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

Zircon is the main mineral in the majority of igneous and metamorphic rocks with Zr as an essential structural constituent. It is a host for significant fractions of the whole-rock abundance of U, Th, Hf, and the REE (Sawka 1988, Bea 1996, O’Hara et al. 2001). These elements are important geochemically as process indicators or parent isotopes for age determination. The importance of zircon in crustal evolution studies is underscored by its predominant use in U-Th-Pb geochronology and investigations of the temporal evolution of both the crust and lithospheric mantle. In the past decade an increasing interest in the composition of zircon, trace-elements in particular, has been motivated by the effort to better constrain in situ microprobe-acquired isotopic ages. Electron-beam compositional imaging and isotope-ratio measurement by in situ beam techniques—and the micrometer-scale spatial resolution that is possible—has revealed in many cases that single zircon crystals contain a record of multiple geologic events. Such events can either be zircon-consuming, alteration, or zircon-forming and may be separated in time by millions or billions of years. In many cases, calculated zircon isotopic ages do not coincide with ages of geologic events determined from other minerals or from whole-rock analysis. To interpret the geologic validity and significance of multiple ages, and ages unsupported by independent analysis of other isotopic systems, has been the impetus for most past investigations of zircon composition. Some recent compositional investigations of zircon have not been directly related to geochronology, but to the ability of zircon to influence or record petrogenetic processes in igneous and metamorphic systems.

Sedimentary rocks may also contain a significant fraction of zircon. Although authigenic zircon has been reported (Saxena 1966, Baruah et al. 1995, Hower et al. 1999), it appears to be very rare and may in fact be related to …

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The Composition of Zircon and Igneous and Metamorphic Petrogenesis

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

Amphibole thermodynamics are approximated with the symmetric formalism (regular solution model for within-site non-ideality and a reciprocal solution model for cross-site-terms) in order to formulate improved thermometers for amphibole-plagioclase assemblages. This approximation provides a convenient framework with which to account for composition-dependence of the ideal (mixing-on-sites) equilibrium constants for the equilibria:
 For A and B all possible within-site and cross-site interactions among the species □−K−Na−Ca−Mg−Fe2+−Fe3+−Al−Si on the A, M4, M1, M3, M2 and T1 amphibole crystallographic sites were examined. Of the 36 possible interaction energy terms, application of the symmetric formalism results in a dramatic simplification to eight independent parameters. Plagioclase nonideality is modelled using Darken's quadratic formalism. We have supplemented an experimental data set of 92 amphibole-plagioclase pairs with 215 natural pairs from igneous and metamorphic rocks in which the pressure and temperature of equilibration are well constrained. Regression of the combined dataset yields values for the eight interaction parameters as well as for apparent enthalpy, entropy and volume changes for each reaction. These parameters are used to formulate two new thermometers, which perform well (±40°C) in the range 400–1000°C and 1–15 kbar over a broad range of bulk compositions, including tschermakitic amphiboles from garnet amphibolites which caused problems for the simple thermometer of Blundy and Holland (1990). For silica-saturated rocks both thermometers may be applied: in silica-undersaturated rocks or magmas thermometer B alone can be applied. An improved procedure for estimation of ferric iron in calcic amphiboles is presented in the appendix.

Non-ideal interactions in calcic amphiboles and their bearing on amphibole-plagioclase thermometry

The composition of chromian spinel in alpine-type peridotites has a large reciprocal range of Cr and Al, with increasing Cr# (Cr/(Cr+Al)) reflecting increasing degrees of partial melting in the mantle. Using spinel compositions, alpine-type peridotites can be divided into three groups. Type I peridotites and associated volcanic rocks contain spinels with Cr# 0.60, and Type II peridotites and volcanics are a transitional group and contain spinels spanning the full range of spinel compositions in Type I and Type II peridotites. Spinels in abyssal peridotites lie entirely within the Type I spinel field, making ophiolites with Type I alpine-type peridotites the most likely candidates for sections of ocean lithosphere formed at a midocean ridge. The only modern analogs for Type III peridotites and associated volcanic rocks are found in arc-related volcanic and intrusive rocks, continental intrusive assemblages, and oceanic plateau basalts. We infer a sub-volcanic arc petrogenesis for most Type III alpine-type peridotites. Type II alpine-type peridotites apparently reflect composite origins, such as the formation of an island-arc on ocean crust, resulting in large variations in the degree and provenance of melting over relatively short distances. The essential difference between Type I and Type III peridotites appears to be the presence or absence of diopside in the residue at the end of melting.

