Reactions Leading to the Disappearance of Pumpellyite in Low-grade Metamorphic Rocks of the Sanbagawa Metamorphic Belt in Central Shikoku, Japan

The major mineral assemblages of the metabasites of the Omoiji-Nagasawaarea in central Shikoku are hematite+epidote+chlorite+actinolite,riebeckitic actinolite+epidote+chlorite, epidote+chlorite+actinolite,and pumpellyite+epidote+chlorite+actinolite. The constituentminerals are often heterogeneous and assemblages in the fieldof a thin section sometimes do not obey the phase rule, butif grains apparently in non-equilibrium with others are excludedand domains of chemical equilibrium are appropriately chosenthe assemblages approximately obey the phase rule. The stability of hematite, pumpellyite, and epidote associatedwith chlorite and actinolite can be dealt with in terms of aternary system with appropriate excess phases. By fixing theFe²⁺/(Fe²⁺ +Mg) ratio of chlorite, it is dealt with in termsof stability relations in the system Ca₂Al₃Si₃O₁₂(OH)–Ca₂AlFe₂Si₃O₁₂(OH)with excess chlorite, actinolite, quartz, and controlled P_H2O.The maximum and minimum Fe³⁺ contents of epidote in this modelsystem are determined by hematite+epidote+chlorite+actinoliteand pumpellyite+epidote+chlorite+actinolite assemblages. Themaximum Fe³⁺ of the three phase assemblage epidote+chlorite+actinoliteis insensitive to temperature, but the minimum Fe³⁺ contentof epidote is sensitive to temperature and can be used to definethe metamorphic grade by a continuous quantity related to temperature.The phase relations expected for the model system are in goodagreement with the parageneses of the Sanbagawa terrain in centralShikoku and offer an explanation to the rule of Miyashiro &Seki (1958a) that the compositional range of epidote enlargeswith increasing temperature. The model also makes it possibleto estimate semi-quantitatively the temperature range in whichthe assemblage pumpellyite+epidote+chlorite+actinolite is stable.The possible maximum range is about 120 ?C, but the assemblageis stable in metabasite only for about 90 ?C. The higher temperaturelimit of the pumpellyite-actinolite facies defined by the disappearanceof pumpellyite in metabasite corresponds to the temperatureat which epidote with Fe³⁺/(Fe³⁺ +Al) = 0.10 0.15 coexistswith pumpellyite, actinolite, and chlorite. The compositions of epidotes in the metabasites of the Omoiji-Nagasawaarea cluster around Fe³⁺/(Fe³⁺ +Al) = 0.33. The grade of thisarea is close to the lower temperature stability limit of thepumpellyite+epidote+chlorite+actinolite assemblage.     

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.     

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.     

Chloritoid: Its Composition, X-ray and Optical Properties, Stability, and Occurrence

The nomenclature of the chloritoid group, which includes ottrelite,is reviewed. Five new chemical analyses, and all published analysesthat are considered reliable, indicate that the chloritoid groupcan be represented by the general formula H₂FeAI₂SiO₇ with upto two-fifths of the ferrous iron replaced by magnesium, upto one-sixth by manganese, and up to one-seventh of the aluminiumreplaced by ferric iron. Chloritoid crystallizes in both monoclinicand triclinic polymorphs. The triclinic unit cell is one-halfthe monoclinic unit cell. Both polymorphs are widely distributed;they may be distinguished by their X-ray diffraction powderpatterns. In most monoclinic chloritoids the optic plane isnormal to (010), whereas in most triclinic chloritoids it isnearly parallel to (010). Replacement of iron by magnesium lowersthe indices of refraction. With increasing temperatures chloritoid breaks down to ironcordierite+hercynite+vapour at low pressures and to staurolite+almandine+hercynite+vapourat high pressures. Chloritoid was synthesized only at pressuresof about 10,000 bars, but natural chloritoids were stable athigher pressures. At lower pressures chloritoid was not synthesizedbecause of the persistence of a metastable chamosite with a7 ? basal spacing. Natural chloritoids did not decompose belowabout 600? C at these lower pressures. Stress as defined byHarker is not necessary for the growth of chloritoid. Chloritoid-bearing rocks have a high content of alumina relativeto potash, soda, lime, and mafic components, and have more ferrousoxide than magnesium oxide. In pelitic and lateritic sedimentshaving these characteristics, chloritoid is one of the firstnew minerals to form during regional or contact metamorphism.In higher metamorphic grades it is accompanied by cordierite,andalusite, kyanite, or staurolite. It also grows in hydrothermalveins. Various reactions in which chloritoid is produced orconsumed are presented. ¹Present address: Research Council of Alberta, Edmonton, Alberta, Canada.     

