The Four-Phase AFM Assemblage Staurolite--Aluminum Silicate--Biotite--Garnet: Extra Components and Implications for Staurolite--Out Isograds

The prograde disappearance of staurolite can be described inthe model system K₂O-FeO-MgO-Al₂O₃-SiO₂-H₂O (KFMASH) by thereaction: staurolite + muscovite + quartz = biotite + aluminumsilicate + garnet + water. The common occurrence and world—widedistribution of the assemblage staurolite-biotite-aluminum silicate-garnet(SBAG) in quartz-mica-schist suggest that the model reactionmay be over-simplified. Previous workers have suggested thatthe SBAG assemblage (1) is a strictly divariant assemblage thatbuffered water activity, (2) is stabilized by non-KFMASH components,and (3) did not attain equilibrium. We used least-squares regression to show that balanced reactionsdo not exist among the minerals in samples of SBAG assemblagesfrom Califonia and New England. The absence of reaction relationshipscan be explained by imbalances in two or three of the minorelements Zn, Mn, and either Ca or Na. The assemblage is apparentlystabilized by non-KFMASH components. Criteria for mapping staurolite-out isograds that representthe conditions of the KFMASH staurolite-out reaction dependon which of the four phases is the ‘extra’ phase,and require an understanding of the thermodynamic effects ofall the ‘extra’ components. Our results suggestthat transition zones of SBAG assemblages near staurolite-outisograds are the result of ‘extra’ components. However,it is uncertain whether µH²O of fluids in equilibriumwith SBAG assemblages varied across such zones.     

Mineral Compositions and Equilibria in the Metamorphosed Iron Formation of the Gagnon Region, Quebec, Canada

Forty-seven specimens of the Wabush Iron Formation were collectedfrom ten outcrop areas. Twenty-five specimens contain the assemblage(1), quartz+clinopyroxene+calcite with or without orthopyroxene,grunerite, magnetite, ankerite, and siderite. Five specimenscontain assemblage (2), quartz+clinopyroxene+actinolite+calcite+magnetite+hematite,and two contain assemblage (3), quartz+orthopyroxene+actinolite+magnetite+hematite.In three specimens of assemblage (1), graphite occurs in theabsence of magnetite; pyrrhotite and pyrite occur separatelyor together in specimens with assemblage (1). Thirty-nine clinopyroxenes, 38 orthopyroxenes, 18 grunerites,7 actinolites, 16 calcites, 1 ankerite, and 1 siderite wereanalyzed for iron, manganese, and calcium by X-ray emissionspectrography. Magnesium contents were estimated by assumingstoichiometric proportions. Minerals occurring with hematite show low Fe/(Fe+Mg) ratios,and those in the other assemblages show higher values with awide range of variation. In orthopyroxene, Fe/(Fe+ Mg) rangesfrom 0·17 (with hematite) to 0·77. Regularity in the distributions of Fe, Mn, and Ca between pairsof coexisting minerals shows that equilibrium was attained inmost of the rocks studied. This regularity is also accomplishedin the distribution of Mn between calcite and coexisting silicatesas well as between the silicates themselves. Small differencesin the distributions of Ca and Fe depend on both outcrop areaand mineral assemblage. Phase rule considerations suggest that the specimens with dolomite-ankeriteor magnesitesiderite do not represent equilibrium assemblages.Variations in orthopyroxene compositions in assemblages withpyrite or pyrrhotite, or both, and magnetite indicate non-equilibrationof sulfides with silicates. The presence of the oxygen buffer,magnetite+hematite, attests to the immobility of oxygen duringmetamorphism. Within each outcrop area, over which the temperature and pressureare assumed to have been uniform, variations in the compositionsof the silicates in the sub-assemblages quartz+ orthopyroxene+gruneriteand quartz+orthopyroxene+clinopyroxene+calcite indicate gradientsof µ_H2O µ_CO2 and respectively. As characterizedby the composition of orthopyroxene, both gradients are relativelylow along strike, and high across strike. The direction of gradientsacross strike is almost without reversals, which is consistentwith intergranular diffusion of H₂O and CO₂. Phase rule restrictionsfor a majority of assemblages are not in accord with the simultaneousimposition of µ_H2O and µ_CO2 gradients on the rocks,nor the formation of an H₂O-CO₂ fluid phase during metamorphism.     

