Polymetamorphic origin of muscovite+cordierite+staurolite+ biotite assemblages: implications for the metapelitic petrogenetic grid and for P–T paths

Metapelites containing muscovite, cordierite, staurolite and biotite (Ms+Crd+St+Bt) are relatively rare but have been reported from a number of low-pressure (andalusite–sillimanite) regional metamorphic terranes. Paradoxically, they do not occur in contact aureoles formed at the same low pressures, raising the question as to whether they represent a stable association. A stable Ms+Crd+St+Bt assemblage implies a stable Ms+Bt+Qtz+Crd+St+Al₂SiO₅+Chl+H₂O invariant point (IP1), the latter which has precluded construction of a petrogenetic grid for metapelites that reconciles natural phase relations at high and low pressure. Petrogenetic grids calculated from internally consistent thermodynamic databases do not provide a reliable means to evaluate the problem because the grid topology is sensitive to small changes in the thermodynamic data. Topological analysis of invariant point IP1 places strict limits on possible phase equilibria and mineral compositions for metamorphic field gradients at higher and lower pressure than the invariant point. These constraints are then compared with natural data from contact aureoles and reported Ms+Crd+St+Bt occurrences. We find that there are numerous topological, textural and compositional incongruities in reported natural assemblages that lead us to argue that Ms+Crd+St+Bt is either not a stable association or is restricted to such low pressures and Fe-rich compositions that it is rarely if ever developed in natural rocks. Instead, we argue that reported Ms+Crd+St+Bt assemblages are products of polymetamorphism, and, from their textures, are useful indicators of P–T  paths and tectonothermal processes at low pressure. A number of well-known Ms+Crd+St+Bt occurrences are discussed within this framework, including south-central Maine, the Pyrenees and especially SW Nova Scotia.     

Singularities in NCKFMASH (Na2O–CaO–K2O–FeO–MgO–Al2O3–SiO2–H2O)

A new petrogenetic grid is presented for the system NCKFMASH (Na₂O–CaO–K₂O–FeO–MgO–Al₂O₃–SiO₂–H₂O), in which Ca is incorporated in garnet, and CaAlNa₋₁Si₋₁ solid solution is considered for both the plagioclase and white-mica structures. A compatibility diagram for plagioclase-bearing metapelitic assemblages within the NCKFMASH system also has been derived. A dominant feature of the NCKFMASH grid is the singularities and associated singular reactions which occur along plagioclase+margarite- and plagioclase+paragonite-bearing univariant equilibria. The singularities represent compositional coplanarities which occur in response to the CaAlNa₋₁Si₋₁ substitution occurring at different rates in plagioclase and white-mica. This is controlled by a fundamental difference in the mixing within the two mineral structures. The singularities give rise to a number of intriguing phase diagram features, including azeotropes. From the results presented here, it is predicted that the occurrence of margarite and paragonite in pelitic rocks is controlled by equilibria related to the singularities. The presence of these white-micas is strongly dependent upon bulk composition, and plagioclase-bearing, margarite/paragonite-free assemblages, typical of Barrovian-type terranes, are predicted for bulk compositions of Mg/(Mg+Fe)≈0.4 and Ca/(Ca+Na)≈0.4 at for example 5.5  kbar.     

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.     

Eclogites from the south Tianshan, NW China: petrological characteristic and calculated mineral equilibria in the Na2O–CaO–FeO–MgO–Al2O3–SiO2–H2O system

Eclogites from the south Tianshan, NW China are grouped into two types: glaucophane and hornblende eclogites, composed, respectively, of garnet + omphacite + glaucophane + paragonite + epidote + quartz and garnet + omphacite + hornblende (sensu lato) + paragonite + epidote + quartz, plus accessory rutile and ilmenite. These eclogites are diverse both in mineral composition and texture not only between the two types but also among the different selected samples within the glaucophane eclogite. Using thermocalc 3.1 and recent models of activity–composition relation for minerals, a P–T projection and a series of P–T pseudosections for specific samples of eclogite have been calculated in the system Na₂O–CaO–FeO–MgO–Al₂O₃–SiO₂–H₂O (NCFMASH) with quartz and water taken to be in excess. On the basis of these phase diagrams, the phase relations and P–T conditions are well delineated. The three selected samples of glaucophane eclogite AK05, AK11 and AK17 are estimated to have peak P–T conditions, respectively, of 540–550 °C at c. 16 kbar, c. 560 °C at 15–17 kbar and c. 580 °C at 15–19 kbar, and two samples of hornblende eclogite AK10 and AK30 of 610–630 °C and 17–18 kbar. Together with H₂O‐content contours in the related P–T pseudosections and textural relations, both types of eclogite are inferred to show clockwise P–T paths, with the hornblende eclogite being transformed from the glaucophane eclogite assemblage dominantly through increasing temperature.     

