Revised empirical garnet–biotite–muscovite–plagioclase geobarometer in metapelites

The garnet–biotite–muscovite–plagioclase (GBMP) barometer was empirically revised for P–T conditions of 1–14 kbar and 450–840 °C, using 263 metapelitic rock samples from all over the world. This barometer is based on activity models for garnet, biotite and plagioclase identical to those of the well‐calibrated garnet–biotite thermometer and the garnet–aluminosilicate–plagioclase–quartz (GASP) barometer. The GBMP barometer is less temperature dependent than the GASP barometer and can be applied to either Al₂SiO₅‐absent or Al₂SiO₅‐bearing metapelites. The total error of the GBMP barometer is estimated to be about ±1.2 kbar on considering input temperature error and analytical errors of chemical compositions of the phases involved. The random error of the GBMP barometer is evenly distributed with respect to pressure, temperature and mineral composition. Simultaneous application of the GBMP barometer and the garnet–biotite thermometer identifies the correct stability field for Al₂SiO₅‐bearing metapelites. Application of the GBMP barometer to metapelitic rocks within the same geological terranes or thermal contact aureoles yielded similar pressures within error. A spreadsheet for implementing the proposed GBMP geobarometer is supplied on the journal's website.     

The metapelitic garnet–biotite–muscovite–aluminosilicate–quartz (GBMAQ) geobarometer

In this contribution we have empirically calibrated the garnet–biotite–muscovite–aluminosilicate–quartz (GBMAQ) barometer using low- to medium–high-pressure, mid-grade metapelites. Application of the barometer suggests that the GBMAQ and GASP barometers show quite similar pressure estimates. Furthermore, metapelites within thermal contact aureole or very limited geographic area show no meaningful pressure diversity determined by the GBMAQ and GASP barometers which is the geological reality. The random error of the GBMAQ barometer is expected to be around ± 0.8 kbar, and this barometer shows no systematic bias with respect to either pressure, or temperature, or Al^VI in muscovite, or Fe in biotite, or Fe in garnet. The GBMAQ barometer is thermodynamically consistent with the garnet–biotite geothermometer because they share the same activity models of both garnet and biotite. This barometer is especially useful for assemblages with Ca-poor garnet or Ca-poor plagioclase or plagioclase-absent metapelites. Application of this barometer beyond the calibration ranges, i.e., P–T range and chemical ranges of the minerals, is not encouraged.     

A recalibration of the garnet-olivine geothermometer and a new geobarometer for garnet peridotites and garnet-olivine-plagioclase-bearing granulites

The garnet-olivine Fe-Mg exchange geothermometer and the garnet-olivine-plagioclase geobarometer have been simultaneously calibrated using reversed experimental data based on the model reactions and between 900 and 1500 °C at 9.1–95.0 kbar and between 4.7 and 7.0 kbar at 750–1050 °C, respectively. The resulting garnet-olivine thermometer reproduces experimental temperatures mostly within ±75 °C and the garnet-olivine-plagioclase barometer reproduces experimental pressures well within ±0.19 kbar. These new thermobarometers use the same garnet and olivine activity models and are thermodynamically consistent. Application of these thermobarometers to garnet peridotites from mantle xenoliths, orogenic garnet peridotites over the world and the Adirondack olivine-bearing metagabbros yielded reasonable P–T results. The present garnet-olivine thermometer can be used to measure medium-high-grade to ultrahigh-grade, low-pressure to ultrahigh–high-pressure garnet peridotites and metagabbros, whereas the garnet-olivine-plagioclase barometer has limited application to garnet-olivine-plagioclase-bearing granulites.     

Garnet and spinel lherzolite assemblages in MgO–Al2O3–SiO2 and CaO–MgO–Al2O3–SiO2: thermodynamic models and an experimental conflict