A petrogenetic grid for pelitic schists in the system SiO2-Al2O3-FeO-MgO-K2O-H2O

A quantitative petrogenetic grid for pelitic schists in the system KFMASH that includes the phases garnet, chlorite, biotite, chloritoid, cordierite, staurolite, talc, kyanite, andalusite, sillimanite, and pyrophyllite (with quartz, H₂O and muscovite or K-feldspar in excess) is presented. The grid is based on thermodynamic data of Berman et al. (1985) and Berman (1988) for endmember KFASH and KMASH equilibria and natural Fe-Mg partitioning for the KFMASH system. Calculation of P-T slopes and the change in Fe/(Fe+Mg) along reactions in the KFMASH system were made using the Gibbs method. In addition, the effect on the grid of MnO and CaO is evaluated quantitatively. The resulting grid is consistent with typical Buchan and Barrovian parageneses at medium to high grades. At low grades, the grid predicts an extensive stability field for the paragenesis chloritoid+biotite which arises because of the unusual facing of the reaction chloritoid+biotite + quartz+H₂O = garnet+chlorite+muscovite, which proceeds to the right with increasing T in the KFMASH system. However, the reaction proceeds to the left with increasing T in the MnKFASH system so the assemblage chloritoid + biotite is restricted to bulk compositions with high Fe/(Fe+Mg+Mn). Typical metapelites will therefore contain garnet+chlorite at low grades rather than chloritoid + biotite.     

Ferric iron partitioning between plagioclase and silicate liquid: thermodynamics and petrological applications

A series of Fe and Mg partition experiments between plagioclase and silicate liquid were performed in the system SiO₂-Al₂O₃-Fe₂O₃-FeO-MgO-CaO-Na₂O under oxygen fugacities from below the IW buffer up to that of air. A thermodynamic model of plagioclase solid solution for the (CaAl,NaSi,KSi)(Fe³⁺,Al³⁺)Si₂O₈-Ca(Fe²⁺,Mg)Si₃O₈ system is proposed and is calibrated by regression analysis based on new and previously reported experimental data of Fe and Mg partitioning between plagioclase and silicate liquid, and reported thermodynamic properties of end members, ternary feldspar and silicate liquid. Using the derived thermodynamic model, FeO^t, MgO content and Mg/(Fe^t+Mg) in plagioclase can be predicted from liquid composition with standard deviations of ǂ.34 wt% (relative error =9%) and ǂ.08 wt% (14%) and ǂ.7 (8%) respectively. Calculated Fe³⁺-Al exchange chemical potentials of plagioclase, m_{Fe^{3 +} ( Al )- 1} ^Pl{\rm \mu }_{{\rm Fe}^{{\rm 3 + }} \left( {{\rm Al}} \right)_{{\rm - 1}} }^{{\rm Pl}} agree with those calculated using reported thermodynamic models for multicomponent spinel, m_{Fe^{3 +} ( Al )- 1} ^Sp{\rm \mu }_{{\rm Fe}^{{\rm 3 + }} \left( {{\rm Al}} \right)_{{\rm - 1}} }^{{\rm Sp}} and clinopyroxene, m_{Fe^{3 +} ( Al )- 1} ^Cpx{\rm \mu }_{{\rm Fe}^{{\rm 3 + }} \left( {{\rm Al}} \right)_{{\rm - 1}} }^{{\rm Cpx}} . The FeO^t content of plagioclase coexisting with spinel or clinopyroxene is affected by Fe³⁺/(Fe³⁺+Al) and Mg/(Fe+Mg) of spinel or clinopyroxene and temperature, while it is independent of the anorthite content of plagioclase. Three oxygen barometers based on the proposed model are investigated. Although the oxygen fugacities predicted by the plagioclase-liquid oxygen barometer are scattered, this study found that plagioclase-spinel-clinopyroxene-oxygen and plagioclase-olivine-oxygen equilibria can be used as practical oxygen barometers. As a petrological application, prediction of plagioclase composition and f_O2 are carried out for the Upper Zone of the Skaergaard intrusion. The estimated oxygen fugacities are well below QFM buffer and consistent with the estimation of oxidization states in previous studies.     

