Rutile geochemistry and thermometry of eclogites and associated garnet-mica schists in the Biga Peninsula,NW Turkey

In northwest Turkey, high-pressure metamorphic rocks occur as exotic blocks within the Çetmi mélange located on the south of the Biga Peninsula. Rutile chemistry and rutile thermometry obtained from the eclogite and associated garnet-mica schist in the Çetmi mélange indicate significant trace element behaviour of subducted oceanic crust and source-rock lithology of detrital rutiles. Cr and Nb contents in detrital rutile from garnet-mica schist vary from 355 to 1026 μg/g and 323 and 3319 μg/g, respectively. According to the Cr-Nb discrimination diagram, the results show that 85% of the detrital rutiles derived from metapelitic and 15% from metamafic rocks. Temperatures calculated for detrital rutiles and rutiles in eclogite range from 540 °C to 624 °C with an average of 586 °C and 611 °C to 659 °C with an average of 630 °C at P = 2.3 GPa, respectively. The calculated formation temperatures suggest that detrital rutiles are derived from amphibolite- and eclogite-facies metamorphic rocks. Amphibolite-facies rocks of the Kazdağ Massif could be the primary source rocks for the rutiles in the garnet-mica schist from the Çetmi mélange. Nb/Ta ratios of metapelitic and metamafic rutiles fall between 7–24 and 11–25, respectively. Nb/Ta characteristics in detrital rutiles may reflect a change in source-rock lithology. However, Nb/Ta ratios of rutiles in eclogite vary from 9 to 22. The rutile grains from eclogites are dominated by subchondritic Nb/Ta ratios. It can be noted that subchondritic Nb/Ta may record rutile growth from local sinks of aqueous fluids from metamorphic dehydration.     

超高压榴辉岩金红石中高场强元素变化的控制因素及其地球动力学意义

利用LA-ICP-MS对CCSD-MH超高压榴辉岩中金红石进行了详细的原位微区微量元素组成分析.金红石中高场强元素Nb和Ta含量主要受全岩Nb、Ta和TiO₂含量控制, Zr、Hf含量比较稳定基本不受全岩含量影响.粒间金红石中, 同一颗粒金红石核部Zr含量系统高于边部, 而边部则出现了明显的Pb和Sr富集特征.CCSD-MH榴辉岩中金红石与全岩的Nb/Ta比值呈现明显的不一致性.全岩Nb/Ta比值明显低于金红石且与全岩TiO₂含量负相关, 而金红石的Nb/Ta比值与全岩Nb、Ta含量和Nb/Ta比值没有明显的相关关系.金红石和全岩之间非完全耦合的Nb/Ta组成表明, 金红石并非形成于原岩的结晶过程中而是在超高压变质作用过程中形成, 尽管金红石是榴辉岩中Nb、Ta含量的主要载体矿物, 但金红石的Nb/Ta比值并不一定能完全代表全岩的特征, 而与全岩Nb、Ta和TiO₂的含量有关.粒间金红石核部Zr含量所记录的温度与粒径之间具有明显的正相关性, 反映金红石中的Zr在其形成后没有封闭.粒间金红石所表现出的明显的边部富集Pb和Sr的特征, 反映了后期流体活动对金红石组成的影响.这些研究结果为金红石中Zr在高温下的扩散作用和后期流体活动的影响提供了重要证据, 这可能是利用金红石Zr含量地质温度计计算的苏鲁-大别榴辉岩变质温度(598~827℃) 偏低的主要原因.      

Constraints from eclogite and MARID xenoliths on origins of mantle Zr/Hf–Nb/Ta variability

New trace-element data of rutile in kimberlite-borne ~1.85 Ga eclogite and pyroxenite xenoliths from the central Slave craton, as well as ~110 Ma MARID xenoliths from the Kaapvaal craton, provide constraints on the origins of lithospheric and sublithospheric mantle variability in high field strength element ratios. Rutiles in eclogites and pyroxenites have Zr/Hf ranging from 20 to 62 and Nb/Ta ranging from 10 to 40. Rutiles in MARID xenoliths have Zr/Hf from 24 to 33 and Nb/Ta from 10 to 41. Calculated whole-rock Zr/Hf is suprachondritic for eclogites with suggested gabbroic protoliths and subchondritic for boninite-like eclogites; the latter is consistent with cpx-controlled depletion in the protolith source. Within each eclogite type, positive correlations of Zr/Hf with La/Lu and negative correlations with Lu/Hf likely reflect fractionation of cpx and/or plagioclase during crystallisation of the protoliths. Zr/Hf–Nb/Ta relationships of some MARID-type rocks, which are products of lithospheric mantle metasomatism, and eclogite xenoliths plot on a silicate differentiation trend, whereas other samples have higher Nb/Ta at a given Zr/Hf. Fractionation of a few percent rutile from an HFSE-rich mafic melt can generate a trend towards strongly increased Nb/Ta at minimally changed Zr/Hf in the residual melt. Superposition of rutile fractionation on the effects of silicate differentiation, which fractionates Zr/Hf more strongly than Nb/Ta, can explain the Zr/Hf–Nb/Ta relationships of most eclogites from the central Slave craton as well as those of MARID rocks, metasomatised peridotites and group II kimberlites. By contrast, Zr/Hf–Nb/Ta relationships suggest that Group I kimberlites are mixtures between depleted peridotite and carbonatite. Thus, high Nb/Ta is a signature of lithospheric processes and may not be important in deeply subducted eclogites that bypass extended residence in the lithosphere. Conversely, considerable primary Zr/Hf variability was inherited by the eclogites, which is indicative of the compositional diversity of ancient subducted oceanic crust, which is expected to have generated substantial heterogeneity in sublithospheric basalt sources.     

