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.

An internally consistent thermodynamic data set for phases of petrological interest

We present the first finding of continental crust-derived Precambrian zircons in garnet/spinel pyroxenite veins within mantle xenoliths carried by the Neogene Hannuoba basalt in the central zone of the North China Craton (NCC). Petrological and geochemical features indicate that these mantle-derived composite xenoliths were formed by silicic melt^lherzolite interaction. The Precambrian zircon ages can be classified into three age groups of 2·4^2·5 Ga, 1·6^2·2 Ga and 0·6^1·2 Ga, coinciding with major geological events in the NCC. These Precambrian zircons fall in the field of continental granitoid rocks in plots of U/Yb vs Hf and Y. Their igneous-type REE patterns and metamorphic zircon type CL images indicate that they were not crystallized during melt^peridotite interaction and subsequent high-pressure metamorphism.The 2·5 Ga zircons have positive eHf(t) values (2·9^10·6), whereas the younger Precambrian zircons are dominated by negative eHf(t) values, indicating an ancient continental crustal origin.These observations suggest that the Precambrian zircons were xenocrysts that survived melting of recycled continental crustal rocks and were then injected with silicate melt into the host peridotite. In addition to the Precambrian zircons, igneous zircons of 315 3 Ma (2 ), 80^170 Ma and 48^64 Ma were separated from the garnet/spinel pyroxenite veins; these provide evidence for lower continental crust and oceanic crust recycling-induced multi-episodic melt^peridotite interactions in the central zone of the NCC. The combination of the positive eHf(t) values (2·91^24·6) of the 315 Ma zircons with the rare occurrence of 302^324 Ma subduction-related diorite^granite plutons in the northern margin of the NCC implies that the 315 Ma igneous zircons might record melt^peridotite interactions in the lithospheric mantle induced by Palaeo-Asian oceanic crust subduction. Igneous zircons of age 80^170 Ma generally coexist with the Precambrian metamorphic zircons and have lower Ce/Yb and Th/U ratios, higher U/Yb ratios and greater negative Eu anomalies.The eHf(t) values of these zircons vary greatly from ^47·6 to 24·6.The 170^110 Ma zircons are generally characterized by negative eHf(t) values, whereas the 110^100 Ma zircons have positive eHf(t) values.These observations suggest that melt^peridotite interactions at 80^170 Ma were induced by partial melting of recycled continental crust. The 48^64 Ma igneous zircons are characterized by negligible Ce anomalies, unusually high REE, U and Th contents, and positive eHf(t) values.These features imply that the melt^peridotite interactions at 48^64 Ma could be associated with a depleted mantle-derived carbonate melt or fluid.

Continental and Oceanic Crust Recycling-induced Melt^Peridotite Interactions in the Trans-North China Orogen: U^Pb Dating, Hf Isotopes and Trace Elements in Zircons from Mantle Xenoliths

A revised regular solution-type thermodynamic model for twelve-component silicate liquids in the system SiO2-TiO2-Al2O3-Fe2O3-Cr2O3-FeO-MgO-CaO-Na2O-K2O-P2O5-H2O is calibrated. The model is referenced to previously published standard state thermodynamic properties and is derived from a set of internally consistent thermodynamic models for solid solutions of the igneous rock forming minerals, including: (Mg,Fe2+,Ca)-olivines, (Na,Mg,Fe2+,Ca)M2 (Mg,Fe2+, Ti, Fe3+, Al)M1 (Fe3+, Al,Si)2TETO6-pyroxenes, (Na,Ca,K)-feldspars, (Mg,Fe2+) (Fe3+, Al, Cr)2O4-(Mg,Fe2+)2 TiO4 spinels and (Fe2+, Mg, Mn2+)TiO3-Fe2O3 rhombohedral oxides. The calibration utilizes over 2,500 experimentally determined compositions of silicate liquids coexisting at known temperatures, pressures and oxygen fugacities with apatite ±feldspar ±leucite ±olivine ±pyroxene ±quartz ±rhombohedral oxides ±spinel ±whitlockite ±water. The model is applicable to natural magmatic compositions (both hydrous and anhydrous), ranging from potash ankaratrites to rhyolites, over the temperature (T) range 900°–1700°C and pressures (P) up to 4 GPa. The model is implemented as a software package (MELTS) which may be used to simulate igneous processes such as (1) equilibrium or fractional crystallization, (2) isothermal, isenthalpic or isochoric assimilation, and (3) degassing of volatiles. Phase equilibria are predicted using the MELTS package by specifying bulk composition of the system and either (1) T and P, (2) enthalpy (H) and P, (3) entropy (S) and P, or (4) T and volume (V). Phase relations in systems open to oxygen are determined by directly specifying the fo2 or the T-P-fo2 (or equivalently H-P-fo2, S-P-fo2, T-V-fo2) evolution path. Calculations are performed by constrained minimization of the appropriate thermodynamic potential. Compositions and proportions of solids and liquids in the equilibrium assemblage are computed.

