The thermodynamic properties of 254 end-members, including 210 mineral end-members, 18 silicate liquid end-members and 26 aqueous fluid species are presented in a revised and updated internally consistent thermodynamic data set. The PVT properties of the data set phases are now based on a modified Tait equation of state (EOS) for the solids and the Pitzer & Sterner (1995) equation for gaseous components. Thermal expansion and compressibility are linked within the modified Tait EOS (TEOS) by a thermal pressure formulation using an Einstein temperature to model the temperature dependence of both the thermal expansion and bulk modulus in a consistent way. The new EOS has led to improved fitting of the phase equilibrium experiments. Many new end-members have been added, including several deep mantle phases and, for the first time, sulphur-bearing minerals. Silicate liquid end-members are in good agreement with both phase equilibrium experiments and measured heat of melting. The new dataset considerably enhances the capabilities for thermodynamic calculation on rocks, melts and aqueous fluids under crustal to deep mantle conditions. Implementations are already available in thermocalc to take advantage of the new data set and its methodologies, as illustrated by example calculations on sapphirine-bearing equilibria, sulphur-bearing equilibria and calculations to 300 kbar and 2000 °C to extend to lower mantle conditions.

An improved and extended internally consistent thermodynamic dataset for phases of petrological interest, involving a new equation of state for solids

The Al-in-hornblende barometer, which correlates Altot content of magmatic hornblende linearly with crystallization pressure of intrusion (Hammarstrom and Zen 1986), has been calibrated experimentally under water-saturated conditions at pressures of 2.5–13 kbar and temperatures of 700–655°C. Equilibration of the assemblage hornlende-biotite-plagioclase-orthoclasequartz-sphene-Fe-Ti-oxide-melt-vapor from a natural tonalite 15–20° above its wet solidus results in hornblende compositions which can be fit by the equation: P(±0.6 kbar) = −3.01 + 4.76 Al
 hbl
 tot
 
r
2=0.99, where Altot is the total Al content of hornblende in atoms per formula unit (apfu). Altot increase with pressure can be ascribed mainly to a tschermak-exchange (
 
$$t\vec k,{\text{ Mg}}_{{\text{ - 1 }}} {\text{Al}}^{{\text{VI}}} {\text{Si}}_{{\text{ - 1}}} {\text{ Al}}^{{\text{IV}}}$$

 ) accompanied by minor plagioclase-substitution (
 
$$\vec pl,{\text{ Ca}}_{{\text{ - 1 }}} {\text{Na}}^{{\text{M(4)}}} {\text{ Al}}_{{\text{ - 1}}}^{{\text{IV}}} {\text{ Si}}$$

 ). This experimental calibration agrees well with empirical field calibrations, wherein pressures are estimated by contact-aureole barometry, confirming that contact-aureole pressures and pressures calculated by the Al-in-hornblende barometer are essentially identical. This calibration is also consistent with the previous experimental calibration by Johnson and Rutherford (1989b) which was accomplished at higher temperatures, stabilizing the required buffer assemblage by use of mixed H2O-CO2 fluids. The latter calibration yields higher Altot content in hornblendes at corresponding pressures, this can be ascribed to increased edenite-exchange (
 
$$\vec ed,{\text{ }}\square _{{\text{ }} - {\text{ }}1}^{ A} {\text{ Na}}^{\text{A}} {\text{Si }}_{ - {\text{ }}1} {\text{Al}}^{{\text{IV}}}$$

 ) at elevated temperatures. The comparison of both experimental calibrations shows the important influence of the fluid composition, which affects the solidus temperature, on equilibration of hornblende in the buffering phase assemblage.

Amphibole composition in tonalite as a function of pressure: an experimental calibration of the Al-in-hornblende barometer

A pyrope-quartzite originally described by Vialon (1966) from the Dora Maira massif was resampled and reinvestigated. Garnet (up to 25 cm in size), phengite, kyanite, talc and rutile are in textural equilibrium in an undeformed matrix of polygonal quartz. The garnet is a pyrope-almandine solid solution with 90 to 98 mol % Mg end-member. It contains inclusions of coesite which has partially inverted to quartz, resulting in a typical radial cracking of the host garnet around the inclusions. Several lines of evidence show that coesite crystallised under nearly static pressure conditions and that the whole matrix has once been coesite. The formidable pressures of formation implied (≧28 kbar) are independently indicated by i) the coexistence of nearly pure pyrope with free silica and talc, ii) the coexistence of jadeite with kyanite, iii) the high Si content of phengite. Water activity must have been low. The stability of talc-phengite and the presence of rare glaucophane inclusions in pyrope point to low formation temperatures (about 700 °C) and to a probable Alpine age for the assemblage. This is evidence that low temperature gradients, how essentially transient they are, may nevertheless persist to considerable depths. Moreover, the upper crustal (evaporite-related?) origin of the quartzite and its interbedding within a continental unit implies that continental crust may also be subducted to depths of 90 km or more. The return back to the surface is problematic; the retrograde assemblages observed show that it must be tectonic. If the rocks remain at depth, new perspectives open for the genesis of intermediate to acidic magmas. Eventually, the role of continental crust in geodynamics may have to be reconsidered.

Coesite and pure pyrope in high-grade blueschists of the Western Alps: a first record and some consequences

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.

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

T. J. B. Holland

Papers

The reaction albite = jadeite+quartz determined experimentally in the range 600–1200 ° C