New mineral activity–composition relations for thermodynamic calculations in metapelitic systems

New activity–composition (a–x) relations for minerals commonly occurring in metapelites are presented for use with the internally consistent thermodynamic dataset of Holland & Powell ( 2011 , Journal of Metamorphic Geology, 29 , 333–383). The a–x relations include a broader consideration of Fe₂O₃ in minerals, changes to the formalism of several phases and order–disorder in all ferromagnesian minerals where Fe–Mg mixing occurs on multiple sites. The a–x relations for chlorite, biotite, garnet, chloritoid, staurolite, cordierite, orthopyroxene, muscovite, paragonite and margarite have been substantially reparameterized using the approach outlined in the companion paper in this issue. For the first time, the entire set of a–x relations for the common ferromagnesian minerals in metapelitic rocks is parameterized simultaneously, with attention paid to ensuring that they can be used together to calculate phase diagrams of geologically appropriate topology. The a–x relations developed are for use in the Na₂O–CaO–K₂O–FeO–MgO–Al₂O₃–SiO₂–H₂O–TiO₂–O₂ (NCKFMASHTO) system for both subsolidus and suprasolidus conditions. Petrogenetic grids in KFMASH and KFMASHTO are similar in topology to those produced with earlier end‐member datasets and a–x relations, but with some notable differences. In particular, in subsolidus equilibria, the FeO/(FeO + MgO) of garnet is now greater than in coexisting staurolite, bringing a number of key staurolite‐bearing equilibria into better agreement with inferences from field and petrographic observations. Furthermore, the addition of Fe³⁺ and Ti to a number of silicate phases allows more plausible equilibria to be calculated in relevant systems. Pseudosections calculated with the new a–x relations are also topologically similar to equivalent diagrams using earlier a–x relations, although with many low variance fields shifting in P–T space to somewhat lower pressure conditions.     

The effect of Mn on mineral stability in metapelites revisited: new a–x relations for manganese‐bearing minerals

The a–x relations recently presented in White et al. ( 2014 , Journal of Metamorphic Geology, 32, 261–286) are extended to include MnO. This provides a set of internally consistent a–x relations for metapelitic rocks in the MnO–Na₂O–CaO–K₂O–FeO–MgO–Al₂O₃–SiO₂–H₂O–TiO₂–O₂ (MnNCKFMASHTO) system. The mixing parameters for the Mn‐bearing minerals were estimated using the micro‐? approach of Powell et al. ( 2014 , Journal of Metamorphic Geology, 32, 245–260). Then the Mn‐end‐member thermodynamic properties were calibrated using a database of co‐existing minerals involving literature data from rocks and from experiments on natural materials. Mn‐end‐members were calibrated for orthopyroxene, cordierite, staurolite, chloritoid, chlorite, biotite, ilmenite and hematite, assuming known properties for the garnet end‐member spessartine. The addition of MnO to phase diagram calculations results in a marked expansion of the stability of garnet‐bearing assemblages. At greenschist facies conditions garnet stability is extended down temperature. At amphibolite facies conditions, the garnet‐in boundary shifts to lower pressure. While the addition of MnO greatly influences the stability of garnet, it has relatively little effect on the stability of other common metapelitic minerals, with the resultant diagrams being topologically very similar to those calculated without MnO. Furthermore, the addition of MnO in the amounts measured in most metapelites has only a small effect on the mode of garnet, with calculated garnet modes remaining smaller than 1% in the P–T range outside its predicted Mn‐free P–T range.     

Activity–composition relations for phases in petrological calculations: an asymmetric multicomponent formulation