CCSD主孔榴辉岩中金红石微量元素特征：LA-ICPMS分析及其意义

对中国大陆科学钻探（CCSD）主孔200~1005m范围内8件榴辉岩样品的金红石进行了LA-ICPMS原位微区微量元素分析,结合前人已发表的全岩和金红石分析数据,研究结果发现：在不同类型榴辉岩中,金红石的微量元素与其全岩成分具有不同的相关关系。金红石中的Nb和Ta元素含量不同程度地受控于全岩Nb和Ta含量。在高钛和低镁钛榴辉岩中,金红石的Cr与全岩Cr/TiO₂正相关;在富镁榴辉岩中,金红石的Cr含量受全岩MgO含量的控制;在高钛和富镁榴辉岩中,全岩成分明显影响着金红石的Zr含量,金红石Zr温度计可能不适用。低镁钛榴辉岩的金红石的平衡温度普遍低于榴辉岩峰期变质温度,可能是变质流体参与下的扩散作用和退变质作用所致;多数情况下,单个样品中大部分金红石颗粒的Zr含量是均匀的,金红石Zr温度计所给出的温度可能代表着退变质再平衡的温度;CCSD榴辉岩的全岩Nb/Ta比值普遍低于其中金红石的Nb/Ta比值,不支持金红石榴辉岩可能是地球上超球粒陨石Nb/Ta比值储库的观点。     

HFSE systematics of rutile-bearing eclogites: New insights into subduction zone processes and implications for the earth’s HFSE budget

The depleted mantle and the continental crust are generally thought to balance the budget of refractory and lithophile elements of the Bulk Silicate Earth (BSE), resulting in complementary trace element patterns. However, the two high field strength elements (HFSE) niobium and tantalum appear to contradict this mass balance. All reservoirs of the silicate Earth exhibit subchondritic Nb/Ta ratios, possibly as a result of Nb depletion.In this study a series of nineteen orogenic MORB-type eclogites from different localities was analyzed to determine their HFSE concentrations and to contribute to the question of whether subducted oceanic crust could form a hidden reservoir to account for the mass imbalance of Nb/Ta between BSE and the chondritic reservoir. Concentrations of HFSE were analyzed with isotope dilution (ID) techniques. Additionally, LA-ICPMS analyses of clinopyroxene, garnet and rutile have been performed. Rutile is by far the major host for Nb and Ta in all analyzed eclogites. However, many rutiles revealed zoning in Nb/Ta ratios, with cores being higher than rims. Accordingly, in situ analyses of rutiles have to be evaluated carefully and rutile cores do not necessarily reflect a bulk rock Nb and Ta composition, although over 90% of these elements reside in rutile.The HFSE concentration data in bulk rocks show that the orogenic eclogites have subchondritic Nb/Ta ratios and near chondritic Zr/Hf ratios. The investigated eclogites show neither enrichment of Nb compared to similarly incompatible elements (e.g. La), nor fractionation of Nb/Ta ratios relative to MOR-basalts, the likely precursor of these rocks. This indicates that during the conversion of the oceanic crust to eclogites in most cases, (1) HFSE and REE have similar mobility on average, possibly because both element groups remain in the down going slab, and (2) no significant fractionation of Nb/Ta occurs in subducted oceanic crust. With an average Nb/Ta ratio of 14.2 ± 1.4 (2s.e.), the investigated eclogites cannot balance the differences between BSE and chondrite. Additionally, as their average Nb/Ta is indistinguishable from the Nb/Ta of MORB, they are also an unlikely candidate to balance the potentially small differences in Nb/Ta between the continental crust and the mantle.     

Geochemistry and magmatic history of eclogites and ultramafic rocks from the Chinese continental scientific drill hole: Subduction and ultrahigh-pressure metamorphism of lower crustal cumulates

Three distinct groups of eclogites (low-Mg–Ti eclogites, high-Ti eclogites and Mg-rich eclogites) and ultramafic rocks from the depth interval of 100–680 m of the Chinese Continental Scientific Drill Hole were studied. The low Mg#s (= 100^?molar Mg/(Mg + Fe)) (81–84%) and low Ni (1150–1220 ppm) and high Fe₂O₃^total (13–15 wt.%) contents of ultramafic rocks suggest a cumulate origin. Mg-rich eclogites show middle and heavy REE enrichments, which could not be produced by metamorphic growth of garnet. Instead, if the rocks formed from a light REE enriched magma, there may be an igneous precursor for some garnets in their protolith. Alternatively, perhaps they formed from a light REE depleted magma without garnet. The high-Ti eclogites are characterized by unusually high Fe₂O₃^total contents (up to 24.5 wt.%) and decoupling of high TiO₂ from low Nb and Ta contents. These features cannot be produced by concentration of rutile during UHP metamorphism (even for samples with TiO₂ > 4 wt.%) of high-Ti basalts, but could be attributed to crystal fractionation of titanomagnetite (for those with TiO₂ < ～ 4 wt.%) or titanomagnetite + ilmenite (for those with TiO₂ > ～ 4 wt.%). Thus, we suggest that protoliths of the high-Ti eclogites were titanomagnetite/ilmenite-rich gabbroic cumulates. As a whole, the low-Mg–Ti eclogites are geochemically complementary to the high-Ti eclogites, Mg-rich eclogites and ultramafic rocks, and could be metamorphic products of gabbroic/dioritic cumulates formed by high degree crystal fractionation. All these observations suggest that parental materials of the ultramafic rock-eclogite assemblage could represent a complete sequence of fractional crystallization of tholeiitic or picritic magmas at intermediate to high pressure, which were later carried to ultrahigh-pressure conditions during a continental collision event.     