Chemical mass transfer in magmatic processes IV. A revised and internally consistent thermodynamic model for the interpolation and extrapolation of liquid-solid equilibria in magmatic systems at elevated temperatures and pressures

羟氨苄青霉素引起大疱性类天疱疮样疹

Knowledge of temperature and pressure, however qualitative, has been central to our views of geology since at least the early 19th century. In 1822, for example, Charles Daubeny presented what may be the very first “Geological Thermometer,” comparing temperatures of various geologic processes (Torrens 2006). Daubeny (1835) may even have been the first to measure the temperature of a lava flow, by laying a thermometer on the top of a flow at Vesuvius—albeit several months following the eruption, after intervening rain (his estimate was 390°F). In any case, pressure ( P ) and temperature ( T ) estimation lie at the heart of fundamental questions: How hot is Earth, and at what rate has the planet cooled. Are volcanoes the products of thermally driven mantle plumes? Where are magmas stored, and how are they transported to the surface—and how do storage and transport relate to plate tectonics? Well-calibrated thermometers and barometers are essential tools if we are to fully appreciate the driving forces and inner workings of volcanic systems.

This chapter presents methods to estimate the P-T conditions of volcanic and other igneous processes. The coverage includes a review of existing geothermometers and geobarometers, and a presentation of approximately 30 new models, including a new plagioclase-liquid hygrometer. Our emphasis is on experimentally calibrated “thermobarometers,” based on analytic expressions using P or T as dependent variables. For numerical reasons (touched on below) such expressions will always provide the most accurate means of P-T estimation, and are also most easily employed. Analytical expressions also allow error to be ascertained; in the absence of estimates of error, P-T estimates are nearly meaningless. This chapter is intended to complement the chapters by Anderson et al. (2008), who cover granitic systems, and by Blundy and Cashman (2008) and Hansteen and Klugel (2008), who consider additional methods …

Thermometers and Barometers for Volcanic Systems

Geothermobarometry in Four-phase Lherzolites II. New Thermobarometers, and Practical Assessment of Existing Thermobarometers

Calcium exchange between olivine and clinopyroxene calibrated as a geothermobarometer for natural peridotites from 2 to 60 kb with applications

Mineral-aqueous fluid partitioning of trace elements at 900–1200°C and 3.0–5.7 GPa: new experimental data for garnet, clinopyroxene, and rutile, and implications for mantle metasomatism