For petrological calculations, including geothermobarometry and the calculation of phase diagrams (for example, P–T petrogenetic grids and pseudosections), it is necessary to be able to express the activity–composition (a–x) relations of minerals, melt and fluid in multicomponent systems. Although the symmetric formalism—a macroscopic regular model approach to a–x relations—is an easy-to-formulate, general way of doing this, the energetic relationships are a symmetric function of composition. We allow asymmetric energetics to be accommodated via a simple extension to the symmetric formalism which turns it into a macroscopic van Laar formulation. We term this the asymmetric formalism (ASF). In the symmetric formalism, the a–x relations are specified by an interaction energy for each of the constituent binaries amongst the independent set of end members used to represent the phase. In the asymmetric formalism, there is additionally a "size parameter" for each of the end members in the independent set, with size parameter differences between end members accounting for asymmetry. In the case of fluid mixtures, for example, H₂O–CO₂, the volumes of the end members as a function of pressure and temperature serve as the size parameters, providing an excellent fit to the a–x relations. In the case of minerals and silicate liquid, the size parameters are empirical parameters to be determined along with the interaction energies as part of the calibration of the a–x relations. In this way, we determine the a–x relations for feldspars in the systems KAlSi₃O₈–NaAlSi₃O₈ and KAlSi₃O₈–NaAlSi₃O₈–CaAl₂Si₂O₈, for carbonates in the system CaCO₃–MgCO₃, for melt in the melting relationships involving forsterite, protoenstatite and cristobalite in the system Mg₂SiO₄–SiO₂, as well as for fluids in the system H₂O–CO₂. In each case the a–x relations allow the corresponding, experimentally determined phase diagrams to be reproduced faithfully. The asymmetric formalism provides a powerful and flexible way of handling a–x relations of complex phases in multicomponent systems for petrological calculations.     

A new thermodynamic model for sapphirine: calculated phase equilibria in K2O–FeO–MgO–Al2O3–SiO2–H2O–TiO2–Fe2O3

The activity–composition (a–x) relations of sapphirine are re‐evaluated in the light of a recent new internally‐consistent data set of phase end‐members for use in phase equilibria modelling, particularly of ultra‐high‐temperature (UHT) rocks. This is achieved with the aid of relatively oxidized sapphirine+quartz‐bearing granulites from Wilson Lake, Canada. Calculated P–T projections and compatibility diagrams in the K₂O–FeO–MgO–Al₂O₃–SiO₂–H₂O–TiO₂–Fe₂O₃ (KFMASHTO) system are used to illustrate sapphirine+quartz‐bearing phase equilibria in the context of UHT metamorphism. These new a–x relations for sapphirine should allow pseudosection thermobarometry in NCKFMASHTO for estimating peak P–T conditions of sapphirine‐bearing rocks.     

Calculation of partial melting equilibria in the system Na2O–CaO–K2O–FeO–MgO–Al2O3–SiO2–H2O (NCKFMASH)

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.     

A comparison of observed and thermodynamically predicted phase equilibria and mineral compositions in mafic granulites

Recently published activity–composition (a–x) relations for minerals in upper amphibolite‐ and granulite facies intermediate and basic rocks have expanded our ability to interpret the petrological evolution of these important components of the lower continental crust. If such petrological modelling is to be reliable, the abundances and compositions of phases calculated at the interpreted conditions of metamorphic equilibration should resemble those in the sample under study. Here, petrological modelling was applied to six granulite facies rocks that formed in different tectonic environments and reached different peak metamorphic pressure–temperature (P–T) conditions. While phase assemblages matching those observed in each sample can generally be calculated at P–T conditions that approximate those of peak metamorphism, a consistent discrepancy was found between the calculated and observed compositions of amphibole and clinopyroxene. In amphibole, Si, Ca and A‐site K are underestimated by the model, while Al and A‐site Na are overestimated; comparatively, in clinopyroxene, Mg and Si are generally underestimated, while Fe²⁺ and Al are typically overestimated, compared to observed values. One consequence is a reversal in the Fe–Mg distribution coefficient (K_D) between amphibole and clinopyroxene compared to observations. Some of these mismatches are attributed to the incorrect partitioning of elements between the predicted amphibole and clinopyroxene compositions; however, other discrepancies are the result of the incorrect prediction of major substitution vectors in amphibole and clinopyroxene. These compositional irregularities affect mineral modal abundance estimates and in turn the position and size (in P–T space) of mineral assemblage fields, the effect becoming progressively more marked as the modal abundance of hornblende increases; hence, this study carries implications for estimating P–T conditions of high‐temperature metabasites using these new a–x relations.     