Nb/Ta fractionation observed in eclogites from the Chinese Continental Scientific Drilling Project

This paper reports detailed analyses of Nb and Ta concentrations of 19 eclogite samples and their principal mineral constituents from the main drill hole of the Chinese Continental Scientific Drilling Project (CCSD) and nearby outcrops. We observe highly fractionated and overall suprachondritic Nb/Ta values in minerals, e.g., rutile (4.8–87), titanite (12–62) and amphibole (2.0–67). Amphiboles in amphibolites (retrograded from eclogite) can be classified into two groups: a low Nb/Ta group that bears higher Al contents and is thus of higher pressure origin, and a high Nb/Ta, lower pressure group. The former group was likely formed during subduction; the latter may have formed during exhumation in the presence of rutile and titanite. The significant Nb/Ta fractionation in rutile and other minerals may reflect early dehydration of the subducted slab at shallow depths before the formation of rutile, which occurs at depths ≥50 km. The dehydration, with amphiboles existing as the main Nb–Ta-bearing phase, would lead to Nb/Ta fractionation, i.e., forming subchondritic Nb/Ta ratios in the released fluids and, complementarily, suprachondritic Nb/Ta ratios in the residual phases. While a large proportion of the fluids may escape from the slab to the mantle wedge, considerable amounts of the fluids can be retained in hydrous minerals within the descending slab, thus forming hydrated cold eclogites with subchondritic Nb/Ta characteristics. As subduction continues to depths over 50 km, rutile appears and consequently controls the Nb–Ta budget. In the presence of rutile, melting of the hydrated cold eclogites with very low Nb/Ta ratios would form magmas with negative Nb, Ta anomalies and subchondritic Nb/Ta. Further dehydration of the continuously descending slab results in even more fractionated Nb/Ta ratios in subsequently released fluids and residues, providing a feasible explanation for the large Nb/Ta variation observed in the modern arc magmas and residual eclogites.     

Natural and experimental constraints on formation of the continental crust based on niobium–tantalum fractionation

Fractionation between Nb and Ta, elements generally regarded as geochemical ‘identical twins’, is a key to deciphering the formation of the continental crust (CC). Here we show that Nb/Ta of rutile grains in eclogitic rocks from the Chinese Continental Scientific Drilling (CCSD) project are remarkably heterogeneous but overall subchondritic at core depths of 100–700 m, and are less variable and mainly suprachondritic at core depths of 700–3025 m, indicating clear Nb/Ta fractionation across a subducted slab. To understand the potential mechanism of Nb/Ta fractionation within the subducted plate, we analysed by laser ablation ICPMS a thermal migration experiment in which a wet andesite was placed in a large thermal gradient (300°C/cm with ends ranging from 950–350°C) at 0.5Gpa. Results show that Nb, Ta and Ti, driven by the thermal gradient, preferentially migrate by diffusion through supercritical fluids into the cooler end of the experiment (at 650–350°C). Due to contrasting Nb and Ta thermal migration patterns, dramatic fractionation between Nb, Ta, and Ti took place in the cooler end. Experimental results are consistent with the measured Nb, Ta in rutile from CCSD drillhole samples. We consider that major fractionation between Nb, Ta must occur before rutile appears, most likely during the prograde blueschist to amphibole–eclogite transformation, when Ti is also mobile. Before rutile appears, partitioning between Ti‐rich dominant minerals such as amphiboles and fluids in the hotter region where dehydration preferentially occurs, produces Nb–Ta–Ti‐rich fluids with subchondritic Nb/Ta, and dehydration residues with suprachondritic Nb/Ta. Meanwhile, owing to evolution of the thermal gradient within the subducting slab, thermal migration of Nb, Ta, and Ti in aqueous fluids result in Nb, Ta, and Ti enrichment in the cooler region and depletion in the hotter region. As a result of high‐pressure metamorphism, hydrous rutile‐rich eclogites with overall subchondritic Nb/Ta form in the cooler region, whereas relatively anhydrous rutile‐poor eclogites with suprachondritic Nb/Ta form in the hotter region. Subsequently, partial melting of hydrous rutile‐rich eclogites with initial subchondritic Nb/Ta at deeper levels transfers overall subchondritic Nb/Ta coupled with Nb, Ta, and Ti depletion characteristics to the CC, leaving dry rutile‐poor eclogites with suprachondritic Nb/Ta and rutile‐rich residual eclogites with overall, heterogeneous subchondritic Nb/Ta as a complementary reservoir to the CC.     

