Eclogite-facies Mineral Assemblages Research Articles

Magmatic genesis, hydration, and subduction of the tholeiitic eclogite-facies Allalin gabbro (Western Alps, Switzerland)

The Allalin gabbro of the Zermatt-Saas meta-ophiolite consists of variably metamorphosed Mg- to Fe-Ti-gabbros, troctolites, and anorthosites, which are crosscut by basaltic dykes. Field relationships of the various rock types and petrographic studies together with bulk rock and mineral chemical composition data allow the reconstruction of the complete geological history of the Allalin gabbro. With increasing magmatic differentiation, the incompatible element content in clinopyroxene increases (e.g., REEs and Zr by a factor of 5), whereas the Mg# decreases (from 86.4 to 74.6) as do the compatible element contents (e.g., Cr and Ni by factors of 3.5 and 5, respectively). Exhumation to shallower depths led to subsolidus ductile deformation and cooling of the gabbro followed by the intrusion of fine-grained basaltic dykes, which display chilled margins. Bulk rock data of these dykes reveal strong similarities in fluid-immobile trace element patterns to tholeiitic pillow basalts of the Zermatt-Saas and nearby meta-ophiolites. The recalculated REE patterns of the melt in equilibrium with igneous clinopyroxene is very similar to the REE patterns of the mafic dykes, indicating a cogenetic origin of pillow basalts, dykes, and gabbros. Together with the previously determined Jurassic intrusion age of the gabbro, our observations demonstrate that the Allalin gabbro intruded as a tholeiitic magma in a slow spreading MOR environment of the Piemonte-Ligurian ocean of the Alpine Tethys. Subduction of the Allalin gabbro resulted in different eclogitization extents of the Mg-gabbros as a function of variable hydration degrees. Metagabbros with low extents of hydration record incomplete eclogitization; the magmatic mineralogy (olivine + clinopyroxene + plagioclase) is preserved together with disequilibrium textures in the form of reaction coronae surrounding mineral boundaries. Metagabbros with high extents of hydration are completely eclogitized and display pseudomorphic replacement textures of magmatic minerals by eclogite-facies mineral assemblages, which required significant major to trace element transport across mineral domains. The locally variable extents of hydration took place near the sea floor, as recorded by the presence of Cl-apatite (6.28 wt% Cl), and an increase in B concentrations of minerals pseudomorphically replacing olivine (e.g., chlorite with 0.20–0.31 µg/g B and omphacite with 0.22–0.25 µg/g B) compared to magmatic olivine (0.12–0.16 µg/g B). Moreover, the chemical zonation pattern of metamorphic garnet coronae is different in completely eclogitized gabbros and gabbros with relic igneous minerals, in agreement with a main hydration event prior to subduction. The Allalin gabbro therefore represents a classical example of an oceanic gabbro formed in a slow spreading setting in the mid Jurassic that experienced heterogeneous hydration near the sea floor. Paleogene subduction of the gabbro to 70–80 km depth produced variably equilibrated gabbroic eclogites. In eclogite-facies Mg-gabbros, the water-rich minerals chlorite, talc, and chloritoid pseudomorphing magmatic olivine remained stable to these depths, revealing the potential relevance of hydrated Mg-gabbros as a fluid source at subarc depths in subduction zones.

Reactive fluid flow guided by grain-scale equilibrium reactions during eclogitization of dry crustal rocks

Fluid flow in crystalline rocks in the absence of fractures or ductile shear zones dominantly occurs by grain boundary diffusion, as it is faster than volume diffusion. It is, however, unclear how reactive fluid flow is guided through such pathways. We present a microstructural, mineral chemical, and thermodynamic analysis of a static fluid-driven reaction from dry granulite to ‘wet’ eclogite. Fluid infiltration resulted in re-equilibration at eclogite-facies conditions, indicating that the granulitic protolith was out of equilibrium, but unable to adjust to changing P–T conditions. The transformation occurred in three steps: (1) initial hydration along plagioclase grain boundaries, (2) complete breakdown of plagioclase and hydration along phase boundaries between plagioclase and garnet/clinopyroxene, and (3) re-equilibration of the rock to an eclogite-facies mineral assemblage. Thermodynamic modelling of local compositions reveals that this reaction sequence is proportional to the local decrease of the Gibbs free energy calculated for ‘dry’ and ‘wet’ cases. These energy differences result in increased net reaction rates and the reactions that result in the largest decrease of the Gibbs free energy occur first. In addition, these reactions result in a local volume decrease leading to porosity formation; i.e., pathways for new fluid to enter the reaction site thus controlling net fluid flow. Element transport to and from the reaction sites only occurs if it is energetically beneficial, and enough transport agent is available. Reactive fluid flow during static re-equilibration of nominally impermeable rocks is thus guided by differences in the energy budget of the local equilibrium domains.

