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.     

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.     

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.     

Fluids in deeply subducted continental crust: Petrology, mineral chemistry and fluid inclusion of UHP metamorphic veins from the Sulu orogen, eastern China

The complex vein associations hosted in southern Sulu ultrahigh-pressure (UHP) eclogites contain quartz ± omphacite (or jadeite) ± kyanite ± allanite ± zoisite ± rutile ± garnet. These minerals have chemical compositions similar to those of host eclogites. Inclusions of polycrystalline quartz pseudomorphs after coesite were identified in vein allanite and garnet, and coesite inclusions were found in vein zircon. These facts suggest that the veins together with host eclogites have been subjected to synchronous UHP metamorphism. The vein minerals contain relatively high concentrations of rare earth elements (REE), high-field-strength elements (HFSE) and transition metal elements (TME). A kyanite-quartz vein has a whole-rock composition similar to adjacent UHP metamorphic granitic gneisses. Abundant primary multi-solid fluid inclusions trapped within UHP vein minerals contain complex daughter minerals of muscovite, calcite, anhydrite, magnetite, pyrite, apatite, celestite and liquid and gas phase of H₂O with solids up to 30-70% of the inclusion volume. The presence of daughter minerals anhydrite and magnetite indicates the subduction fluids were oxidizing, and provides a possible interpretation for the high oxygen fugacity of subduction zone magmas. These characteristics imply that the UHP vein minerals were crystallized from supercritical silicate-rich aqueous fluids that were in equilibrium with peak-UHP minerals, and that the fluids in deeply subducted continental crust may contain very high concentrations of silicate as well as HREE, HFSE and TME. Such fluids might have resulted in major fractionation between Nb and Ta, i.e. the UHP fluids have subchondritic Nb/Ta values, whereas the host eclogites after extraction of the fluids have suprachondritic Nb/Ta values. Therefore, voluminous residual eclogites with high Nb/Ta ratios may be the complementary suprachondritic reservoir capable of balancing the subchondritic depleted mantle and continental crust reservoirs.     

金红石榴辉岩——一个可能的超球粒陨石Nb/Ta储库

Nb,Ta的硅酸盐地球质量不平衡问题争论由来已久,备受关注。近年来研究发现,含金红石的榴辉岩Nb/Ta往往高于球粒陨石值(Nb/Ta=17.5),暗示其可能是平衡地球Nb亏损的独立储库。而洋壳玄武岩部分熔融实验表明Ta比Nb更倾向进入金红石晶格,这意味着作为俯冲洋壳部分熔融残留相的榴辉岩Nb/Ta不可能高于原岩。为了解释地质观察和实验结果之间的矛盾,系统分析了中国大陆科学钻探工程(CCSD)主孔、先导孔及附近地表榴辉岩的矿物微量元素。结果发现:榴辉岩中的Nb,Ta主要存在于金红石之中,其他矿物中含量极少;Nb,Ta之间存在着强烈分异(Nb/Ta=5.3～96.2),并总体上具有超球粒陨石的特征;韭闪石和多硅白云母的Nb/Ta平均分别为48.6,21.8,显示了很强的Nb,Ta分异能力;其他矿物如石榴石、绿辉石、绿帘石、磷灰石等的Nb、Ta含量及Nb/Ta都很低,对Nb-Ta分异不造成影响。认为导致Nb-Ta分异的不是金红石,而应出现在洋壳俯冲过程中金红石相出现之前的脱水和部分熔融阶段。富含Ti的角闪石(韭闪石)和白云母可能对Nb-Ta分异起到了决定性的作用。等金红石相出现之后,由于其对Nb,Ta的绝对控制作用,此前阶段的分异结果便被固定在金红石中而继承下来。因此,含金红石的榴辉岩常常表现出超球粒陨石Nb/Ta的特征,与金红石不能有效地分异Na,Ta的实验结果之间并不矛盾。在不均匀的上地幔中含金红石的榴辉岩是可能的超球粒陨石Nb/Ta储库之一。     