Chromian spinel as a petrogenetic indicator in abyssal and alpine-type peridotites and spatially associated lavas

High-P/T metamorphic belts were classified into types A and B according to their protoliths. The A-type (collision-type) blueschists possess passive-margin protoliths characterized by platform-type carbonates, bimodal volcanics, and peraluminous sediments. B-type (Cordilleran-type) blueschists consist of active continental-margin protoliths in an accretionary complex characterized by bedded chert, MORB and ocean-island basalts, reef limestones, and graywackes. The spatiotemporal distribution of blueschists and eclogites of the world was compiled; among 250 recognized high-P/T belts, about 20% belong to the A type and the rest to the B type. Most A-type zones lie in Europe and the Tethyan domain, include ultrahigh-pressure metamorphic terranes, and have metamorphic pressure up to 45 kbar. B-type zones occur mainly in the circum-Pacific orogenic belts and intracontinental orogens in Asia, and were recrystallized at P <12 kbar. Associated peridotites include garnet peridotite in the A type and strongly serpe...

Blueschists and Eclogites of the World and Their Exhumation

Coesite and Coesite pseudomorphs are recognized in eclogite from the Dabie Mountains, a collision zone between the Sino-Korean and Yangtze cratons in central China. This third known occurrence of Coesite in deep crustal rocks is within an Archean gneiss terrane and is the first locality where Coesite has been identified as an inclusion in both omphacite and garnet crystals at the same location. Coesite-bearing eclogite is estimated to form at pressures of >28 kbar and temperatures from 600 to 710 °C. The Dabie Mountains eclogite underwent retrograde metamorphism to amphibolite facies after its formation. The preservation of Coesite in eclogite is found to be strongly controlled by the pressure-temperature-time path that coesite- bearing eclogite followed during its uplift and retrograde metamorphism.

Coesite-bearing eclogite from the Dabie Mountains in central China

China is principally a part of the Eurasian plate, but the margins of the Indian and Philippine Sea plates are involved in the Himalayas and in the Coastal Range of Taiwan, respectively. Within the Eurasian plate, the Cathaysian paleoplate is separated from the Angaraian paleoplate by the Junggar-Hegen suture, which contains Paleozoic ophiolites and rare blueschists. The three microplates of the Cathaysian paleoplate consist of Precambrian cratons and/or Phanerozoic accretionary fold belts. These coalesced Precambrian cratons record at least six stages of intense orogeny before cratonization. The Paleozoic to Cenozoic accretionary fold belts of China can be correlated with similar events now found in west Pacific-, Andean-, and Atlantic-type active continental margins. Ophiolites occupying many of these tectonic zones provide evidence for the age and igneous history of oceanic crust formed during the Paleozoic to Cenozoic. The presence of blueschist in some of these Chinese sutures reveals evidence of large-scale subduction and tectonic exhumation during consolidation of the Eurasian plate. Cenozoic collision of the Eurasian and Indian plates produced deformation and uplift of the Himalayas, strongly influencing the tectonics of western China. In contrast, Mesozoic-Tertiary evolution of eastern China is typical basin-range geology, similar to that of the western United States, which included development of deep sedimentary basins along with calc-alkaline plutonic and volcanic activity associated with crustal thinning and high heat flow. The complicated tectonic evolution of China is greatly illuminated by the presence of ophiolites and blueschists in Proterozoic to Tertiary convergent boundaries. These petrotectonic assemblages provide evidence of an extremely mobile history of plate movement in China.

An outline of the plate tectonics of China

Continental crust (density ~2.8 g·cm-3) resists subduction into the earth's mantle (~3.3 g·cm-3) because of buoyancy. However, more than 20 recognized ultrahigh-pressure (UHP) terranes have been documented; these occurrences demonstrate that not only is continental crust subducted to depths as great as 150 km, but also that some supracrustal rocks were then exhumed to the earth's surface. UHP terranes are composed of mainly supracrustal rocks that contain minor amounts of minerals such as coesite or diamond, indicative of P > 2.5 GPa. In general, quartzofeldspathic units are thoroughly back reacted, and only mafic eclogite lenses and boudins retain scattered UHP phases. These index minerals are restricted to micron-scale inclusions in chemically and mechanically resistant zircon, garnet, and a few other strong container minerals, and are difficult to identify by conventional petrologic studies. The continental rocks were subjected to UHP metamorphism at T ranging from ~700 to 950°C and P > 2.8 to 5.0 GPa,...

Global UHP metamorphism and continental subduction/collision: The himalayan model

Zircon as the best mineral for P-T-time history of UHP metamorphism: A review on mineral inclusions and U-Pb SHRIMP ages of zircons from the Dabie-Sulu UHP rocks

Juhn G. Liou

Papers

Blueschists and Eclogites of the World and Their Exhumation

Coesite-bearing eclogite from the Dabie Mountains in central China

An outline of the plate tectonics of China

Global UHP metamorphism and continental subduction/collision: The himalayan model

Zircon as the best mineral for P-T-time history of UHP metamorphism: A review on mineral inclusions and U-Pb SHRIMP ages of zircons from the Dabie-Sulu UHP rocks