Zircon geochemistry of two contrasting types of eclogite: Implications for the tectonic evolution of the North Qaidam UHPM belt,northern Tibet

Compared to the extensively documented ultrahigh-pressure metamorphism at North Qaidam, the pre-metamorphic history for both continental crust and oceanic crust is poorly constrained. Trace element compositions, U–Pb ages, O and Lu–Hf isotopes obtained for distinct zircon domains from eclogites metamorphosed from both continental and oceanic mafic rocks are linked to unravel the origin and multi-stage magmatic/metamorphic evolution of eclogites from the North Qaidam ultrahigh-pressure metamorphic (UHPM) belt, northern Tibet.For continental crust-derived eclogite, magmatic zircon cores from two samples with U–Pb ages of 875–856 Ma have both very high δ¹⁸O (10.6 ± 0.5‰) and mantle-like δ¹⁸O (averaging at 5.2 ± 0.7‰), high Th/U and ¹⁷⁶Lu/¹⁷⁷Hf ratios, and steep MREE-HREE distribution patterns (chondrite-normalized) with negative Eu anomalies. Combined with positive ε_Hf (t) of 3.9–14.3 and T_DM (1.2–0.8 Ga and 1.3–1.0 Ga, respectively), they are interpreted as being crystallized from either subduction-related mantle wedge or recycled material in the mantle. While the metamorphic rims from the eclogites have U–Pb ages of 436–431 Ma, varying (inherited, lower, and elevated) oxygen isotopes compared with cores, low Th/U and ¹⁷⁶Lu/¹⁷⁷Hf ratios, and flat HREE distribution patterns with no Eu anomalies. These reflect both solid-state recrystallization from the inherited zircon and precipitation from external fluids at metamorphic temperatures of 595–622 °C (T_Ti-in-zircon).For oceanic crust-derived eclogite, the magmatic cores (510 ± 19 Ma) and metamorphic rims (442.0 ± 3.7 Ma) also show distinction for Th/U and ¹⁷⁶Lu/¹⁷⁷Hf ratios, and the REE patterns and Eu anomalies. Combined with the mantle-like δ¹⁸O signature of 5.1 ± 0.3 ‰ and two groups of model age (younger T_DM close to the apparent ages and older > 700 Ma), two possible pools, juvenile and inherited, were involved in mixing of mantle-derived magma with crustal components. The relatively high δ¹⁸O of 6.6 ± 0.3‰ for metamorphic zircon rims suggests either the protolith underwent hydrothermal alteration prior to the ~ 440 Ma oceanic crust subduction, or external higher δ¹⁸O fluid activities during UHP metamorphism at ~ 440 Ma.Therefore, the North Qaidam UHPM belt witnesses multiple tectonic evolution from Late Mesoproterozoic–Neoproterozoic assembly/breakup of the Rodinia supercontinent with related magmatic emplacement, then Paleozoic oceanic subduction, and finally transition of continental subduction/collision related to UHP metamorphism.     

Metamorphic growth and recrystallization of zircon: Distinction by simultaneous in-situ analyses of trace elements,U–Th–Pb and Lu–Hf isotopes in zircons from eclogite-facies rocks in the Sulu orogen

Simultaneous in-situ analyses of trace elements, U–Th–Pb and Lu–Hf isotopes were carried out on distinct domains of zircons in ultrahigh-pressure (UHP) eclogite-facies metamorphic rocks from the main hole of the Chinese Continental Scientific Drilling (CCSD) in the Sulu orogen. For the first time, trace elements are directly linked to Lu–Hf isotopes in metamorphic zircons with reference to their U–Pb dates. This enables methodological integration to distinguish four types of metamorphic zircon: solid-state, replacement and dissolution recrystallizations of protolith zircons, and new growth from the aqueous fluid. Metamorphically grown zircons are characterized by concordant U–Pb ages for the metamorphism, flat HREE patterns typical of the garnet effect, low contents of REE (especially HREE), Y, Nb + Ta and Th + U, high contents of Hf, low (Lu/Gd)_N, Lu/Hf and Th/U (< 0.1) ratios, and elevated ¹⁷⁶Hf/¹⁷⁷Hf ratios relative to solid-state recrystallized zircons. This suggests the effects of both garnet and fluid on the growth of metamorphic zircons. In contrast, metamorphic recrystallization has reset the U–Th–Pb isotope system of protolith zircons to different extents, depending on the extents of fluid action during metamorphism. Solid-state recrystallized zircons exhibit the lowest degrees of resetting and thus almost inherit all geochemical features from the protolith zircons, which are characterized by discordant U–Pb ages close to or below the protolith age, steep MREE–HREE patterns typical of magmatic origin, high contents of trace elements and their ratios, and low ¹⁷⁶Hf/¹⁷⁷Hf ratios. On the other hand, dissolution recrystallized zircons show the highest degrees of reworking and thus have concordant or nearly concordant U–Pb ages for the metamorphism, steep MREE–HREE patterns, lowered contents of trace elements such as REE, Th, U, Y, Nb, Ta and Ti relative to the protolith zircons, and almost unchanged Hf isotope ratios. Replacement recrystallized zircons display intermediate degrees of reworking and thus have their many features of elements and isotopes in between. While the metamorphic growth in the presence of both garnet and fluid is characterized by both depletion of HREE with flat pattern and the low contents of trace elements, the metamorphic recrystallization in the presence of aqueous fluid is indicated by gradual decreases of MREE to HREE without the flat HREE pattern. Therefore, the simultaneous in-situ analyses of metamorphic zircons have the advantage over single-term analyses in making distinction between the new growth and the different types of recrystallization.     