H2O in metamorphism and unexpected behaviour in the preservation of metamorphic mineral assemblages

The preservation of mineral assemblages that were fluid‐present during their prograde history is primarily related to the consumption of the fluid by growth of more hydrous minerals as the retrograde history begins. The range of behaviour relating to the preservation of mineral assemblages is examined using calculated phase diagrams for fluid‐saturated conditions, contoured for the H₂O content of the mineral assemblage. At equilibrium, as a mineral assemblage crosses contours of decreasing H₂O content along a pressure–temperature path, it dehydrates, the fluid being lost from the rock. If the assemblage crosses contours of increasing H₂O content, the mineral assemblage starts to rehydrate using any fluid on its grain boundaries. When the rock has consumed its fluid, the resulting mineral assemblage is that preserved in the rock. Conditions relating to the preservation of mineral assemblages are discussed, and examples of the consequences of different pressure–temperature paths on preservation in a metapelitic and a metabasic rock composition are considered on phase diagrams calculated with thermocalc .     

Experimental study of the stability of sudoite and magnesiocarpholite and calculation of a new petrogenetic grid for the system FeO–MgO–Al2O3–SiO2–H2O

The solid-solid reaction magnesiocarpholite = sudoite + quartz has been bracketed between 350 and 500°C, 6.3 and 7.8 kbar. Because it is impossible to synthesize end-member sudoite, all experiments were carried out using natural minerals as starting materials. Although mineral compositions were very close to those of the end-members, the effect of the fluorine content in carpholite was significant. Particularly in those experiments where sudoite grows at the expense of carpholite, electron microprobe analysis of the run products shows that a more stable F-rich carpholite crystallizes too, and consumes the fluorine released in solution by the breakdown of the original carpholite.
Our experimental results are combined, through a thermodynamic analysis, with a previous data set and with previous experimental data concerning the relative stability of chlorite, talc and magnesiocarpholite with excess of quartz and water as a function of P–T and AlAl(SiMg)_-1 substitutions in phyllosilicates. This allows us to constrain the feasible thermodynamic parameters (H°_f, sud; S ° sud) and (H°_f,car; S °_car) for the Mg end-members. Using the partition coefficients calculated from natural parageneses, we have computed a petrogenetic grid for the system FeO–MgO–Al₂O₃–SiO₂–H₂O. It demonstrates that parageneses involving sudoite and carpholite can be used as indicators of P–T conditions, up to 600° C, 8 kbar for sudoite, and at higher pressure for carpholite.     

The formation of eclogite facies metatroctolites and a general petrogenetic grid in Na2O–CaO–FeO–MgO–Al2O3–SiO2–H2O (NCFMASH)

Eclogite facies metatroctolites from a variety of Western Alps localities (Voltri, Monviso, Lanzo, Allalin, Zermat–Saas, etc.) that preserve textural evidence of their original form as bimineralic olivine‐plagioclase rocks are considered in terms of calculated mineral equilibria in the system Na₂O‐CaO‐FeO‐MgO‐Al₂O₃‐SiO₂‐H₂O (NCFMASH). Pseudosections, based on a new petrogenetic grid for NCFMASH presented here, are used to unravel the metamorphic history of the metatroctolites, considering the rocks to consist of different composition microdomains corresponding to the original olivine and plagioclase grains. On the basis that the preservation of the mineral assemblage in each microdomain will tend to be from where on a rock's P–T path the metamorphic fluid phase is used up via rehydration reactions, P–T pseudosections contoured for water content, and P–T path‐M_H2O (amount of water) pseudosections, are used to examine fluid behaviour in each microdomain. We show that the different microdomains are likely to preserve their mineral assemblages from different places on the P–T path. For the olivine microdomain, the diagnostic mineral assemblage is chloritoid + talc (+ garnet + omphacite). The preservation of this assemblage, in the light of the closed system P–T path‐M_H2O relationships, implies that the microdomain loses its metamorphic fluid as it starts to decompress, and, in the absence of subsequent hydration, the high pressure mineral assemblage is then preserved. In the plagioclase microdomain, the diagnostic assemblage is epidote (or zoisite) + kyanite + quartz suggesting a lower pressure (of about 2 GPa) than for the olivine microdomain. In the light of P–T path‐M_H2O relationships, development of this assemblage implies breakdown of lawsonite across the lawsonite breakdown reaction, regardless of the maximum pressure reached. It is likely that the plagioclase microdomain was mainly fluid‐absent prior to lawsonite breakdown, only becoming fluid‐present across the reaction, then immediately becoming fluid‐absent again.     