The recent publication of an updated thermodynamic dataset for petrological calculations provides an opportunity to illustrate the relationship between experimental data and the dataset, in the context of a new set of activity–composition models for several key minerals. These models represent orthopyroxene, clinopyroxene and garnet in the system CaO–MgO–Al₂O₃–SiO₂ (CMAS), and are valid up to 50 kbar and at least 1800 °C; they are the first high‐temperature models for these phases to be developed for the Holland & Powell dataset. The models are calibrated with reference to phase‐relation data in the subsystems CaO–MgO–SiO₂ (CMS) and MgO–Al₂O₃–SiO₂ (MAS), and will themselves form the basis of models in larger systems, suitable for calculating phase equilibria in the crust and mantle. In the course of calibrating the models, it was necessary to consider the reaction orthopyroxene + clinopyroxene + spinel = garnet + forsterite in CMAS, representing a univariant transition between simple spinel and garnet lherzolite assemblages. The high‐temperature segment of this reaction has been much disputed. We offer a powerful thermodynamic argument relating this reaction to the equivalent reaction in MAS, that forces us to choose between good model fits to the data in MAS or to the more recent data in CMAS. We favour the fit to the MAS data, preserving conformity with a large body of experimental and thermodynamic data that are incorporated as constraints on the activity–composition modelling via the internally consistent thermodynamic dataset.     

The stability of sapphirine + quartz: calculated phase equilibria in FeO–MgO–Al2O3–SiO2–TiO2–O

The presence in rocks of coexisting sapphirine + quartz has been widely used to diagnose conditions of ultra‐high‐temperature (UHT) metamorphism (>900 °C), an inference based on the restriction of this assemblage to temperatures >980 °C in the conventionally considered FeO–MgO–Al₂O₃–SiO₂ (FMAS) chemical system. With a new thermodynamic model for sapphirine that includes Fe₂O₃, phase equilibra modelling using thermocalc software has been undertaken in the FeO–MgO–Al₂O₃–SiO₂–O (FMASO) and FeO–MgO–Al₂O₃–SiO₂– TiO₂–O (FMASTO) chemical systems. Using a variety of calculated phase diagrams for quartz‐saturated systems, the effects of Fe₂O₃ and TiO₂ on FMAS phase relations are shown to be considerable. Importantly, the stability field of sapphirine + quartz assemblages extends down temperature to 850 °C in oxidized systems and thus out of the UHT range.     

Geothermobarometry of Al2SiO5-bearing metapelites in the western Austroalpine Ötztal-basement

Summary The dominant amphibolite-facies Variscan event in the Austroalpine Ötztal basement can best be studied in the northwestern part of the Ötztal block. Further to the southeast it is overprinted by Alpine metamorphism. Metapelites with the assemblage garnet-staurolite-kyanite-sillimanite±andalusite-biotite-muscovite-plagioclase were used to reconstruct pressure and temperature conditions with exchange thermometry, net transfer equilibria and multi-equilibrium methods. Assuming kyanite as equilibrium Al₂SiO₅ polymorph, conditions of 570–640°C and 5.8–7.5kbar are derived using garnet rim compositions. Typical nonequilibrium textures are (1) continuous chemical zoning of garnets, (2) inclusions of kyanite and fibrolite in andalusite porphyroblasts and (3) the spectacular replacement of garnet by fibrolite and biotite. The latter two textures were used to decipher the retrograde part of the P-T path. Application of the differential thermodynamics approach (Gibbs method) indicates prograde garnet growth during pressure release. Addition of CaO to the KFASH-system allows the garnet breakdown within the staurolite stability field and its quantification, using the quartz-garnet-aluminosilicate-muscovite geothermobarometer, revealed temperatures of 530–630°C and 3.5–5.7kbar. Andalusite formation is thought to constrain the final stage of the P-T path. Textural and chemical data clearly indicate a continuous pre-Alpine metamorphic evolution.

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Geothermobarometrie in Al₂SiO₅ führenden Metapeliten des westlichen Ötztal Kristallins

