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.      

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.     

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.     

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.     

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.     

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.     

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。     

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.     

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。     

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.     

Mobilization of Ti-Nb-Ta during subduction: Evidence from rutile-bearing dehydration segregations and veins hosted in eclogite, Tianshan, NW China

Field evidence from the western Tianshan subduction complex in northwestern China indicates that the high field strength elements Ti, Nb, and Ta were mobilized and thereby fractionated from Zr and Hf during the dehydration process that transformed blueschist into eclogite. Both a segregation with a depletion halo, thought to represent initial mobilization during dehydration, and a transport vein, indicative of the long distance transport were investigated. In each case, centimeter-sized rutile grains grew as needle-like crystals in the segregation and as prismatic crystals in the vein. Within the host rock of the segregation, the Ti contents of garnet and omphacite, the modal abundances of rutile and titanite and the bulk rock Ti, Nb, and Ta contents decrease towards the segregation. These observations are consistent with transport of Ti, Nb, and Ta from the host rock into the segregation. Textural and geochemical data for the eclogite-facies vein minerals indicate that Ti-Nb-Ta-rich fluids were transported over long-distances (at minimum meter-scale) during fracture-controlled fluid flow. Complex forming ligands (e.g., Na-Si-Al polymers and F⁻) may have enhanced the solubility of Ti, Nb, and Ta in the fluid. Changes in fluid composition (e.g., X_CO2) may both precipitate rutile and fractionate Ti, Nb, and Ta from LILE and REE.     

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-榍石转变过程中元素地球化学行为——以雅鲁藏布江缝合带角闪岩为例

金红石边缘形成榍石冠状边结构在变质中-基性岩中普遍存在,是金红石与退变质流体携带的SiO_2与CaO作用的结果,反应形成的榍石微量元素特征受到金红石和流体的共同影响。雅鲁藏布江缝合带中角闪岩LZ06-04在抬升过程经历近等温降压退变质作用,石榴子石分解导致同一样品中含石榴子石部分与不含石榴子石部分的退变质流体成分的差异。两种流体分别与金红石反应,对应形成的榍石具有相似的Nb、Ta含量和Nb/Ta比值特征,但截然不同的REE特征。榍石的Nb、Ta来源于金红石,残余金红石与含水流体再平衡Nb、Ta的分配系数增大,且D_(Nb)~(Rt/Fluid)≥D_(Ta)~(Rt/Fluid);虽然Nb和Ta在含水流体中都表现为不活动元素,但相对于Nb,Ta在含水流体中活动性较高。榍石的Zr-Hf体系特征受到锆石、石榴子石等矿物的综合影响,并且Zr-Hf在含水流体中表现出比Nb-Ta更高的活动性。榍石的REE特征受流体中REE特征、榍石与流体配分系数以及共生矿物的影响。在岩浆或变质体系,榍石形成过程中,REE富集矿物(如石榴子石、锆石、褐帘石、独居石、磷灰石等)形成或分解将影响榍石的REE分布特征或形成REE环带结构。含水流体中金红石退变质形成榍石反应的进行受流体中TiO_2、CaO和SiO_2活度的影响。因此榍石常见于钙碱性岩浆岩、富Ca基性变质岩和矽卡岩中。流体中CaO活度的变化影响榍石的形成,进而影响Ti、Nb、Ta在流体中的运移能力。俯冲板片产生流体在交代上覆富Ca地幔楔物质过程中形成榍石残留同样可以造成部分熔融体具有亏损HFSE特征。     

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.     

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.     

Metamorphic P–T conditions and thermal structure of Chinese Continental Scientific Drilling main hole eclogites: Fe–Mg partitioning thermometer vs. Zr-in-rutile thermometer

Core rocks recovered from the main hole (5158 m deep) of the Chinese Continental Scientific Drilling (CCSD‐MH) project, southern Sulu UHP terrane, east‐central China, consist of eclogites, various gneisses and minor metaperidotite cumulates; this lithological section underwent subduction‐zone UHP metamorphism. Coesite‐bearing eclogites are mainly present between the depths of 100–2000 m, but below 2000 m, mafic eclogites are rare. Selected elements (Zr, Nb, Cr, Fe, Si, Mg, Al & Ti) in rutile from 39 eclogite cores from 100 to 2774 m, and major elements of minerals from representative eclogites were analysed by electron microprobe. Zirconium and Nb concentrations of rutile cluster ～100–400 and 200–700 ppm respectively. However, Zr and Nb contents in rutile from strongly retrograded eclogites show larger variations than those of fresh or less retrograded eclogites, implying that somehow fluid infiltration affected rutile chemistry during retrograde metamorphism. Zr contents in rutile inclusions in garnet and omphacite are slightly lower than those of the matrix rutile, suggesting that the rutile inclusions formed before or close to the peak temperature. The P–T conditions of the CCSD‐MH eclogites were estimated by both Fe–Mg exchange and Zr‐in‐rutile thermometers, as well as by the Grt–Cpx–Phn–Ky geothermobarometer. The maximum temperature range of 700–811 °C calculated at 40 kbar using the Zr‐in‐rutile thermometer is comparable with temperature estimates by the Fe–Mg exchange thermometer. The temperature estimates of eclogites in a ～3000 m thick section define a continuous gradient, and do not show a distinct temperature gap, suggesting that the rocks from 100 to 3000 m depth might belong to a single, large‐scale UHP slab. These data combined with P–T calculations for CCSD‐MH peridotites yield a low geotherm (～5 °C km^?1) for the Triassic subduction zone between the Sino‐Korean and Yangtze cratons; it lies ～30–35 mW m^?2 conductive model geotherm.     