Microstructure,composition and P–T conditions of rutile from diamondiferous gneiss of the Saxonian Erzgebirge,Germany

The chemical composition and microstructure of rutile grains in a ultra-high pressure metamorphic gneiss of the Saxonian Erzgebirge, Germany have been studied by Raman spectroscopy, SEM, EMPA and TEM. Rutile inclusions in garnet contain free dislocations, iron-enriched dislocations and exsolved ilmenite lamellae, while subgrain boundaries are observed in rutile grains of the rock matrix. The previously reported α-PbO₂ type TiO₂ phase could not be confirmed by our TEM observations. On the basis of Zr solubility in the rutile and the presence of microdiamonds, minimum metamorphic peak conditions of 3.95 GPa and 915 °C are estimated.     

Making continental crust through slab melting: Constraints from niobium-tantalum fractionation in UHP metamorphic rutile

The formation of the continental crust (CC) is one of the most important processes in the evolution of the silicate Earth. Exactly how the CC formed is the subject of ongoing debate that focuses on its subchondritic Nb/Ta ratio. Nb and Ta are “geochemical identical twins,” so they usually do not fractionate from each other. Here, we show that rutile grains from hydrous rutile-bearing eclogitic layers recovered from drillcores in the Dabie-Sulu ultrahigh pressure terrain have highly variable Nb/Ta values (ranging from 5.4 to 29.1, with an average of 9.8 ± 0.6), indicating major fractionation of Nb and Ta most likely occurred during blueschist to amphibole-eclogite transformation in the absence of rutile. It is suggested that the released fluids with subchondritic Nb/Ta were transported to, and retained by, hydrous rutile-bearing eclogite in colder regions, resulting in suprachondritic Nb/Ta ratios for drier eclogite in hotter regions. Further dehydration of hydrous rutile-bearing eclogites cannot transfer the fractionated Nb/Ta values to the CC due to the low solubility of Nb and Ta in fluids in the presence of rutile, while dehydration-melting results in a major component of the CC, the tonalite-trondhjemite-granodiorite (TTG) component, which is responsible for the low Nb/Ta of the CC. Consequently, residual eclogites have variable but overall suprachondritic Nb/Ta.     

Origin of the Alxa Block,western China: New evidence from zircon U–Pb geochronology and Hf isotopes of the Longshoushan Complex

The NW–SE trending Longshoushan is in the southwestern margin of the Alxa Block, which was traditionally considered the westernmost part of the North China Craton (NCC). Precambrian crystalline basement exposed in the Longshoushan area was termed the “Longshoushan Complex”. This complex's formation and metamorphism are significant to understand the geotectonics and early Precambrian crustal evolution of the western NCC. In this study, field geology, petrology, and zircon U–Pb and Lu–Hf isotopes of representative orthogneisses and paragneisses in the Longshoushan Complex were investigated. U–Pb datings reveal three Paleoproterozoic magmatic episodes (ca. 2.33, ca. 2.17 and ca. 2.04 Ga) and two subsequent regional metamorphic events (ca. 1.95–1.90 Ga and ca. 1.85 Ga) for metamorphic granitic rocks in the Longshoushan Complex. U–Pb dating of the detrital magmatic zircons from two paragneisses yields concordant ²⁰⁷Pb/²⁰⁶Pb ages between 2.2 Ga and 2.0 Ga, and a small number of metamorphic zircon rims provide a ca. 1.95 Ga metamorphic age, suggesting that the depositional time of the protolith was between 2.0 and 1.95 Ga and that the sedimentary detritus was most likely derived from the granitic rocks in the Longshoushan Complex itself. Zircon Lu–Hf isotopic analyses indicate that nearly all magmatic zircons from ca. 2.0 Ga to ca. 2.17 Ga orthogneisses have positive εHf(t) values with two-stage Hf model ages (T_DMC) ranging from 2.45 to 2.65 Ga (peak at ca. 2.5 Ga), indicating that these Paleoproterozoic granitic rocks were derived from the reworking of the latest Neoarchean–early Paleoproterozoic juvenile crust. Detrital magmatic zircons from two paragneisses yield scattered ¹⁷⁶Hf/¹⁷⁷Hf ratios, εHf(t) and T_DMC values, further indicating that the sedimentary detritus was not only derived from these plutonic rocks but also from other unreported or denuded Paleoproterozoic igneous rocks. The ca. 2.15 Ga detrital magmatic zircons from one paragneiss have negative εHf(t) values with T_DMC ranging from 2.76 to 3.04 Ga, indicating another important crustal growth period in the Longshoushan region. These data indicate that the Longshoushan Complex experienced Neoarchean–Early Paleoproterozoic crustal growth, approximately ca. 2.3–2.0 Ga experienced multiphase magmatic events, and approximately ca. 1.95–1.90 Ga and ca. 1.85 Ga experienced high-grade metamorphic events. The sequence of tectonothermal events is notably similar to that of the main NCC. Together with the datasets from an adjacent area, we suggest that the western Alxa Block was most likely an integrated component of the NCC from the Neoarchean to the Paleoproterozoic.     

