions can be significant factors affecting heat and masstransfer, and the kinetic inhibition of equilibration enablesus to trace the history of natural samples. Samples were selectedfrom a metamorphic aureole for study because they show measurabledisequilibrium, and the approximate P—T path and timeof metamorphism are known. Detailed analysis of compositional variations of crystals andreaction textures suggests that biotite was being produced bythe breakdown of garnet at a faster rate than it was consumedby reaction with sillimanite. Some of the compositional variationsof biotite and cordierite can be explained by the process ofintergranular diffusion; however, the co-existence of metastablebiotite and sillimanite and the widespread distribution of Fe-richbiotite in the sample argue for a partial equilibrium modelfor which reaction rate was controlled by surface kinetic processes. Quantitative modelling was accomplished by breaking the overallreaction into three component reactions. The rate of one ofthese component reactions through time can be estimated fromgarnet zoning profiles, and the relative abundance of productphases is used then to estimate the absolute rates of the othercomponent reactions. A plausible interpretation of the datais that rate of dissolution of sillimanite was the rate-controllingprocess, and took place at a rate of 10^–7 to 10^–8cm/year in this sample. Analysis of this sample illustrates possible significant effectsof the kinetics of reaction in dry rocks in the deep crust.Even though biotite would have been unstable at final equilibriumand the overall reaction did not involve significant gain orloss of water, the particular kinetic path under taken resultedin production of biotite and consumption of water at the stageof reaction preserved in this sample.     

P-T Conditions and the Influence of Graphite on Pelitic Phase Relations in the Ballachulish Aureole, Scotland

Pressure-temperature conditions of pelites in the Ballachulishaureole, Scotland, have been determined from a calibrated petrogeneticgrid and from published geothermometers and geobarometers. Tocalibrate the mineral reactions in the grid, thermodynamic datafor appropriate end members of Ms, Chi, Qtz, And, Sil, Ky, Crn,Crd, Kfs, and Bt were derived from experimental data. This approachwas hampered by the unknown compositions of many of the mineralsused in the experiments, and by apparent inconsistency betweenthe experiments. A best compromise grid that satisfies mostof the data was obtained, which is applicable to the Ballachulishand other contact aureoles. In this grid, the first developmentof sillimanite is constrained to lie between the Richardsonet al. (1969) and Holdaway (1971) andalusite-sillimanite boundaries. A pressure estimate of 3.0 + 0.5 kb is obtained from the calibratedgrid, within 0.3 kb of estimates from geobarometry and fromtwo other independent petrological studies. Temperatures rangedfrom 560?20?C at the first development of cordierite in theassemblage Ms+Qtz+Chl+Crd+Bt to 750–800?C in Grt+Crd+Hyassemblages in pelitic screens within the igneous complex. In graphitic slates, in contrast to non-graphitic pelites, anentire andalusite-bearing subzone is developed, and initialcordierite development occurs further from the igneous contacts.The presence of graphite lowered a_H2o in the slaters, expandingthe stability field of the andalusite-bearing assemblage And+Qtz+Bt+Ms+Crdrelative to the assemblage Kfs+Qtz+Bt+Ms+Crd developed in non-graphiticunits. Initial development of cordierite in the assemblage Ms+Qtz+Chl+Crd+Btwas also promoted by reduced a_H2o in graphitic slates. The regular sequence and spacing of mineral zones in the aureolesuggests that gross equilibrium was attained during contactmetamorphism, even though the thermal metamorphic pulse is estimatedto have been less than 0.2 Ma (Buntebarth, in press). Thereis no evidence for reaction overstepping in cordierite-producingreactions.     

The Garnet+Hornblende Isograd in Calcic Schists from an Andalusite-Type Regional Metamorphic Terrain, Panamint Mountains, California