Granulite-Facies Metamorphism at Molodezhnaya Station, East Antarctica

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

Transition from the Zeolite to Prehnite-Pumpellyite Facies in the Karmutsen Metabasites, Vancouver Island, British Columbia

The upper Triassic Karmutsen metabasites from northeast VancouverIsland, B.C., are thermally metamorphosed by the intrusion ofthe Coast Range Batholith. The amygdaloidal metabasites developedin the outer portion of the contact aureole show a progressivemetamorphism from zeolite to prehnite-pumpellyite facies. Thesize of an equilibrium domain is extremely small for these metabasites,and the individual amygdule assemblages are assumed to be inequilibrium. Two major calcite-free assemblages (+chlorite+quartz)are characteristic: (i) laumontite+pumpellyite+epidote in thezeolite facies and (ii) prehnite+pumpellyite+epidote in theprehnite-pumpellyite facies. The assemblages and compositionsof Ca-Al silicates are chemographically and theoretically interpretedon the basis of the predicted P-T grid for the model basalticsystem, CaO-MgO-A1₂O₃-Fe₂O₃-SiO₂-H₂O. The results indicate:(1) local equilibrium has been approached in mineral assemblagesand compositions; (2) the X_Fe³⁺ values in the coexisting Ca-Alsilicates decrease from epidote, through pumpellyite to prehnite;(3) with increasing metamorphic grade, the Fe³⁺ contents ofepidotes in reaction assemblages decrease in the zeolite facies,then increase in the prehnite-pumpellyite facies rocks. Suchvariations in the assemblages and mineral compositions are controlledby a sequence of continuous and discontinuous reactions, andallow delineation of T-X_Fe³⁺ relations at constant pressure.The transition from the zeolite to prehnite-pumpellyite faciesof the Karmutsen metabasites is defined by a discontinuous reaction:0·18 laumontite+pumpellyite+0·15 quartz = 1·31prehnite+ 0·78 epidote+0·2 chlorite+ 1·72H₂O, where the X_Fe³⁺ values of prehnite, pumpellyite and epidoteare 0·03, 0·10 and 0·18, respectively.These values together with available thermodynamic data andour preliminary experimental data are used to calculate theP-T condition for the discontinuous reaction as P = 1·1±0·5 kb and T = 190±30°C. The effectsof pressure on the upper stability of the zeolite facies assemblagesare discussed utilizing T-X_Fe³⁺ diagrams. The stability of thelaumontite-bearing assemblages for the zeolite facies metamorphismof basaltic rocks may be defined by either continuous or discontinuousreactions depending on the imposed metamorphic field gradient.Hence, the zeolite and prehnite-pumpellyite facies transitionboundary is multivariant.     

The Mineralogy and Petrology of the Transition from the Lower to Upper Sillimanite Zone in the Oquossoc Area, Maine

Systematic changes in the assemblages and compositions of mineralssuggest that the transition from lower to upper sillimanitezone in the Oquossoc area, Maine, is marked by the reaction Staurolite+Sodic Muscovite+QuartzSillimanite+Biotite+K-richerMuscovite+Albite+Garnet+H₂O. Moreover, the mineralogic data for the silicates suggest thatH₂ O is buffered by some of the assemblages present but PH₂O<P_total. A consideration of the equilibria among the opaqueminerals enables a calculation of the composition of the fluidphase assuming specific PT conditions and that P_fluid = P_total.At several reasonable PT conditions the calculated fluid phaseis reasonable in terms of the model for P_H2O based upon thesilicate equilibria. Probable PT conditions for the metamorphism considered in thisstudy range from 575 to 630°C and 3 to 5 kb.     