We have experimentally investigated the phase and melting relations of garnet + clinopyroxene + carbonate assemblages at 2.5–5.5  GPa, to assess the feasibility of carbonated eclogite as a source for some crustally emplaced carbonatites. The solidus of our composition was at ≈1,125 °C at 2.5 GPa, ≈1,225 °C at 3.5 GPa and ≈1,310 °C at 5.0 GPa. Melts were sodic calcio-dolomitic carbonatites, and were markedly more calcic than the dolomitic melts produced by partial melting of carbonated peridotite. Na contents of the experimental carbonatites decreased with increasing pressure when compared at similar degrees of melting, and SiO2 contents increased with degree of melting. Experiments on a second composition with enhanced Na2O demonstrated its strong effect in lowering melting temperatures in carbonate eclogite. Natural carbonated eclogite bodies in the peridotitic upper mantle will have a range of solidus temperatures. In many cases, carbonate will be molten in the upper ≥250 km. Carbonate melt would segregate from its source eclogite at very low melt fractions and infiltrate surrounding peridotitic wall rock. This would result in metasomatic enrichment of the peridotitic wall rock, but its exact nature will depend on the relative P–T positions of the eclogite + CO2 and peridotite + CO2 solidii. As a result of these inevitable metasomatic interactions, it is considered unlikely that carbonatite melts derived from carbonated eclogite in the upper mantle could be emplaced into the crust unmodified. However, they may have a role in metasomatically enriching and carbonating parts of the upper mantle, producing sources suitable for subsequent production of silica undersaturated silicate liquids and carbonatites ultimately emplaced in the crust.

Phase relations of carbonate-bearing eclogite assemblages from 2.5 to 5.5 GPa: implications for petrogenesis of carbonatites

Partial melting of magnesite-bearing peridotites was studied at 6-10 GPa and 1300-1700°C. Experiments were performed in a multianvil apparatus using natural mineral mixes as starting material placed into olivine containers and sealed in Pt capsules. Partial melts originated within the peridotite layer, migrated outside the olivine container and formed pools of quenched melts along the wall of the Pt capsule. This allowed the analysis of even small melt fractions. Iron loss was not a problem, because the platinum near the olivine container became saturated in Fe as a result of the reaction Fe 2 SiO 4 Ol = Fe Fe-Pt alloy + FeSiO 3 Opx + O 2 . This reaction led to a gradual increase in oxygen fugacity within the capsules as expressed, for example, in high Fe 3+ in garnet. Carbonatitic to kimberlite-like melts were obtained that coexist with olivine + orthopyroxene + garnet ± clinopyroxene ± magnesite depending on P-T conditions. Kinetic experiments and a comparison of the chemistry of phases occasionally grown within the melt pools with those in the residual peridotite allowed us to conclude that the melts had approached equilibrium with peridotite. Melts in equilibrium with a magnesite-bearing garnet lherzolite are rich in CaO (20-25 wt %) at all pressures and show rather low MgO and SiO 2 contents (20 and 10 wt %, respectively). Melts in equilibrium with a magnesite-bearing garnet harzburgite are richer in SiO 2 and MgO. The contents of these oxides increase with temperature, whereas the CaO content becomes lower. Melts from magnesite-free experiments are richer in SiO 2 , but remain silicocarbonatitic. Partitioning of trace elements between melt and garnet was studied in several experiments at 6 and 10 GPa. The melts are very rich in incompatible elements, including large ion lithophile elements (LILE), Nb, Ta and light rare earth elements. Relative to the residual peridotite, the melts show no significant depletion in high field strength elements over LILE. We conclude from the major and trace element characteristics of our experimental melts that primitive kimberlites cannot be a direct product of single-stage melting of an asthenospheric mantle. They rather must be derived from a previously depleted and re-enriched mantle peridotite.

Gerhard P. Brey

Papers

Geothermobarometry in Four-phase Lherzolites II. New Thermobarometers, and Practical Assessment of Existing Thermobarometers

Calcium exchange between olivine and clinopyroxene calibrated as a geothermobarometer for natural peridotites from 2 to 60 kb with applications

Mineral-aqueous fluid partitioning of trace elements at 900–1200°C and 3.0–5.7 GPa: new experimental data for garnet, clinopyroxene, and rutile, and implications for mantle metasomatism

Phase relations of carbonate-bearing eclogite assemblages from 2.5 to 5.5 GPa: implications for petrogenesis of carbonatites

Experimental Melting of Carbonated Peridotite at 6-10 GPa