A field and theoretical analysis of garnet+chlorite+chloritoid+biotite assemblages from the tri-state (MA,CT, NY) area,USA

The prograde evolution of minerals in metapelites of a Barrovian sequence from the tri-state area (Massachusetts, Connecticut, New York) of the Taconic Range involves assemblages with garnet (Ga), chlorite (Ch), chloritoid (Ct), biotite (Bi) and staurolite (St). Detailed petrologic observations, mineral compositions and chemical zoning in garnet show: (1) garnet high in Mn and Fe but low in Mg is stable with chlorite at grades below those where chloritoid+biotite is found; (2) early formed garnet reacted partially to form Ct+Bi at intermediate grades; (3) at higher grades garnet (with low Mn)+chlorite is again produced, at the expense of chloritoid+biotite, suggesting a reversal in the continuous reaction involving the phases Ga, Ch, Ct and Bi. Thermodynamic modeling of the assemblage Ga+Ch+Ct+Bi±St in the MnKFMASH system reveals: (1) in the MnKFASH system the prograde reaction is Ga+Ch=Ct+Bi whereas in the KFMASH system the prograde reaction is the opposite: Ct+Bi=Ga+Ch; (2) the Ga–Ch–Ct–Bi–St invariant point in the KFMASH system occurs twice, at approximately 6.5 kbar, 545° C and 14.8 kbar, 580° C (although one of them may be metastable in a complex phase system); the appearance of the petrogenetic grid is markedly different from that of Albee, but similar to that of Spear and Cheney; (3) as a consequence, in the KFMASH system, chloritoid+biotite are stable over a wide range of P-T conditions whereas garnet+chlorite assemblages are restricted to a narrow band of P-T conditions; (4) MnO increases the stability field of Ga+Ch relative to both Ct+Bi at low temperatures, and St+Bi at high temperatures; (5) in natural samples the occurrence of Ct+Bi is controlled more by bulk Mg–Fe(-Mn) composition than P-T conditions. Specifically, Ct+Bi is restricted to bulk compositions with Fe/(Mg+Fe+Mn)>0.6. Rocks with Fe/(Mg+Fe+Mn)<0.5 are likely to display only chlorite+biotite at low grade. These observations are consistent with Wang and Spear and Spear and Cheney.     

Calculated phase equilibria for low- and medium-pressure metapelites in the KFMASH and KMnFMASH systems

Petrogenetic grids in the KFMASH and KMnFMASH model systems calculated with the software thermocalc 3.1 are presented for the P–T range 0.5–12 kbar and 450–900 °C, for assemblages involving garnet, muscovite, chloritoid, biotite, chlorite, staurolite, cordierite, spinel, orthopyroxene, K‐feldspar, Al₂SiO₅ phases, quartz, water and melt. Based on calculated compatibility diagrams and P–T and T–M_Mn [Mn/(Mg + Fe + Mn)] pseudosections for different metapelitic bulk compositions, the principal conclusions are that the addition of Mn to the KFMASH system: (i) enhances the stability of garnet, and, to a lesser extent, aluminosilicates; (ii) reduces the stability of staurolite, cordierite and, to a lesser extent, chlorite; and (iii) extends the medium pressure stability of muscovite and the low‐P stability field of K‐feldspar. The influence of Mn on individual mineral stabilities is strongly related to rock composition, in particular, to the relative contents of Al₂O₃ and K₂O. For metapelites of a range of compositions and M_Mn values, P–T pseudosections in the KFMASH system, in most cases, do not adequately predict the mineral assemblages observed in natural assemblages under medium and low‐pressure conditions. In contrast, the P–T pseudosections in the KMnFMASH system generally provide more satisfactory results, suggesting that MnO is one of the non‐KFMASH components that should not be neglected in documenting the phase equilibria of medium‐ and low‐P metapelites.     