A North-South Transect across the Central Mexican Volcanic Belt at ~100{degrees}W: Spatial Distribution, Petrological, Geochemical, and Isotopic Characteristics of Quaternary Volcanism

Within the Zitácuaro–Valle de Bravo (ZVB) regionof the central Mexican Volcanic Belt (MVB), three lava serieshave erupted during the Quaternary: (1) high-K₂O basaltic andesitesand andesites; (2) medium-K₂O basaltic andesites, andesitesand dacites; (3) high-TiO₂ basalts and basaltic andesites. Thedominant feature of the first two groups is the lack of plagioclaseaccompanying the various ferromagnesian phenocrysts (olivine,orthopyroxene, augite, and hornblende) in all but the dacites.This absence of plagioclase in the phenocryst assemblages ofthe high-K₂O and medium-K₂O intermediate lavas is significantbecause it indicates high water contents during the stage ofphenocryst equilibration. In contrast, the high-TiO₂ group ischaracterized by phenocrysts of plagioclase and olivine. Thespatial distribution of these three lava series is systematic.The southern section of the ZVB transect, 280–330 km fromthe Middle America Trench (MAT), is characterized by high-K₂Omelts that are relatively enriched in fluid-mobile elementsand have the highest ⁸⁷Sr/⁸⁶Sr ratios. Medium-K₂O basaltic andesiteand andesite lavas are present throughout the transect, butthose closest to the MAT are MgO-rich (3·5–9·4wt %) and have phenocryst assemblages indicative of high magmaticwater contents (3·5–6·5 wt % water) andrelatively low temperatures (950–1000°C). In markedcontrast, the northern section of the ZVB transect (380–480km from the MAT) has high-TiO₂, high field strength element(HFSE)-enriched magmas that have comparatively dry (< 1·5wt % magmatic water) and hot (1100–1200°C) phenocrystequilibration conditions. The central section of the ZVB transect(330–380 km from the MAT) is a transition zone and producesmoderately light rare earth element (LREE) and large ion lithophileelement (LILE)-enriched, medium-K₂O lavas with phenocryst assemblagesindicative of intermediate (1·5–3·5 wt %)water contents and temperatures. The high-K₂O series compositionsare the most enriched in LILE and LREE, with a narrow rangeof radiogenic ⁸⁷Sr/⁸⁶Sr from 0·704245 to 0·704507,¹⁴³Nd/¹⁴⁴Nd values ranging from 0·512857 to 0·512927(_Nd = 4·27–5·63), and ²⁰⁸Pb/²⁰⁴Pb valuesfrom 38·248 to 38·442, ²⁰⁷Pb/²⁰⁴Pb values from15·563 to 15·585, and ²⁰⁶Pb/²⁰⁴Pb values from18·598 to 18·688. The medium-K₂O series compositionsare only moderately enriched in the LILE and LREE, with a broaderrange of ⁸⁷Sr/⁸⁶Sr, but similar ¹⁴³Nd/¹⁴⁴Nd and ²⁰⁸Pb/²⁰⁴Pbvalues to those of the high-K₂O series. In contrast, the high-TiO₂series compositions have little enrichment in LILE or LREE andinstead are enriched in the HFSE and heavy rare earth elements(HREE). The high-TiO₂ lavas are isotopically distinct in theirlower and narrower range of ¹⁴³Nd/¹⁴⁴Nd. The isotopic variationsare believed to reflect the upper mantle magma source regionsas the low content of phenocrysts in most lavas precludes significantupper crustal assimilation or magma mixing, other than thatrepresented by the presence of quartz xenocrysts (< 2 vol.%) with rhyolitic glass inclusions, which are found in manyof these lavas. The systematic spatial variation in compositionof the three lava series is a reflection of the underlying subduction-modifiedmantle and its evolution. KEY WORDS: central Mexico; geochemistry; isotopes; Quaternary volcanism; hydrous lavas     

Metamorphism of Calcareous Rocks in Three Roof Pendants in the Sierra Nevada, California

Two roof pendants in the Hope Valley area, Alpine County, containabundant calc-silicate assemblages which can be related to univariantor invariant equilibria in the CaO-Al₃O₃-SiO₂-H₂O-CO₂ system.Such assemblages are considered to represent components of reactionsthat buffered the chemistry of the pore fluid. Through dataobtained from microprobe analysis it is concluded that solidsolution in plagioclase, garnet, and clinozoisite are importantvariables such that on a TXco₂ projection each sample had aunique path during metamorphism. Differences in the plagioclasecomposition of nearby samples with assemblages related by thereaction: grossularite_(s.s)+quartz = anorthite_(s.s.)+wollastonite, suggest unique equilibration temperatures for assemblages inlocal domains. In the Twin Lakes pendant in Fresno County, thereaction: clinohumite+calcite+CO₂= 4forsterite+dolomite+H₂O, is importantin magnesian marbles. Contrasting parageneses, which are relatedby this equilibrium, are considered to reflect variations influid composition. Constrasting assemblages in calc-silicaterocks, which are linked by the reactions: calcite+quartz= wollastonite+CO₂, tremolite+calcite= dolomite+diopside+CO₂+H₂O, exist down to the scale of a thin section. Variation in Ti contentof idocrase may be an important factor in assemblages linkedby reactions involving this phase. This study suggests that during contact metamorphism of calcareousrocks in the Sierra Nevada, H₂O and CO₂ behaved as ‘initialvalue components’ (Zen, 1963) whose activities were controlledby reactions withion local systems.     