Sapphirine parageneses from the Caraiba complex, Bahia, Brazil: the influence of Fe2+–Fe3+ distribution on the stability of sapphirine in natural assemblages

Abstract Sapphirine-bearing rocks occur in three conformable, metre-size lenses in intrusive quartzo-feldspathic orthogneisses in the Curaçà valley of the Archaean Caraiba complex of Brazil. In the lenses there are six different sapphirine-bearing rock types, which have the following phases (each containing phlogopite in addition): A: Sapphirine, orthopyroxene; B: Sapphirine, cordierite, orthopyroxene, spinel; C: Sapphirine, cordierite; D: Sapphirine, cordierite, orthopyroxene, quartz; E: Sapphirine, cordierite, orthopyroxene, sillimanite, quartz; F: Sapphirine, cordierite, K-feldspar, quartz. Neither sapphirine and quartz nor orthopyroxene and sillimanite have been found in contact, however. During mylonitization, introduction of silica into the three quartz-free rocks (which represent relict protolith material) gave rise to the three cordierite and quartz-bearing rocks. Stable parageneses in the more magnesian rocks were sapphirine–orthopyroxene and sapphirine–cordierite. In more iron-rich rocks, sapphirine–cordierite, sapphirine-cordierite–sillimanite, cordierite–sillimanite, sapphirine–cordierite–spinel–magnetite and quartz–cordierite–orthopyroxene were stable. The iron oxide content in sapphirine of the six rocks increases from an average of 2.0 to 10.5 wt % (total Fe as FeO) in the order: C,F–A,D–B,E. With increase in Fe there is an increase in recalculated Fe₂O₃ in sapphirine. The four rock types associated with the sapphirine-bearing lenses are: I: Orthopyroxene, cordierite, biotite, quartz, feldspar tonalitic to grandioritic gneiss; II: Biotite, quartz, feldspar gneiss; III: Orthopyroxene, clinopyroxene, hornblende, plagioclase meta-norite; IV: Biotite, orthopyroxene, quartz, feldspar, garnet, cordierite, sillimanite granulite gneiss. The stable parageneses in type IV are orthopyroxene–cordierite–quartz, garnet–sillimanite–quartz and garnet–cordierite–sillimanite. Geothermobarometry suggests that the associated host rocks equilibrated at 720–750°C and 5.5–6.5 kbar. Petrogenetic grids for the FMASH and FMAFSH (FeO–MgO–Al₂O₃–Fe₂O₃–SiO₂–H₂O) model systems indicate that sapphirine-bearing assemblages without garnet were stabilized by a high Fe³⁺ content and a high X_Mg= (Mg/ (Mg+Fe²⁺)) under these P–T conditions.     

Desilication veins in the Cadillac Mountain granite (Maine, USA): a record of reversals in the SiO2 solubility of H2O-rich vapour released during subsolidus cooling

Late-stage hydrous fluids, which evolved during the cooling of the Cadillac Mountain granite, Maine, USA, produced narrow veins that transect the pluton. The vein margins contain microstructures transitional between granite and the vein centre. They preserve the vestige shapes of original Na-rich alkali feldspar crystals that have been pseudomorphed by cordierite+quartz+K-rich alkali feldspar. Closer to the centres of the veins, the minerals change from an outer zone with cordierite, hercynitic–galaxite spinel, minor corundum, K-feldspar and plagioclase to an inner zone with remnant cordierite, hercynitic gahnite, strongly zoned almandine–spessartine garnet, chlorite and quartz. Three allochemical reactions are inferred to have occurred with the influx of hydrous fluids during the replacement process. Reaction (1) is Na-rich alkali feldspar+iron ions in solution=Fe-cordierite+quartz+K-feldspar+sodium ions in solution. Reactions (2) and (3) occurred during desilication. Reaction (2) is Fe-cordierite=hercynite+silica in solution, and reaction (3) is Fe-cordierite+water=corundum+iron hydroxide in solution+silicic acid in solution. Two independent techniques, experimental silica-solubility data and spinel–cordierite thermobarometry, constrain the conditions of vein formation to c.   1.0  kbar and both methods indicate that the progressive mineral reactions occurred during cooling of the hydrous fluids from c. 775° to 400–340  °C. This cooling trend is consistent with the petrographic evidence, which demonstrates that reactions occurred before desilication, during desilication, and then diminished with a final phase of resilication. Although the veins are minor features of the Cadillac Mountain granite, they provide insight into the conditions that prevailed during cooling of the pluton, and similar features may be important for constraining the cooling history of shallow-level plutonic complexes elsewhere.     