A calculated petrogenetic grid for the system K2O-FeO-MgO-Al2O3-SiO2-H2O, with particular reference to contact-metamorphosed pelites

A petrogenetic grid is presented for the system KFMASH (K₂O-FeO-MgO-Al₂O₃-SiO₂-H₂O), including biotite, muscovite, K-feldspar, chlorite, chloritoid, staurolite, cordierite, garnet, orthoamphibole, orthopyroxene, spinel, andalusite, sillimanite, kyanite, quartz and corundum with H₂O in excess, which was calculated using the computer program THERMOCALC and the Powell and Holland internally consistent thermodynamic dataset. By removing the normal constraint of having quartz in excess, both quartz-bearing and quartz-absent equilibria are shown. Quartz-absent equilibria are particularly relevant at high- T and low- P conditions, because of their common occurrence at these conditions. The calculated mineral assemblage and mineral compositional variations in terms of FeMg-1 and (Fe, Mg)SiAl_-2 exchange vectors are broadly compatible with observations on natural rocks, particularly when non-KFMASH components are taken into account.     

On the interpretation of peak metamorphic temperatures in light of garnet diffusion during cooling

Abstract Finite difference models of Fe-Mg diffusion in garnet undergoing cooling from metamorphic peak conditions are used to infer the significance of temperatures calculated using garnet-biotite Fe-Mg exchange thermometry. For rocks cooled from high grades where the garnet was initially homogeneous, the calculated temperature (T_calc) using garnet core and matrix biotite depends on the size of the garnet, the ratio of garnet to biotite in the rock (V_garnet/V_biotite) and the cooling rate. For garnets with radii of 1 mm and V_garnet/V_biotite<1, T_calc is 633, 700 and 777°C for cooling rates of 1, 10 and 100°C/Ma. For V_garnet/V_biotite= 1 and 4 and a cooling rate of 10° C/Ma, T_calc is approximately 660 and 610° C, respectively. Smaller and larger garnets have lower and higher T_calc, respectively. These results suggest that peak metamorphic temperatures may be reliably attained from rocks crystallized at conditions below T_calc of the garnet core, provided that V_garnet/V_biotite is sufficiently small (<0.1) and that the composition of the biotite at the metamorphic peak has not been altered during cooling. Numerical experiments on amphibolite facies garnets with nominal peak temperatures of 550–600° C generate a ‘well’in Fe/(Fe + Mg) near the rim during cooling. Maximum calculated temperatures for the assemblage garnet + chlorite + biotite + muscovite + plagioclase + quartz using the Fe/(Fe + Mg) at the bottom of the ‘well’with matrix biotite range from 23–43° C to 5–12° C below the peak metamorphic temperature for cooling rates of 1 and 100° C/Ma, respectively. Maximum calculated temperatures for the assemblage garnet + staurolite + biotite + muscovite + plagioclase + quartz are approximately 70° C below the peak metamorphic temperature and are not strongly dependent on cooling rate. The results of this study indicate that it may be very difficult to calculate peak metamorphic temperatures using garnet-biotite Fe-Mg exchange thermometry on amphibolite facies rocks (T_max > 550° C) because the rim composition of the garnet, which is required to calculate the peak temperature, is that most easily destroyed by diffusion.     

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.     

The effect of whole-rock MnO content on the stability of garnet in pelitic schists during metamorphism

Garnet-bearing mineral assemblages are commonly observed in pelitic schists regionally metamorphosed to upper greenschist and amphibolite facies conditions. Modelling of thermodynamic data for minerals in the system Na₂O–K₂O–FeO–MgO–Al₂O₃–SiO₂–H₂O, however, predicts that garnet should be observed only in rocks of a narrow range of very high Fe/Mg bulk compositions. Traditionally, the nearly ubiquitous presence of garnet in medium- to high-grade pelitic schists is attributed qualitatively to the stabilizing effect of MnO, based on the observed strong partitioning of MnO into garnet relative to other minerals. In order to quantify the dependence of garnet stability on whole-rock MnO content, we have calculated mineral stabilities for pelitic rocks in the system MnO–Na₂O–K₂O–FeO–MgO–Al₂O₃–SiO₂–H₂O for a moderate range of MnO contents from a set of non-linear equations that specify mass balance and chemical equilibrium among minerals and fluid. The model pelitic system includes quartz, muscovite. albite, pyrophyllite, chlorite, chloritoid, biotite, garnet, staurolite, cordierite, andalusite, kyanite. sillimanite, K-feldspar and H₂O fluid. In the MnO-free system, garnet is restricted to high Fe/Mg bulk compositions, and commonly observed mineral assemblages such as garnet–chlorite and garnet–kyanite are not predicted at any pressure and temperature. In bulk compositions with X_Mn= Mn/(Fe + Mg + Mn) > 0.01, however, the predicted garnet-bearing mineral assemblages are the same as the sequence of prograde mineral assemblages typically observed in regional metamorphic terranes. Temperatures predicted for the first appearance of garnet in model pelitic schist are also strongly dependent on whole-rock MnO content. The small MnO contents of normal pelitic schists (X_Mn= 0.01–0.04) are both sufficient and necessary to account for the observed stability of garnet.     