Experimental constraints on major and trace element partitioning during partial melting of eclogite

Isobaric partial melting experiments were performed on an Fe-free synthetic composition to simulate partial melting of subducted oceanic crust. Nominally anhydrous experiments at 3.0 GPa yielded melts in equilibrium with garnet (13 to 16 mol.% grossular) and aluminous clinopyroxene (14 to 16 wt.% Al₂O₃). Melt compositions show decreasing Si and alkalis and increasing Ca, Mg, and Ti contents with increasing temperatures. Experiments at 1200 and 1300°C were rutile saturated, whereas experiments at 1400°C contained no residual rutile. We argue that during the initial stages of subduction, accessory rutile is likely to be stable in subsolidus eclogites of average midocean ridge basalt composition and that only large degrees of partial melting will eradicate rutile from an eclogitic source. At 3 GPa, any eclogites with a bulk TiO₂ content of ≥1.5 wt.% rutile will produce rutile-saturated partial melts, except at very high degrees of melting. At higher pressures, all bulk Ti may dissolve in clinopyroxene and garnet, leaving no accessory rutile.Trace element partition coefficients for 24 trace elements between clinopyroxene, garnet, and melt were determined by secondary-ion mass spectrometry analysis of experimental run products at 1400°C and 3 GPa. Partition coefficients for the rare earth elements agree well with previous studies and have been evaluated using the lattice strain model. Partitioning data for high-field strength elements indicate complementary D_Zr/D_Hf for clinopyroxene and garnet. Partial melting of an eclogitic component of different modal compositions may therefore explain both subchondritic and superchondritic Zr/Hf ratios. Superchondritic Zr/Hf has recently been observed in some ocean island basalts (OIB), and this may be taken as further evidence for components of recycled oceanic crust in OIB. The data also indicate slight Nb/Ta fractionation during partial melting of bimineralic eclogite, which is not, however, sufficient to explain some recently observed Nb/Ta fractionation in island arc rocks. Accessory rutile, however, can explain such fractionation.     

Melting-induced fluid flow during exhumation of gneisses of the Sulu ultrahigh-pressure terrane

Hydrothermally altered rocks are products of fluid–rock interactions, and typically preserve numerous quartz veins that formed as chemical precipitates from fluids that fill up cracks. Thus, quartz veins are the record of the fluid system that involved fracture flow in the direction of changing temperature or pressure. In order to decipher the fluid activity in the Sulu ultrahigh-pressure (UHP) terrane in eastern China, quartz veins together with an adjacent eclogite lens and the host gneiss were studied. In one location a deformed quartz vein is located at the boundary between the host gneiss and the eclogite lens. The amphibolite-facies overprinting of the eclogite lens decreases from the rim to the core of the lens, with fresh eclogite preserved in the core. The foliated biotite gneiss contains felsic veins and residual phengites. Zircon rims from the gneiss are characterized by melt-related signatures with steep HREE patterns, high Hf contents and negative Eu anomalies, and a pool of weighted average ²⁰⁶Pb/²³⁸U analyses reveal an age of 219 ± 3 Ma (2σ), which is younger than the UHP metamorphic age (236 ± 2 Ma, 2σ) recorded by zircons from the eclogite lens. This suggests that the gneiss in the Sulu UHP terrane could have suffered from partial melting due to phengite dehydration during the “hot” exhumation stage.The formation age of the quartz vein (219 ± 2 Ma, 2σ) defined by zircon rims agrees well with the partial melting time (219 ± 3 Ma, 2σ) of the host gneiss. The initial ¹⁷⁶Hf/¹⁷⁷Hf ratios of zircon rims from the quartz vein are obviously lower than zircons from the eclogite lens, but overlap with the coeval zircon domains from the nearby granite dikes produced by partial melting of orthogneiss. These observations suggest that the quartz vein and corresponding fluid flow could be associated with partial melting of the host gneiss. On the other hand, amphibole-bearing and HREE-rich zircon rims from the amphibolite pool an amphibolite-facies metamorphic age of 217 ± 5 Ma (2σ), overlap with the formation age of the quartz vein. This implies that retrogression of the eclogite lens could have been caused by melting-induced fluid flow. Based on the above observations, we speculate that partial melting of the gneiss in the continental subduction-related UHP belt could have induced a significant fluid flow during the exhumation stage, and thus contributed significantly to the extensive retrogression of eclogites in the Sulu UHP terrane.     