A thermodynamic model for Ca–Na clinoamphiboles in Na2O–CaO–FeO–MgO–Al2O3–SiO2–H2O–O for petrological calculations

A calibration is presented for an activity–composition model for amphiboles in the system Na₂O–CaO–FeO–MgO–Al₂O₃–SiO₂–H₂O–O (NCFMASHO), formulated in terms of an independent set of six end‐members: tremolite, tschermakite, pargasite, glaucophane, ferroactinolite and ferritschermakite. The model uses mixing‐on‐sites for the ideal‐mixing activities, and for the activity coefficients, a macroscopic multicomponent van Laar model. This formulation involves 15 pairwise interaction energies and six asymmetry parameters. Calibration of the model is based on the geometrical constraints imposed by the size and shape of amphibole solvi inherent in a data set of 71 coexisting amphibole pairs from rocks, formed over 400–600 °C and 2–18 kbar. The model parameters are calibrated by combining these geometric constraints with qualitative consideration of parameter relationships, given that the data are insufficient to allow all the model parameters to be determined from a regression of the data. Use of coexisting amphiboles means that amphibole activity–composition relationships are calibrated independently of the thermodynamic properties of the end‐members. For practical applications, in geothermobarometry and the calculation of phase diagrams, the amphibole activity–composition relationships are placed in the context of the stability of other minerals by evaluating the properties of the end‐members in the independent set that are in internally consistent data sets. This has been performed using an extended natural data set for hornblende–garnet–plagioclase–quartz, giving the small adjustments necessary to the enthalpies of formation of tschermakite, pargasite and glaucophane for working with the Holland and Powell data set.     

Organic matters and acid‐sulfate alteration in Itomuka mercury mine,Hokkaido, Japan: Implications for the transportation and deposition mechanisms of Hg

In order to examine the transportation and deposition mechanisms of Hg, we investigated the ore and hydrothermal alteration minerals and solid organic matters from Itomuka mercury mine located in the eastern part of central Hokkaido. In addition to the ore minerals, native mercury and cinnabar, quartz, marcasite, alunite, kaolinite, and minor amounts of pyrite and smectite were identified in the Hg ore by powder X‐ray diffraction (XRD) analysis. This mineral assemblage of acid sulfate alteration was likely developed under the conditions of low temperature (≤100°C) and low pH (≤2) in the steam‐heated environment. The H₂SO₄ was produced above the water table by the oxidation of H₂S separated from deep, near‐neutral fluids by boiling. The dominance of native mercury over cinnabar in Hg ore indicates that the greater part of mineralized Hg was transported as Hg⁰ in aqueous solution and vapor with low sulfur fugacity. The solid organic matters found in the Hg ore were analyzed with SEM‐EDS, micro‐XRD, and micro‐Fourier transform infrared (FTIR) spectroscopy, and these results suggest that the organic matters contributed to keeping the low fO₂ of the Hg‐bearing fluid and transportation of Hg as Hg⁰ in S‐poor condition. Because the solubility of Hg in acidic fluid is low, neutral to alkaline fluid seems to have leached Hg from the basement sedimentary rocks of Hidaka Group which also supplied the organic matters to the fluid. The oxidation and cooling of Hg‐bearing solution and vapor triggered the deposition of liquid Hg as a primary phase.     

Relating discrete element method parameters to rock properties using classical and micropolar elasticity theories

Micro–macro relations for discrete element method (DEM) media are derived using both classical and micropolar elasticity theories. The DEM media are classified into two main categories: dense packing, and loose packing. For both categories, relations for Young modulus (E), Poisson's ratio (ν) to represent static behaviors, and wave velocities (P‐wave and S‐wave) to represent dynamic behaviors are derived using the internal DEM parameters (k_n, k_s) and compared with values obtained from static and dynamic numerical tests. Whereas the dynamic behaviors for the two categories and the static behaviors for the dense packing match the analytical relations, the static behavior for the loose packing does not. Micropolar elasticity theory is also used to study the behaviors of the DEM media, where it is shown that if element rotation is included, DEM media behave according to linear elasticity theory. However, if element rotation is constrained, asymmetrical stresses arise in the DEM media, and a new expression is derived for the S‐wave, which allows it, under certain conditions, to travel faster than the P‐wave. Copyright © 2011 John Wiley & Sons, Ltd.     