The upper thermal stability of chlorite + quartz: an experimental study in the system MgO-Al2O3-SiO2-H2O

Experiments up to water pressures of 21 kbar have been undertaken to bracket the reactions chlorite + quartz = talc + kyanite + H₂O, chlorite + quartz = talc + cordierite + H₂O, and talc + kyanite + quartz = cordierite ± H₂O by reversed runs in the system MgO-Al₂O₃-SiO₂-H₂O (MASH). These reaction curves intersect at an invariant point (IP1) at PH₂O = 6.4 ± 0.2 kbar and a temperature of 624 ± 4°C. The curve of the chlorite + quartz breakdown to talc + kyanite + H₂O at water pressures above 6.4 kbar shows a negative dP/dT, with the slope decreasing with rising pressure, whereas the slope of the breakdown curve to talc + cordierite + H₂O at water pressures is clearly positive. The composition of the chlorite solid solution reacting with quartz has been estimated to be approximately Mg_4.85Al_1.15[Al_1.15Si_2.85O₁₀](OH)₈ over the entire pressure range investigated. The composition of the talc solid solution forming by the breakdown of chlorite + quartz appears to be Mg_2.94Al_0.06[Al_0.06Si_3.94O₁₀](OH)₂ at PH₂O = 2kbar. With increasing pressure, the Al content of talc decreases, reaching a value of about 0.06 atoms per formula unit at P,H₂O = 21 kbar. As a consequence of the new experimental data, the existing phase topologies of the MASH-system and K₂O-MASH-system have been revised. For example, the invariant point IP1 and the univariant reaction curve kyanite + talc + H₂O = chlorite + cordierite are stable. For this reason, the development of medium- to high-temperature metamorphic rocks compositionally approximating the MASH-system must be reconsidered. The whiteschists from Sar e Sang, Afghanistan, are treated as an example. The application of the present experimental data to metamorphic rocks of more normal composition requires the examination of the influence of further components. This leads to the conclusion that the introduction of Fe²⁺ into magnesian chlorite extends its stability field in the presence of quartz by 10°-15°C in comparison with pure Mg-chlorite.     

Talc-Phengite: a Widespread Assemblage in High-Grade Pelitic Blueschists of the Western Alps