Petrology and Tectonic Geophysics of Massive and Foliated Eclogites in the North Qilian Orogenic Belt: Changes in Mineral Composition, Oxygen Fugacity, and Fabric during Exhumation

The North Qilian orogenic belt is a typical area of “cold” subduction of the early Paleozoic oceanic plate, forming a series of high pressure and low temperature metamorphic rock assemblages. Among them, eclogite is a kind of protolith, which is basaltic or gabbro high pressure metamorphic rock, mainly composed of garnet and chlorite which are two kinds of minerals. Eclogites record the entire history of subduction zone metamorphism and later exhumation. Due to the crystal habit and the developed joints, the strength of the pyroxene in the matrix is weak, so it is subjected to the main strain during deformation, whereas garnet tends to show only passive rotational deformation. This paper presents some new results in petrology and tectonic geophysics of eclogite block-like and planar eclogite. The massive and facial eclogite rocks contain eclogite facies mineral assemblages, and the peak temperature and pressure conditions are [Formula: see text]°C and [Formula: see text] GPa, which are consistent with the adjacent eclogite. Combined with the characteristics of in situ Lu-Hf isotopes, Ce4+/Ce3+ ratios of zircons, relative oxygen fugacity, and absolute oxygen fugacity, it is shown that the oxygen fugacity of the granodiorite porphyry (BL023, BLO31, DB048) of the folio chemical and massive eclogite deposits are all located in MH (magnetite-hematite) buffer zone. Through the calculation results of absolute oxygen fugacity of rock mass, it can be seen that the absolute oxygen fugacity of ore-bearing rock mass is significantly higher than that of non-ore-bearing rock mass. This paper systematically summarizes the research progress of the microscopic and ultrastructural deformation of eclogite minerals in high-pressure metamorphic zones, and discusses the changes of mineral composition, oxygen fugidity, and fabric of eclogite deformation characteristics during the recovery of subduction and reentry.

A New HP–UHP Eclogite Belt Identified in the Southeastern Tibetan Plateau: Tracing the Extension of the Main Palaeo-Tethys Suture Zone

Abstract The Changning–Menglian orogenic belt (CMOB) in the southeastern Tibetan Plateau is an important link between the Longmu Co–Shuanghu suture (LCSS) in the northern Tibetan Plateau and the Chiang Mai–Inthanon and Bentong–Raub sutures in Thailand and Peninsular Malaysia. These belts and sutures are generally regarded as containing the remnants of the oceanic crust of the Palaeo-Tethys that formed by seafloor spreading as a result of the separation of Gondwana- and Eurasia-derived blocks during the Middle Cambrian. In this paper we report the first discovery of abundant unaltered and retrograde eclogites that occur as irregular lenses and blocks in metasedimentary rocks of the CMOB, and these eclogites form an elongate and almost north–south-trending high-pressure (HP)–ultrahigh-pressure (UHP) metamorphic belt that is ∼200 km long and ∼50 km wide. The newly discovered phengite/talc/epidote–glaucophane eclogites, lawsonite–talc–phengite eclogites, dolomite/magnesite–kyanite eclogites and phengite–kyanite-bearing retrograde eclogites have enriched (E-) and normal mid-ocean ridge basalt (N-MORB)-like affinities and mainly positive as well as some negative whole-rock εNd values (–4·34 to +7·89), which suggest an enriched and depleted oceanic lithosphere source for their protoliths. Magmatic zircons separated from the epidote–glaucophane, magnesite–kyanite and (phengite–kyanite-bearing) retrograde eclogites gave protolith ages of 317–250 Ma, which fit well within the time frame of the opening of the Palaeo-Tethys during the Middle Cambrian and its closure during the Triassic. Abundant metamorphic zircons in the eclogites indicate a Triassic metamorphic event related to the subduction of the Palaeo-Tethys oceanic crust from 235 to 227 Ma. Taking into account previous isotopic age data, we now establish the periods of Early–Middle Triassic (246–227 Ma) and Late Triassic (222–209 Ma) as the ages of subduction and exhumation of the Palaeo-Tethyan oceanic crust, respectively. Thermodynamic modelling revealed that the eclogites record distinct HP–UHP peak metamorphic conditions of 23·0–25·5 kbar and 582–610 °C for the phengite–glaucophane eclogites, 24·0–25·5 kbar and 570–586 °C for the talc–glaucophane eclogites, 29·0–31·0 kbar and 675–712 °C for the dolomite–kyanite eclogites, and 30·0–32·0 kbar and 717–754 °C for the magnesite–kyanite eclogites. These P–T estimates and geochronological data indicate that the Palaeo-Tethys oceanic slab was subducted to different mantle depths from 75 km down to 95 km, forming distinct types of eclogite with a variety of peak eclogite-facies mineral assemblages. The eclogites consistently record clockwise metamorphic P–T–t paths characterized by a heating–compression prograde loop under a low geothermal gradient of 5–10 °C km–1, indicating the rapid subduction of cold oceanic crust at a rate of 4·5–6·0 km Ma–1, followed by isothermal or cooling–decompressive retrogression and exhumation at an average rate of 3·2–4·2 km Ma–1. The newly discovered eclogites of the CMOB with their signatures of ocean-crust subduction are petrologically, geochemically and geochronologically comparable with those of the LCSS, providing powerful support for the idea that a nearly 2000 km long HP–UHP eclogite belt extends from the northern Tibetan Plateau to the southeastern Tibetan Plateau, and that it represents the main boundary suture of the Palaeo-Tethyan domain. These results have far-reaching implications for the tectonic framework and complex metamorphic evolution of the Palaeo-Tethyan domain.