Zusammenfassung Die dominierende variszische Metamorphose im ostalpinen Ötztal Kristallin kann aufgrund der Zunahme der alpidischen Überprägung nach Südosten am besten im nordwestlichen Teil des Ötztal Kristallins untersucht werden. Die Metamorphosebedingungen wurden in den Metapeliten anhand der Paragenese Granat-Staurolith-Kyanit-Sillimanit±Andalusit-Biotit-Muskovit-Plagioklas mit Hilfe von Kationenaustauschthermometrie, kontinuierlichen Mineralreaktionen und der Berechnung aller formulierbaren Mineral-Gleichgewichte durchgeführt. Mit der Annahme von Kyanit als Teil der Gleichgewichtsparagenese wurden Temperaturen von 570–640°C und Drucke von 5.8–7.5kbar für die Granatränder ermittelt. Folgende Ungleichgewichtsphänomene wurden zur Belegung des Metamorphosepfades herangezogen: (1) Kontinuierlicher Granatzonarbau (2) Andalusitporphyroblasten mit Kyanit-und Fibrolitheinschlüssen und (3) die Reaktion von Granat zu Biotit und Fibrolith Pseudomorphosen. Die Anwendung der Gibbs-Methode lässt Rückschlüsse auf ein progrades Granatwachstum bei fallenden Drücken und steigenden Temperaturen zu. Die Erweiterung des KFASH-Systems mit CaO ermöglicht den Granatzerfall noch im Stabilitätsfeld von Staurolith und die Anwendung des Granat-Muskovit-Aluminiumsilikat-Quarz Geothermobarometers belegt den Granatzerfall bei 530–630°C und 3.5–5.7kbar. Die Andalusitkristallisation wird als letztes Stadium des Druck-Temperatur Pfades angenommen. Texturelle und chemische Untersuchungen lassen den Schluss auf eine einphasige variszische Metamorphose zu.

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With 9 Figures     

Epitaxial quartz inclusions in corundum from a sapphirine–garnet boudin,Bamble Sector,SE Norway: SiO2–Al2O3 miscibility at high P–T dry granulite facies conditions

An Al‐rich, SiO₂‐deficient sapphirine–garnet‐bearing rock occurs as a metapelitic boudin within granulite facies Proterozoic charnockitic gneisses and migmatites on the island of Hisøy, Bamble Sector, SE Norway. The boudin is made up of peraluminous sapphirine, garnet, corundum, spinel, orthopyroxene, sillimanite, cordierite, staurolite and biotite in a variety of assemblages. Thermobarometric calculations based on coexisting sapphirine–spinel, garnet–corundum–spinel–sillimanite, sapphirine–orthopyroxene, and garnet–orthopyroxene indicate peak‐metamorphic conditions near to 930 °C at 10 kbar. Corundum occurs as single 200 to 3000 micron sized skeletal crystal intergrowths in cores of optically continuous pristine garnet porphyroblasts. Quartz occurs as 5–60 micron‐sized euhedral to lobate inclusions in the corundum where it is in direct contact with the corundum with no evidence of a reaction texture. Some crystal inclusions exhibit growth zoning, which indicates that textural equilibrium was achieved. Electron Back‐Scatter Diffraction (EBSD) studies reveal that the quartz inclusions share a common c‐axis with the host corundum crystal. The origin of the quartz inclusions in corundum is enigmatic as recent experimental studies have confirmed the instability of quartz–corundum over geologically realistic P–T ranges. The combined EBSD and textural observations suggest the presence of a former silica‐bearing proto‐corundum, which underwent exsolution during post‐peak‐metamorphic uplift and cooling. Exsolution of quartz in corundum is probably confined to fluid‐absent conditions where phase transitions by coupled dissolution–precipitation mechanisms are prevented.     

Two-stage growth of porphyroblastic biotite and garnet in the Barrovian metapelites of the Imjingang belt, central Korea

Porphyroblastic biotite and garnet in the Barrovian metapelites of the Imjingang belt, Korea, were investigated to unravel the sequence and mechanism of mineral growth. Poikiloblastic biotite contains straight inclusion trails (S_i) discontinuous to the major foliation, and develops clear zones at the grain margin. These microstructures suggest an initial growth of biotite between two contractional deformations (D_n−1 and D_n) followed by an overgrowth during D_n. Although garnet poikiloblasts contain variable S_i patterns, their major growth is likely to have occurred during D_n on the basis of compositional relationships among variable garnet types. Early poikiloblasts of both minerals were formed by chemical replacement of the matrix that consisted mainly of chlorite, muscovite and quartz. Subsequent growth of biotite was governed by a crack-filling mechanism, and was accompanied by the production of extensional cracks inside or around biotite, providing fluid pathways. The overgrowth of garnet was favoured at the biotite–garnet interface, and the consequence was a partial replacement of inclusion-poor garnet after biotite subsequent to D_n. In addition, clear zones and pressure shadows as well as the matrix around biotite porphyroblasts were replaced by garnet, suggesting an inheritance of various pre-existing microstructures in the S_i pattern of garnet. Further attention is thus required for any attempt to delineate the microstructural interaction between deformation and metamorphism, particularly in a sample containing early-grown porphyroblasts. Microstructural evidence for the two-stage growth of biotite and garnet is present up to the kyanite zone, indicating that this growth mechanism is prevalent during progressive metamorphism of Barrovian metapelites.     