Modelling of mineral equilibria in ultrahigh-temperature metamorphic rocks from the Anápolis–Itauçu Complex, central Brazil

A new quantitative approach to constraining mineral equilibria in sapphirine‐bearing ultrahigh‐temperature (UHT) granulites through the use of pseudosections and compatibility diagrams is presented, using a recently published thermodynamic model for sapphirine. The approach is illustrated with an example from an UHT locality in the Anápolis–Itauçu Complex, central Brazil, where modelling of mineral equilibria indicates peak metamorphic conditions of about 9 kbar and 1000 °C. The early formed, coarse‐grained assemblage is garnet–orthopyroxene–sillimanite–quartz, which was subsequently modified following peak conditions. The retrograde pressure–temperature (P–T) path of this locality involves decompression across the FeO–MgO–Al₂O₃–SiO₂ (FMAS) univariant reaction orthopyroxene + sillimanite = garnet + sapphirine + quartz, resulting in the growth of sapphirine–quartz, followed by cooling and recrossing of this reaction. The resulting microstructures are modelled using compatibility diagrams, and pseudosections calculated for specific grain boundaries considered as chemical domains. The sequence of microstructures preserved in the rocks constrains a two‐stage isothermal decompression–isobaric cooling path. The stability of cordierite along the retrograde path is examined using a domainal approach and pseudosections for orthopyroxene–quartz and garnet–quartz grain boundaries. This analysis indicates that the presence or absence of cordierite may be explained by local variation in a_H2O. This study has important implications for thermobarometric studies of UHT granulites, mainly through showing that traditional FMAS petrogenetic grids based on experiments alone may overestimate P–T conditions. Such grids are effectively constant a_H2O sections in FMAS‐H₂O (FMASH), for which the corresponding a_H2O is commonly higher than that experienced by UHT granulites. A corollary of this dependence of mineral equilibria on a_H2O is that local variations in a_H2O may explain the formation of cordierite without significant changes in P–T conditions, particularly without marked decompression.     

Integrated pressure–temperature–time constraints for the Tso Morari dome (Northwest India): implications for the burial and exhumation path of UHP units in the western Himalaya

Northward subduction of the leading edge of the Indian continental margin to depths greater than 100 km during the early Eocene resulted in high‐pressure (HP) quartz‐eclogite to ultrahigh‐pressure (UHP) coesite–eclogite metamorphism at Tso Morari, Ladakh Himalaya, India. Integrated pressure–temperature–time determinations within petrographically well‐constrained settings for zircon‐ and/or monazite‐bearing assemblages in mafic eclogite boudins and host aluminous gneisses at Tso Morari uniquely document segments of both the prograde burial and retrograde exhumation path for HP/UHP units in this portion of the western Himalaya. Poikiloblastic cores and inclusion‐poor rims of compositionally zoned garnet in mafic eclogite were utilized with entrapped inclusions and matrix minerals for thermobarometric calculations and isochemical phase diagram construction, the latter thermodynamic modelling performed with and without the consideration of cation fractionation into garnet during prograde metamorphism. Analysis of the garnet cores document (M1) conditions of 21.5 ± 1.5 kbar and 535 ± 15 °C during early garnet growth and re‐equilibration. Sensitive high resolution ion microprobe (SHRIMP) U–Pb analysis of zircon inclusions in garnet cores yields a maximum age determination of 58.0 ± 2.2 Ma for M1. Peak HP/UHP (M2) conditions are constrained at 25.5–27.5 kbar and 630–645 °C using the assemblage garnet rim–omphacite–rutile–phengite–lawsonite–talc–quartz (coesite), with mineral compositional data and regional considerations consistent with the upper P–T bracket. A SHRIMP U–Pb age determination of 50.8 ± 1.4 Ma for HP/UHP metamorphism is given by M2 zircons analysed in the eclogitic matrix and that are encased in the garnet rim. Two garnet‐bearing assemblages from the Puga gneiss (host to the mafic eclogites) were utilized to constrain the subsequent decompression path. A non‐fractionated isochemical phase diagram for the assemblage phengite–garnet–biotite–plagioclase–quartz–melt documents a restricted (M3) P–T stability field centred on 12.5 ± 0.5 kbar and 690 ± 25 °C. A second non‐fractionated isochemical phase diagram calculated for the lower pressure assemblage garnet–cordierite–sillimanite–biotite–plagioclase–quartz–melt (M4) documents a narrow P–T stability field ranging between 7–8.4 kbar and 705–755 °C, which is consistent with independent multiequilibria P–T determinations. Th–Pb SHRIMP dating of monazite cores surrounded by allanite rims is interpreted to constrain the timing of the M4 equilibration to 45.3 ± 1.1 Ma. Coherently linking metamorphic conditions with petrographically constrained ages at Tso Morari provides an integrated context within which previously published petrological or geochronological results can be evaluated. The new composite path is similar to those published for the Kaghan UHP locality in northern Pakistan, although the calculated 12‐mm a^?1 rate of post‐pressure peak decompression at Tso Morari would appear less extreme.     