Thermobarometric constraints on burial and exhumation of 2-billion-year-old eclogites and their metapelitic hosts

One of the first appearances of eclogite-facies mineral assemblages in the geological record occurs in the c. 2000 Ma Palaeoproterozoic Usagaran Belt in central Tanzania, where the extended margin of the Tanzanian Craton is interpreted to have been subducted. Mafic rocks are interpreted to have contained the mineral assemblage garnet + omphacite + rutile + quartz ± amphibole. This high-pressure assemblage has been overprinted by a secondary mineral assemblage containing clinopyroxene + plagioclase + hornblende + ilmenite ± orthopyroxene. Mineral equilibria forward modelling indicates that the eclogite-facies assemblages reached minimum peak pressure–temperature (P–T) conditions of ~17 kbar and ~700 °C. Inclusions in garnet document a prograde P–T history consistent with burial through upper amphibolite-facies conditions and possible partial melting. Petrological and compositional evidence from garnet suggests that following peak metamorphism, the eclogite-facies rocks were heated while stalled at approximate peak pressures. Temperature estimates derived from Zr concentrations in interpreted texturally retrograde rutile support a near-isothermal post-peak P–T evolution for the eclogite-facies rocks – an evolution that terminates at retrograde P–T conditions of approximately 7.6–8.2 kbar and 680–790 °C. The relict eclogite domains form part of a larger assemblage with enclosing migmatitic metapelitic lithologies (the Isimani Suite). The metapelitic gneisses contain garnet + kyanite + biotite + staurolite + hornblende + plagioclase + muscovite + rutile + quartz and preserve minimal evidence of a high-pressure history, conceivably due to post-peak mineralogical recrystallisation. P–T modelling, inclusion assemblages and compositional zonation patterns in porphyroblastic garnet suggests the metapelitic gneisses — similarly to the relict eclogites — experienced burial to minimum peak pressures of approximately 16.5–17 kbar. Compositional zoning patterns in eclogitic garnet suggest the Isimani system was buried, reached peak metamorphic conditions, and was subsequently exhumed within a timeframe of up to 20 Myr. A tectonic regime involving crustal thickening and subduction, followed by extensional exhumation of the entire Isimani Suite is our preferred model for the development of the c. 2000 Ma Usagaran Belt.

Cambrian eclogite-facies metamorphism in the central Transantarctic Mountains, East Antarctica: Extending the record of early Palaeozoic high-pressure metamorphism along the eastern Gondwanan margin

The Nimrod Complex in the Miller and Geologists ranges of the central Transantarctic Mountains comprises Mesoarchean and Palaeoproterozoic crust that was incorporated into the Ross Orogen during metamorphism and deformation along the eastern Gondwanan convergent margin in the late Neoproterozoic and early Palaeozoic. In the Miller Range, boudinaged mafic domains are hosted within upper-amphibolite- to granulite-facies mylonitic rocks that were deformed during the Ross Orogeny. The mafic rocks preserve evidence of a precursor eclogite-facies mineral assemblage containing garnet, omphacite, amphibole, quartz and rutile. Mineral equilibria forward modelling and Zr-in-rutile thermometry indicate that the eclogite assemblage records peak pressure-temperature conditions of 16–18 kbar and 675–760 °C. A secondary metamorphic assemblage of clinopyroxene-plagioclase symplectite, plagioclase coronae rimming garnet, fine-grained amphibole, and interstitial ilmenite orthopyroxene overprint the high-pressure assemblage. Compositions and modal proportions of retrograde garnet, orthopyroxene and amphibole suggest near isothermal exhumation to conditions of 8–10 kbar and 660–840 °C, followed by a long-lived mid-crustal residence. In-situ LA–ICP–MS UPb dating of zircon and rutile yields concordant ages of 536 ± 14 Ma and 536 ± 20 Ma, respectively. The Cambrian-aged zircons show an absent to weakly negative Eu anomaly signature and flat heavy rare earth element (HREE) distributions that are typical of zircons crystallised in the absence of plagioclase and presence of garnet, and which is diagnostic of eclogite-facies conditions. The Cambrian-aged zircon population contrasts with older, highly discordant Palaeoproterozoic zircons that have negative Eu anomalies and are HREE enriched. These zircons are interpreted to be protolithic, and their ages are consistent with existing geochronology from host rocks in the region. The Cambrian-aged zircon and rutile are inferred to represent eclogite-facies metamorphism associated with Ross orogenesis. The early Palaeozoic eastern Gondwanan margin contains a diverse array of eclogite precursors that document contrasting geodynamic styles. Eclogites in northern Victoria Land and central Tasmania record comparatively warm thermal gradients, short-lived high-pressure conditions, and rapid exhumation within their continental crust hosts, whereas oceanic eclogites in the southern New England Fold Belt record refrigerated, long-lived convergent-margin metamorphism. The Miller Range eclogite-facies rocks in this study appear to have been derived from shallow subduction of ancient continental crust, after which they stalled at thermally elevated mid-crustal depths prior to their final exhumation. The discovery of Cambrian-aged eclogite-facies rocks in the Miller Range expands the spatial footprint of high-pressure metamorphism during the Ross Orogeny along the early Palaeozoic eastern Gondwanan margin.

High-P amphibolite-facies metamorphism in the Adrar–Souttouf Metamafic Complex, Oulad Dlim Massif (West African Craton margin, Morocco)

The Oulad Dlim Massif represents the northern segment of the Mauritanide belt that thrusts over the western margin of the Reguibat Shield, north of the West African Craton (WAC). This belt includes various metamorphic units of Archean, Neoproterozoic and Palaeozoic ages that were stacked and thrust eastward during the Variscan orogeny. The core of the Oulad Dlim Massif comprises the Adrar–Souttouf Metamafic Complex that represents a large tectonic unit made of high-grade mafic rocks and vast exposures of amphibolites. A characterisation of the metamorphism in these amphibolites is essential to understand the relationships of the Oulad Dlim Massif with the southern segments of the Mauritanide belt and to provide constraints on the geodynamic evolution of the western margin of the WAC. Here we determine the P–T conditions of metamorphism of two samples of garnet amphibolites collected at the northernmost end of the Adrar–Souttouf Metamafic Complex. The samples show a main mineral assemblage of garnet+low-Ti pargasite+oligoclase+phengite+epidote+quartz+rutile±paragonite±K-feldspar. We calculated their P–T conditions using the amphibole–plagioclase NaSi–CaAl exchange thermometer, and the garnet–amphibole–plagioclase–quartz and the amphibole–plagioclase Si–Al partitioning barometers. The thermobarometric results indicate that this mineral assemblage was formed at high-P amphibolite-facies conditions at 650–700°C and 10–13 kbar. The observed stability of paragonite and phengite reveals fluid-absent conditions or the presence of a fluid phase with reduced H2O activity during the peak of metamorphism. We found no relicts of eclogite-facies mineral assemblage in the garnet amphibolites. This contrasts with the eclogite-facies metamorphism found due south in the Tarf Magneïna unit. This suggests that the northernmost end of the Adrar–Souttouf Metamafic Complex may have been buried to shallower depths than the units further south, probably during the Variscan orogeny. However, precise absolute radiometric dating of the high-P amphibolite-facies metamorphism is required to confirm these findings.