Talc-phengite, an assemblage hitherto believed to be rare, isfound in regional distribution in the Gran Paradiso area, whereit occurs in the characteristic mineral association chloritoid-talc-phengite(Si_3·4–_3·5). Talc contains up to 15 moleper cent minnesotaite, and chloritoid up to 45 mole per centof the magnesium end member. The talc-phengite stability resultsbasically from the disappearance of chlorite + quartz in rockswith low and moderate MgO/FeO ratios through the divariant reactionsfirst recognized here: Fe-Mg-Chlorite+quartz talc + garnet + H₂O and Fe-Mg-chlorite + quartz talc + Chloritoid + H₂O These reactions imply the disappearance of the join biotite-chloritein the presence of quartz and thus open a talc-phengite stabilityfield (±garnet or chloritoid or Mg-chlorite) which extends,with increasing P and T, toward Mg-richer compositions. Whetheror not it reaches the magnesian subsystem in the Gran Paradisoarea cannot be ascertained. However, the sporadic occurrenceof the high-pressure assemblage talc-kyanite-chloritoid 50 to70 km further northeast in the vicinity of the Monte Rosa massifwithin the same lithological unit (Zermatt-Saas Fee zone s.l.)indicates the instability of any chlorite in quartz-bearingrocks, and implies that talc-phengite must also be stable forpurely magnesian compositions in that area. This progressivestabilization of talc-phengite with increasing metamorphic gradesupports Abraham & Schreyer's (1976) hypothesis of a high-pressurefield for this assemblage, and rules out Chernosky's construction(1978) implying a low-pressure field. The following paragenetic sequence is proposed for pelitic compositionswith intermediate Mg/Fe ratios and excess quartz subjected tohigh-pressure metamorphism with maximum temperatures near 400–500°C: chlorite-illite chlorite-phengite chloritoid-talc-phengite.The absence of biotite is a compositional effect due to thehigh degree of phengite substitution in the white mica. ^*Present address: Institut fr Mineralogic, Ruhr-Universitt, Postfach 10 21 48, D-4630 Bochum 1, Federal Republic of Germany.     

Garnet–chloritoid equilibria in eclogitic pelitic rocks from the Sesia zone (Western Alps): their bearing on phase relations in high pressure metapelites

Abstract A detailed study of garnet–chloritoid micaschists fom the Sesia zone (Western Alps) is used to constrain phase relations in high pressure (HP) metapelitic rocks. In addition to quartz, phengite, paragonite and rutile, the micaschists display two distinct parageneses, namely garnet + chloritoid + chlorite and garnet + chloritoid + kyanite. Talc has never been observed. Garnet and chloritoid are more magnesian when chlorite is present instead of kyanite. The distinction of the two equilibria results from different bulk rock chemistries, not from P–T conditions or redox state. Estimated P–T conditions for the eclogitic metamorphism are 550–600°C, 15–18 kbar.
The presence of primary chlorite in association with garnet and chloritoid leads us to construct two possible AFM topologies for the Sesia metapelites. The paper describes a KFMASH multisystem for HP pelitic rocks, which extends the grid of Harte & Hudson (1979) towards higher pressures and adds the phase talc. Observed parageneses in HP metapelites are consistent with predicted phase relations. Critical associations are Gt–Ctd–Chl and Gt–Ctd–Ky at relatively low temperatures and Gl–Chl–Ky and Gt–Tc–Ky at relatively high temperatures.     

Crystallization of Chromite and Chromium Solubility in Basaltic Melts

The equilibrium between chromite and melt has been determinedon four basalts at temperatures of 1200–1400?C over arange of oxygen fugacity (f_o2) and pressures of 1 atm and 10kb. The Cr content of chromite-saturated melts at 1300?C and1 atm ranges from 0?05 wt.% Cr₂O₃ at a log f_o2= –3 to1?4 wt.% at a log f_o2=–12?8. The Cr²⁺/Cr³⁺ of melt increaseswith decreasing f_o2 and is estimated by assuming a constantpartitioning of Cr³⁺ between chromite and melt at constant temperature.The estimated values of Cr²⁺/Cr³⁺ in the melt are at f_o2 valuesof 4–5 orders of magnitude lower than the equivalent Fe²⁺/Fe³⁺values. The Cr/(Cr+Al) of chromite coexisting with melt at constanttemperature changes little with variation of f_o2 below log f_o2=–6.Five experiments at 10 kb indicate that Cr₂O₃ dissolved in themelt is slightly higher and the Cr/(Cr + Al) of coexisting chromiteis slightly lower than experiments at 1 atm pressure. Thus variationin total pressure cannot explain the large variations of Cr/(Cr+ Al) that are common to mid-ocean ridge basalt (MORB) chromite. Experiments on a MORB at 1 atm at f_o2 values close to fayalite-magnetite-quartz(FMQ) buffer showed that the Al₂O₃ content of melt is highlysensitive to the crystallization or melting of plagioclase,and consequently coexisting chromite shows a large change inCr/(Cr + Al). It would appear, therefore, that mixing of a MORBmagma containing plagioclase with a hotter MORB magma undersaturatedin plagioclase may give rise to the large range of Cr/(Cr +Al) observed in some MORB chromite.     