Calcic schists in the andalusite-type regional metamorphic terrainin the Panamint Mountains, California, contain the low-varianceassemblage quartz+epidote+muscovite+biotite+calcic amphibole+chlorite+plagioclase+spheneat low grade. Near the sillimanite isograd, chlorite in thisassemblage is replaced by garnet. The low variance in many calcicschists allows the determination of the nature of the reactionthat resulted in the coexistence of garnet+hornblende. A graphicalanalysis of the mineral assemblages shows that the reactioncan not be of the form biotite+epidote+chlorite+plagioclase+quartz=garnet+hornblende+muscovite+sphene+H₂Obecause garnet+chlorite never coexisted during metamorphismand the chlorite-bearing and garnet-bearing phase volumes donot overlap. The compositions of the minerals show that withincreasing grade amphibole changed from actinolite to pargasitichornblende with no apparent miscibility gap, the partitioningof Fe and Mg between chlorite and hornblende changed from K_D(Mg/Fe, chl&amp) < 1 to K_D > 1, the partitioning betweenbiotite and hornblende changed from K_D (Mg/Fe, bio/amp) <1 in chlorite-zone samples to K_D > 1 in garnet + hornblende-zonesamples, and the transition to the garnet-bearing assemblageoccurred when the composition of plagioclase was between An₅₅and An₈₀. Both the graphical analysis and an analytical analysisof the compositions of the minerals using simplified componentsderived from the natural mineral compositions indicate thatat the garnet+hornblende isograd the composition of hornblendewas colinear with that of plagioclase and biotite, as projectedfrom quartz, epidote, muscovite, and H₂O. During progressivemetamorphism, chlorite+biotite+epidote+quartz continuously brokedown to form hornblende+muscovite+sphene until the degeneracywas reached. At that point, tie lines from hornblende couldextend to garnet without allowing garnet to coexist with chlorite.Thus, the garnet+hornblende isograd was established throughcontinuous reactions within the chlorite-grade assemblage ratherthan through a discontinuous reaction. In this type of isograd,the low-grade diagnostic assemblage occurs only in Mg-rich rocks;whereas the high-grade assemblage occurs only in Fe-rich rocks.This relation accounts for the restricted occurrence of garnet+hornblendeassemblage in low-pressure terrains. In Barrovian terrains,garnet+chlorite commonly occurs, and the first appearana ofgarnet+hornblende can simply result from the continuous shiftof the garnet+chlorite tie line to Mg-rich compositions.     

Continental Lithospheric Contribution to Alkaline Magmatism: Isotopic (Nd, Sr, Pb) and Geochemical (REE) Evidence from Serra de Monchique and Mount Ormonde Complexes

Isotopic results (Sr, Nd, Pb), as well as concentrations ofmajor and trace elements (REE) are reported for whole-rock samplesand mineral separates from the onland alkaline complex of Serrade Monchique (South Portugal) and the offshore alkali basaltvolcanic suite of Mount Ormonde (Gorringe Bank). These two geneticallyrelated alkaline complexes were emplaced at the east Atlanticcontinent–ocean boundary during the Upper Cretaceous,i.e. 66–72 m.y. ago. Taken together, Serra de Monchiqueand Mount Ormonde may be seen as one of the few examples ofwithin-plate magmatism that straddles the continent–oceanboundary. Major and trace element compositions fail to revealany significant differences between onland and offshore complexes.This is particularly true regarding less differentiated samples(mg-number 0.40) which show the same progressive and continuousenrichment of their trace element patterns, with no specificanomaly (e.g. negative Nb anomaly) being present in samplesfrom the onland complex. Initial Pb and Sr isotopic compositionsalso do not allow any distinction to be made between Serra deMonchique and Mount Ormonde samples. Initial Pb isotope ratiosare moderately high (19.1 < ²⁰⁶Pb/²⁰⁴Pb < 19.8; ²⁰⁷Pb/²⁰⁴Pb= 15.6) in both cases. Moreover, once the effects of Sr contaminationby seawater are taken into account and the most contaminatedsamples discarded using data from fresh clinopyroxene separatesand results of leaching experiments, the initial Sr isotopiccompositions of Mount Ormonde samples are found to be unradiogenic(⁸⁷Sr/⁸⁶Sr = 0.7031±1) and identical to those obtainedat Serra de Monchique (⁸⁷Sr/⁸⁶Sr = 0.7032±1). In contrast,a systematic mean difference of 2 _Nd units is observed betweenSerra de Monchique [_Nd(T) = +4.8] and Mount Ormonde [_Nd(T) =+6.6] whole-rock samples. Surprisingly, a variation is alsoobserved at Mount Ormonde between the whole-rock samples andone of the two analysed clinopyroxene separates. Whereas MountOrmonde whole-rock samples invariably yielded _Nd(T) = +6.6 (meanvalue), a value of +0.5 is obtained for one clinopyroxene separate,whereas another gives +6.0. The above geochemical and isotopicresults make it possible to assign respective roles to the asthenosphere,lithosphere and crust in the petrogenesis of Serra de Monchiqueand Mount Ormonde complexes. We propose that both complexesshare a common mantle source whose isotopic characteristicsare very similar to the source of oceanic island basalts. Continentalmantle lithosphere, already characterized isotopically by studiesof peridotite massifs within the Iberian peninsula, acts asa contaminant which is evident onland on the whole-rock scale,and also present offshore as discrete clinopyroxene xenocrysts.The continental crust appears to play no role in the petrogenesisof the Serra de Monchique alkaline rocks. KEY WORDS: alkaline complexes; continental lithosphere; isotope geochemistry; passive continental margin; within-plate volcanics     