Separate or shared metamorphic histories of eclogites and surrounding rocks? An example from the Bohemian Massif

Eclogite boudins occur within an orthogneiss sheet enclosed in a Barrovian metapelite‐dominated volcano‐sedimentary sequence within the Velké Vrbno unit, NE Bohemian Massif. A metamorphic and lithological break defines the base of the eclogite‐bearing orthogneiss nappe, with a structurally lower sequence without eclogite exposed in a tectonic window. The typical assemblage of the structurally upper metapelites is garnet–staurolite–kyanite–biotite–plagioclase–muscovite–quartz–ilmenite ± rutile ± silli‐manite and prograde‐zoned garnet includes chloritoid–chlorite–paragonite–margarite, staurolite–chlorite–paragonite–margarite and kyanite–chlorite–rutile. In pseudosection modelling in the system Na₂O–CaO–K₂O–FeO–MgO–Al₂O₃–SiO₂–H₂O (NCKFMASH) using THERMOCALC, the prograde path crosses the discontinuous reaction chloritoid + margarite = chlorite + garnet + staurolite + paragonite (with muscovite + quartz + H₂O) at 9.5 kbar and 570 °C and the metamorphic peak is reached at 11 kbar and 640 °C. Decompression through about 7 kbar is indicated by sillimanite and biotite growing at the expense of garnet. In the tectonic window, the structurally lower metapelites (garnet–staurolite–biotite–muscovite–quartz ± plagioclase ± sillimanite ± kyanite) and amphibolites (garnet–amphibole–plagioclase ± epidote) indicate a metamorphic peak of 10 kbar at 620 °C and 11 kbar and 610–660 °C, respectively, that is consistent with the other metapelites. The eclogites are composed of garnet, omphacite relicts (jadeite = 33%) within plagioclase–clinopyroxene symplectites, epidote and late amphibole–plagioclase domains. Garnet commonly includes rutile–quartz–epidote ± clinopyroxene (jadeite = 43%) ± magnetite ± amphibole and its growth zoning is compatible in the pseudosection with burial under H₂O‐undersaturated conditions to 18 kbar and 680 °C. Plagioclase + amphibole replaces garnet within foliated boudin margins and results in the assemblage epidote–amphibole–plagioclase indicating that decompression occurred under decreasing temperature into garnet‐free epidote–amphibolite facies conditions. The prograde path of eclogites and metapelites up to the metamorphic peak cannot be shared, being along different geothermal gradients, of about 11 and 17 °C km^?1, respectively, to metamorphic pressure peaks that are 6–7 kbar apart. The eclogite–orthogneiss sheet docked with metapelites at about 11 kbar and 650 °C, and from this depth the exhumation of the pile is shared.     

Regression Modelling of Metamorphic Reactions in Metapelites, Snow Peak, Northern Idaho