Mineral textural evolution and PT-path of relict eclogite-facies rocks in the Paleoproterozoic Nagssugtoqidian Orogen, South-East Greenland

The Nagssugtoqidian Orogen in South-East Greenland is a deeply eroded, Paleoproterozoic collision orogen. It consists of a variety of Archean and Paleoproterozoic rocks, most notably TTG gneiss, a variety of supracrustal rocks and basic dykes. This study aims at providing new insight into the geodynamic processes and subduction depth of this orogen by investigating the metamorphic evolution of garnet pyroxenite, retrogressed eclogite and amphibolite-facies rocks that are exposed within the Kuummiut Terrane of the Nagssugtoqidian Orogen. The garnet-pyroxenite has a dominant mineral assemblage of garnet, orthopyroxene, clinopyroxene and hornblende, while garnet-amphibolite and garnet-kyanite schist are made up of garnet, hornblende, plagioclase and quartz, and garnet, kyanite, biotite and quartz, respectively. Relicts of, and pseudomorphs after, eclogite-facies mineral assemblages are frequently found within basic metavolcanic rocks and Paleoproterozoic discordant basic dykes. In the retrogressed eclogite, the retrograde mineral reactions ceased prior to completion, resulting in the formation of two domains. A clinopyroxene domain consists of diopside-plagioclase symplectites, which are interpreted to have grown at the expense of omphacite. The symplectites are surrounded and partly replaced by hornblende and plagioclase. Omphacite (XJd 25–42) is preserved in a Na-rich sample, where it occurs in the core of large clinopyroxene and as inclusion in garnet and hornblende. In a garnet domain, garnet is variably replaced by an inner corona of plagioclase and an outer corona of amphibole +/− orthopyroxene and clinopyroxene. The degree of retrogression as well as the type of the retrograde assemblage in both domains appears to be dependent on fluid activity. Large garnet grains preserve Ca-rich cores, interpreted as prograde in origin, while Mg-rich garnet rims formed during eclogite-facies metamorphism and later re-equilibration. Pseudosection modelling combined with conventional geothermobarometry reveals a clockwise PT-evolution, involving eclogite-facies conditions of 17–19kbar and 740–810°C, followed by near-isothermal decompression to medium-pressure granulite-facies conditions (13.8–15.4kbar, 760–880°C) and subsequent decompression with minor cooling to high-pressure amphibolite-facies grades (8.8–10.9kbar, 660–840°C). These data show that rocks of the Kuummiut Terrane were exhumed from 70 to about 30km into the mid- and lower crust. The PT-path implies that exhumation initially was rapid and tectonically-controlled.

Age and P–T conditions of the Gridino‐type eclogite in the Belomorian Province, Russia

ABSTRACTAlthough eclogites in the Belomorian Province have been regarded as Archean in age and among the oldest in the world, there are also multiple studies that have proposed a Paleoproterozoic age. Here, we present new data for the Gridino‐type eclogites, which occur as boudins and metamorphosed dykes within tonalite–trondhjemite–granodiorite gneisses. Zircon from these eclogites has core and rim structures. The cores display high Th/U ratios (0.18–0.45), negative Eu anomalies and strong enrichment in HREE, and have Neoarchean U–Pb ages of c. 2.70 Ga; they are interpreted to be magmatic in origin. Zircon cores have δ18O of 5.64–6.07‰ suggesting the possibility of crystallization from evolved mantle‐derived magmas. In contrast, the rims, which include the eclogite facies minerals omphacite and garnet, are characterized by low Th/U ratios (<0.035) and flat HREE patterns, and yield U–Pb ages of c. 1.90 Ga; they are interpreted to be metamorphic in origin. Zircon rims have elevated δ18O of 6.23–6.80‰, which was acquired during eclogite facies metamorphism. Based on petrography and phase equilibria modelling, we recognize a prograde epidote amphibolite facies mineral assemblage, the peak eclogite facies mineral assemblage and a retrograde high‐P amphibolite facies mineral assemblage. The peak metamorphic conditions of 695–755°C at >18 kbar for the Gridino‐type eclogites suggest an apparent thermal gradient of <39–42°C/kbar for the Lapland–Kola collisional orogeny.

Felsic granulite with layers of eclogite facies rocks in the Bohemian Massif; did they share a common metamorphic history?