Empirical calibration of the silica–Ca-tschermak's–anorthite (SCAn) geobarometer

The pressure-sensitive equilibrium among anorthite, quartz and the Ca-tschermak component in clinopyroxene (CaAl₂SiO₆; CaTs), CaAl₂SiOCpx6+SiOQtz2=CaAl₂Si₂OPl8 (SCAn) ,can be used as a geobarometer in granulites with the proper assemblage, and has been calibrated using mineral composition data from partial melting experiments of natural assemblages and from phase equilibrium experiments on the end-member CMAS system. The experimental data cover the P – T  range 4–32  kbar and 900–1400  °C. Linear least-squares regression analysis of the experimental data resulted in the following empirical expressions for pressure in terms of composition and temperature: P = 5.066 [±0.760]+ 1300 [±800] T  −ln K 276 [±16] · T  [±2.5  kbar]or P = 6.330 [±0.116]−ln K 301 [±9]· T  [±1.0  kbar] ,where K = a PlAn a CpxCaTs  .The first equation incorporates an enthalpy term, but is less accurate than the second equation, in which the enthalpy of reaction is ignored. Application of these expressions to natural and experimental equilibrium mineral assemblages demonstrates that the empirical barometers are applicable over a wide range of pressures (≥4  kbar), temperatures (≥700  °C) and bulk compositions (Mg#≥32.5).     

Distribution of Ferric Iron in some Upper-Mantle Assemblages

The distribution of ferric iron among the phases of upper-mantlerocks, as a function of pressure (P), temperature (T) and bulkcomposition, has been studied using ⁵⁷Fe Mssbauer spectroscopyto determine the Fe³⁺/Fe ratios of mineral separates from 35peridotite and pyroxenite samples. The whole-rock Fe³⁺ complementof a peridotite is typically shared approximately evenly amongthe major anhydrous phases (spinel and/or garnet, orthopyroxeneand clinopyroxene), with the important exception of olivine,which contains negligible Fe³⁺. Whole-rock Fe³⁺ contents areindependent of the T and P of equilibration of the rock, butshow a well-defined simple inverse correlation with the degreeof depletion in a basaltic component. Fe³⁺ in spinel and inboth pyroxenes from the spinel Iherzolite facies shows a positivecorrelation with temperature, presumably owing to the decreasein the modal abundance of spinel. In garnet peridotites, theFe³⁺ in garnet increases markedly with increasing T and P, whereasthat in clinopyroxene remains approximately constant. The complexnature of the partitioning of Fe³⁺ between mantle phases resultsin complicated patterns of the activities of the Fe³⁺ -bearingcomponents, and thus in calculated equilibrium f_O2, which showlittle correlation with whole-rock Fe³⁺ or degree of depletion.Whether Fe³⁺ is taken into account or ignored in calculatingmineral formulae for geothermobarometry can have major effectson the resulting calculated T and P. For Fe-Mg exchange geothermometers,large errors must occur when applied to samples more oxidizedor reduced than the experimental calibrations, whose f_O2 conditionsare largely unknown. Two-pyroxene thermometry is more immuneto this problem, and probably provides the most reliable P—Testimates. Accordingly, the convergence of P—T valuesderived for a given garnet peridotite assemblage may not necessarilybe indicative of mineral equilibrium. The prospects for thecalculation of accurate Fe³⁺ contents from electron microprobeanalyses by assuming stoichiometry are good for spinel, uncertainfor garnet, and distinctly poor for pyroxenes. KEY WORDS: mantle; oxidation; partitioning; peridotite; thermobarometry ^*Corresponding author. Present address: School of Earth and Ocean Sciences, University of Victoria, P.O. Box 1700, Victoria, B.C., V8W 2Y2, Canada     

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.     