The second of two periods of regional metamorphism that affectedpelitic rocks near Snow Peak caused complete re-equilibrationof mineral assemblages and resulted in a consistent set of metamorphicisograds. Metamorphic chlorite and biotite occur in the lowestgrade rocks. With increasing grade, garnet, staurolite, andkyanite join the assemblage, resulting in a transition zonecontaining all the above phases. At higher grade, chlorite,and finally staurolite disappear. Mass balance relations at isograds and among minerals of low-varianceassemblages have been modelled by a non-linear least-squaresregression technique. The progressive sequence can be describedin terms of schematic T-X_H2O relations among chlorite, biotite,garnet, staurolite, and kyanite at P_total above the KFMASH invariantpoint involving those phases. The first appearance of garnetwas the result of an Fe-Mg-Mn continuous reaction. As temperaturerose, the garnet zone assemblage encountered the stauroliteisograd reaction, approximated by the model reaction: 3?0 chlorite + 1?5 garnet + 3?3 muscovite + 05 ilmenite = 1?0staurolite + 3?1 biotite + 1?5 plagioclase + 3?3 quartz + 10?3H₂O. The staurolite zone corresponds to buffering along this reactionto the intersection where chlorite, biotite, garnet, staurolite,and kyanite coexist. The transition zone assemblage formed byreaction at this T–X _H2O intersection which migrates towardmore H2O-rich fluid composition with progressive reaction. Thenet reaction at the intersection is approximated by the transitionzone reaction: 1?0 chlorite +1?1 muscovite + 0?2 ilmenite = 2?7 kyanite + 1?0biotite + 0?4 albite + 4?2 H₂O. Chlorite was commonly the first phase to have been exhaustedand the remaining assemblage was buffered along a staurolite-outreaction, represented by the model reaction: 1?0 staurolite + 3?4 quartz + 0?4 anorthite + 1?4 garnet + 0?1ilmenite + 7?9 kyanite + 2?0 H₂O. Consumption of staurolite by this reaction resulted in the highestgrade assemblage, which contains kyanite, garnet, biotite, muscovite,quartz, plagioclase, ilmenite, and graphite.     

Petrology of an Andalusite-Type Regional Metamorphic Terrane, Panamint Mountains, California

The terrane in the Panamint Mountains, California, was regionallymetamorphosed under low-pressure conditions and subsequentlyunderwent retrograde metamorphism. Prograde metamorphic isogradsthat mark the stability of tremolite + calcite, diopside, andsillimanite indicate a westward increase in grade. The studywas undertaken to determine the effects of the addition of Caon the types of assemblages that may occur in pelitic schists,to contribute to the understanding of the stability limits inP – T – aH₂O – X_Fe of the pelitic assemblagechlorite + muscovite + quartz, and to estimate the change inenvironment from prograde to retrograde metamorphism. Peliticassemblages are characterized by andalusite + biotite + stauroliteand andalusite + biotite + cordierite. Within a small changein grade, chlorite breaks down over nearly the entire rangein Mg/(Mg + Fe) to biotite + aluminous mineral. Chlorite withMg/(Mg + Fe) = 0.55 is stable to the highest grade, and thegeneralized terminal reaction is chlorite + muscovite + quartz= andalusite + biotite + cordierite + H₂O. Calcic schists arecharacterized by the assemblage epidote + muscovite + quartz+ chlorite + actinolite + biotite + calcite + plagioclase atlow grades and by epidote + muscovite + quartz + garnet + hornblende+ biotite + calcite + plagioclase at high grades. Epidote doesnot coexist with any AFM phase that is more aluminous than garnetor chlorite. Lithostatic pressure ranged from 2.3 kb to 3.0kb. During prograde-metamorphism temperatures ranged from lessthan 400° to nearly 700°C, and X_H2O (assuming P_H2O +P_CO3 = P_total) is estimated to be 0.25 in siliceous dolomite,0.8 in pelitic schist, and 1.0 in calcic schist. Temperatureduring retrograde metamorphism was 450° ± 50°C,and all fluid were H₂O-rich. A flux of H₂O-rich fluid duringfolding is believed to have caused retrograde metamorphism.The petrogenetic grid of Albee (1965b) is modified to positionthe (A, Cd) invariant point relative to the aluminosilicatetriple point, which allows the comparison of facies series thatinvolve different chloritoid-reactions.     

Reactions to define the biotite isograd in the Ryoke metamorphic belt,Kii Peninsula,Japan

Two types of biotite isograd are defined in the low-grade metamorphism of the Wazuka area, a Ryoke metamorphic terrain in the Kii Peninsula, Japan. The first, BI₁, is defined by the reaction of chlorite+K-feldspar= biotite+muscovite+quartz+H₂O that took place in psammitic rocks, and the second, BI₂, by the continuous reaction between muscovite, chlorite, biotite and quartz in pelitic rocks. The Fe/Mg ratios of the host rocks do not significantly affect the reactions. From the paragenesis of pelitic and psammitic metamorphic rocks, the following mineral zones were established for this low-pressure regional metamorphic terrain: chlorite, transitional, chlorite-biotite, biotite, and sillimanite. The celadonite content of muscovite solid solution in pelitic rocks decreases systematically with the grade of metamorphism from 38% in the chlorite zone to 11% in the biotite zone. Low pressure does not prohibit muscovite from showing the progressive change of composition, if only rocks with appropriate paragenesis are chosen. A qualitative phase diagram of the AKF system relevant to biotite formation suggests that the higher the pressure of metamorphism, the higher the celadonite content of muscovite at BI₁, which is confirmed by comparing the muscovites from the Barrovian and Ryoke metamorphism.     