Zr-in-rutile thermometry of eclogites from the Karakaya Complex in NW Turkey: Implications for rutile growth during subduction zone metamorphism

Eclogites occur as a tectonic slice within a metabasite-phyllite-marble unit of the Karakaya Complex in northwest Turkey. The high-pressure mineral assemblage in eclogite is mainly composed of garnet + omphacite + glaucophane + epidote + quartz. Trace element characteristics of rutile and Zr-in-rutile temperatures were determined for eclogites from the Karakaya Complex. Core-rim analyses of rutile grains yield remarkable trace element zoning with lower contents of Zr, Nb and Ta in the core than in the rim. The variations in Zr, Nb and Ta can be ascribed to growth zoning rather than diffusion effects. The Nb/Ta and Zr/Hf ratios increase with a decrease in Ta and Hf contents, which could be ascribed to the effect of metamorphic dehydration in subduction zones on rutile Nb/Ta differentiation. The rutile grains from eclogites in the Karakaya Complex are dominated by subchondritic Nb/Ta and Zr/Hf ratios. It can be noted that subchondritic Nb/Ta may record rutile growth from local sinks of aqueous fluids from metamorphic dehydration.The Zr contents of all rutile grains range between 81 and 160 ppm with an average of 123 ppm. The Zr-in-rutile thermometry yields temperatures of 559–604 °C with an average temperature of 585 °C for eclogites from the Karakaya Complex. This average temperature suggests growth temperature of rutile before peak pressure during the subduction. However, some rutile grains have higher Zr contents in the outermost rims compared to the core. Zr-in-rutile temperatures of the rims are about 20 °C higher than those of the cores. This suggests that the outermost rims would have grown from a distinct fluid at higher temperatures than that of the cores. Moreover, Zr contents and calculated temperatures in both inclusion rutile and matrix rutile from eclogites are identical, which suggests that eclogites within the Karakaya Complex belong to the same tectonic slice and underwent similar metamorphic evolution.     

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.     

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.     

Nb–Ta fractionation induced by fluid‐rock interaction in subduction‐zones: constraints from UHP eclogite‐ and vein‐hosted rutile from the Dabie orogen,Central‐Eastern China

Niobium and Ta concentrations in ultrahigh‐pressure (UHP) eclogites and rutile from these eclogites and associated high pressure (HP) veins were used to study the behaviour of Nb–Ta during dehydration and fluid‐rock interaction. Samples were collected through a ～2 km profile at the Bixiling complex in the Dabie orogenic belt, Central‐Eastern China. All but one eclogite away from veins (EAVs) display nearly constant Nb/Ta ratios ranging from 16.1 to 19.2, with an average of 16.9 ± 0.8 (2 SE), similar to that of their gabbroic protolith from the Yangtze Block. Nb/Ta ratios of rutile from the EAVs range from 12.7 to 25.3 among different individual grains, with the average values close to those of the corresponding bulk rocks. These observations show that Nb and Ta were not significantly fractionated by prograde metamorphism up to eclogite facies when no significant fluid‐rock interaction occurs. In contrast, Nb/Ta ratios of rutile from eclogites close to veins (ECVs) are highly variable from 17.8 to 49.8, which are systematically higher (by up to 17) than those of rutile from the veins. These observations demonstrate that Nb and Ta were mobilized and fractionated during localized fluid flow and intensive fluid‐rock interaction. This is strongly supported by Nb/Ta zoning patterns in single rutile grains revealed by in situ LA‐ICP‐MS analysis. Ratios of Nb/Ta in the ECV‐hosted rutile decrease gradually from cores towards rims, whereas those in the EAV‐hosted rutile are nearly invariable. Furthermore, the vein rutile shows Nb/Ta zoning patterns that are complementary to those in rutile from their immediate hosts (ECVs), suggesting an internal origin for the vein‐forming fluids. The Nb/Ta ratios of such fluids evolved from low values at the early stage of subduction to higher values at later supercritical conditions with increased temperature and pressure. Quantitative modelling was conducted to constrain the compositional evolution of metamorphic fluids during dehydration and fluid‐rock interaction focusing on Nb–Ta distribution. The modelling results based on our proposed multistage fluid phase evolution path can essentially reproduce the natural observations reported in the present study.     