Equilibrium and Disequilibrium Trace Element Partitioning in Hydrous Eclogites (Trescolmen, Central Alps)

Despite the widespread presence of hydrous phases in subduction-related systems, experimental D^Min/Fluid trace element valuesfor many hydrous phases are lacking. To fill this gap, we presenta set of D^{Min/Clinopyroxene} values (where Min indicates amphibole,zoisite, phengite, paragonite or apatite) derived from equilibriumparageneses of eclogites from Trescolmen (Central Alps, Switzerland).These data can be combined with experimental data for D^{Clinopyroxene/Fluid},to estimate D^Min/Fluid values for the hydrous phases, thus circumventingexperimental problems with the direct determination of suchvalues. We analysed Li, Be, B, Sr, Y, Zr, Nb, Ba, Ce, Nd, Sm,Pb, Th and U in coexisting phases by laser ablation microprobeinductively coupled plasma mass spectrometry. Many of the valuesare extremely low; for example, Nb, Ba, Ce, Th and U are inthe lower ppb range in clinopyroxene. Attainment of equilibriumwas evaluated by textural, and major and trace element characteristics.Non-equilibrated assemblages are common in most eclogite localities,including Trescolmen, and using such samples would lead to thederivation of erroneous values for equilibrium partitioning.However, four of the 10 studied eclogites from Trescolmen havinghomogeneous clinopyroxene compositions and preferred orientationof high-pressure phases yielded consistent D^{Min/Clinopyroxene}values in all four samples (where Min indicates amphibole, phengite,paragonite, apatite), and hence were studied in detail. Thelow abundances in some phases result from strong preferentialincorporation of trace elements into other minor phases. Fromthe investigated hydrous phases (amphibole, zoisite, clinozoisite,phengite, paragonite, apatite and talc), zoisite was found tobe the most important carrier of Sr, light rare earth elements,Pb, Th and U, whereas phengite hosts Ba and is, along with clinopyroxeneand paragonite, an important phase for B. However, because oftheir low modal abundance in eclogite-facies rocks, phengiteand paragonite do not control the B whole-rock budget. We inferthat estimated D^{Min/Clinopyroxene} values from equilibrium assemblagescan be used as a good approximation for partition coefficientsunder the given PT conditions (     

Natural staurolite breakdown reactions at moderate to high pressures

Existing staurolite breakdown reactions are briefly discussed and examples of each of the main types suggested from textural evidence from different well studied areas are analyzed. From the staurolite textural data, it is shown that: the pseudomorphic replacement is generally equal area; the replacement is usually by a single mineral or, where a number occur, one volumetrically greatly predominates; and successive reaction coronas exist around a single reactant grain. The analogy between the textural coronas and “monomineralic zones” at the contact of dissimilar rock types is drawn with the subsequent inference that reaction coronas in some, if not most, cases are out of equilibrium with the rest of the assemblage as well as the reactant mineral. In staurolite reaction textures, different grains in a single thin section normally have: different amounts (ratios) of product minerals, different product minerals, some grains which have reacted while others have not and different grains which have reacted to different degrees. Traverses of essentially total chemical analyses across staurolite grains in two test sections showed that considerable intertextural chemical variation in single thin sections exist which is much greater than the chemical variations within textures. Variations of, from 0.59 to 1.86 weight percent ZnO in different homogeneous staurolite grains occur in a single thin section (Z-5670911) and measurable variations of Si, Al, Fe, Mg and Mn are recorded. In all the textures analyzed both Zn and Al was deficient on the product side of balanced reactions, and particularly Zn can be shown to have been lost from the area of the section. The chemical and textural conclusions show that the limits of equilibrium systems, from which metamorphic reactions can be inferred, must be confined to the boundaries of the pseudomorphic texture, which means that ionic (complex bearing ?) species are involved and these systems must be treated as being open.     

A Clinopyroxene Paragenesis of Albite--Epidote--Amphibolite Facies in Meta-Syenites from the South-East Tauern Window, Austria

Mineral assemblages and textures are described from clinopyroxene-bearingmeta-syenites and related rocks from a small area in the PenninicBasement Complex of the south-east Tauern Window. Evidence from mineral textures, mineral compositions and geobarometryindicate that the clinopyroxene, a sodic salite, crystallizedas part of an equilibrium albite-epidote-amphibolite faciesparagenesis in the 35–40 Ma meso-Alpine metamorphic event.Phase relations in co-facial quartz + albite + K-feldspar +sphene-bearing meta-syenites and meta-granites are examinedusing a projection from these minerals onto the plane (A1₂O₃+ Fe₂O₃)-CaO-(MgO + FeO + MnO). The projection demonstratesthat salitic clinopyroxene can only be a stable phase in suchrocks if the bulk-rock Al/Na + K ratios are low. This is confirmedby comparing the whole-rock analyses of clinopyroxene-bearingmeta-syenites with those of clinopyroxene-free meta-syenitesand meta-granites. Mineral assemblages in a variety of lithologies from the south-eastTauern Window are used to construct a generalized AKM diagramfor magnesian albite + epidote + quartz-bearing rocks of thealbite-epidote-amphibolite facies. Thermochemical calculations indicate that the meta-syeniteswere metamorphosed at temperatures close to 500 C and at a pressureof 6+2 –4 kb. Fluids in equilibrium with meta-syeniteand meta-granite mineral assemblages had X_H2O values of 0–95,assuming X_H2O + X_CO2O= 1.0.     