Phase relations in high-pressure metapelites in the system KFMASH (K2O–FeO–MgO–Al2O3–SiO2–H2O) with application to natural rocks

Using a previously published, internally consistent thermodynamic dataset and updated models of activity–composition relations for solid solutions, petrogenetic grids in the model system KFMASH (K₂O–FeO–MgO–Al₂O₃–SiO₂–H₂O) and the subsystems KMASH and KFASH have been calculated with the software THERMOCALC 3.1 in the P–T range 5–36 kbar and 400–810 °C, involving garnet, chloritoid, biotite, carpholite, talc, chlorite, staurolite and kyanite/sillimanite with phengite, quartz/coesite and H₂O in excess. These grids, together with calculated AFM compatibility diagrams and pseudosections, are shown to be powerful tools for delineating the phase equilibria and P–T conditions of pelitic high-P assemblages for a variety of bulk compositions. The calculated equilibria and mineral compositions are in good agreement with petrological observation. The calculation indicates that the typical whiteschist assemblage kyanite–talc is restricted to the rocks with extremely high X_Mg values, decreasing X_Mg in a bulk composition favoring the stability of chloritoid and garnet. Also, the chloritoid–talc paragenesis is stable over 19–20 kbar in a temperature range of ca. 520–620 °C, being more petrologically important than the previously highlighted assemblage talc–phengite. Moreover, contours of the calculated Si isopleths in phengite in P–T and P–X pseudosections for different bulk compositions extend the experimentally derived phengite geobarometers to various KFMASH assemblages.     

Phase equilibria and the pressure-temperature path of the highest-grade Ryoke metamorphic rocks in the Yanai district, SW Japan

The garnet-cordierite zone, the highest-grade zone of the Ryoke metamorphic rocks in the Yanai district, SW Japan, is defined by the coexistence of garnet and cordierite in pelitic rocks. Three assemblages in this zone are studied in detail, i.e. spinel + cordierite + biotite, garnet + cordierite + biotite and garnet + biotite, all of which contain quartz, K-feldspar and plagioclase. The Mg/(Fe + Mg) in the coexisting minerals decreases in the following order: cordierite, biotite, garnet and spinel. Two facts described below are inconsistent with the paragenetic relation in the K₂OFeOMgOAl₂O₃SiO₂H₂O (KFMASH) system in terms of an isophysical variation. First, garnet and biotite in the last assemblage have Mg/(Fe + Mg) higher than those in the second. Second, the first two assemblages are described by the reaction,

Evolution of a kyanite-bearing belt within a HT-LP orogen: the case of NW Variscan Iberia

Kyanite replaces andalusite in a belt of Ordovician and Silurian pelitic rocks that form a narrow synform pinched between high-grade antiforms in NW Variscan Iberia. Kyanite occurs across the belt in Al-rich, black pelites in assemblages I: kyanite–chloritoid–chlorite–muscovite and II: kyanite–staurolite– chlorite–muscovite. In I, kyanite occurs in the matrix and in kyanite–muscovite aggregates that pseudomorph earlier andalusite porphyroblasts. The aggregates are found across the belt and can still be recognized in assemblage II and even in III: andalusite–staurolite–biotite–muscovite, this latter being a hornfelsic Silurian schist where kyanite is relic and staurolite occurs in the matrix, and is resorbed inside new massive pleochroic andalusite. KFMASH and MnKFMASH pseudosections have been constructed using Thermocalc for Al-rich and Al-poorer compositions from the belt. Chloritoid zoning in Al-rich rocks containing assemblage I, plus chloritoid–chlorite thermometry complemented with garnet–chlorite thermometry in Al-poorer lithologies, mean that the path is one of increasing pressure and temperature. Conditions prior to assemblage I, with earlier andalusite stable, are those of the andalusite–chloritoid– chlorite field as testified by chloritoid enclosed in andalusite porphyroblast rims. The passage from assemblage I to II implies a prograde path within the kyanite field. Assemblage III represents peak conditions, indicating a prograde staurolite-consuming reaction across a KFMASH field, leading eventually to a locally found andalusite–biotite–muscovite hornfels. The lowest pressure stages are recorded by cordierite–biotite in Al-poor pelites. Garnet-bearing MnKFMASH assemblages in Al-poorer pelites record conditions similar to assemblages II and III. The replacement of andalusite by kyanite in assemblage I is attributed to downdragging of andalusite-bearing rocks into a synform as testified by the strained andalusite porphyroblasts affected by a subvertical crenulation cleavage. Prograde metamorphism in the eastern contact of the belt is due to heat transferred to the belt from the ascending high grade antiform across the Vivero fault.     