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

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

Phase Equilibria of Amphibolites from the Post Pond Volcanics, Mt. Cube Quadrangle, Vermont

Amphibolites of the Post Pond Volcanics, south-west corner ofthe Mt. Cube Quadrangle, Vermont, are characterized by a greatdiversity of bulk rock types that give rise to a wide varietyof low-variance mineral assemblges. Original rock types arebelieved to have been intrusive and extrusive volcanics, hydrothermallyaltered volcanics and volcanogenic sediments with or withoutadmixtures of sedimentary detritus. Metamorphism was of staurolite-kyanitegrade. Geothermometry yields a temperature of 535 ± 20°C at pressures of 5–6 kb. Partitioning of Fe and Mg between coexisting phases is systematic,indicating a close approach to chemical equilibrium was attained.Relative enrichment of Fe/Mg is garnet > staurolite >gedrite > anthophyllite cummingtonite hornblende > biotite> chlorite > wonesite > cordierite dolomite > talc;relative enrichment in Mn/Mg is garnet > dolomite > gedrite> staurolite cummingtonite > hornblende > anthophyllite> cordierite > biotite > wonesite > chlorite >talc. between coexisting amphiboles varies as a function ofbulk Fe/Mg, which is inconsistent with an ideal molecular solutionmodel for amphiboles. Mineral assemblages are conveniently divided into carbonate+ hornblende-bearing, hornblende-bearing (carbonate-absent)and hornblende-absent. The carbonate-bearing assemblages allcontain hornblende + dolomite+ calcite + plagioclase (andesineand/or anorthite) + quartz with the additional phases garnetand epidote (in Fe-rich rocks) and chlorite ± cummingtonite(in magnesian rocks). Carbonate-bearing assemblages are restrictedto the most calcic bulk compositions. Hornblende-bearing (carbonate absent) assemblages occur in rocksof lower CaO content than the carbonate-bearing assemblages.All of these assemblages contain hornblende + andesine ±quartz + Fe-Ti oxide (rutile in magnesian rocks and ilmenitein Fe-rich rocks). In rocks of low Al content, cummingtoniteand two orthoamphiboles (gedrite and anthophyllite) are common.In addition, garnet is found in Fe-rich rocks and chlorite isfound in Mg-rich rocks. Several samples were found that containhornblende + cummingtonite + gedrite + anthophyllite ±garnet +chlorite + andesine + quartz + Fe-Ti oxide ±biotite. Aluminous assemblages contain hornblende + staurolite+ garnet ± anorthite/bytownite (coexisting with andesine)± gedrite ± biotite ± chlorite ±andesine ± quartz ± ilmenite. Hornblende-absentassemblages are restricted to Mg-rich, Ca-poor bulk compositions.These rocks contain chlorite ± cordierite ± staurolite± talc ± gedrite ± anthophyllite ±cummingtonite ± garnet ± biotite ± rutile± quartz ± andesine. The actual assemblage observeddepends strongly on Fe/Mg, Ca/Na and Al/Al + Fe + Mg. The chemistry of these rocks can be represented, to a firstapproximation, by the model system SiO₂–Al₂O₃–MgO–FeO–CaO–Na₂O–H₂O–CO₂;graphical representation is thus achieved by projection fromquartz, andesine, H₂O and CO₂ into the tetrahedron Fe–Ca–Mg–Al.The volumes defined by compositions of coexisting phases filla large portion of this tetrahedron. In general, the distributionof these phase volumes is quite regular, although in detailthere are a large number of phase volumes that overlap otherphase volumes, especially with respect to Fe/Mg ratios. Algebraicand graphical analysis of numerous different assemblages indicatethat every one of the phase volumes should shift to more magnesiancompositions with decreasing µ_H2O. It is therefore suggestedthat the overlapping phase volumes are the result of differentassemblages having crystallized in equilibrium with differentvalues of µ_H2O or µ_CO2 and that the different valuesmay have been inherited from the original H₂O and CO₂ contentof the volcanic prototype. If true, this implies that eithera fluid phase was not present during metamorphism, or that fluidflow between rocks was very restricted.     