Distribution of Fe and Mg between coexisting garnet and hornblende in synthetic and natural systems: an empirical calibration of the garnet–hornblende Fe–Mg geothermometer

Multiple regression analysis of a compilation of the Fe²⁺–Mg distribution between garnet and hornblende from experimental runs on basaltic to intermediate compositions (n=22) and coexisting garnet–clinopyroxene–hornblende from natural (intermediate to basaltic) rocks (n=43) has been performed to define ln K_{D(Fe²⁺/Mg)}^Grt–Hbl as a function of temperature and garnet composition. The regression of data covering a large span in pressure (5–16 kbar), temperature (515–1025°C) and composition yields the ln K_{D(Fe²⁺/Mg)}^Grt–Hbl–P–T compositional relationship (r²=0.93):

where

Application of this expression to natural garnet–hornblende pairs in intermediate to basaltic and semipelitic rock types from various settings gives temperatures that are consistent with other methods.     

The P–T evolution of ultra high temperature garnet‐bearing ultramafic rocks from the Saxonian Granulitgebirge Core Complex,Bohemian Massif

Garnet‐bearing ultramafic rocks (GBUR) enclosed in granulite or high‐grade gneiss are rare, yet typical constituents of alpine‐type collisional orogens. The Bohemian Massif of the European Variscides is exceptional for the occurrence of a large variety of mantle‐derived rocks, including GBUR (garnet peridotite and garnet pyroxenite). GBUR occur in several metamorphic units belonging to both the Saxothuringian and the Moldanubian zones of the Bohemian Massif. The northernmost outcrops of GBUR in the Bohemian Massif are situated in the Saxonian Granulitgebirge Core Complex in the Saxothuringian zone and are the subject of this study. Thermobarometric results and exsolution textures imply that the Granulitgebirge GBUR belong to the ultra high temperature group of peridotites. They experienced a decompression‐cooling path being constrained by the following four stages: (i) ～1300–1400 °C and 32 kbar, (ii) 1000–1050 °C and 26 kbar, (iii) 900–940 °C and 22 kbar, and (iv) 860 °C and 12–13 kbar. Occasional layers of garnet pyroxenite within GBUR lenses are interpreted as high pressure cumulates that crystallized at 32–36 kbar by cooling below 1400 °C. The GBUR were most probably derived from upwelling asthenosphere and came in contact with crustal granulite at ～60 km depth. Slab break‐off is suggested here as the most probable cause for: (i) asthenosphere upwelling and cooling of the latter as well as (ii) ultra high temperature granulite facies metamorphism of the crustal host rocks. The Granulitgebirge‐type peridotite is very similar to the Mohelno‐type peridotite from the Gföhl unit, Moldanubian zone, in the southern part of the Bohemian Massif. In contrast, peridotite from the adjacent Erzgebirge (also within the Saxothuringian zone) is derived from the subcontinental mantle and much resembles the Nove Dvory‐type peridotite from the Gföhl unit (Moldanubian zone). The fact that the Saxothuringian and Moldanubian zones host the same types of mantle rocks (asthenospheric and lithospheric) of the same metamorphic ages suggests that the classic distinction into the Saxothuringian and Moldanubian zones cannot be supported, at least as far as high‐grade units hosting GBUR are concerned.     

A new thermodynamic model for sapphirine: calculated phase equilibria in K2O–FeO–MgO–Al2O3–SiO2–H2O–TiO2–Fe2O3

The activity–composition (a–x) relations of sapphirine are re‐evaluated in the light of a recent new internally‐consistent data set of phase end‐members for use in phase equilibria modelling, particularly of ultra‐high‐temperature (UHT) rocks. This is achieved with the aid of relatively oxidized sapphirine+quartz‐bearing granulites from Wilson Lake, Canada. Calculated P–T projections and compatibility diagrams in the K₂O–FeO–MgO–Al₂O₃–SiO₂–H₂O–TiO₂–Fe₂O₃ (KFMASHTO) system are used to illustrate sapphirine+quartz‐bearing phase equilibria in the context of UHT metamorphism. These new a–x relations for sapphirine should allow pseudosection thermobarometry in NCKFMASHTO for estimating peak P–T conditions of sapphirine‐bearing rocks.     