Stability of sapphirine + quartz in the oxidized rocks of the Wilson Lake terrane,Labrador: calculated equilibria in NCKFMASHTO

The equilibrium coexistence of sapphirine + quartz is inferred to record temperatures in excess of 980 °C, based on the stability of this assemblage in the simplified chemical system FeO–MgO–Al₂O₃–SiO₂ (FMAS) system. However, the potential for sapphirine to contain significant Fe³⁺ suggests that the stability of sapphirine + quartz could extend to lower temperatures than those constrained in this ideal system. The Wilson Lake terrane in the Grenville Province of central Labrador preserves sapphirine + quartz‐bearing assemblages in highly oxidized bulk compositions, and provides an opportunity to explore the stability of sapphirine + quartz in such rock compositions within the Na₂O–CaO–K₂O–FeO–MgO–Al₂O₃–SiO₂–H₂O–TiO₂–O (NCKFMASHTO) chemical system. Starting with the phase equilibria in FeO–MgO–Al₂O₃–SiO₂–TiO₂–O (FMASTO), expansion into K₂O–FeO–MgO–Al₂O₃–SiO₂–H₂O–TiO₂–O (KFMASHTO) allows the effect of the stability of the additional phases, biotite, K‐feldspar and melt, on the stability of sapphirine + quartz to be assessed. These phase relations are evaluated generally using P–T projections, and the ultimate extension into NCKFMASHTO is done with pseudosections. Conditions of peak metamorphism in the Wilson Lake terrane are constrained using P–T pseudosections, and the appropriate H₂O and O contents to use in the modelled compositions are investigated using T–M_H2O and T–M_O pseudosections. The peak P–T estimates from a sapphirine + quartz‐bearing sample are ～960 to 935 °C at ～10 to 8.6 kbar, similar to estimates from orthopyroxene + sillimanite + quartz ± garnet‐bearing samples. Whereas the sapphirine + quartz‐bearing sample is more Fe‐rich than the orthopyroxene + sillimanite‐bearing sample on an all‐Fe‐as‐FeO basis, once the oxidation state is taken into account, the former is effectively more magnesian than the latter, accounting for the sapphirine occurrence.     

Quartz OSL chronology and dust accumulation rate changes since the Last Glacial at Weinan on the southeastern Chinese Loess Plateau

The fine‐grained (4–11 μm) quartz Optically Stimulated Luminescence (OSL) dating technique was applied to the Weinan section on the southeastern Chinese Loess Plateau (CLP) with a high luminescence sampling resolution (10‐ and 20‐cm intervals). Fifty‐eight OSL ages, spanning c. 1–74 ka, were obtained for the 10‐m loess–palaeosol sequences. The reliability of the OSL dating and the constructed chronology was confirmed by comparing the OSL ages with independent dates from other studies and by correlation with palaeoclimatic time series. The closely spaced OSL ages at Weinan indicate that the mean dust accumulation rate (DAR) of L_1–1 (MIS 2, 7.0±0.9 cm ka^?1) is lower than those of L_1–3 (MIS 4, 19.1±6.1 cm ka^?1) and L_1–2 (MIS 3, 16.0±0.7 cm ka^?1) and that the mean DAR c. 30–20 ka ago (11.4±2.4 cm ka^?1) is higher than that c. 20–10 ka ago (3.0±0.1 cm ka^?1) in L_1–1. The subsequent calculation of the mass accumulation rate (MAR) indicates that the MAR of L_1–1 (107 g m^?2 a^?1) is much lower than those of L_1–2 (247 g m^?2 a^?1) and L_1–3 (307 g m^?2 a^?1). By comparing the mean DAR results during the Last Glacial at Weinan with those at a further six sites from other studies, we observed that the mean DAR of L_1–2 is higher (lower) than that of L_1–1 on the eastern (western) CLP, and that the mean DAR during MIS 2 has an evident transition from high to low at c. 20 ka on the entire CLP. Possible mechanisms for the above mean DAR changes at orbital and sub‐orbital time scales are presented.     