The Distribution of H2O between Cordierite and Granitic Melt: H2O Incorporation in Cordierite and its Application to High-grade Metamorphism and Crustal Anatexis

Experiments defining the distribution of H₂O [D_w = wt % H₂O(melt)/wt% H₂O(crd)]) between granitic melt and coexisting cordieriteover a range of melt H₂O contents from saturated (i.e. coexistingcordierite + melt + vapour) to highly undersaturated (cordierite+ melt) have been conducted at 3–7 kbar and 800–1000°C.H₂O contents in cordierites and granitic melts were determinedusing secondary ion mass spectrometry (SIMS). For H₂O vapour-saturatedconditions D_w ranges from 4·3 to 7 and increases withrising temperature. When the system is volatile undersaturatedD_w decreases to minimum values of 2·6–5·0at moderate to low cordierite H₂O contents (0·6–1·1wt %). At very low aH₂O, cordierite contains less than 0·2–0·3wt % H₂O and D_w increases sharply. The D_w results are consistentwith melt H₂O solubility models in which aH₂O is proportionalto X_w² (where X_w is the mole fraction of H₂O in eight-oxygenunit melt) at X_w     

Phase Equilibria of Margarite-Bearing Schists and Chloritoid + Hornblende Rocks from Western New Hampshire, USA

A variety of uncommon garnet-grade assemblages have been foundin rocks from three outcrops in the western part of centralNew Hampshire, and include the associations Grt+MrgCld, Grt+Bt+CldMrg,and Mrg+Cld+HblGrt (all rocks contain Ms, Chl, Ilm, and Qtz).These unusual rocks coexist with more typical Grt+Bt+Chl+Plmetapelites and amphibolites. Rim P–T conditions are {smalltilde}49035C and 5•751•25 kbar. Projection of the assemblages from Qtz, H₂O, and Ilm into theCa–Al'–Na–(Fe+Mg) tetrahedron, and from Qtz,Ilm, H₂O, and Chl into the Ca–Al'–Fe'–Mn tetrahedronindicates that Ca/(Ca+Na) and Mn differ among the assemblagesin a systematic fashion. Common Grt+Bt+Chl+Pl assemblages arerestricted to relatively high Mn and low Ca/(Ca+Na) values,whereas Cld+Bt+Mrg and Cld+Hbl+Mrg assemblages are stable atlow Mn and high Ca/(Ca+Na). These data suggest that at thisgrade Cld+Bt is more stable than Grt+Chl in the KFMASH system,whereas in the Ca—KFMASH system, Hbl+Cld assemblages arestable. Composition space analysis using the singular value decompositionmethod indicates that compositions of minerals from individualsamples are consistent with local equilibrium, but that differentoutcrops may not have all equilibrated at the same P–T–a_H2Oconditions. Thermodynamic analysis suggests that a garnet-zoneprograde sequence of ferromagnesian associations for these bulkcompositions would be Hbl+Cld+Grt+ChlBt+Cld+Grt+ChlBt+Grt+Chl. Staurolite-grade rocks from the same stratigraphic units areexposed across strike, and contain the assemblage Grt+StBtPl(all rocks contain Ms, Qtz, Chl, and Ilm). Margarite is commonlypresent as inclusions in the cores of garnets, but is absentas inclusions near garnet rims and from the matrix; conversely,staurolite inclusions are present towards the rims of the garnets,but are absent from the cores. These inclusion relations suggestthat margarite may react to form staurolite and garnet withincreasing grade via a reaction such as chlorite+margarite=staurolite+garnet+H₂O. Biotite is common in the matrix but is not typically abundant,and appears to have been the last phase to join the assemblage.Biotite is inferred to have joined the Grt+St+Chl assemblagesafter margarite breakdown through the reaction Grt+Chl+Ms=St+Bt+H₂O. Thus, uncommon margarite assemblages may evolve into commonGrt+Bt+St+Chl assemblages. ^* Present address: Department of Geology and Geophysics, University of Wisconsin-Madison, Madison, Wisconsin 53706.     

