Notes: A petrogenetic grid in the model system CaO–FeO–MgO–Al2O3–SiO2–H2O is presented, illustrating the phase relationships among the minerals grunerite, hornblende, garnet, clinopyroxene, chlorite, olivine, anorthite, zoisite and aluminosilicates, with quartz and H2O in excess. The grid was calculated with the computer software thermocalc, using an upgraded version of the internally consistent thermodynamic dataset HP98 and non-ideal mixing activity models for all solid solutions. From this grid, quantitative phase diagrams (P–T pseudosections) are derived and employed to infer a P–T path for grunerite–garnet-bearing amphibolites from the Endora Klippe, part of the Venetia Klippen Complex within the Central Zone of the Limpopo Belt. Agreement between calculated and observed mineral assemblages and garnet zonation indicates that this part of the Central Zone underwent a prograde temperature and pressure increase from c. 540 °C/4.5 kbar to 650 °C/6.5 kbar, followed by a post-peak metamorphic pressure decrease. The inferred P–T path supports a geotectonic model suggesting that the area surrounding the Venetia kimberlite pipes represents the amphibolite-facies roof zone of migmatitic gneisses and granulites that occur widely within the Central Zone. In addition, the P–T path conforms to an interpretation that the Proterozoic evolution of the Central Zone was controlled by horizontal tectonics, causing stacking and differential heating at c. 2.0 Ga.

Notes: Metabasic rocks from the Adula Nappe in the Central Alps record a regional high-pressure metamorphic event during the Eocene, and display a regional variation in high-pressure mineral assemblages from barroisite, or glaucophane, bearing garnet amphibolites in the north to kyanite eclogites in the central part of the nappe. High-pressure rocks from all parts of the nappe show the same metamorphic evolution of assemblages consistent with prograde blueschist, high-pressure amphibolite or eclogite facies conditions followed by peak-pressure eclogite facies conditions and decompression to the greenschist or amphibolite facies. Average PT calculations (using thermocalc) quantitatively establish nested, clockwise P–T paths for different parts of the Adula Nappe that are displaced to higher pressure and temperature from north to south. Metamorphic conditions at peak pressure increase from about 17 kbar, 640 °C in the north to 22 kbar, 750 °C in the centre and 25 kbar, 750 °C in the south. The northern and central Adula Nappe behaved as a coherent tectonic unit at peak pressures and during decompression, and thermobarometric results are interpreted in terms of a metamorphic field gradient of 9.6 ± 2.0 °C km−1 and 0.20 ± 0.05 kbar km−1. These results constrain the peak-pressure position and orientation of the nappe to a depth of 55–75 km, dipping at an angle of approximately 45° towards the south. Results from the southern Adula Nappe are not consistent with the metamorphic field gradient determined for the northern and central parts, which suggests that the southern Adula Nappe may have been separated from central and northern parts at peak pressure.

Notes: 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–XCO2–fO2 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.

Notes: On the basis of fluid inclusion evidence, pervasive influx of deep-seated CO2-rich fluids has been invoked to account for mid- to upper amphibolite facies (M2B) metamorphism on the island of Naxos (Cyclades, Greece). In this paper, mineral devolatilization and melt equilibria are used to constrain the composition of both syn- and post-peak-M2B fluids in the deepest exposed levels of the metamorphic complex. The results indicate that peak-M2B fluids were spatially and compositionally heterogeneous throughout the high-grade core of the complex, whereas post-peak-M2B fluids were generally water-rich. The observed heterogeneities in syn-M2B fluid composition are inconsistent with pervasive CO2-flushing models invoked by previous workers on the basis of fluid inclusion evidence. It is likely that few CO2-rich fluid inclusions on Naxos preserve fluids trapped under peak metamorphic conditions. It is suggested that many of these inclusions have behaved as chemically open systems during the intense deformation that accompanied the uplift of the metamorphic complex. A similar process may explain the occurrence of some CO2-rich fluid inclusions in granulite facies rocks.

Notes: Abstract This, the second of two papers, represents the application of a least squares approach, discussed in the previous paper, to the generation of an internally consistent thermodynamic dataset involving 60 reactions among 43 phases, in the system K2O–Na2O–CaO–MgO–Al2O3–SiO2–H2O–CO2. We make the assumption that all the thermodynamic data, with the exception of enthalpies of formation of the phases, are well known, and solve for an internally consistent set of enthalpies which reproduces the 60, experimentally determined, phase equilibrium reactions. An important difference between our dataset and that of previous alternatives in the literature is that we are able to determine the uncertainties on, and correlations between, the enthalpies of formation for all phases in the set, and hence are able to apply simple error propagation techniques to determine the uncertainties in any phase equilibrium calculations performed using this dataset. Selection of reactions, for geothermometry and geobarometry, may be more readily made by choosing equilibria with small uncertainties in their thermodynamics. Our data are in reasonably close agreement with the high temperature molten oxide calorimetry results on silicate minerals where available, a fact which lends a degree of confidence to the results.