High pressure granulite and granulite gneiss from the Rychleby Mountains in the East Sudetes form an approximately 7km long and 0.8km wide body, which is enclosed by amphibolite facies orthogneiss with a steep foliation. Well preserved felsic granulite is located in the central part of the body, where several small bodies of mafic granulite are also present. In comparison to other high pressure granulites in the Bohemian Massif, which show strong mineral and textural re-equilibration under granulite facies conditions, the mafic granulite samples preserve eclogite facies minerals (garnet, omphacite, kyanite, rutile and phengite) and their field and textural relations indicate that both mafic and felsic granulites shared common metamorphic history during prograde eclogite facies and subsequent granulite facies events. Garnet from both granulite varieties shows prograde compositional zoning and contains inclusions of phengite. Yttrium and REEs in garnet show typical bell-shaped distributions with no annular peaks near the grain rims. Investigation of major and trace elements zoning, including REEs distribution in garnet, was combined with thermodynamic modelling to constrain the early eclogite facies metamorphism and to estimate pressure-temperature conditions of the subsequent granulite facies overprint. The first (U)HP metamorphism occurred along a low geothermal gradient in a subduction-related environment from its initial stage at 0.8GPa/460°C and reached pressures up to 2.5GPa at 550°C. The subsequent granulite facies overprint (1.6–1.8GPa/800–880°C) affected the rocks only partially; by replacement of omphacite into diopside+plagioclase symplectite and by compositional modification of garnet rims. The mineral textures and the preservation of the eclogite facies prograde compositional zoning in garnet cores confirm that the granulite facies overprint was either too short or too faint to cause recrystallisation and homogenisation of the eclogite facies mineral assemblage. The results of this study are compared with other granulite massifs in the Moldanubian Zone. In addition, a possible scenario for the Variscan eclogite and subsequent granulite facies metamorphism in the Bohemian Massif is discussed.

The relationship between mantle pH and the deep nitrogen cycle

Nitrogen is distributed throughout all terrestrial geological reservoirs (i.e., the crust, mantle, and core), which are in a constant state of disequilibrium due to metabolic factors at Earth’s surface, chemical weathering, diffusion, and deep N fluxes imposed by plate tectonics. However, the behavior of nitrogen during subduction is the subject of ongoing debate. There is a general consensus that during the crystallization of minerals from melts, monatomic nitrogen behaves like argon (highly incompatible) and ammonium behaves like potassium and rubidium (which are relatively less incompatible). Therefore, the behavior of nitrogen is fundamentally underpinned by its chemical speciation. In aqueous fluids, the controlling factor which determines if nitrogen is molecular (N2) or ammonic (inclusive of both NH4+ and NH30) is oxygen fugacity, whereas pH designates if ammonic nitrogen is NH4+ or NH30. Therefore, to address the speciation of nitrogen at high pressures and temperatures, one must also consider pH at the respective pressure–temperature conditions. To accomplish this goal we have used the Deep Earth Water Model (DEW) to calculate the activities of aqueous nitrogen from 1–5GPa and 600–1000°C in equilibrium with a model eclogite-facies mineral assemblage of jadeite+kyanite+quartz/coesite (metasediment), jadeite+pyrope+talc+quartz/coesite (metamorphosed mafic rocks), and carbonaceous eclogite (metamorphosed mafic rocks+elemental carbon). We then compare these data with previously published data for the speciation of aqueous nitrogen across these respective P-T conditions in equilibrium with a model peridotite mineral assemblage (Mikhail and Sverjensky, 2014). In addition, we have carried out full aqueous speciation and solubility calculations for the more complex fluids in equilibrium with jadeite+pyrope+kyanite+diamond, and for fluids in equilibrium with forsterite+enstatite+pyrope+diamond.Our results show that the pH of the fluid is controlled by mineralogy for a given pressure and temperature, and that pH can vary by several units in the pressure-temperature range of 1–5GPa and 600–1000°C. Our data show that increasing temperature stabilizes molecular nitrogen and increasing pressure stabilizes ammonic nitrogen. Our model also predicts a stark difference for the dominance of ammonic vs. molecular and ammonium vs. ammonia for aqueous nitrogen in equilibrium with eclogite-facies and peridotite mineralogies, and as a function of the total dissolved nitrogen in the aqueous fluid where lower N concentrations favor aqueous ammonic nitrogen stabilization and higher N concentrations favor aqueous N2.Overall, we present thermodynamic evidence for nitrogen to be reconsidered as an extremely dynamic (chameleon) element whose speciation and therefore behavior is determined by a combination of temperature, pressure, oxygen fugacity, chemical activity, and pH. We show that altering the mineralogy in equilibrium with the fluid can lead to a pH shift of up to 4 units at 5GPa and 1000°C. Therefore, we conclude that pH imparts a strong control on nitrogen speciation, and thus N flux, and should be considered a significant factor in high temperature geochemical modeling in the future. Finally, our modelling demonstrates that pH plays an important role in controlling speciation, and thus mass transport, of Eh-pH sensitive elements at temperatures up to at least 1000°C.

First-report on Mesozoic eclogite-facies metamorphism preceding Barrovian overprint from the western Rhodope (Chalkidiki, northern Greece)