Interpreting prograde-growth histories of Al2SiO5 triple-point rocks using oxygen-isotope thermometry: an example from the Truchas Mountains, USA

Oxygen‐isotope compositions of kyanite, andalusite, prismatic sillimanite and fibrolite from the Proterozoic terrane in the Truchas Mountains, New Mexico differ from one another, suggesting that these minerals did not grow in equilibrium at the Al₂SiO₅ (AS) polymorph‐invariant point as previously suggested. Instead, oxygen‐isotope temperature estimates indicate that growth of kyanite, andalusite and prismatic sillimanite occurred at c. 575, 615 and 640 °C respectively. Temperature estimates reported in this paper are interpreted as those of growth for the different AS polymorphs, which are not necessarily the same as peak metamorphic temperatures for this terrane. Two distinct temperature estimates of c. 580 °C and c. 700 °C are calculated for most fibrolite samples, with two samples yielding clear evidence of quartz‐fibrolite oxygen‐isotope disequilibrium. These data indicate that locally, and potentially regionally, oxygen‐isotope disequilibrium between quartz and fibrolite may have resulted from rapid fibrolite nucleation. Pressures of mineral growth that were extrapolated from oxygen‐isotope thermometry results and calculated using petrological constraints suggest that kyanite and one generation of fibrolite grew during M1 at 5 kbar, and that andalusite, prismatic sillimanite and a second generation of fibrolite grew during M2 at 3.5 kbar. M1 and M2 therefore represent two distinct metamorphic events that occurred at different crustal levels. The ability of the AS polymorphs to retain δ¹⁸O values of crystallization make these minerals ideal to model prograde‐growth histories of mineral assemblages in metamorphic terranes and to understand more clearly the pressure–temperature histories of multiple metamorphic events.     

Oxygen isotope study of quartz-Al2SiO5 pairs from the Mica Creek area, British Columbia: implications for the recovery of peak metamorphic temperatures

Oxygen isotope analyses of quartz-Al₂SiO₅ pairs have been made for samples from the Mica Creek area, British Columbia. We have analysed quartz–kyanite nodules and quartz–kyanite and quartz–sillimanite in multiphase pelitic rocks from the staurolite–kyanite, kyanite, and sillimanite zones. Apparent temperatures calculated from oxygen isotopic fractionation range from 555 °C (staurolite–kyanite zone) to 695 °C (sillimanite zone). Temperatures from the quartz–kyanite nodules range from 630 to 675 °C. Some of the nodules show isotopic disequilibrium. Most of the results confirm predictions that bimineralic rocks will yield an estimate of peak metamorphic temperatures, when the less abundant mineral (an aluminium silicate) is the slower oxygen diffuser. Using cooling rates of 10–100 °C Ma^?1 for the multiphase rocks, measured crystal sizes and modes, the Fast Grain Boundary diffusion model with ‘wet’ diffusion data (P_H2O?1.0 kbar) yields predicted apparent temperatures which are generally lower than the measured apparent temperatures. The agreement is improved if slower diffusion coefficients are used. This suggests that f (H₂O) during cooling was lower than that of the hydrothermal experiments and thus that there was little interaction with aqueous fluids of internal or external origin to modify the isotopic compositions. The measured apparent isotopic temperatures and apparent garnet–biotite Fe–Mg exchange temperatures show very poor agreement for the sillimanite zone samples, with the garnet–biotite Fe–Mg exchange temperatures generally higher than the oxygen isotope temperatures. Compared with the other calibrations that we tested the measured apparent temperatures using the Sharp calibration show the best agreeement with recently published P–T grids, although some variability in agreement is expected due to variable f (H₂O) during cooling.     

Calculated mineral equilibria for eclogites in CaO–Na2O–FeO–MgO–Al2O3–SiO2–H2O: application to the Pouébo Terrane, Pam Peninsula, New Caledonia

The high- P , medium- T  Pouébo terrane of the Pam Peninsula, northern New Caledonia includes barroisite- and glaucophane-bearing eclogite and variably rehydrated equivalents. The metamorphic evolution of the Pouébo terrane is inferred from calculated P–T  and P–T  – X H2O pseudosections for bulk compositions appropriate to these rocks in the model system CaO–Na₂O–FeO–MgO–Al₂O₃–SiO₂–H₂O. The eclogites experienced a clockwise P–T  path that reached P ≈19  kbar and T  ≈600  °C. The eclogitic mineral assemblages are preserved because reaction consequent upon decompression consumed the rocks' fluid. Extensive reaction occurred only in rocks with fluid influx during decompression of the Pouébo terrane.