Experimental Melting of Carbonated Peridotite at 6-10 GPa

Partial melting of magnesite-bearing peridotites was studiedat 6–10 GPa and 1300–1700°C. Experiments wereperformed in a multianvil apparatus using natural mineral mixesas starting material placed into olivine containers and sealedin Pt capsules. Partial melts originated within the peridotitelayer, migrated outside the olivine container and formed poolsof quenched melts along the wall of the Pt capsule. This allowedthe analysis of even small melt fractions. Iron loss was nota problem, because the platinum near the olivine container becamesaturated in Fe as a result of the reaction Fe₂SiO₄^Ol = Fe^Fe–Ptalloy + FeSiO₃^Opx + O₂. This reaction led to a gradual increasein oxygen fugacity within the capsules as expressed, for example,in high Fe³⁺ in garnet. Carbonatitic to kimberlite-like meltswere obtained that coexist with olivine + orthopyroxene + garnet± clinopyroxene ± magnesite depending on P–Tconditions. Kinetic experiments and a comparison of the chemistryof phases occasionally grown within the melt pools with thosein the residual peridotite allowed us to conclude that the meltshad approached equilibrium with peridotite. Melts in equilibriumwith a magnesite-bearing garnet lherzolite are rich in CaO (20–25wt %) at all pressures and show rather low MgO and SiO₂ contents(20 and 10 wt %, respectively). Melts in equilibrium with amagnesite-bearing garnet harzburgite are richer in SiO₂ andMgO. The contents of these oxides increase with temperature,whereas the CaO content becomes lower. Melts from magnesite-freeexperiments are richer in SiO₂, but remain silicocarbonatitic.Partitioning of trace elements between melt and garnet was studiedin several experiments at 6 and 10 GPa. The melts are very richin incompatible elements, including large ion lithophile elements(LILE), Nb, Ta and light rare earth elements. Relative to theresidual peridotite, the melts show no significant depletionin high field strength elements over LILE. We conclude fromthe major and trace element characteristics of our experimentalmelts that primitive kimberlites cannot be a direct productof single-stage melting of an asthenospheric mantle. They rathermust be derived from a previously depleted and re-enriched mantleperidotite. KEY WORDS: multianvil; carbonatite melt; peridotite; kimberlite; element partitioning     

The Stability of Chloritoid Below 10 kb PH2o

The stability of chloritoid, FeAl₂SiO₆H₂O, was investigatedat fluid pressures less than 10 kb. At oxygen fugacities definedby the Ni-NiO buffer, chloritoid reacts to Fe-cordierite andhercynite spinel at 550 and 575 °C at 1 and 2 kb fluid pressure.At pressures between 2.5 and 3.5 kb the assemblage aluminousferro-anthophyllite, staurolite and hercynite spinel appears.The breakdown of chloritoid to this assemblage takes place at625, 650, and 675 °C at 5.5, 7.0, and 8.7 kb, respectively.The aluminous ferro-anthophyllite assemblage is stable onlyover 50 °C, reacting with increasing temperature to almandine,staurolite, and hercynite spinel. Under the QFM buffer, thesame equilibria are displaced to higher temperatures and thealuminous ferro-anthophyllite bearing field is further restrictedwith respect to temperature. The 7 Å chamosite assemblage,previously considered to be the metastable equivalent of chloritoidat low pressures, is shown to be unstable and chloritoid canbe synthesized at pressures as low as 1 kb. An analysis of the equilibria and related experimental datapermits the construction of a schematic P-T grid which outlinesthe stability limits of several important mineral assemblagesin this system. Although the experimental and natural systemsare not strictly analogous, there is an excellent degree ofcorrespondence between the defined upper limit of chloritoidstability and previous estimates of the facies boundaries itserves to define.     