大陆俯冲带的深部流体及变质化学地球动力学 ——以苏鲁超高压变质带为例

通过苏鲁超高压变质带的岩石学、矿物化学、地球化学和年代学研究,在大陆俯冲带深部流体与变质化学地球动力学方面取得了重要的创新性成果。研究证明大陆俯冲带的深部流体是高氧逸度、富硅酸盐的超临界流体,揭示出超高压变质极端条件下的流体－矿物(岩石)相互作用可以导致不活动元素发生溶解和迁移,可以导致金红石的Nb/Ta之间发生强烈的分异,提出俯冲到地幔深处的超高压榴辉岩是地球内部“隐藏”的超球粒陨石Nb/Ta比值的物质源区,与低球粒陨石Nb/Ta比值的物质源区大陆地壳和亏损地幔在化学成分上形成互补。     

变质玄武岩体系相平衡及矿物 熔体微量元素分配：限定TTG/埃达克岩形成条件和大陆壳生长模型

埃达克质岩石是高Na、Al和Sr、低Y和HREE以及Nb、Ta亏损的钠质花岗质岩石,奥长花岗岩-英云闪长岩-花岗闪长岩(TTG)是早期(太古宙)大陆壳主要组分,成分与埃达克质岩石相似,这些成分独特的岩石总体上认为是俯冲洋壳、下地壳和拆沉的下地壳中变质玄武岩部分熔融的产物。文中综述我们近年来在变质玄武岩体系相平衡和矿物-熔体微量元素分配实验研究成果:相平衡实验和熔体微量元素特征研究表明,变质玄武岩部分熔融过程中金红石是导致TTG/埃达克岩浆Nb、Ta亏损的必要残留矿物,从而否定了前人“TTG由无金红石的角闪岩熔融产生”的观点;证实金红石仅仅在压力1.5GPa以上才能稳定存在,从而限定TTG/埃达克岩熔体必定产生在大约50km以上,表明TTG/埃达克岩是在相对较深的含金红石榴辉岩相条件下熔融产生的。矿物(石榴子石、角闪石,单斜辉石和金红石)-熔体微量元素分配系数测定和部分熔融模拟结果进一步限定俯冲洋壳和下地壳起源的TTG/埃达克岩浆由含金红石角闪榴辉岩熔融产生,而拆沉下地壳起源的埃达克岩浆的产生要求软流圈地幔高温,由无水或含有少量含水矿物的榴辉岩熔融产生。     

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.      

Mechanisms of Archean crust formation inferred from high-precision HFSE systematics in TTGs