Notes: Mixing properties for muscovite–celadonite–ferroceladonite solid solutions are derived from combining available experimental phase equilibrium data with tabulated thermodynamic data for mineral end-members. When a partially ordered solution model is assumed, the enthalpy of mixing among the end-members muscovite–celadonite–ferroceladonite is nearly ideal, although the Gibbs energies of muscovite–celadonite and muscovite–ferroceladonite solutions are asymmetric due to an asymmetry in the entropy of mixing. Thermodynamic consistency is achieved for data on phengite compositions inassemblages with (a) pyrope+kyanite+quartz/coesite (b) almandine+kyanite+quartz/coesite (c)talc+kyanite+quartz/coesite and (d) garnet–phengite pairs equilibrated both experimentally at high temperatures and natural pairs from low-grade schists. The muscovite–paragonite solvus has been reanalysed using the asymmetric van Laar model, and the effects of the phengite substitution into muscovite have been quantitatively addressed in order to complete the simple thermodynamic mixing model for the solid solution among the mica end-members. Results are applied to a natural pyrope–coesite–phengite–talc rock from the Western Alps, and to investigate the conditions under which biotite-bearing mica schists transform to whiteschist-like biotite-absent assemblages for average pelite bulk compositions.

Notes: The thermodynamic properties of 154 mineral end-members, 13 silicate liquid end-members and 22 aqueous fluid species are presented in a revised and updated data set. The use of a temperature-dependent thermal expansion and bulk modulus, and the use of high-pressure equations of state for solids and fluids, allows calculation of mineral–fluid equilibria to 100 kbar pressure or higher. A pressure-dependent Landau model for order–disorder permits extension of disordering transitions to high pressures, and, in particular, allows the alpha–beta quartz transition to be handled more satisfactorily. Several melt end-members have been included to enable calculation of simple phase equilibria and as a first stage in developing melt mixing models in NCKFMASH. The simple aqueous species density model has been extended to enable speciation calculations and mineral solubility determination involving minerals and aqueous species at high temperatures and pressures. The data set has also been improved by incorporation of many new phase equilibrium constraints, calorimetric studies and new measurements of molar volume, thermal expansion and compressibility. This has led to a significant improvement in the level of agreement with the available experimental phase equilibria, and to greater flexibility in calculation of complex mineral equilibria. It is also shown that there is very good agreement between the data set and the most recent available calorimetric data.

Notes: 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.

Notes: Calculations based on a KMnFMASH petrogenetic grid derived using an internally consistent thermodynamic dataset indicate that the principal effect of the presence of Mn in average subaluminous pelite compositions is to stabilize garnet to higher and lower pressures and temperatures over a wide range of bulk compositions. Garnet-bearing fields expand to lower temperatures and pressures with the addition of Mn, and garnet appears as an extra phase at low pressures. The addition of Mn also increases the number and extent of four AMnFM phase assemblages and stabilizes five AMnFM phases along univariant reactions. The KMnFMASH system predictions for typical subaluminous pelite bulk compositions match the sequence of isograds and assemblages observed in the Barrovian zones. The sequence of assemblages observed in the Stonehaven section can also be predicted if there is variation in bulk composition within the stratigraphic section. Mn appears to be less important in producing the sequence of isograds and garnet-absent assemblages in the low-pressure Buchan zones. The addition of Mn to the calculations does not change the sequence of isograds that are predicted to be stable in a regional metamorphic terrane, but the P–T position of these isograds does change. In particular, the predicted temperature of the garnet-in isograd is lowered by as much as 100 °C by the addition of Mn to KFMASH. Mn also increases the range of metapelite bulk compositions that develop the assemblages traditionally identified as metapelite isograds.

Notes: Sapphirine, coexisting with quartz, is an indicator mineral for ultrahigh-temperature metamorphism in aluminous rock compositions. Here a new activity-composition model for sapphirine is combined with the internally consistent thermodynamic dataset used by THERMOCALC, for calculations primarily in K2O-FeO-MgO-Al2O3-SiO2-H2O (KFMASH). A discrepancy between published experimentally derived FMAS grids and our calculations is understood with reference to H2O. Published FMAS grids effectively represent constant aH2O sections, thereby limiting their detailed use for the interpretation of mineral reaction textures in compositions with differing H2O.For the calculated KFMASH univariant reaction grid, sapphirine + quartz assemblages occur at P–T in excess of 6–7 kbar and 1005 °C. Sapphirine compositions and composition ranges are consistent with natural examples. However, as many univariant equilibria are typically not ‘seen’ by a specific bulk composition, the univariant reaction grid may reveal little about the detailed topology of multi-variant equilibria, and therefore is of limited use for interpreting the P–T evolution of mineral assemblages and reaction sequences. Calculated pseudosections, which quantify bulk composition and multi-variant equilibria, predict experimentally determined KFMASH mineral assemblages with consistent topology, and also indicate that sapphirine stabilizes at increasingly higher pressure and temperature as XMg increases. Although coexisting sapphirine and quartz can occur in relatively iron-rich rocks if the bulk chemistry is sufficiently aluminous, the P–T window of stability shrinks with decreasing XMg. An array of mineral assemblages and mineral reaction sequences from natural sapphirine + quartz and other rocks from Enderby Land, Antarctica, are reproducible with calculated pseudosections. That consistent phase diagram calculations involving sapphirine can be performed allows for a more thorough assessment of the metamorphic evolution of high-temperature granulite facies terranes than was previously possible. The establishment of a a-x model for sapphirine provides the basis for expansion to larger, more geologically realistic chemical systems (e.g. involving Fe3+).