Reaction of zoning of garnet

Compositional zoning of garnet in metamorphic or igneous rocks preserves evidence of the equilibration history of the sample and can be interpreted in terms of a growth-fractionation, diffusion-exchange, or diffusion-reaction model. Diffusion zoning is usually assumed to result from exchange reactions between garnet and other phases as the partitioning coefficient varies in response to changing environmental conditions, primarily temperature. However, in many natural environments where garnet grew originally in divariant equilibrium with other phases, changing conditions can promote continuous or “divariant” reactions and consequent compositional shifts of phases that can be much greater in some systems showing these reactions than those related to the small changes of partitioning. Diffusional zoning related to overstepping of these continuous reactions must be related to incongruent reaction and necessitates formulation of a kinetic diffusion-reaction model involving moving phase boundaries as well as solid-state diffusion. Three samples containing zoned garnets from the metamorphic aureole around the Ronda ultramafic intrusion in southern Spain are used to illustrate two possible models of diffusion-reaction processes. The examples are particularly informative because the reactions are demonstrably irreversible and evidence of the reaction system is preserved. Partitioning data indicates that compositions of product phases are not in equilibrium with the original garnet and do not vary with extent of reaction; therefore, exchange reactions with garnet were not possible and garnet changed composition only by incongruent reaction. After a small amount of reaction, Mg/Fe of the rim composition approaches a value apparently in equilibrium with product phases, but the garnets are zoned inward to the original garnet composition preserved in the interior. Grossularite content is approximately constant and spessartite content variable but small, thus, the rim composition of pyrope or almandine is assumed to be fixed by the external reaction process and is taken as a boundary condition in the following models. The zoning profile of pyrope or almandine component between the fixed rim and core compositions (assumed to extend to ∞) is described in semiinfinite, half-space models appropriate for large garnets with narrow rims. The first model corresponds to a reaction system in which all garnet compositions are metastable (case 1) and zoning depends on the independent variables of the diffusion constant, velocity of the interface between garnet and matrix, and time. The second model, corresponding to systems in which the initial garnet composition is metastable but an equilibrium composition is stable (case 2), depends on the independent variables diffusion constant, time, and a function of reaction compositions. In case 1 the consumption velocity is assumed constant and a steady state zoning profile is reached at large time, whereas, in case 2, the velocity decreases with the concentration gradient and steady state is not possible. The models were tested using a reaction time estimated from cooling models of the aureole, mass of garnet consumed, determined petrographically, and phase compositions. The two cases are somewhat independent in that different parameters are independent variables. The estimate of the diffusion constant of 10^?18±2 cm²/sec (assumed to be a mutual or binary coefficient for almandine and pyrope) is considered reasonable for the temperature range of reaction (probably 600–900° C), and the two models are consistent considering the probable error and possible real temperature differences. It is obvious that details of the metamorphic reaction system must be known to successfully apply diffusion models. Kinetic models, involving consumption or growth of the phase as well as diffusion are probably necessary when dealing with natural rocks. Several possible and interesting complications, such as cross coupling between components, can be investigated if more data were available. Experimental determination of diffusion constants allow natural reaction rates to be estimated by this method. Diffusion zoning is an important consideration that could increase the efficiency of experimentation with chemically recalcitrant phases.     

Matrix analysis of metamorphic mineral assemblages and reactions

Assemblage diagrams are widely used in interpreting metamorphic mineral assemblages. In simple systems, they can help to identify assemblages which may represent equilibrium states; to determine whether differences between assemblages reflect changes in metamorphic grade or variations in bulk composition; and to characterize isograd reactions. In multicomponent assemblages these questions can be approached by investigating the rank, composition space (range) and reaction space (null-space) of a matrix representing the compositions of the phases involved. Singular value decomposition (SVD) provides an elegant way of (1) finding the rank of a matrix and detemining orthonormal bases for both the composition space and the reaction space needed to represent an assemblage or pair of assemblages; and (2) finding a model matrix of specified rank which is closest in a least squares sense to an observed assemblage. Although closely related to least squares techniques, the SVD approach has the advantages that it tolerates errors in all observations and is computationally simpler and more stable than non-linear least squares algorithms. Models of this sort can be used to interpret multicomponent mineral assemblages by straightforward generalizations of the methods used to interpret assemblage diagrams in simpler systems. SVD analysis of mineral assemblages described by Lang and Rice (1985) demonstrates the utility of the approach.