The Chalkidiki block in Northern Greece represents the southwesternmost piece of the ultrahigh-pressure Rhodope and has played an important role in the evolution of the North Aegean. The eastern part of the Chalkidiki block is a basement complex (Vertiskos Unit) that is made largely of Palaeozoic granitoids and clastic sediments that metamorphosed during the Mesozoic. This basement is traditionally considered as part of the Rhodopean hanging-wall, an assignment mainly supported by the absence of high-pressure mineral indicators and the presence of a regional medium-pressure/medium-temperature amphibolite-facies Barrovian metamorphic imprint. Toward the west, the basement is juxtaposed with meta-sedimentary (Circum-Rhodope belt) and arc units (Chortiatis Magmatic Suite) that carry evidence of a Mesozoic high-pressure/low-temperature event. In this study, garnet–staurolite-mica schists from the eastern part of the basement were examined by means of micro-textures, mineral chemistry and isochemical phase-diagram sections in the system NCKFMASHMn(Ti) [Na2O–CaO–K2O–FeO–MgO–Al2O3–SiO2–H2O–MnO–(TiO2)]. The schists represent former Mesozoic sedimentary sequences deposited on the Palaeozoic basement. We document the presence of a relict eclogite-facies mineral assemblage (garnet+chloritoid+phengite+rutile) in an amphibolite-facies matrix composed of garnet+staurolite+phengite±kyanite. Model results suggest the existence of a high-pressure/medium-temperature metamorphic event (1.9GPa/520°C) that preceded regional re-equilibration at medium-pressure/medium-temperature conditions (1.2GPa/620°C). Clearly, the eastern part of the Chalkidiki block (basement complex) retains memory of an as yet unidentified Mesozoic eclogitic metamorphic event that was largely erased by the later Barrovian overprint. In light of our findings, the basement complex of the Chalkidiki block shares a common tectono-metamorphic evolution with both the high-pressure units to the west, and the high-grade Rhodopean gneisses further to the northeast. Our results are consequential for the geodynamic reconstruction of the Rhodope since they require participation of the Chalkidiki block to the well-established Mesozoic subduction system.

Constraining cooling histories: rutile and titanite chronology and diffusion modelling in NW Bhutan

AbstractU–Pb analyses of rutile and titanite commonly yield ages that constrain the timing of cooling rather than the timing of their crystallization. Rutile which grew at or close to peak temperature conditions in a mafic granulite, intermediate granulite and mafic amphibolite within juxtaposed litho/tectonostratigraphic units in the Greater Himalayan Sequence (GHS) of NW Bhutan yield LA–MC–ICP–MS U–Pb lower intercept cooling ages of 10.1 ± 0.4, 10.8 ± 0.1 and 10.0 ± 0.3 Ma, respectively. Numerical finite‐difference diffusion models constrained by previously published temperature–time and Pb diffusion data suggest that these ages are best explained by rapid cooling from peak temperature conditions of ∼800 °C at 14 Ma in the granulite‐bearing unit and ∼650 °C at 12 Ma in the amphibolite‐bearing unit. The good fit between the model and analysed ages confirms the relatively high retention of Pb in rutile suggested by the experimental data. Titanite that grew during an exhumation‐related amphibolite facies overprint on an eclogite facies mineral assemblage from the neighbouring Jomolhari Massif yields a U–Pb lower intercept cooling age of 14.6 ± 1.2 Ma. Diffusion modelling suggests that this age is too old to be consistent with the temperature–time paths inferred for the rutile‐bearing samples. Instead, the titanite age suggests cooling from ∼650 °C at an earlier time of 17–15 Ma, implying that the high‐grade rocks in the Jomolhari Massif experienced a different cooling history from the rest of the GHS in NW Bhutan. Together these data show that high‐grade rocks from three apparently different structural levels of the GHS in NW Bhutan experienced rapid cooling at >40 °C Ma−1 at varying times. The highest grade granulite facies rocks were exhumed from deeper structural levels that are not exposed, not preserved, or not yet recognized west of eastern Nepal. A progressive along‐strike change in tectonic regime, metamorphic history and/or exhumation mechanism across the orogen is implied by these thermochronologic data.

High-pressure partial melting and melt loss in felsic granulites in the Kutná Hora complex, Bohemian Massif (Czech Republic)

Felsic granulites from the Kutná Hora complex in the Moldanubian zone of central Europe preserve mineral assemblage that records transition from early eclogite to granulite facies conditions, and exhibits leucocratic banding, which is interpreted as an evidence for melt loss during the decompression path. The granulites are layered and consist of variable proportions of quartz, ternary feldspar, garnet, biotite, kyanite, and rutile. In the mesocratic layers, garnet grains show relatively high Ca contents corresponding to 28–41mol% grossular end member. They have remarkably flat compositional profiles in their cores but their rims exhibit an increase in pyrope and a decrease in grossular and almandine components. In contrast, garnets from the leucocratic layers have relatively low Ca contents (15–26mol% grossular) that further decrease towards the rims. In addition to modeling of pressure–temperature pseudosections, compositions of garnet core composition, garnet rim-ternary feldspar–kyanite–quartz equilibrium, ternary feldspar composition, and the garnet–biotite equilibrium provide five constraints that were used to reconstruct the pressure–temperature path from eclogite through the granulite and amphibolite facies. In both layers, garnet cores grew during omphacite breakdown and phengite dehydration melting at 940°C and 2.6GPa. Subsequent decompression heating to 1020°C and 2.1GPa produced Ca- and Fe-poor garnet rims due to the formation of Ca-bearing ternary feldspar and partial melt. In both the mesocratic and leucocratic layer, the maximum melt productivity was 26 and 18vol.%, respectively, at peak temperature constrained by the maximum whole-rock H2O budget, ~1.05–0.75wt.%, prior to the melting. The preservation of prograde garnet-rich assemblages required nearly complete melt loss (15–25vol.%), interpreted to have occurred at 1000–1020°C and 2.2–2.4GPa by garnet mode isopleths, followed by crystallization of small amounts of residual melt at 760°C and 1.0GPa. Phase formation and melt productivity were independently determined by experiments in the piston-cylinder apparatus at 850–1100°C and 1.7–2.1GPa. Both the thermodynamic calculations and phase equilibrium experiments suggest that the partial melt was produced by the dehydration melting: muscovite+quartz=melt+K-feldspar+kyanite. The presence of partial melt facilitated attainment of mineral equilibria at peak temperature thus eliminating any potential relics of early high-pressure phases such as phengite or omphacite. By contrast, adjacent mafic granulites and eclogites, which apparently share the same metamorphic path but have not undergone partial melting commonly preserve relics or inclusions of eclogite-facies mineral assemblages.