A model for garnet and plagioclase growth in pelitic schists: implications for thermobarometry and P-T path determinations

Numerical models of the progressive evolution of pelitic schists in the NCMnKFMASH system with the assemblage garnet + biotite + chlorite ± staurolite + plagioclase + muscovite + quartz + H₂O are presented with the goal of predicting compositional changes in garnet and plagioclase along different P-T paths. The numerical models support several conclusions that should prove useful for interpreting the P-T paths of natural parageneses: (i) Garnet may grow along P-T vectors ranging from heating with decompression to cooling with compression. P-T paths deduced from garnet zoning that are inconsistent with these growth vectors are self-contradictory. (ii) There is a systematic relation between garnet and plagioclase composition and growth such that for most P-T paths, garnet growth requires plagioclase consumption. Furthermore, mass balance in a closed system requires that as plagioclase is consumed the remaining plagioclase becomes increasingly albitic. Inclusions of plagioclase in the core of garnet should be more anorthitic than those near the rim and zoned matrix plagioclase should have rims that are more albitic than the cores. Complex plagioclase textures may arise from the local variability of growth and precipitation kinetics. (iii) A decrease of Fe/(Fe + Mg) in a garnet zoning profile is a reliable indicator of increasing temperature for the assemblage modelled. However, there is no single reliable ΔP monitor and inferences about ΔP can only be made by considering plagioclase and garnet together. (iv) Consumption of garnet during the production of staurolite removes material from the outer shell of a garnet and may make recovery of peak metamorphic compositions and P-T conditions impossible. Low ‘peak’temperatures typically recorded by staurolite-bearing assemblages may reflect this phenomenon. (v) Diffusional homogenization of garnet affects the computed P-T path and results in a clockwise rotation of the computed P-T vector relative to the true P-T path.     

Thermodynamic modelling of the reaction muscovite+cordierite→Al2SiO5+biotite+quartz+ H2O: constraints from natural assemblages and implications for the metapelitic petrogenetic grid

The reaction muscovite+cordierite→biotite+Al₂SiO₅ +quartz+H₂O is of considerable importance in the low pressure metamorphism of pelitic rocks: (1) its operation is implied in the widespread assemblage Ms + Crd +And± Sil + Bt + Qtz, a common mineral assemblage in contact aureoles and low pressure regional terranes; (2) it is potentially an important equilibrium for pressure estimation in low pressure assemblages lacking garnet; and (3) it has been used to distinguish between clockwise and anticlockwise P–T paths in low pressure metamorphic settings. Experiments and thermodynamic databases provide conflicting constraints on the slope and position of the reaction, with most thermodynamic databases predicting a positive slope for the reaction. Evidence from mineral assemblages and microtextures from a large number of natural prograde sequences, in particular contact aureoles, is most consistent with a negative slope (andalusite and/or sillimanite occurs upgrade of, and may show evidence for replacement of, cordierite). Mineral compositional trends as a function of grade are variable but taken as a whole are more consistent with a negative slope than a positive slope. Thermodynamic modelling of reaction 1 and associated equilibria results in a low pressure metapelitic petrogenetic grid in the system K₂O–FeO–MgO–Al₂O₃–SiO₂–H₂O (KFMASH) which satisfies most of the natural and experimental constraints. Contouring of the Fe–Mg divariant interval represented by reaction 1 allows for pressure estimation in garnet‐absent andalusite+cordierite‐bearing schists and hornfelses. The revised topology of reaction 1 allows for improved analysis of P–T paths from mineral assemblage sequences and microtextures in the same rocks.     