Calculation of partial melting equilibria in the system Na2O–CaO–K2O–FeO–MgO–Al2O3–SiO2–H2O (NCKFMASH)

A thermodynamic model for haplogranitic melts in the system Na₂O–CaO–K₂O–Al₂O₃–SiO₂–H₂O (NCKASH) is extended by the addition of FeO and MgO, with the data for the additional end‐members of the liquid incorporated in the Holland & Powell (1998) internally consistent thermodynamic dataset. The resulting dataset, with the software thermocalc , is then used to calculate melting relationships for metapelitic rock compositions. The main forms for this are P–T and T–X pseudosections calculated for particular rock compositions and composition ranges. The relationships in these full‐system pseudosections are controlled by the low‐variance equilibria in subsystems of NCKFMASH. In particular, the solidus relationships are controlled by the solidus relationships in NKASH, and the ferromagnesian mineral relationships are controlled by those in KFMASH. However, calculations in NCKFMASH allow the relationships between the common metapelitic minerals and silicate melt to be determined. In particular, the production of silicate melt and melt loss from such rocks allow observations to be made about the processes involved in producing granulite facies rocks, particularly relating to open‐system behaviour of rocks under high‐grade conditions.     

An enlarged and updated internally consistent thermodynamic dataset with uncertainties and correlations: the system K2O–Na2O–CaO–MgO–MnO–FeO–Fe2O3–Al2O3–TiO2–SiO2–C–H2–O2

We present, as a progress report, a revised and much enlarged version of the thermodynamic dataset given earlier (Holland & Powell, 1985). This new set includes data for 123 mineral and fluid end-members made consistent with over 200 P–T–X_CO2–f_O2 phase equilibrium experiments. Several improvements and advances have been made, in addition to the increased coverage of mineral phases: the data are now presented in three groups ranked according to reliability; a large number of iron-bearing phases has been included through experimental and, in some cases, natural Fe:Mg partitioning data; H₂O and CO₂ contents of cordierites are accounted for with the solution model of Kurepin (1985); simple Landau theory is used to model lambda anomalies in heat capacity and the Al/Si order–disorder behaviour in some silicates, and Tschermak-substituted end-members have been derived for iron and magnesium end-members of chlorite, talc, muscovite, biotite, pyroxene and amphibole. For the subset of data which overlap those of Berman (1988), it is encouraging to find both (1) very substantial agreement between the two sets of thermodynamic data and (2) that the two sets reproduce the phase equilibrium experimental brackets to a very similar degree of accuracy. The main differences in the two datasets involve size (123 as compared to 67 end-members), the methods used in data reduction (least squares as compared to linear programming), and the provision for estimation of uncertainties with this dataset. For calculations on mineral assemblages in rocks, we aim to maximize the information available from the dataset, by combining the equilibria from all the reactions which can be written between the end-members in the minerals. For phase diagram calculations, we calculate the compositions of complex solid solutions (together with P and T) involved in invariant, univariant and divariant assemblages. Moreover we strongly believe in attempting to assess the probable uncertainties in calculated equilibria and hence provide a framework for performing simple error propagation in all calculations in thermocalc, the computer program we offer for an effective use of the dataset and the calculation methods we advocate.     

Internally consistent data for sulphur‐bearing phases and application to the construction of pseudosections for mafic greenschist facies rocks in Na2O–CaO–K2O–FeO–MgO–Al2O3–SiO2–CO2–O–S–H2O