Progressive Low-Grade Metamorphism of a Black Shale Formation, Central Swiss Alps, with Special Reference to Pyrophyllite and Margarite Bearing Assemblages

The unmetamorphosed equivalents of the regionally metamorphosedclays and marls that make up the Alpine Liassic black shaleformation consist of illite, irregular mixed-layer illite/montmorillonite,chlorite, kaolinite, quartz, calcite, and dolomite, with accessoryfeldspars and organic material. At higher grade, in the anchizonalslates, pyrophyllite is present and is thought to have formedat the expense of kaolinite; paragonite and a mixed-layer paragonite/muscovitepresumably formed from the mixed-layer illite/montmorillonite.Anchimetamorphic illite is poorer in Fe and Mg than at the diageneticstage, having lost these elements during the formation of chlorite.Detrital feldspar has disappeared. In epimetamorphic phyllites, chloritoid and margarite appearby the reactions pyrophyllite + chlorite = chloritoid + quartz+ H₂O and pyrophyllite + calcite ± paragonite = margarite+ quartz + H₂O + CO₂, respectively. At the epi-mesozone transition,paragonite and chloritoid seem to become incompatible in thepresence of carbonates and yield the following breakdown products:plagioclase, margarite, clinozoisite (and minor zoisite), andbiotite. The maximum distribution of margarite is at the epizone-mesozoneboundary; at higher metamorphic grade margarite is consumedby a continuous reaction producing plagioclase. Most of the observed assemblages in the anchi-and epizone canbe treated in the two subsystems MgO (or FeO)-Na₂O–CaO–Al₂O₃–(KAl₃O₅–SiO₂–H₂O–CO₂).Chemographic analyses show that the variance of assemblagesdecreases with increasing metamorphic grade. Physical conditions are estimated from calibrated mineral reactionsand other petrographic data. The composition of the fluid phasewas low in X_CO2 throughout the metamorphic profile, whereasX_CH4 was very high, particularly in the anchizone where a_H2Owas probably as low as 0.2. P-T conditions along the metamorphicprofile are 1–2 kb/200–300 °C in the anchizone(Glarus Alps), and 5 kb/500–550 °C at the epi-mesozonetransition (Lukmanier area). Calculated geothermal gradientsdecrease from 50 °C/km in the anchimetamorphic Glarus Alpsto 30 °C/km at the epi-mesozone transition of the Lukmanierarea.     

Mineralogy,petrology, and phase relations of glaucophane-lawsonite zone blueschists from the Tavşanli Region,Northwest Turkey

Glaucophane-lawsonite facies blueschists representing a metamorphosed sequence of basic igneous rocks, cherts and shales have been investigated northeast of the district of Tav?anli in Northwest Turkey. Sodic amphiboles are rich in magnesium reflecting the generally high oxidation states of the blueschists. Lawsonite has a very uniform composition with up to 2.5 wt.% Fe₂O₃. Sodic pyroxenes show an extensive range of compositions with all the end-members represented. Chlorites are uniform in their Al/(Al+Fe+Mg) ratio but show variable Fe/ (Fe+Mg) ratios. Garnets from metacherts are rich in spessartine (>50%) whereas those from metabasites are largely almandine. Pistacite rich epidote is found in metacherts coexisting with lawsonite. Phengites are distinctly higher in their Fe, Mg and Si contents than those from greenschist facies. Hematites with low TiO₂ are ubiquitous in metacherts. Fe²⁺/Mg partitioning between chlorite and sodic amphibole is strongly controlled by the calcium content of the sodic amphibole and ranges from 1.1 for low calcium substitution to 0.8 for higher calcium substitution. The Al/Fe³⁺ partition coefficient between sodic amphibole and sodic pyroxene is 2.1. A model system has been constructed involving projections from lawsonite, iron-oxide and quartz onto a tetrahedron with Na, Al, Fe²⁺ and Mg at its apices. Calcite is treated as an indifferent phase. The model system illustrates the incompatibility of the sodic pyroxene with chlorite in the glaucophanelawsonite facies; this assemblage is represented by sodic amphibole. Sodic amphibole compositions are plotted in terms of coexisting ferromagnesian minerals. Five major areas on the sodic amphibole compositional field are delineated, each associated with one of the following minerals: chlorite, stilpnomelane, talc, almandine, deerite.     