Mobility of elements in a continental subduction zone: evidence from the UHP metamorphic complex of the Kokchetav massif

We studied clastics of high-alumina garnet-kyanite-mica schists and garnet-kyanite-quartz granofelses, including diamond-bearing ones, found in the eluvial sediments near Lake Barchi. In contents of major elements the studied rocks correspond to argillaceous shales. The garnet-kyanite-quartz granofelses are poorer in K (0.49-1.35 wt.% K₂O) than the garnet-kyanite-mica schists (4.9-2.2 wt.% K₂O) but have the same contents of other major components. The REE patterns of most of the garnet-kyanite-phengite schists are similar to those of the Post-Archean Australian Shale (PAAS) (xLa/Yb = 13). All garnet-kyanite-quartz rocks are much stronger depleted in LREE (x_La/Yb = 1.4) and other incompatible elements. Our studies show that allanite and monazite are the main concentrators of LREE and Th in the garnet-kyanite-phengite rocks of the Barchi site. Monazite, occurring as inclusions in garnet, contains not only LREE but also Th, U, and Pb. Rutile of the nondepleted rocks is enriched in Fe and Nb impurities only. The garnet-kyanite-quartz granofelses bear rutile, apatite, and xenotime as accessory phases. Rutile of the depleted rocks shows wide variations in contents of Nb, Ta, and V impurities. In places, the contents of Nb and Ta reach 10.5 and 2.3 wt.%, respectively. The rutile decomposes into rutile with Nb (1.4 wt.%) and Fe (0.87 wt.%) impurities and titanium oxide rich in Fe (6.61 wt.%), Nb (up to 20.8 wt.%), and Ta (up to 2.81%) impurities. Based on the measured contents of incompatible elements in differently depleted high-alumina rocks, the following series of element mobility during UHP metamorphism has been established: Th > Ce > La > Pr > Nd > K > Ba > Rb > Cs > Sm > Eu. The contents of U, P, and Zr in the depleted rocks are similar to those in the nondepleted rocks. The studies have shown that metapelites subducted to the depths with diamond stability conditions can be depleted to different degrees. This might be either due to their exhumation from different depths of the subduction zone or to the presence of an external source of water controlling the temperature of dissolution of phengite and the formation of supercritical fluid/melt.     

Application of Zr-in-rutile thermometry: a case study from ultrahigh-temperature granulites of the Khondalite belt, North China Craton

Zr-in-rutile thermometry was applied to ultrahigh-temperature (UHT) granulites from three localities, Dongpo, Tuguishan, and Dajing/Tuguiwula of the Khondalite belt, North China Craton. Zr concentrations of analyzed rutiles were detected by LA-ICP-MS and EMP, which display a mutative composition zoning, a large inter-grain variation, a bimodal distribution at around 1,500 and 6,000?ppm, and no relationship with the textural setting (matrix vs. inclusion). These characteristics were likely caused by post-peak diffusional resetting associated with slow cooling rates and the presence of a CO₂-rich fluid. The grains with lower Zr concentrations (~500 to ~3,000?ppm) and temperature estimates (~650 to ~850°C) occur close to or in contact with zircon, which was easily affected by post-peak processes (for example: diffusion, dissolution/reprecipitation). The lowest temperatures (~650 to ~700°C) we obtained represent the closure temperature of Zr-in-rutile. Rutiles with higher Zr concentrations (~3,000 to ~8,000?ppm) and calculated temperatures (~850 to ~1,000°C) were least affected by late resetting, giving near-peak metamorphic temperatures. These temperature results higher than 900°C, even in excess of 1,000°C from the three localities, reconfirm the presence of UHT metamorphism. Our results also suggest that Zr-in-rutile thermometry is valid for ultrahigh-temperature estimates. In addition, there are positive correlations between concentrations of Zr and Hf, Nb and Ta of the investigated rutiles, but the correlations weaken as the concentrations increase, especially for Nb and Ta, implying fractionation of Nb and Ta.     

麻粒岩相金红石微量元素体系

麻粒岩是研究地壳演化最重要的变质岩类,金红石作为麻粒岩中常见的副矿物之一,深入探究其微量元素体系特点,可为大陆地壳演化研究提供新的视角.根据麻粒岩金红石的基础数据（显微结构、微量元素、离子替换方式）以及地壳常见造岩矿物的微量元素特点,初步探讨了麻粒岩变质过程中微量元素行为和扩散效应.麻粒岩金红石Zr含量可记录不同阶段的变质温度,但次生锆石和钛铁矿可对其Zr含量有较大影响,作为孤立体系（不与锆石和石英平衡）的金红石不能用于温度计算;金红石Nb、Ta、Cr和V不仅受全岩成分控制,还与变质过程中黑云母、钛铁矿、蓝晶石等矿物的形成和分解紧密相关;金红石与富Fe矿物之间有强烈的Fe扩散效应.深入理解麻粒岩变质过程中金红石微量元素行为,可为限定大陆地壳变质演化和动力学过程提供重要的矿物学信息.      

Early to late Neoproterozoic magmatism and magma mixing–mingling in Sri Lanka: Implications for convergent margin processes during Gondwana assembly