Thermodynamic properties and crystal growth behavior of the hashemite (BaSO4–BaCrO4) solid solution

Thermodynamic properties of the BaSO₄–BaCrO₄ hashemite solid solution were calculated using molecular principles. Force-field potentials and physical properties of the end member BaCrO₄ were derived using the program package GULP. Subsequently, anion–anion (SO₄²⁻–CrO₄²⁻, SO₄²⁻–SO₄²⁻, CrO₄²⁻–CrO₄²⁻) interaction energies were fitted to a number of random and ordered anion distributions, which were energy-optimized using these empirical potentials. With these interaction energies, diagrams for the enthalpy and free energy of mixing could be computed for the entire range of the hashemite solid solution between the BaSO₄ and BaCrO₄ end members and for a number of annealing temperatures. These thermodynamic data show that the solid solution is close to ideal and ordering is not observed at low temperatures for any composition. However, according to our calculations, exsolution may occur at the nanoscale due to a slight tendency of sulfate–chromate avoidance.Growth experiments of chromate-rich hashemite on barite using atomic force experiments (AFM) in a fluid cell indicate that hashemite does not show the same degree of growth anisotropy as barite. In the case of barite, this anisotropy leads to a structural self-inhibition of spiral growth. In contrast, hashemite exhibits a spatially more extended spiral growth, which can contribute more to overall volume growth than in the case of barite. This finding is confirmed by a higher growth rate of hashemite than of barite in macroscopic batch-reactor and flow-through experiments.Molecular simulations indicate that there is a less pronounced step energy difference between bounding steps of growth islands for hashemite than for barite, which may partially explain the difference in growth anisotropy of the two minerals. Differences in adsorption energies to the corners of growth islands, which are the limiting steps of growth, do not seem to be high enough to explain differences in growth anisotropies. Therefore, kinetic effects or differences in the interfacial free energies of the two minerals may serve as an additional explanation for differences in the growth behavior.     

Cretaceous evolution of a metamorphic core complex,the Veporic unit,Western Carpathians (Slovakia): P–T conditions and in situ40Ar/39Ar UV laser probe dating of metapelites

Alpine metamorphism, related to the development of a metamorphic core complex during Cretaceous orogenic events, has been recognized in the Veporic unit, Western Carpathians (Slovakia). Three metamorphic zones have been distinguished in the metapelites: 1, chloritoid + chlorite + garnet; 2, garnet + staurolite + chlorite; 3, staurolite + biotite + kyanite. The isograds separating the metamorphic zones have been modelled by discontinuous reactions in the system K₂O–FeO–MgO–Al₂O₃–SiO₂–H₂O (KFMASH). The isograds are roughly parallel to the north‐east‐dipping foliation related to extensional updoming along low‐angle normal faults. Thermobarometric data document increasing P–T conditions from c. 500 °C and 7–8 kbar to c. 620 °C and 9–10 kbar, reflecting a coherent metamorphic field gradient from greenschist to middle amphibolite facies. ⁴⁰Ar/³⁹Ar data obtained by high spatial resolution in situ ultraviolet (UV) laser ablation of white micas from the rock slabs constrain the timing of cooling and exhumation in the Late Cretaceous. Mean dates are between 77 and 72 Ma; however, individual white mica grains record a range of apparent ⁴⁰Ar/³⁹Ar ages indicating that cooling below the blocking temperature for argon diffusion was not instantaneous. The reconstructed metamorphic P–T–t path is ‘clockwise’, reflecting post‐burial decompression and cooling during a single Alpine orogenic cycle. The presented data suggest that the Veporic unit evolved as a metamorphic core complex during the Cretaceous growth of the Western Carpathian orogenic wedge. Metamorphism was related to collisional crustal shortening and stacking, following closure of the Meliata Ocean. Exhumation was accomplished by synorogenic (orogen‐parallel) extension and unroofing in an overall compressive regime.     