Experimental study of chloritoid stability at high pressure and various fO2 conditions

The reaction chloritoid (ctd)=almandine (alm)+diaspore+H₂O (CAD) has been reversed using Fe³⁺-free synthetic chloritoid and almandine, under fO₂ conditions of the solid oxygen buffer Fe/FeO (CADWI), and using partially oxidized synthetic minerals under fO₂ conditions of the solid oxygen buffer Ni/NiO (CADNNO). Experiments have been conducted between 550 and 700°C, 25 and 45 kbar. The equilibrium pressure and temperature conditions are strongly dependent on the fO₂ conditions (CADNNO lies some-what 50°C higher than CADWI). This can be explained by a decrease in aH₂O for experiments conducted on the Fe/FeO buffer, and a decrease in actd and aalm (through incorporation of ferric iron preferentially in chloritoid) for experiments conducted on the Ni/NiO buffer. The H₂O activity has been calculated using the MRK equation of state, and the values obtained checked against the shift of the equilibrium diaspore=corundum+H₂O bracketed on the Fe/FeO buffer and under unbuffered fO₂ conditions. For fO₂ buffered by the assemblage Fe/FeO, aH₂O increases with pressure from about 0.85 at 600°C, 12 kbar to about 0.9 at 605°C, 25 kbar and 1 above 28 kbar. For fO₂ buffered by the assemblage Ni/NiO, aH₂O=1. The aH₂O decrease from Ni/NiO to Fe/FeO is, however, too small to be entirely responsible for the temperature shift between CADNNO and CADWI. In consequence, the amount of ferric iron in almandine and chloritoid growing in the CADNNO experiments must be significant and change along the CADNNO, precluding calculation of the thermodynamic properties of chloritoid from this reaction. Our experimental data obtained on the Fe/FeO buffer are combined, using a thermodynamic analysis, with Ganguly's (1969) reversal of the reaction chloritoid=almandine+corundum +H₂O (CAC) on the same oxygen buffer. Experimental brackets are mutually consistent and allow extraction of the thermodynamic parameters H ^o f,ctd and S ^octd. Our thermodynamic data are compared with others, generally calculated using Ganguly's bracketing of CACNNO. The agreement between the different data sets is relatively good at low pressure, but becomes rapidly very poor toward high pressure conditions. Using our thermodynamic data for chloritoid and K_D=(Fe³⁺/Al)ctd/(Fe³⁺/Al)alm estimated from natural assemblages, we have calculated the composition of chloritoid and almandine growing from CADNNO and CACNNO. The Fe³⁺ content in chloritoid and almandine increases with pressure, from less than 0.038 per FeAl₂SiO₅(OH)₂ formula unit at 10 kbar to at least 0.2 per formula unit above 30 kbar. This implies that chloritoid and almandine do contain Fe³⁺ in most natural assemblages. The reliability of our results compared to natural systems and thermodynamic data for Mg-chloritoid is tested by comparing the equilibrium conditions for the reaction chloritoid+quartz=garnet (gt)+kyanite+H₂O (CQGK), calculated for intermediate Fe–Mg chloritoid and garnet compositions, from the system FASH and from the system MASH. For 0.65<(XFe)gt<0.8, CQKG calculated from FASH and MASH overlap for K_D=(Mg/Fe)ctd/(Mg/Fe)gt=2. This is in good agreement with the K_D values reported from chloritoid+garnet+quartz+kyanite natural assemblages.     

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.     

Chemical processes and migration of elements during retrogression of a staurolite-zone assemblage in western North Carolina