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.     

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

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

A Talc--Phengite Assemblage in Piemontite Schist from Brezovica, Serbia, Yugoslavia

Talc occurs in direct contact with phengite in a manganiferousschist containing piemontite, spessartine, quartz, chlorite,hematite, braunite, and occasional phlogopite. The resultingtalc-phengite tie line in the AKF plot is a novelty for bothnatural rocks and the synthetic model system K₂O-MgO-Al₂O₃-SiO₂-H₂Owhich contains about 95 per cent of the components making upthe four phyllosilicates present in the schist. The remainingcomponents are CuO, MnO, and minor Fe₂O₃, CoO, NiO in the chlorite,talc, and phlogopite, as well as Fe₂O₃ in the phengite. Two possibilities for the origin of the talc-phengite assemblageare discussed: 1. The presence of the components CuO etc. in the phyllosilicatesprovides additional degrees of freedom or causes shifts of reactioncurves in the synthetic model system thus creating a hypotheticalnew invariant point at intermediate pressures allowing a talc-phengitefield. 2. The rock was formed under very high water pressures whichpermit the coexistence of talc and phengite even in the puresynthetic system according to a theoretical prediction of phaserelations from limited experimental data available.     

Location of OH groups and oxidation processes in triclinic chloritoid

Triclinic Fe²⁺ and Fe³⁺-chloritoid end members, as well as Fe²⁺-Fe³⁺-chloritoid solid solutions were synthesized in order to determine the location of the OH groups in the structure and to investigate the possibility of Fe³⁺ incorporation on the M1B site and the corresponding oxidation mechanism. The samples were analyzed using transmission electron microscopy, electron energy-loss and ⁵⁷Fe Mössbauer spectroscopy, polarized single-crystal, KBr powder and in situ high-pressure infrared spectroscopy. The structure of a natural triclinic chloritoid was refined by single-crystal X-ray diffraction in order to locate the proton-accepting oxygens in the triclinic structure. The results of valence bond calculations, polarized single-crystal and in situ high-pressure IR spectroscopy revealed that the orientations of the OH dipoles are the same as those in monoclinic chloritoid. The annealing experiments in air show that the incorporation of Fe³⁺ on M1B increases with temperature. After 3?h at 530?°C all Fe²⁺ was oxidized to Fe³⁺ without decomposition of the structure. This also holds true for a heating duration of 24?h. The incorporation of Fe³⁺ at M1B sites is coupled with a dehydration process starting at about 350?°C during which the H1A protons leave first.     