Garnet and spinel lherzolite assemblages in MgO–Al2O3–SiO2 and CaO–MgO–Al2O3–SiO2: thermodynamic models and an experimental conflict

The recent publication of an updated thermodynamic dataset for petrological calculations provides an opportunity to illustrate the relationship between experimental data and the dataset, in the context of a new set of activity–composition models for several key minerals. These models represent orthopyroxene, clinopyroxene and garnet in the system CaO–MgO–Al₂O₃–SiO₂ (CMAS), and are valid up to 50 kbar and at least 1800 °C; they are the first high‐temperature models for these phases to be developed for the Holland & Powell dataset. The models are calibrated with reference to phase‐relation data in the subsystems CaO–MgO–SiO₂ (CMS) and MgO–Al₂O₃–SiO₂ (MAS), and will themselves form the basis of models in larger systems, suitable for calculating phase equilibria in the crust and mantle. In the course of calibrating the models, it was necessary to consider the reaction orthopyroxene + clinopyroxene + spinel = garnet + forsterite in CMAS, representing a univariant transition between simple spinel and garnet lherzolite assemblages. The high‐temperature segment of this reaction has been much disputed. We offer a powerful thermodynamic argument relating this reaction to the equivalent reaction in MAS, that forces us to choose between good model fits to the data in MAS or to the more recent data in CMAS. We favour the fit to the MAS data, preserving conformity with a large body of experimental and thermodynamic data that are incorporated as constraints on the activity–composition modelling via the internally consistent thermodynamic dataset.     

Luobusaite： A New Mineral

A group of mantle minerals including about 70-80 subtypes of minerals are discovered from a podiform chromitite in Tibet, China. Recovered minerals include diamond, coesite, moissanite, wustite, Fe-silides and a new mineral, luobusaite. All of these minerals were hand-picked from heavymineral separates of the podiform chromitite in the mantle peridotite of an ophiolite. The grains of luobusaite are as host mineral with inclusions of native silicon or as an intergrowth with native silicon and Fe-Si phase. Luobusaite occurs as irregular grains, with 0.1-0.2 mm in size, consisting of very finegrained aggregates. The mineral is steel-grey in color, metallic luster, and opaque. The empirical formula （based on 2 for Si） is Fe0.83Si2, according to the chemical compositions of luobusaite. X-ray powder-diffraction data： orthorhombic system, space group Cmca, a = 9.874 （14） A, b = 7.784 （5） A, c= 7.829（7） A, Z=16.     

Exhumation of oceanic eclogites: thermodynamic constraints on pressure,temperature, bulk composition and density