The Holland and Powell internally consistent data set version 5.5 has been augmented to include pyrite, troilite, trov (Fe_0.875S), anhydrite, H₂S, elemental S and S₂ gas. Phase changes in troilite and pyrrhotite are modelled with a combination of multiple end‐members and a Landau tricritical model. Pyrrhotite is modelled as a solid solution between hypothetical end‐member troilite (trot) and Fe_0.875S (trov); observed activity–composition relationships fit well to a symmetric formalism model with a value for w_trot?trov of ?3.19 kJ mol^?1. The hypothetical end‐member approach is required to compensate for iron distribution irregularities in compositions close to troilite. Mixing in fluids is described with the van Laar asymmetric formalism model with a_ij values for H₂O–H₂S, H₂S–CH₄ and H₂S–CO₂ of 6.5, 4.15 and 0.045 kJ mol^?1 respectively. The derived data set is statistically acceptable and replicates the input data and data from experiments that were not included in the initial regression. The new data set is applied to the construction of pseudosections for the bulk composition of mafic greenschist facies rocks from the Golden Mile, Kalgoorlie, Western Australia. The sequence of mineral assemblages is replicated successfully, with observed assemblages predicted to be stable at X(CO₂) increasing with increasing degree of hydrothermal alteration. Results are compatible with those of previous work. Assemblages are insensitive to the S bulk content at S contents of less than 1 wt%, which means that volatilization of S‐bearing fluids and sulphidation are unlikely to have had major effects on the stable mineral assemblage in less metasomatized rocks. The sequence of sulphide and oxide phases is predicted successfully and there is potential to use these phases qualitatively for geobarometry. Increases in X(CO₂) stabilized, in turn, pyrite–magnetite, pyrite–hematite and anhydrite–pyrite. Magnetite–pyrrhotite is predicted at temperatures greater than 410 °C. The prediction of a variety of sulphide and oxide phases in a rock of fixed bulk composition as a function of changes in fluid composition and temperature is of particular interest because it has been proposed that such a variation in phase assemblage is produced by the infiltration of multiple fluids with contrasting redox state. The work presented here shows that this need not be the case.     

A thermodynamic model for silicate melt in CaO–MgO–Al2O3–SiO2 to 50 kbar and 1800 °C

A fully thermodynamic model for mafic melt in CaO–MgO–Al₂O₃–SiO₂ (CMAS) has been calibrated, for calculation of melting equilibria in the pressure range 0–50 kbar. It is intended as a preliminary step towards a large‐system melt model, suitable for exploring melting, melt loss and crystallization processes in a wide range of natural rock compositions. Calibration was performed with attention to the model's behaviour in its compositional subsystems, as a rigorous test of model structure and parameterization. The model is consistent with the latest Holland & Powell thermodynamic data set, and can therefore be used to calculate phase relations in conjunction with the many solid‐phase activity–composition models written for the data set. Model calculations successfully reproduce experimental melting reactions in CMAS spinel lherzolite and garnet lherzolite assemblages, as well as sapphirine‐ and kyanite‐bearing assemblages, at moderate to high pressure. Thermodynamically sensitive features, such as thermal divides are also recovered. However, some changes to the model structure will be required before the model can describe the full range of mafic and ultramafic melt compositions known from experiment at low pressures.     

ELF isosurface maps for the Al2SiO5 polymorphs

This study examines the electron localization function (ELF) isosurfaces of the Al₂SiO₅ polymorphs kyanite, sillimanite, and andalusite to see how differences in coordination and geometry of the cations and anions affect the ELF isosurfaces. Examination of the ELF isosurfaces indicates that their shapes are dependent on the coordination and geometry of the oxygen atoms and are not sensitive to coordination of the surrounding cations. Of the 18 crystallographically distinct oxygen atoms in the Al₂SiO₅ polymorphs, 13 are bonded to two aluminum atoms and one silicon atom (Al₂–O–Si) and are associated with two different ELF isosurface shapes. The shape of the ELF isosurface is dependent on the distance at which the oxygen atom lies from a plane defined by the three surrounding cations: at a distance greater than 0.2 Å the ELF can be defined as horseshoe-shaped and at a distance less then 0.2 Å it can be described as concave hemispherical. This feature is also seen in the ELF isosurfaces for the oxygens bonded to three aluminum atoms (Al₃–O) where the isosurfaces can be defined as trigonally toroidal and uniaxially trigonally toroidal. The changes in the ELF isosurfaces for the three coordinated oxygens are also indicative of changes in hybridization. The ELF isosurface for the two-fold coordinated oxygen (Al–O–Si) has a large mushroom-shaped isosurface along the Al–O bond and a concave hemispherical isosurface along the Si–O. The four-fold coordinated oxygen (Al₄–O) contains two concave hemispherical isosurfaces along the shorter Al–O bonds and a banana-shaped isosurface, which encompasses the longer Al–O bonds. In addition, this study shows the homeomorphic relationship between the ELF isosurfaces and electron density difference maps with respect to number and arrangement of domains.     