It has been proposed that Archean tonalitic-trondhjemitic-granodioritic magmas (TTGs) formed by melting of mafic crust at high pressures. The residual mineralogy of the TTGs (either (garnet)-amphibolite or rutile-bearing eclogite) is believed to control the trace element budget of TTGs. In particular, ratios of high-field-strength elements (HFSE) can help to discriminate between the different residual lithologies. In order to place constraints on the source mineralogy of TTGs, we performed high-precision HFSE measurements by isotope dilution (Nb, Ta, Zr, Hf) together with Lu-Hf and Sm-Nd measurements on representative, ca. 3.85-2.8 Ga TTGs and related rock types from southern West Greenland, W-India and from the Superior Province. These measurements are complemented by major and trace element data for the TTGs. Texturally homogeneous early Archean (3.85-3.60 Ga old) and Mesoarchean (ca. 3.1-2.8 Ga old) TTGs have both low Ni (<11 ppm) and Cr contents (<20 ppm), indicating that there was little or no interaction with mantle peridotite during ascent. Ratios of Nb/Ta in juvenile Eoarchean TTGs range from ca. 7 to ca. 24, and in juvenile Mesoarchean TTGs from ca. 14 to ca. 27. Even higher Nb/Ta (14-42) were obtained for migmatitic TTGs and intra-crustal differentiates, most likely mirroring further fractionation of Nb from Ta as a consequence of partial melting, fluid infiltration and migmatisation. In the juvenile TTGs, positive correlations between Nb/Ta and Gd/Yb, La/Yb, Sr/Y, Zr/Sm and Zr/Nb are observed. These compositional arrays are best explained by melting of typical Isua tholeiites in both, the rutile-bearing eclogite stability field (>15 kbar, high Nb/Ta) and the garnet-amphibolite stability field (10-15 kbar, low Nb/Ta). With respect to the low end of Nb/Ta found for TTGs, there is currently some uncertainty between the available experimental datasets for amphibole. Independent of these uncertainties, the TTG compositions found here still require the presence of both endmember residues. A successful geological model for the TTGs therefore has to account for the co-occurrence of both low- and high-Nb/Ta TTGs within the same geologic terrane. An additional feature observed in the Eoarchean samples from Greenland is a systematic co-variation between Nb/Ta and initial εHf(t), which is best explained by a model where TTG-melting occured at progressively increasing pressures in a pile of tectonically thickened mafic crust. The elevated Nb/Ta in migmatitic TTGs and intra-crustal differentiates can shed further light on the role of intra-crustal differentiation processes in the global Nb/Ta cycle. Lower crustal melting processes at granulite facies conditions may generate high-Nb/Ta domains in the middle crust, whereas mid-crustal melting at amphibolite facies conditions may account for the low Nb/Ta generally observed in upper crustal rocks.     

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.     

Subduction channel fluid-rock interaction:Indications from rutile-quartz veins within eclogite from the Yuka terrane,North Qaidam orogen

High-pressure(HP)or ultrahigh-pressure(UHP)rutile-quartz veins that form at mantle depths due to fluid-rock interaction can be used to trace the properties and behavior of natural fluids in subduction zones.To explore the fluid flow and the associated element mobility during deep subduction and exhumation of the continental crust,we investigated the major and trace elements of Ti-rich minerals.Additionally,U–Pb dating,trace element contents,and Lu–Hf isotopic composition of zircon grains in the UHP eclogite and associated rutile-quartz veins were examined in the North Qaidam UHP metamorphic belt,Yuka terrane.The zircon grains in the rutile-quartz veins have unzoned or weak oscillatory zonings,and show low Th/U ratios,steep chondrite-normalized patterns of heavy rare earth elements(HREEs),and insignificant negative Eu anomalies,indicating their growth in metamorphic fluids.These zircon grains formed in 431
3 Ma,which is consistent with the 432
2 Ma age of the host eclogite.As for the zircons in the rutile-quartz veins,they showed steep HREE patterns on one hand,and were different from the zircons present in the host eclogite on the other.This demonstrates that their formation might have been related to the breakdown of the early stage of garnet,which corresponds to the abundance of fluids during the early exhumation stage.The core-rim profile analyses of rutile recorded a two-stage rutile growth across a large rutile grain;the rutile core has higher Nb,Ta,W,and Zr contents and lower Nb/Ta ratios than the rim,indicating that the rutile domains grew in different metamorphic fluids from the core towards the rim.The significant enrichment of high field strength elements(HFSEs)in the rutile core suggests that the peak fluids have high solubility and transportation capacity of these HFSEs.Furthermore,variations in the Nb vs.Cr trends in rutile indicate a connection of rutile to mafic protolith.The zircon grains from both the rutile-quartz veins and the host eclogite have similar Hf isotopic compositions,indicating that the vein-forming fluids are internally derived from the host eclogite.These fluids accumulated in the subduction channel and were triggered by local dehydration of the deeply subducted eclogite during the early exhumation conditions.     