Structure and PT estimates across late-collisional plutons: constraints on the exhumation of western Alpine continental HP units

The ∼30 Ma Biella and Traversella late-collisional intermediate to granitic plutons intruded the innermost part of the Sesia-Lanzo Zone (SLZ) in the western Alps. The SLZ represents an early-Alpine continental high-pressure (HP) metamorphic complex and forms part of the subducted Adria margin along the Periadriatic lineament, the internal boundary of the axial Alpine belt. Intrusions postdate ductile deformation of the country rocks, but predate most of the late-orogenic brittle deformation. These plutons cut across regional ductile foliations that are dominated by eclogite-facies mineral assemblages generated during the Alpine subduction cycle. Structural mapping across the contact aureoles suggests that the late-stage ductile folds coeval with exhumation-related greenschist-facies assemblages are transected by the igneous stocks. Thermobarometry of the igneous and contact metamorphic rocks reveals that both plutons crystallized at a depth between ∼3.5 (shallower part) and ∼7 (deeper part) km at a temperature of ∼700–750°C. Comparative thermobarometry and multi-scale structural analyses across the aureole zones show that shallow crustal decompression-exhumation of the HP SLZ complexes under greenschist-facies conditions predated the late-orogenic intrusions. The pressure and temperature (PT) conditions and ages of the eclogitic metamorphic peak (∼65 Ma) and the Periadriatic intrusives (∼30 Ma) were taken into account to estimate an average pre-intrusive exhumation rate of ∼2 km/million years. The lower post-intrusive exhumation rate of these two plutons (∼0.2 km/million years) with respect to that of the Bergell pluton (∼0.6 km/million years) suggests that, in the internal central Alps, a larger volume of Oligocene intrusive rocks has been eroded than in the internal western Alps, where most of the plutons may still be buried.

Experimental constraints on element mobility from subducted sediments using high-P synthetic fluid/melt inclusions

A series of hydrothermal piston-cylinder experiments have been performed to determine the composition of representative fluids and fluid/melt/rock interaction in subduction zones. Experiments were conducted under H 2O saturated conditions at 2.2 GPa over a temperature range from 600–750 °C. The experiments contained synthetic, trace-element-doped pelitic starting material and fractured quartz chips to trap and preserve synthetic fluid/melt inclusions. Pelite residues from the subsolidus experiments (600–650 °C) consist of an eclogite-facies mineral assemblage including quartz, phengite, epidote, rutile, garnet, amphibole, apatite, and zircon. Coexisting hydrous fluids are expected to be completely buffered for trace elements by this mineral assemblage. At 2.2 GPa the wet solidus for the pelitic starting material is located at approximately 675 °C and hydrous fluid and melt coexist as immiscible phases at least up to 750 °C. Residue phases in the supersolidus experiments (700–750 °C) are garnet, rutile, and zircon, which suggest that HREE and HFSE are largely retained in slab residues during very high degrees of H 2O saturated melting. Laser ablation ICPMS analysis and quantification of trapped fluid inclusions from the experiments indicate that subsolidus hydrous fluids released from subducted sediments have relatively high LILE contents compared to REE and HFSE, but overall are remarkably dilute. Total solute contents are approximately 5 wt.%, of which > 75% is SiO 2 and around 15% is Na 2O + Al 2O 3. The experimental results are used to show that subducting sedimentary rocks do not undergo significant element loss during metamorphic dehydration up to eclogite facies. If these fluids are representative of aqueous fluids released at sub-arc depths then simple slab dehydration models may be unable to account for element transfer from the slab to arc magmas. Instead, element recycling through subduction zones may be a product of complex fluid-melt-rock interaction processes involving multiple slab components.

P–T evolution and reaction textures in retrogressed eclogites from Svetlik, the Moldanubian Zone (Czech Republic)

Summary Lenses and pods of mafic rocks from the Monotonous Unit near Svetlik are characterized by eclogite facies mineral assemblages; however some inclusion patterns (oriented quartz rods in clinopyroxene and cuboids of disordered graphite in garnet) that are usually known from ultra-high pressure rocks were also observed in one sample. Conventional thermobarometry yielded maximum P–T conditions of 2.0–2.5 GPa and 750 � C. Decompression and heating at amphibolite and granulite facies conditions resulted in the formation of at least five distinct types of symplectites. These include symplectitic intergrowth of ilmenite and clinopyroxene after titanite, described here for the first time from the Moldanubian Zone. In addition, symplectites of plagioclase and biotite with accessory amounts of spinel after tabular pseudomorphs (after phengite?) are also reported here. Mass balance relations indicate that symplectites of diopside þ plagioclase after omphacite and plagioclase þ spinel (sapphirine) after kyanite þ garnet, formed by nearly isochemical reactions. All other symplectite-forming reactions were allochemical and were accelerated by the presence of fluid in the primary phases. Preserved zoning pattern in garnet with high compositional gradient in some samples suggests that the rocks were affected briefly by granulite facies overprint.

Franciscan eclogite revisited: Reevaluation of the P–T evolution of tectonic blocks from Tiburon Peninsula, California, U.S.A.