Petrological sStudies of Jilang Eclogite and Constraints on the Subduction and Exhumation Processes of the Paleo‐Tethys Oceanic Crust

The (ultra‐) high pressure eclogites from Sumdo area, recorded the subduction and exhumation process of the Paleo‐Tethys oceanic crust. Previous studies showed that there are significant differences in temperature and pressure conditions of the eclogites in four regions, e.g. Sumdo, Xindaduo, Bailang and Jilang. The cause of this differences remains unclear. Studying the peak metamorphic conditions and P‐T path of Sumdo eclogite is of great significance to reveal the subduction and exhumation mechanism of Paleo‐Tethys ocean. In this paper, we choose the Jilang eclogite as an example, which has a mineral assemblage of garnet, omphacite, phengite, hornblende, rutile, epidote, quartz and symplectit (diopside + amphibole + plagioclase), and minor biotite. Garnet has a “dirty” core with abundant mineral inclusions and a “clear” rim with less mineral inclusions, showing typical growth zoning. From the core to the rim, Prp content in garnet increasing while Grs content decreasing. P‐T pseudosection calculated with Domino constrained peak P‐T conditions of Jilang eclogite as 563°C, 2.4 GPa. Combined with petrographical observation, four stages of metamorphism have been recognized: (1) early stage prograde metamorphism represent by the core of garnet and mineral inclusions therein; (2) peak metamorphism represent by the rim of garnet, omphacite, phengite, glaucophane, rutile and quartz; (3) first stage of retrograde metamorphism characterized by decomposition of lawsonite to zoisite; (4) second stage of retrograde metamorphism characterized by symplectites surrounding omphacite and cornona rimmed garnet. Jilang eclogite shows a clockwise P‐T path, and near isothermal decompression during exhumation. It differs from eclogites in other area, which are hosted by garnet‐bearing mica schists or serpentinites. Jilang eclogites are enclosed in metamorphic quartzites, with relatively low P‐T conditions. We infer that the Jilang eclogite was derived from the shallow part of the subduction zone, and was exhumated by low density materials in the subduction channel.     

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.     

PTtD Path and Fluid Evolution of HighPressure Eclogites from the Dabie Mountains,Central East China

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Metamorphic evolution of relict lawsonite‐bearing eclogites from the (U) HP metamorphic belt in the Chinese southwestern Tianshan

In the Chinese southwestern Tianshan (U)HP belt, former lawsonite presence has been predicted for many (U)HP metamorphic eclogites, but only a very few lawsonite grains have been found so far. We discovered armoured lawsonite relicts included in quartz, which, on its part, is enclosed in porphyroblastic garnet in an epidote eclogite H711‐14 and a paragonite eclogite H711‐29. H711‐14 is mainly composed of garnet, omphacite, epidote and titanite, with minor quartz, paragonite and secondary barroisite and glaucophane. Coarse‐grained titanite occasionally occurs in millimetre‐wide veins in equilibrium with epidote and omphacite, and relict rutile is only preserved as inclusions in matrix titanite and garnet. H711‐29 shows the mineral assemblage of garnet, omphacite, glaucophane, paragonite, quartz, dolomite, rutile and minor epidote. Dolomite and rutile are commonly rimed by secondary calcite and titanite respectively. Porphyroblastic garnet in both eclogites is compositionally zoned and exhibits an inclusion‐rich core overgrown by an inclusion‐poor rim. Phase equilibria modelling predicts that garnet cores formed at the P‐peak (490–505 °C and 23–25.5 kbar) and coexisted with the lawsonite eclogite facies assemblage of omphacite + glaucophane + lawsonite + quartz. Garnet rims (550–570 °C and ~20 kbar) grew subsequently during a post‐peak epidote eclogite facies metamorphism and coexisted with omphacite + quartz ± glaucophane ± epidote ± paragonite. The results confirm the former presence of a cold subduction zone environment in the Chinese southwestern Tianshan. The P–T evolution of the eclogites is characterized by a clockwise P–T path with a heating stage during early exhumation (thermal relaxation). The preservation of lawsonite in these eclogites is attributed to isolation from the matrix by quartz and rigid garnet, which should be considered as a new type of lawsonite preservation in eclogites. The complete rutile–titanite transition in H711‐14 took place in the epidote eclogite facies stage in the presence of an extremely CO₂‐poor fluid with X(CO₂) [CO₂/(CO₂ + H₂O) in the fluid] <<0.008. In contrast, the incomplete rutile–titanite transition in H711‐29 may have occurred after the epidote eclogite facies stage and the presence of dolomite reflects a higher X(CO₂) (>0.01) in the coexisting fluid at the epidote eclogite facies stage.