大别超高压变质过程中流体作用的微量元素效应及其地球化学意义

对大别地区角闪岩相－麻粒岩相和榴辉岩相岩石进行较系统的地球化学研究,探讨了超高压俯冲变质及折返过程中元素的再分配行为,并就其对变质过程中的部分熔融作用和流体交代作用的指示进行了分析。研究表明,大别榴辉岩原岩在其俯冲过程中发生了部分熔融作用,并在其早期脱水和后期退变质作用过程中与变质流体相之间产生了交换。脱水作用使榴辉岩Ｎｂ／Ｔａ比值升高,但后期的退变质作用使榴辉岩与其寄主围岩间的Ｎｂ／Ｔａ比值相对     

南苏鲁超高压变质带东海地区富钛榴辉岩及金红石矿的成因

苏鲁超高压变质带南部的东海地区有富Fe—Ti的钛铁矿榴辉岩和富Ti的金红石榴辉岩。富Fe—Ti榴辉岩的次要矿物主要由钛铁矿和钛磁铁矿组成，可舍少量金红石，具有很低的Si02（38．0％-42．3％）、Na20＋K20（0．48％～2．13％）和Zr、Nb、Ta、Ba、1Kb、REE含量，很高的FeO（18．24％-25．33％）、V和Co含量，并具有不同程度的LREE亏损、明显的正Eu异常；富Ti金红石榴辉岩舍有丰富的金红石和磷灰石，SiO2含量范围（38．0％-54．8％）较宽，FeO含量较低，P2O5含量较高（可达4．1％），而X-TiO2与P205含量具正相关性。相对于原始地慢岩．富Ti金红石榴辉岩具有Rb、Th、K、Nb、Pr、Nd、Eu、Ti、Lu的负异常和Ba、Sr、Zr的正异常．并具相对较高的IKEE含量，LREE富集和HREE亏损的1KEE分配型式。岩石学和地球化学特征揭示，Fe—Ti榴辉岩的原岩是变质的Fe—Ti辉长岩，是基性岩浆强烈分离结晶作用形成的超基性-基性-中酸性层状侵入体的特征组成部分。     

Petrogenesis of Maobei rutile eclogites from the southern Sulu ultrahigh-pressure metamorphic belt, eastern China

The Maobei complex in the southern Sulu ultrahigh‐pressure (UHP) metamorphic belt, eastern China, mainly consists of layered eclogites, garnet peridotites and orthogneisses. Based on the modal mineral and whole‐rock compositions, eclogites from the Maobei complex are divided into quartz eclogite, quartz‐rich eclogite, rutile eclogite, rutile‐rich eclogite and eclogite. The distinct spatial changes in the lithology and related chemical compositions indicate that this complex includes 10 rhythmic layers. The rutile eclogites have high TiO₂ (2.4–5.9 wt%), commonly coupled with high P₂O₅ (up to 4.1 wt%) contents; most show fractionated REE patterns with slight positive Eu anomalies. The rutile‐rich eclogites have very high TiO₂ (3.3–5.7 wt%), FeO^T (17.5–25.3 wt%), V (126–1163 ppm) and Co (14–132 ppm), and very low SiO₂ (38.0–42.3 wt%), Zr (24–85 ppm), Nb (0.3–6.9 ppm), Ta (<0.1–0.6 ppm) and total REE (10.7–334.0 ppm) contents, variable degree of LREE depletion, and positive Eu anomalies (Eu/Eu* = 1.1–2.9), and the Ti is decoupled from other high‐field‐strength elements. These characteristics are consistent with Fe‐Ti gabbros of typical layered intrusions, implying a cumulate of plagioclase, clinopyroxene and abundant accessory magnetite in an evolved basaltic magmatic chamber. Based on a normal stratigraphic sequence, the Maobei complex shows an iron‐enrichment trend, followed by alkaline enrichment with increasing fractionated crystallization and stratigraphic height. These facts, together with SHRIMP U‐Pb zircon ages of 773.7 ± 8.0 Ma, indicate that the protolith of the Maobei complex is a Neoproterozoic layered intrusion consisting of a base of peridogabbro, a main body of gabbro and minor granodiorite. Unusually high Ti, V and P contents in three rutile eclogite layers suggest that they are potential economic ore deposits.     