The exhumation mechanism of high‐pressure (HP) and ultrahigh‐pressure (UHP) eclogites formed by the subduction of oceanic crust (hereafter referred to as oceanic eclogites) is one of the primary uncertainties associated with the subduction factory. The phase relations and densities of eclogites with MORB compositions are modelled using thermodynamic calculations over a P–T range of 1–4 GPa and 400–800 °C, respectively, in the NCKFMASHTO (Na₂O–CaO–K₂O–FeO–MgO–Al₂O₃–SiO₂–H₂O–TiO₂–Fe₂O₃) system. Our modelling suggests that the mineral assemblages, mineral proportions and density of oceanic crust subducted along a cold P–T path are quite different from those of crust subducted along a warm P–T path, and that the density of oceanic eclogites is largely controlled by the stability of low‐density hydrous minerals, such as lawsonite, chlorite, glaucophane and talc. Along a cold subduction P–T path with a geotherm of ~6 °C km^?1, lawsonite is always present at 1.1 to >4.0 GPa, and chlorite, glaucophane and talc can be stable at pressures of up to 2.3, 2.6 and 3.6 GPa respectively. Along such a P–T path, the density of subducted oceanic crust is always lower than that of the surrounding mantle at depths shallower than 110–120 km (< 3.3–3.6 GPa). However, along a warm subduction P–T path with a geotherm of ~10 °C km^?1, the P–T path is outside the stability field of lawsonite, and the hydrous minerals of chlorite, epidote and amphibole break down completely into dry dense minerals at relatively lower pressures of 1.5, 1.85 and 1.9 GPa respectively. Along such a warm subduction P–T path, the subducted oceanic crust becomes denser than the surrounding mantle at depths >60 km (>1.8 GPa). Oceanic eclogites with high H₂O content, oxygen fugacity, bulk‐rock X_Mg [ = MgO/(MgO + FeO)], X_Al [ = Al₂O₃/(Al₂O₃ + MgO + FeO)] and low X_Ca [ = CaO/(CaO + MgO + FeO + Na₂O)] are likely suitable for exhumation, which is consistent with the bulk‐rock compositions of the natural oceanic eclogites on the Earth's surface. On the basis of natural observations and our calculations, it is suggested that beyond depths around 110–120 km oceanic eclogites are not light enough and/or there are no blueschists to compensate the negative buoyancy of the oceanic crust, therefore explaining the lack of oceanic eclogites returned from ultradeep mantle (>120 km) to the Earth's surface. The exhumed light–cold–hydrous oceanic eclogites may have decoupled from the top part of the sinking slab at shallow depths in the forearc region and are exhumed inside the serpentinized subduction channel, whereas the dense–hot–dry eclogites may be retained in the sinking slab and recycled into deeper mantle.     

Phase equilibrium modelling of the amphibolite to granulite facies transition in metabasic rocks (Ivrea Zone,NW Italy)

The development of thermodynamic models for tonalitic melt and the updated clinopyroxene and amphibole models now allow the use of phase equilibrium modelling to estimate P–T conditions and melt production for anatectic mafic and intermediate rock types at high‐T conditions. The Permian mid‐lower crustal section of the Ivrea Zone preserves a metamorphic field gradient from mid amphibolite facies to granulite facies, and thus records the onset of partial melting in metabasic rocks. Interlayered metabasic and metapelitic rocks allows the direct comparison of P–T estimates and partial melting between both rock types with the same metamorphic evolution. Pseudosections for metabasic compositions calculated in the Na₂O–CaO–K₂O–FeO–MgO–Al₂O₃–SiO₂–H₂O–TiO₂–O (NCKFMASHTO) system are presented and compared with those of metapelitic rocks calculated with consistent end‐member data and a–x models. The results presented in this study show that P–T conditions obtained by phase equilibria modelling of both metabasic and metapelitic rocks give consistent results within uncertainties, allowing integration of results obtained for both rock types. In combination, the calculations for both metabasic and metapelitic rocks allows an updated and more precisely constrained metamorphic field gradient for Val Strona di Omegna to be defined. The new field gradient has a slightly lower dP/dT which is in better agreement with the onset of crustal thinning of the Adriatic margin during the Permian inferred in recent studies.     

A thermodynamic model for silicate melt in CaO–MgO–Al2O3–SiO2 to 50 kbar and 1800 °C

A fully thermodynamic model for mafic melt in CaO–MgO–Al₂O₃–SiO₂ (CMAS) has been calibrated, for calculation of melting equilibria in the pressure range 0–50 kbar. It is intended as a preliminary step towards a large‐system melt model, suitable for exploring melting, melt loss and crystallization processes in a wide range of natural rock compositions. Calibration was performed with attention to the model's behaviour in its compositional subsystems, as a rigorous test of model structure and parameterization. The model is consistent with the latest Holland & Powell thermodynamic data set, and can therefore be used to calculate phase relations in conjunction with the many solid‐phase activity–composition models written for the data set. Model calculations successfully reproduce experimental melting reactions in CMAS spinel lherzolite and garnet lherzolite assemblages, as well as sapphirine‐ and kyanite‐bearing assemblages, at moderate to high pressure. Thermodynamically sensitive features, such as thermal divides are also recovered. However, some changes to the model structure will be required before the model can describe the full range of mafic and ultramafic melt compositions known from experiment at low pressures.