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

Zircon and rutile are common accessory minerals whose essential structural constituents, Zr, Ti, and Si can replace one another to a limited extent. Here we present the combined results of high pressure–temperature experiments and analyses of natural zircons and rutile crystals that reveal systematic changes with temperature in the uptake of Ti in zircon and Zr in rutile. Detailed calibrations of the temperature dependencies are presented as two geothermometers—Ti content of zircon and Zr content of rutile—that may find wide application in crustal petrology. Synthetic zircons were crystallized in the presence of rutile at 1–2 GPa and 1,025–1,450°C from both silicate melts and hydrothermal solutions, and the resulting crystals were analyzed for Ti by electron microprobe (EMP). To augment and extend the experimental results, zircons hosted by five natural rocks of well-constrained but diverse origin (0.7–3 GPa; 580–1,070°C) were analyzed for Ti, in most cases by ion microprobe (IMP). The combined experimental and natural results define a log-linear dependence of equilibrium Ti content (expressed in ppm by weight) upon reciprocal temperature:

 $$\log ({\text{Ti}}_{{{\text{zircon}}}}) = (6.01 \pm 0.03) - \frac{{5080 \pm 30}}{{T\;(\hbox{K})}}.$$
 In a strategy similar to that used for zircon, rutile crystals were grown in the presence of zircon and quartz (or hydrous silicic melt) at 1–1.4 GPa and 675–1,450°C and analyzed for Zr by EMP. The experimental results were complemented by EMP analyses of rutile grains from six natural rocks of diverse origin spanning 0.35–3 GPa and 470–1,070°C. The concentration of Zr (ppm by weight) in the synthetic and natural rutiles also varies in log-linear fashion with T
 −1:

 $$\log ({\text{Zr}}_{{{\text{rutile}}}}) = (7.36 \pm 0.10) - \frac{{4470 \pm 120}}{{T\;(\hbox{K})}}.$$
 The zircon and rutile calibrations are consistent with one another across both the synthetic and natural samples, and are relatively insensitive to changes in pressure, particularly in the case of Ti in zircon. Applied to natural zircons and rutiles of unknown provenance and/or growth conditions, the thermometers have the potential to return temperatures with an estimated uncertainty of ±10 ° or better in the case of zircon and ±20° or better in the case of rutile over most of the temperature range of interest (∼400–1,000°C). Estimates of relative temperature or changes in temperature (e.g., from zoning profiles in a single mineral grain) made with these thermometers are subject to analytical uncertainty only, which can be better than ±5° depending on Ti or Zr concentration (i.e., temperature), and also upon the analytical instrument (e.g., IMP or EMP) and operating conditions.

Crystallization thermometers for zircon and rutile

Phase relations in a portion of the granite system, KAlSi3O8-NaAlSi3O8-SiO2-H2O have been studied in the pressure range 4 to 10 kb. At 10 kb, melting begins at 625°C at an isobaric invariant point involving albite + orthoclase + quartz + liquid + vapor. The anhydrous composition of the liquid at this isobaric quaternary eutectic corresponds to 21 orthoclase: 56 albite: 23 quartz in contrast to that at the isobaric quaternary minimum at 0.5 kb, where the liquid corresponds to 31 orthoclase: 30 albite: 39 quartz. This represents a shift of the liquid, in anhydrous projection, almost directly toward NaAlSi with increasing P. The quaternary minimum in this system becomes a eutectic at approximately 3.6 kb. Compositional comparisons among granites, aplites, zoned pegmatites, and the quaternary minimum and eutectic suggest that igneous pegmatites and aplites represent magmas that were saturated or nearly saturated with water when they began to crystallize. Trends in bulk composition among pegmatites further suggest selective losses of alkalies during crystallization, probably by diffusion through aqueous fluids coexisting with the silicate melts and their solid products.

The Granite System at Pressures of 4 to 10 Kilobars

Aqueous fluids and hydrous melts in high-pressure and ultra-high pressure rocks: Implications for element transfer in subduction zones

▪ Abstract The subducted lithosphere is composed of a complex pattern of chemical systems that undergo continuous and discontinuous phase transformation, through pressure and temperature variations. Volatile recycling plays a major geodynamic role in triggering mass transfer, melting, and volcanism. Although buoyancy forces are controlled by modal amounts of the most abundant phases, usually volatile-free, petrogenesis and chemical differentiation are controlled by the occurrence of minor phases, most of them volatile-bearing. Devolatilization of the subducted lithosphere is a continuous process distributed over more than 300 km of the slab-mantle interface. Melting of the subducted crust, if any, along sufficiently hot P-T paths, is governed by fluid-absent reactions, even though the difference between fluid and melt vanishes at pressures above the second critical end point. The density distribution at a depth of 660 km suggests episodic penetration in space and time of subducted slabs into the lower man...

http://www.soest.hawaii.edu/GG/FACULTY/conrad/classes/GG672_S09/topic10/Petrology_Slabs_AnnRevGeophys2002.pdf

Petrology of subducted slabs

Melting relations in the system SiO_2 – H_2O were studied at high temperatures and pressures. A quadruple point for the equilibrium among quartz, tridymite, and 2 fluids was found at 1160° C. and 1500 bars. A second quadruple point for tridymite, 2 fluids, and cristobalite is estimated to be near 1470° C. and 400 bars. The freezing point of SiO_2 in equilibrium with 2 fluid phases is depressed from 1720° C. at one bar to 1130° C. at 2000 bars. This freezing point is diminished by only an additional 50° C. with a further increase in pressure to 9700 bars. The compositions of coexisting fluids along the upper 3-phase boundary have been determined. A critical end point for the univariant equilibrium curve was found at 1080° C. and 9700 bars with a composition of approximately 75 wt% SiO_2 to 25 wt% H_2O.

H. C. Heard

Papers

The upper three-phase region in the system SiO 2 -H 2 O