Experimental constraints on phase relations in subducted continental crust

. Synthesis piston cylinder experiments were carried out in the range 2.0-4.5 GPa and 680-1,050 °C to investigate phase relations in subducted continental crust. A model composition (KCMASH) has been used because all major ultrahigh-pressure (UHP) minerals of the whole range of rock types typical for continental crust can be reproduced within this system. The combination of experimental results with phase petrologic constraints permits construction of a UHP petrogenetic grid. The phase relations demonstrate that the most important UHP paragenesis consists of coesite, kyanite, phengite, clinopyroxene, and garnet in subducted continental crust. Below 700 °C talc is stable instead of garnet. As most of these minerals are also stable at much lower pressure and temperature conditions it is thus not easy to recognize UHP metamorphism in subducted crust. A general feature, however, is the absence of feldspars at H₂O-saturated conditions. Plagioclase is never stable at UHP conditions, but K-feldspar can occur in H₂O-undersaturated rocks. Mineral compositions in the experiments are fully buffered by coexisting phases. The Si content of phengite and biotite increase with increasing pressure. At 4.0 GPa, 780 °C, biotite contains 3.28 Si per formula unit, which is most probably caused by solid solution of biotite with talc. Above 800 °C, the CaAl₂SiO₆ component in clinopyroxene buffered with kyanite, coesite and a Mg-phase increases with increasing temperature, providing a tool to distinguish between 'cold' and 'hot' eclogites. Up to 10% Ca-eskolaite (Ca_0.5[]_0.5AlSi₂O₆) in clinopyroxene has been found at the highest temperature and pressure investigated (>900 °C, 4.5 GPa). Garnet buffered with coesite, kyanite and clinopyroxene displays an increase of grossular component with increasing pressure for a given temperature. Although the investigated system represents a simplification with respect to natural rocks, it helps to constrain general features of subducted continental crust. The observed phase relations and phase compositions demonstrate that at pressures >3.0 GPa and temperatures >800 °C continental crust can retain significant amounts of H₂O (>1 wt%), whereas K-free mafic or ultramafic rocks are dry at these conditions. UHP parageneses are only preserved if the whole exhumation path is situated within the stability field of phengite, i.e. if there is cooling during exhumation or if the whole exhumation occurred at T <700 °C. In contrast, break down of phengite and concomitant partial melting in terranes that show isothermal decompression may lead to a complete recrystallization of the subducted crust during exhumation. The density of UHP rocks can be estimated on the basis of the established phase relations. Pelitic rocks are likely to have a density close to mantle rocks (3.3 g/cm³) because of significant amounts of dense garnet and kyanite whereas granitic rocks are less dense (3.0 g/cm³). Hence, subducted average continental crust is most probably buoyant with respect to mantle rocks and tends to get exhumed as soon as it is detached from the down-going slab. Electronic supplementary material to this paper can be obtained by using the Springer LINK server located at http://dx.doi.org/10.1007/s00410-001-0336-3.     

Fe--Al Oxides: Phase Relationships below 1,000?C

The subsolidus phase relationships of magnetite, hercynite,hematite, corundum, wostite, and iron are described. The phaseswere synthesized from chemical mixtures. Reactions and solidsolution between them were induced under controlled conditionsof composition, temperature, total vapor pressure, and partialpressure of oxygen. Reaction rates are slow, so that the experimentslasted from 1 to 40 days, and quenching is completely successful. A solvus was determined which limits solid solution along themagnetitc-hercynite join at temperatures below 860^o?15^oC. Compositionsof the spinel solid solutions were determined by measuring theshift of the (440) reflection, using a powder X-ray diffractometer.The calibration curve, 20 vs. composition, was made from measurementsof spinel solid solutions synthesized in the one-phase region.The cell edge a_o changes from 8–391?0.002 A (magnetic,Fe⁺²Fe₂⁺²O₄OJ to 8.150?0.004 (hercynite, Fe⁺²Al₂O₄)by a_o?8.391–0.00190x- 0.5X²10^-5 (X is mol per cent FeAl₂O₄ in solid solution). In the system Fe-Al₂-O₃-O there are five univariant assemblages: 1. Hematite-corundum+magnetite +V (vapor) 2. Corundum+magnetite+hercynite+V 3. Magnetite+hercynite+w?stite+V 4. Hercynite+wilstite+iron+V 5. Hercynite+iron+corundum+V The lines were located by determining the composition of themagnetite, hercynite, hematite, and corundum solid solutionsfor each assemblage. The diagrams provide a basis for the discussion of the paragenesisof the oxide minerals. The progressive metamorphism of lateritedeposits can be represented by (1) laterites and bauxites: hematiteH+hydratedaluminum oxides; (2) diasporites: hematite+diaspore+corundum,with magnetite as a rare accessory; (3) emery: corundum+magnetite,with hematite as an accessory. The path of these mineral changeson the diagrams shows the decrease in oxygen content of thesolids with decrease in the partial pressure of oxygen and relatesthe aluminum content of the magnetite to temperature. The occurrences of hercynite are discussed. It is a rare mineralbecause it requires unusual conditions to grow, i.e. relativelylow oxygen pressure and an extremely Fe-Al-rich environment.