High-grade blocks in the Franciscan complex at Tiburon, California, record relatively low temperature eclogite-facies metamorphism and blueschist-facies overprinting. The eclogite-facies mineral assemblage contains prograde-zoned garnet + omphacite + epidote ± hornblende (katophoritic and barroisitic Ca–Na amphibole) ± glaucophane + phengite (∼3.5 Si p.f.u.) ± paragonite + rutile + quartz. The blueschist-facies mineral assemblage contains chlorite + titanite + glaucophane + epidote ± albite ± phengite (∼3.3 Si p.f.u.). Albite is not stable in the eclogite stage. New calculations based on garnet-omphacite-phengite thermobarometry and THERMOCALC average-P–T calculations yield peak eclogite-facies P–T conditions of P = 2.2–2.5 GPa and T = 550–620 °C; porphyroclastic omphacite with inclusions of garnet and paragonite yields an average-P–T of 1.8 ± 0.2 GPa at 490 ± 70 °C for the pre-peak stage. The inferred counterclockwise hairpin P–T trajectory suggests prograde eclogitization of a relatively “cold” subducting slab, and subsequent exhumation and blueschist-facies recrystallization by a decreasing geotherm. Although an epidote-garnet amphibolitic assemblage is ubiquitous in some blocks, P–T pseudosection analyses imply that the epidote-garnet amphibolitic assemblage is stable during prograde eclogite-facies metamorphism. Available geochronologic data combined with our new insight for the maximum pressure suggest an average exhumation rate of ∼5 km/Ma, as rapid as those of some ultrahigh pressure metamorphic terranes.

High-pressure mafic granulites in the Trans-North China Orogen: Tectonic significance and age

High-pressure mafic granulites (including retrograded eclogites) have been reported from the Trans-North China Orogen, a Paleoproterozoic orogenic belt along which two discrete continental blocks, referred to as the Eastern and Western Blocks, were amalgamated to form the North China Craton. Extensive metamorphic investigations and geochronology carried out over the last few years provide important insights into the age and significance of these high-pressure granulites, which are critical in understanding of the timing and tectonic processes involved in the assembly of the North China Craton. Most high-pressure mafic granulites in the Trans-North China Orogen preserve the high-pressure granulite facies assemblage garnet + plagioclase + clinopyroxene + quartz, the medium-pressure granulite facies assemblage garnet + plagioclase + clinopyroxene + orthopyroxene ± quartz, the low-pressure granulite facies assemblage orthopyroxene + clinopyroxene + plagioclase ± quartz, and the amphibolite facies assemblage hornblende + plagioclase. Minor high-pressure granulites preserve the early eclogite facies mineral assemblage of garnet + quartz + omphacite pseudomorph (clinopyroxene + Na-rich plagioclase), indicating that they are retrograded eclogites. These mineral assemblages and their P–T estimates define a clockwise P–T path involving near-isothermal decompression and cooling following the peak high-pressure metamorphism, which suggests that they formed during continent–continent collision. Field mapping and geochronology indicate that the precursors of these high-pressure granulites were mafic dykes which were emplaced at ∼1915 Ma and underwent high-pressure granulite facies metamorphism at ∼1.85 Ga. Taken together, the high-pressure granulites in the Trans-North China are considered to have resulted from final collision between the Eastern and Western Blocks to form the North China Craton at ∼1.85 Ga, not at ∼2.5 Ga as recently proposed by some authors.

Prograde and Retrograde P-T Paths of the Late Paleozoic Glaucophane Eclogite from the Renge Metamorphic Belt, Hida Mountains, Southwestern Japan

Late Paleozoic glaucophane eclogite and garnet glaucophane schist are intercalated with pelitic schist from the Omi eclogitic unit in the Renge metamorphic belt, Hida Mountains, southwestern Japan. Eclogite and garnet glaucophane schist have MORB-like bulk compositions (major and trace), but garnet glaucophane schist is free from omphacite, reflecting a higher Mg/(Mg+Fe) ratio bulk-rock composition. In the eclogite, three different metamorphic stages (stages I to III) are defined on the basis of microstructures and mineral zoning. In particular, prograde-zoned porphyroblastic garnet preserves the transition from blueschist to eclogite facies. The inclusion trails in the rims of garnet are parallel to a penetrative foliation S1 in the matrix, and consist of eclogite-facies minerals (omphacite, glaucophane, epidote, rutile, and quartz). Its core contains the preceding epidote blueschist-facies minerals (glaucophane, epidote, titanite, albite, and quartz) instead of eclogite-facies minerals, and has an internal fabric S0 at a high angle to the surrounding S1 foliation. In the foliated matrix, the eclogite-facies mineral assemblage garnet + omphacite + glaucophane + epidote + rutile + quartz + phengite is partly replaced by secondary minerals such as chlorite, titanite, albite, and calcite, which coexist with recrystallized glaucophane. These petrographic features show a "hair-pin"-like P-T path that passes from the epidote blueschist facies (stage I) through the eclogite facies (stage II), and then is retraced on a nearly coincident path to epidote blueschist facies (stage III). The systematic decrease from core to rim in K D value between garnet and omphacite, and a significant increase in jadeite component of omphacite suggest a rise in both temperature and pressure during prograde eclogitization. The host pelitic schist contains the primary mineral assemblage of quartz + paragonite + phengite + garnet + ferroglaucophane + clinozoisite + rutile, and is strongly replaced by secondary albite, chlorite, and titanite. Pseudomorphs after omphacite and possible kyanite are also found in host pelitic schist. Using geothermobarometry for eclogite and a petrogenetic grid for the host pelitic schist, conditions of peak eclogite-facies metamorphism are estimated to be around 550-600°C and at least 1.8 GPa, indicating an apparent paleo-geothermal gradient of ~10°C/km. The eclogite-bearing Renge metamorphic belt in southwestern Japan may be a new candidate for the eastern extension of a suture zone in east-central China. Late Paleozoic blueschist and eclogite metamorphism may be related to subduction of oceanic crust between the Sino-Korean and Yangtze blocks, prior to their collision.