A detailed study of retrograde alteration of a staurolite porphyroblast and its surrounding matrix of mica schist has made use of petrographic, modal, and microprobe analysis. Retrogression was to the garnet zone of metamorphism and apparently occurred largely after a temperature decline of 70–100° C. The event caused metasomatic removal of Zn but may have been isochemical relative to other analyzed elements. The best estimate of the overall reaction is: 1 staurolite+3.018 biotite+3.550 quartz+0.629 albite +0.014 anorthite+0.678 NaCl+14.004 H₂O =3.274 Na-rich muscovite+3.561 chlorite +0.273 ilmenite+0.110 chloritoid+0.039 garnet +0.339 ZnCl₂.Non-systematic variation in composition of analyzed minerals is revealed by statistical treatment of replicate analyses. Such variation involves monovalent and divalent cations within many minerals, but is most pronounced within retrograde muscovite. Muscovite variation involves Si and Al as well as FM and alkalis and does not follow a phengite law of charge-coupled substitution.Relative to the core of the retrograded staurolite crystal, zoning is seen in averaged muscovite compositions and in development of incompatible mineral assemblages, which include chloritoid well within retrograded staurolite but biotite within the matrix. A local gradient in the chemical potential of an Al-bearing component was likely present during retrogression.Alteration of staurolite was probably accomplished by reaction and diffusion through the medium of an intergranular fluid phase. Relative to staurolite, migration of elements involved immigration of considerable amounts of Mg, Na, K, and H and expulsion of Al, Fe, Zn, and O. It is inferred that concentration of Al within the fluid phase was considerably lower than those of monovalent and divalent cations.Preservation of considerable staurolite and evidence for a local concentration gradient of Al in the fluid phase suggest that limited amounts of H₂O were available. Expulsion of Zn suggests that much water was not consumed locally but exited the terrane. An attempt at resolution of this dilemna involves fracture-channelized infiltration of H₂O into the rock. A more regional petrographic study of retrogression suggests that H₂O which entered the rock may have been liberated initially by prograde dehydration at a moderately greater depth of 2–3 km.Results of this study, especially the non-phengitic nature of crystal-chemical substitution within muscovite, indicate chemical reaction under conditions of disequilibrium. Apparently, extent of retrogression was controlled by availability of H₂O rather than by thermochemical equilibria.     

Coexisting chloritoid-staurolite from the Sillimanite (fibrolite) zone,Sini, district Singhbhum,India

Microprobe analyses of the minerals from an unusual chloritoid-staurolite-garnet (+ muscovite + quartz + ilmenite) assemblage from the sillimanite (fibrolite) zone of Sini, India are presented and the petrological significance of the paragenesis is discussed. The X Mg in the different minerals from the chloritoid-staurolite-bearing rock varies in the order, muscovite > chlorite > chloritoid > staurolite > garnet > ilmenite, and from the associated sillimanite-bearing schists: muscovite > biotite > staurolite > garnet rim > garnet core > ilmenite. A graphical representation of the mineral compositions in an AFM projection displays a consistent topology if the effects of non-AFM components such as Zn in the staurolite and Mn in the garnet are taken into account. Petrographic and mineralogical data are consistent with a prograde formation of the chloritoid-staurolite-garnet assemblage. It is suggested that the paragenesis has been formed at similar PT conditions to the associated sillimanite (fibrolite)-staurolite-garnet-mica schists. These conditions are estimated to be 600–625°C/6±0.5 Kb.     

Reversal of Fe-Mg Partitioning Between Garnet and Staurolite in Eclogite-facies Metapelites from the Champtoceaux Nappe (Brittany, France)

This paper concentrates on the petrology of eclogite-faciesmetapelites and, particularly, the significance of staurolitein these rocks. A natural example of staurolite-bearing eclogitic micaschistsfrom the Champtoceaux nappe (Brittany, France) is first described.The Champtoceaux metapelites present, in addition to quartz,phengite, and rutile, two successive parageneses: (1) chloritoid+staurolite+garnetcores, and (2) garnet rims+kyanite?chloritoid. Detailed microprobe analyses show that garnet and chloritoidevolve towards more magnesian compositions and that stauroliteis more Fe-rich than coexisting garnet. A comparison of thestudied rocks with other known occurrences of eclogitic metapelitesshows that whereas staurolite is always more Fe-rich than garnetin high-pressure eclogites, the reverse is true in low- to medium-pressuremicaschists. Phase relations between garnet, staurolite, chloritoid, biotite,and chlorite are analysed in the KFMASH system (with excessquartz, phengite, rutile, and H₂O). The topology of univariantreactions is depicted for a normal and a reverse Fe-Mg partitioningbetween garnet and staurolite. Mineral compositional changesare also predicted for varying bulk-rock chemistries. In the studied micaschists, the zonal arrangement of garnetinclusions and the progressive compositional changes of ferromagnesianphases record part of the prograde P–T path, before theattainment of ‘peak’ metamorphic conditions (atabout 65O–7OO?C, 18–20 kb). The retrograde path,which records the uplift of the Champtoceaux nappe, occurs underdecreasing temperatures.