Kinetic control of staurolite–Al2SiO5 mineral assemblages: Implications for Barrovian and Buchan metamorphism

The distribution and textural features of staurolite–Al₂SiO₅ mineral assemblages do not agree with predictions of current equilibrium phase diagrams. In contrast to abundant examples of Barrovian staurolite–kyanite–sillimanite sequences and Buchan‐type staurolite–andalusite–sillimanite sequences, there are few examples of staurolite–sillimanite sequences with neither kyanite nor andalusite anywhere in the sequence, despite the wide (~2.5 kbar) pressure interval in which they are predicted. Textural features of staurolite–kyanite or staurolite–andalusite mineral assemblages commonly imply no reaction relationship between the two minerals, at odds with the predicted first development (in a prograde sense) of kyanite or andalusite at the expense of staurolite in current phase diagrams. In a number of prograde sequences, the incoming of staurolite and either kyanite, in Barrovian sequences, or andalusite, in Buchan‐type sequences, is coincident or nearly so, rather than kyanite or andalusite developing upgrade of a significant staurolite zone as predicted. The width of zones of coexisting staurolite and either kyanite, in Barrovian sequences, or andalusite, in Buchan‐type sequences, is much wider than predicted in equilibrium phase diagrams, and staurolite commonly persists upgrade until its demise in the sillimanite zone. We argue that disequilibrium processes provide the best explanation for these mismatches. We suggest that kyanite (or andalusite) may develop independently and approximately contemporaneously with staurolite by metastable chlorite‐consuming reactions that occur at lower P–T conditions than the thermodynamically predicted staurolite‐to‐kyanite/andalusite reaction, a process that involves only modest overstepping (<15°C) of the stable chlorite‐to‐staurolite reaction and which is favoured, in the case of kyanite, by advantageous nucleation kinetics. If so, the pressure difference between Barrovian kyanite‐bearing sequences and Buchan andalusite‐bearing sequences could be ~1 kbar or less, in better agreement with the natural record. The unusual width of coexistence of staurolite and Al₂SiO₅ minerals, in particular kyanite and andalusite, can be accounted for by a combination of lack of thermodynamic driving force for conversion of staurolite to kyanite or andalusite, sluggish dissolution of staurolite, and possibly the absence of a fluid phase to catalyse reaction. This study represents an example of how kinetic controls on metamorphic mineral assemblage development have to be considered in regional as well as contact metamorphism.     

The effect of Mn on mineral stability in metapelites revisited: new a–x relations for manganese‐bearing minerals

The a–x relations recently presented in White et al. ( 2014 , Journal of Metamorphic Geology, 32, 261–286) are extended to include MnO. This provides a set of internally consistent a–x relations for metapelitic rocks in the MnO–Na₂O–CaO–K₂O–FeO–MgO–Al₂O₃–SiO₂–H₂O–TiO₂–O₂ (MnNCKFMASHTO) system. The mixing parameters for the Mn‐bearing minerals were estimated using the micro‐? approach of Powell et al. ( 2014 , Journal of Metamorphic Geology, 32, 245–260). Then the Mn‐end‐member thermodynamic properties were calibrated using a database of co‐existing minerals involving literature data from rocks and from experiments on natural materials. Mn‐end‐members were calibrated for orthopyroxene, cordierite, staurolite, chloritoid, chlorite, biotite, ilmenite and hematite, assuming known properties for the garnet end‐member spessartine. The addition of MnO to phase diagram calculations results in a marked expansion of the stability of garnet‐bearing assemblages. At greenschist facies conditions garnet stability is extended down temperature. At amphibolite facies conditions, the garnet‐in boundary shifts to lower pressure. While the addition of MnO greatly influences the stability of garnet, it has relatively little effect on the stability of other common metapelitic minerals, with the resultant diagrams being topologically very similar to those calculated without MnO. Furthermore, the addition of MnO in the amounts measured in most metapelites has only a small effect on the mode of garnet, with calculated garnet modes remaining smaller than 1% in the P–T range outside its predicted Mn‐free P–T range.     