The Graphical Analysis of Greenschist to Amphibolite Facies Mineral Assemblages in Metabasites

The mineral assemblages of greenschist to amphibolite faciesmetabasites may usually be represented in a system of principalcomponents: CaO-Al₂O₃-(Fe₂O₃)-FeO-MgO-Na₂O-SiO₂-C0₂-H₂O Assemblages co-existing with quartz, ‘albite’, ‘epidote’and a fluid of restricted composition, may be shown by projectionin a CAFM subsystem from ‘epidote’ onto an extendedAFM plane. This projection is analogous to the Thompson projectionfor pelites and is particularly useful in displaying the effectsof Fe/Mg and Al substitution in the silicates as well as incorporatingCaO; it is illustrated by plotting assemblages from the SouthernAlps of New Zealand and the Scottish Highlands and demonstrateschanges occurring with grade in the assemblages. Some commonisograds and facies boundaries are seen to be strongly dependenton bulk rock composition. In some cases MnO must be consideredas an additional component. A model of P_solid=P_fluid, where the fluid is composed of CO₂+H₂Ois consistent with many greenschist to amphibolite facies metabasicassemblages. Natural assemblages indicate this fluid phase tohave restricted mobility. Theoretical consideration of mineralreactions resulting from increasing X_CO2 in conjunction withdata from natural mineral assemblages, leads to the distinctionof five principal types of assemblage which may be expectedas a function of varying X_CO2. Recognition of these assemblagetypes provides a useful guide to relative X_CO2 during metamorphism.     

The Formation of Chrysoberyl in Metamorphosed Pegmatites

Mineral assemblages in pegmatite samples from Kolsva, Swedenand Marikov, Czechoslovakia show that chrysoberyl is alwaysaccompanied by quartz, and is a breakdown product of primarypegmatitic beryl. Textures and the mineral-forming process forthe Kolsva pegmatite are explained by the reactions beryl +K-feldspar + H+ = chrysoberyl + quartz + SiO_{2, aq} + K⁺ + H₂Oor alternatively beryl —K—feldspar + H₂O = chrysoberyl+ quartz + melt. Mineral assemblages from mica-rich parts ofthe pegmatite include sillimanite—K—feldspar, muscovite—K—feldspar—sillimanite,and annite—magnetite—spinel—sillimanite—garnet.Details about the composition and the textural relationshipsof these minerals are given; they indicate a post-pegmatiticmetamorphic event at P—T conditions near to the anatecticregime. The samples from Marikov show textures, which are explainedby the reactions beryl + albite + H⁺ = chrysoberyl + quartz+ Na⁺ + H₂O or alternatively beryl + albite + H₂O = chrysoberyl+ quartz + melt. Breakdown of muscovite produces sillimaniteaccording to the reactions beryl + albite + muscovite + H⁺ =chrysoberyl + quartz + sillimanite + Na⁺ + K⁺ + H₂O or alternativelyberyl + albite + muscovite + H₂O = chrysoberyl + quartz + sillimanite+ melt. Similar reaction textures and mineral assemblages were foundin other chrysoberyl-bearing pegmatites (Maroankora, Madagascar;Helsinki, Finland; Haddam, Greenfield, Greenwood, U.S.A.). Hydrothermal experiments located the reaction beryl + alkalifeldspar + H₂O = chrysoberyl + phenakite + melt at P—Tconditions between the K—feldspar—quartz—H₂Osolidus and the K—feldspar—albite—quartz-H₂Osolidus. It is concluded that the formation of Al-rich minerals likechrysoberyl and sillimanite in pegmatites is due to a post-pegmatiticevent at high P—T conditions. The question as to whichof the alternative set of reactions is more likely, the ionicequilibria or the anatectic chrysoberyl formation, must be leftopen. The previous hypothesis of a desilification of a pegmatitewhich intruded into SiO₂-poor country rocks, or of the assimilationof Al₂O₃-rich country rocks, cannot explain the mineral assemblagesof the two pegmatites.     