The Sri Lankan fragment of Gondwana preserves the records of Neoproterozoic tectonothermal events associated with the final assembly of the supercontinent. Here we investigate a suite of magmatic rocks from the Wanni, Kadugannawa and Highland Complexes through geological, petrological, geochemical and zircon U–Pb and Lu–Hf isotopic techniques. The hornblende biotite gneiss, charnockites, metagabbro and metadiorites investigated in this study show geochemical features consistent with calc-alkaline affinity and subduction-related signature including LILE enrichment relative to HFSE coupled with distinct Nb–Ta depletion and weak negative Zr–Hf anomalies. The felsic suite falls in the volcanic arc granites (VAGs) field and the mafic suite shows island arc basalt affinity in tectonic discrimination plots, suggesting that the protoliths of the rocks were derived from arc-related magmas in a convergent margin setting. LA-ICPMS zircon U–Pb analyses show crystallization of charnockite and dioritic mafic magmatic enclave from the Highland Complex during ca. 565 and 576 Ma corresponding to bimodal magmatism. The diorite also contains metamorphic zircons of ca. 525 Ma. Hornblende–biotite gneiss from the Kadugannawa Complex shows protolith emplacement age at 973–980 Ma, followed by new zircon growth during repeated thermal events through late Neoproterozoic. The dioritic enclaves in these rocks are much younger, and form part of a deformed and metamorphosed dyke suite with emplacement ages of 559 Ma, broadly coeval with the bimodal magmatism in the Highland Complex at that time. The youngest group of zircons in this rock shows ages of 508 Ma, corresponding to the latest thermal event. A charnockite from this locality shows oldest group of zircons at 962 Ma, corresponding to emplacement age similar to that of the magmatic protolith of the hornblende biotite gneiss. This rock also shows zircon growth during repeated thermal events at 832 Ma, 780 Ma, 721 Ma and 661–605 Ma. The lower intercept age of 543 Ma marks the timing of collisional metamorphism. Charnockite from the Wanni Complex shows emplacement age at 1000 Ma, followed by thermal event at 570 Ma, the latter correlating with the bimodal magmatic event in the Highland Complex. The dioritic enclave within this charnockite shows an age of ca. 980 Ma, suggesting intrusion of mafic magma into the felsic magma chamber. Zircons in the diorite also record multiple zircon events during 950 to 750 Ma. Zircons in the Highland Complex charnockite possess negative εHf(t) values in the range − 6.7 to − 12.6 with T_DM^C of 2039–2306 Ma suggesting magma derivation through melting of Paleoproterozoic source. In contrast, the εHf(t) range of − 11.1 to 1.6 suggests a mixed source of both of older crustal and juvenile material. The εHf(t) values of − 4.5 to 4.5 and T_DM^C of 1546–1962 Ma for the hornblende biotite gneiss also shows magma derivation from mixed sources that included Paleoproterozoic components. The younger dioritic intrusive, however, has a more juvenile magma source as indicated by the mean εHf(t) value of 1.3. The associated charnockite shows a tight positive cluster of εHf(t) from 0.6 to 5.1, suggesting juvenile input. Charnockite from the Wanni Complex shows clearly positive εHf(t) values of up to 13.1, and T_DM^C in the range 937–1458 Ma suggesting much younger and depleted mantle source. The diorite enclave also has positive εHf(t) values with an average value of 8.5 and T_DM^C in the range of 709–1443 Ma clearly suggesting younger juvenile sources. The early and late Neoproterozoic bimodal suites are correlated to convergent margin magmatism associated with the assembly of Sri Lanka within the Gondwana supercontinent.     

Magmatic–hydrothermal rare-element mineralization in the Songshugang granite (northeastern Jiangxi,China): Insights from an electron-microprobe study of Nb–Ta–Zr minerals

The Songshugang granite, hidden in the Sinian metasedimentary stratum, is a highly evolved rare-element granite in northeastern Jiangxi province, South China. The samples were systematically taken from the CK-102 drill hole at the depth of 171–423 m. Four types of rocks were divided from the bottom upwards: topaz albite granite as the main body, greisen nodules, topaz K-feldspar granite and pegmatite layer. Electron-microprobe study reveals that the rare-element minerals of the Songshugang granite are very different from those of other rare-element granites. Mn^# [Mn/(Fe + Mn)] and Ta^# [Ta/(Nb + Ta)] of columbite-group minerals and Hf^# [Hf/(Zr + Hf)] of zircon are nearly constant within each type of rocks. However, back-scattered electron imaging revealed that Nb–Ta oxides and zircon of the Songshugang granite, especially those of topaz albite granite, topaz K-feldspar granite and greisen, are commonly characterized by a specific two-stage texture on the crystal scale. The early-stage Nb–Ta oxide is simply subhedral-shaped columbite-(Fe) (CGM-I) with low Mn^# (0.16–0.37) and Ta^# (0.05–0.29). Columbite-(Fe) is penetrated by the later-stage tantalite veinlets (CGM-II) or surrounded by complex Nb–Ta–Sn–W mineral assemblages, including tantalite-(Fe), wodginite (sl), cassiterite, and ferberite. Tantalite has wide range of Mn^# values (0.15–0.88) from Fe-dominance to Mn-dominance. Wodginite with Ta>Nb has large variable concentrations of W, Sn and Ti. Cassiterite and ferberite are all enriched in Nb and Ta (Nb₂O₅ + Ta₂O₅ up to 20.12 wt.% and 31.42 wt.%, respectively), with high Ta^# (>0.5). Similar to Nb–Ta oxides and Nb–Ta–Sn–W mineral assemblages, the early-stage zircon is commonly included by the later-stage zircon with sharply boundary. They have contrasting Hf contents, and HfO₂ of the later-stage zircon is up to 28.13 wt.%. Petrographic features indicate that the early-stage of columbite and zircon were formed in magmatic environment. However, the later-stage of rare-element minerals were influenced by fluxes-enriched fluids. Tantalite, together with wodginite, cassiterite, and ferberite implies a Ta-dominant media. An interstitial fluid-rich melt enriched in Ta and flux at the magmatic–hydrothermal transitional stage is currently a favored model for explaining the later-stage of rare-element mineralization.