Metamorphic petrology of a high‐T/low‐P granulite terrane (Damara belt,Namibia) – Constraints from pseudosection modelling and high‐precision Lu–Hf garnet‐whole rock dating

Migmatites comprise a minor volume of the high‐grade part of the Damara orogen of Namibia that is dominated by granite complexes and intercalated metasedimentary units. Migmatites of the Southern Central Zone of the Damara orogen consist of melanosomes with garnet+cordierite+biotite+K‐feldspar, and leucosomes, which are sometimes garnet‐ and cordierite‐bearing. Field evidence, petrographic observations, and pseudosection modelling suggest that, in contrast to other areas where intrusion of granitic magmas is more important, in situ partial melting of metasedimentary units was the main migmatite generation processes. Pseudosection modelling and thermobarometric calculations consistently indicate that the peak‐metamorphic grade throughout the area is in the granulite facies (~5 kbar at ~800°C). Cordierite coronas around garnet suggest some decompression from peak‐metamorphic conditions and rare andalusite records late, near‐isobaric cooling to <650°C at low pressures of ~3 kbar. The inferred clockwise P–T path is consistent with minor crustal thickening through continent–continent collision followed by limited post‐collisional exhumation and suggests that the granulite facies terrane of the Southern Central Zone of the Damara orogen formed initially in a metamorphic field gradient of ~35–40°C/km at medium pressures. New high‐precision Lu–Hf garnet‐whole rock dates are 530 ± 13 Ma, 522.0 ± 0.8 Ma, 520.8 ± 3.6 Ma, and 500.3 ± 4.3 Ma for the migmatites that record temperatures of ~800°C. This indicates that high‐grade metamorphism lasted for c. 20–30 Ma, which is compatible with previous estimates using Sm–Nd garnet‐whole rock systematics. In previous studies on Damara orogen migmatites where both Sm–Nd and Lu–Hf chronometers have been applied, the dates (c. 520–510 Ma) agree within their small uncertainties (0.6–0.8% for Sm–Nd and 0.1–0.2% for Lu–Hf). This implies rapid cooling after high‐grade conditions and, by implication, rapid exhumation at that time. The cause of the high geothermal gradient inferred from the metamorphic conditions is unknown but likely requires some extra heat that was probably added by intrusion of magmas from the lithospheric mantle, i.e., syenites that have been recently re‐dated at c. 545 Ma. Some granites derived from the lower crust at c. 545 Ma are the outcome rather than the cause of high‐T metamorphism. In addition, high contents of heat‐producing elements K, Th, and U may have raised peak temperatures by 150–200°C at the base of the crust, resulting in the widespread melting of fertile crustal rocks. The continuous gradation from centimetre‐scale leucosomes to decametre‐scale leucogranite sheets within the high‐grade metamorphic zone suggests that leucosome lenses coalesced to form larger bodies of anatectic leucogranites, thereby documenting a link between high‐grade regional metamorphism and Pan‐African magmatism. In view of the close association of the studied high‐T migmatites with hundreds of synmetamorphic high‐T granites that invaded the terrane as metre‐ to decametre‐wide sills and dykes, we postulate that crystallization of felsic lower crustal magma is, at least partly, responsible for heat supply. Late‐stage isobaric cooling of these granites may explain the occurrence of andalusite in some samples.     

The effect of TiO2 and Fe2O3 on metapelitic assemblages at greenschist and amphibolite facies conditions: mineral equilibria calculations in the system K2O–FeO–MgO–Al2O3–SiO2–H2O–TiO2–Fe2O3

Mineral equilibria calculations in the system K₂O–FeO–MgO–Al₂O₃–SiO₂–H₂O–TiO₂–Fe₂O₃ (KFMASHTO) using thermocalc and its internally consistent thermodynamic dataset constrain the effect of TiO₂ and Fe₂O₃ on greenschist and amphibolite facies mineral equilibria in metapelites. The end‐member data and activity–composition relationships for biotite and chloritoid, calibrated with natural rock data, and activity–composition data for garnet, calibrated using experimental data, provide new constraints on the effects of TiO₂ and Fe₂O₃ on the stability of these minerals. Thermodynamic models for ilmenite–hematite and magnetite–ulvospinel solid solutions accounting for order–disorder in these phases allow the distribution of TiO₂ and Fe₂O₃ between oxide minerals and silicate minerals to be calculated. The calculations indicate that small to moderate amounts of TiO₂ and Fe₂O₃ in typical metapelitic bulk compositions have little effect on silicate mineral equilibria in metapelites at greenschist to amphibolite facies, compared with those calculated in KFMASH. The addition of large amounts of TiO₂ to typical pelitic bulk compositions has little effect on the stability of silicate assemblages; in contrast, rocks rich in Fe₂O₃ develop a markedly different metamorphic succession from that of common Barrovian sequences. In particular, Fe₂O₃‐rich metapelites show a marked reduction in the stability fields of staurolite and garnet to higher pressures, in comparison to those predicted by KFMASH grids.