Ultrahigh pressure metamorphic rocks from the Chinese Continental Scientific Drilling Project: I. Petrology and geochemistry of the main hole (0–2,050 m)

The main hole (MH) of the Chinese Continental Scientific Drilling Project (CCSD) in southern Sulu has penetrated into an ultrahigh-pressure (UHP) metamorphic rock slice which consists of orthogneiss, paragneiss, eclogite, ultramafic rock and minor schist. Recovered eclogites have a UHP metamorphic mineral assemblage of garnet + omphacite + rutile ± phengite ± kyanite ± coesite ± epidote. Ultramafic rocks contain garnet + olivine + clinopyroxene + orthopyroxene ± Ti-clinohumite ± phlogopite. Gneisses and schists contain an amphibolite-facies paragenesis, but their zircons have coesite, garnet, omphacite (or jadeite) and phengite inclusions, indicating that eclogites and gneisses have been subjected to in situ UHP metamorphism. Using available geothermobarometers, P–T estimates of 3.1–4.4 GPa and 678–816°C for eclogites were obtained. If surface outcrops and neighboring shallow drill holes are considered together, we suggest that a huge supracrustal rock slab (> 50 km long × 100 km wide × 5 km deep) was subducted to a depth > 100 km and then exhumed to the surface. The depth interval (0–2,050 m) of the CCSD-MH can be divided into six lithological units. Unit 1 consists of alternating layers of quartz-rich and rutile-rich eclogites, with thin interlayers of gneiss and schist. Eclogites of unit 1 are characterized by Nb, Ta, Sr and Ti depletions, low Mg number and general LREE enrichment. Unit 2 comprises rutile- and ilmenite-rich eclogite and minor “normal” eclogite and is characterized by high TiO₂, total Fe, V, Co and Sr, and very low SiO₂, alkali, Zr, Ba, Nb, Ta and total REE contents, and LREE-depleted REE patterns with slightly positive Eu anomalies. Unit 3 contains ultramafic rock and minor MgO-rich eclogite. Protoliths of UHP rocks from units 1, 2 and 3 represent a layered mafic to ultramafic intrusion at crustal depth. Units 4 and 6 consist of interlayered eclogite and paragneiss; the eclogites are characterized by Th, U, Nb, Ta and Ti depletion and K enrichment and LREE-enriched REE patterns. Paragneisses show Nb, Ta, Sr and Ti depletions and LREE-enriched REE patterns occasionally with slightly negative Eu anomalies, indicating that their protoliths represent metamorphic supracrustal series. Unit 5 consists mainly of orthogneisses, showing distinct Nb, Ta, Sr and Ti depletions, and LREE-enriched REE patterns with pronounced negative Eu anomalies, suggesting granitic protoliths. In conclusion it is proposed that the southern Sulu UHP belt consists of a series of meta-supracrustal rocks, a layered mafic–ultramafic complex and granites.     

Eclogites of the Dabie Region: Retrograde Metamorphismand Fluid Evolution

Based upon fluid effects, retrograde metamorphism of eclogites in the Dabie region can be divided into the fluid-poor, fluid-bearing and fluid-rich stages. The fluid-poor stage is marked by polymorphic inversion, recrystallization and exsolution of solid solutions, and is thought to represent eclogite-facies retrograde environments. The fluid-bearing stage is likely to have occurred at the late stage of ecologite-facies diaphthorosis and is represented by kyanite porphyroblasts, rutile, and sodic pyroxene in association with high-pressure hydrous minerals such as phengite and zoisite (clinozoisite) without significant amount of hydrous minerals such as amphibole, epidote and biotite. The fluid-rich stage might have commenced concomitantly with lower amphibolite-facies diaphthoresis and persisted all the way towards the near-surface environment. The product of this stage is characterized by plentiful hydrous and volatile-bearing phases.The dissemination-type rutile mineralizations in eclogites might have