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.     

Volatiles in Submarine Basaltic Glasses from the Northern Kerguelen Plateau (ODP Site 1140): Implications for Source Region Compositions, Magmatic Processes, and Plateau Subsidence

Submarine pillow basalts (34 Ma) recovered from the NorthernKerguelen Plateau at ODP Site 1140 contain abundant unalteredglass, providing the first opportunity to measure the volatilecontents of tholeiitic basaltic magmas related to the Kerguelenmantle plume. The glasses have La/Sm and Nb/Zr ratios that varyfrom values similar to Southeast Indian Ridge (SEIR) MORB (Unit1), to slightly more enriched (Unit 6), to values transitionalbetween SEIR MORB and basaltic magmas formed by melting of theKerguelen plume (Units 2 and 3). Volatile contents for glassesin Units 1 and 6 are similar to depleted mid-ocean ridge basalt(MORB) values (0·25–0·27 wt % H₂O, 1240–1450ppm S, 42–54 ppm Cl). In contrast, H₂O contents are higherfor the enriched glasses (Unit 2, 0·44 wt % H₂O; Unit3, 0·69 wt %), as are S (1500 ppm) and Cl (146–206ppm). Cl/K ratios for all glasses are relatively low (0·03–0·04),indicating that assimilation of hydrothermally altered materialdid not occur during shallow-level crystallization. H₂O/Ce forthe enriched glasses (Units 2 and 3) is significantly lowerthan Pacific and South Atlantic MORB values, suggesting thatlow H₂O/Ce may be an inherent characteristic of the Kerguelenplume source. Vapor saturation pressures calculated using theH₂O and CO₂ contents of the glasses indicate that     

Low-Temperature, Low-Pressure Metamorphism of Mn-rich Rocks in the Lienne Syncline, Venn--Stavelot Massif (Belgian Ardennes), and the Role of Carpholite

Low-grade Mn-rich metamorphic rocks of the Lienne syncline (westernpart of the Venn–Stavelot Massif, Belgian Ardennes) havebeen re-examined to evaluate the petrological significance ofcarpholite proper, Mn^2$ Al₂[Si₂O₆](OH)₄. Metamorphic P–Tconditions of these rocks are estimated to be {small tilde}300C1–2 kbar, which is in accordance with the exclusive occurrenceof carpholite in low-P rocks such as hydrothermal environmentselsewhere. Carpholite of the Lienne syncline exclusively occursin quartz-rich segregations. Its composition is close to end-member.Thermodynamic calculations confirm that carpholite is a stablephase at low-pressure–low-temperature conditions, in contrastto ferro- and magnesiocarpholite, which are high-pressure minerals.No information is available on the high-P behaviour of carpholite.The occurrence of carpholite is partly closely associated withspessartine-bearing country rocks, or carpholite is alteredto assemblages with spessartine, sudoite, chlorite, muscoviteand paragonite. Spessartine in these rocks contains minor amountsof hydrogarnet component {(H/4)/[Si$(H/4)] = 0.03–0.06}.The presence of carpholite-spessartine assemblages in theselow-P rocks is in contrast to high-pressure metamorphic rocksfrom other areas, where parageneses such as fem/magnesiocarpholite–chloritoidor magnesiocarpholite–chlorite–kyanite occur. Theappearance of carpholite–garnet assemblages in low-P Mn-richrocks can be explained by contrasting phase relations becauseof a high Mn–Mg partition coefficient between the mineralsunder consideration. In rhodo-chrosite-bearing veins in theLienne syncline, nearly complete replacement of carpholite byspessartine and chlorite is due to the continuous reaction carpholite$ rhodochrosite $ quartz = spessartine $ chlorite $ H₂O $ CO₂,which defines a very low X_co, in the temperature range underconsideration. It is suggested that spessartine (possibly containingsome hydrogarnet component), during prograde metamorphism atlow pressure, becomes stable at a temperature of {small tilde}300C KEY WORDS: carpholite; spessartine; sudoite; Venn–Stavelot Massif; Ardemes ^*Corresponding author. Fax: x49/531/3918131. e-mail: t.theye{at}tu.bs.de     

Progressive Regional Metamorphism of Thin Calcareous Bands from the Moinian Rocks of N.W. Scotland

Bands and pods of calc-silicate rock a few centimetres thickare widely distributed throughout the Late Precambrian Moiniansequence in N.W. Scotland. They probably originated as late-diageneticcalcareous concretions and were subsequently affected by greenschistto upper middle amphibolite facies (Barrovian) regional metamorphismduring the Caledonian (s.l.) orogeny. The calc-silicate rocks described here are from Inverness-shirein the Western Highlands of Scotland. Distinctive prograde mineralassemblages define four narrow zones which run broadly north-southand increase in grade eastwards. Plagioclase composition changesprogressively from albite to near anorthite with increasinggrade and, together with the presence or absence of zoisitebiotite, and hornblende, is the basis of the zonal divisions.Zoisite Ca₂(Al_0.96, Fe_0.04)₃Si₃O₁₂(OH) with biotite is commonin the lower zones and plagioclase ‘jumps’ in compositionfrom calcic andesine to bytownite with the exit of all, or mostof, the zoisite. Similarly biotite-bearing assemblages giveway to those containing ferro-horn-blende and/or pyroxene. Almandinegarnet with approximately 30–40 per cent grossular ispresent throughout and clinozoisite becomes more common in thehigher grade assemblages. Three main episodes of folding (F1–F3) are recognizedin the area, with the calc-silicate assemblages having developedduring the second deformation (MS2) and immediately followingit (MP2). The metamorphic zones (largely of MP2 age) are foldedby major third folds and there is evidence of widespread superimposed‘retrogression’ of probable MP3 age to the east. New analyses of 21 whole rocks by X.R.F., and of 20 mineralsby microprobe, are presented. AI₂O₃ content varies over a smallrange in the whole rock analyses and aluminium is used as astandard for comparing variations in the other elements. CaO/Al₂O₃ratios show little variation but a progressive decrease in Na₂O/Al₂O₃and K₂O/Al₂O₃ with increasingly calcic plagioclase composition(as assessed by measurements on separated fractions), and hence with metamorphic grade, isnoted. Coupled with the fact that the metamorphic zones cross-cutpreviously folded stratigraphic boundaries, this suggests thatboth Na₂O and K₂O have been in part lost from the higher gradecalc-silicate assemblages during progressive metamorphism. Reactions are proposed for the observed mineral changes, andit is concluded that these are most likely achieved by cationexchange through the medium of the pore fluid and result inpartial elimination from the local system of certain elements.No evidence is found that the reaction often quoted as thatresponsible for the exit of zoisite in semi-calcareous rocks,namely 4zo+qtz5an+gross+vap, has taken place.     

The Graphical Analysis of Greenschist to Amphibolite Facies Mineral Assemblages in Metabasites

The mineral assemblages of greenschist to amphibolite faciesmetabasites may usually be represented in a system of principalcomponents: CaO–Al₂O₃–(Fe₂O₃)–FeO–MgO–Na₂O–SiO₂–CO₂–H₂O Assemblages co-existing with quartz, ‘albite’, ‘epidote’and a fluid of restricted composition, may be shown by projectionin a CAFM subsystem from ‘epidote’ onto an extendedAFM plane. This projection is analogous to the Thompson projectionfor pelites and is particularly useful in displaying the effectsof Fe/Mg and Al substitution in the silicates as well as incorporatingCaO; it is illustrated by plotting assemblages from the SouthernAlps of New Zealand and the Scottish Highlands and demonstrateschanges occurring with grade in the assemblages. Some commonisograds and facies boundaries are seen to be strongly dependenton bulk rock composition. In some cases MnO must be consideredas an additional component. A model of P_solids=P_fluid, where the fluid is composed of CO₂+H₂Ois consistent with many greenschist to amphibolite facies metabasicassemblages. Natural assemblages indicate this fluid phase tohave restricted mobility. Theoretical consideration of mineralreactions resulting from increasing X_co2, in conjunction withdata from natural mineral assemblages, leads to the distinctionof five principal types of assemblage which may be expectedas a function of varying X_Co2. Recognition of these assemblagetypes provides a useful guide to relative X_Co2 during metamorphism. ^* Present Address: Department of Geology, University of California, 405 Hilgard Avenue, Los Angeles, California 90024.     

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

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

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

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