Fluid entrapment and reequilibration during subduction and exhumation: A case study from the high-grade Nestos shear zone, Central Rhodope, Greece

A fluid inclusion study on metamorphic minerals of successive growth stages was performed on highly deformed paragneisses from the Nestos Shear Zone at Xanthi (Central Rhodope), in which microdiamonds provide unequivocal evidence for ultrahigh-pressure (UHP) metamorphism. The correlation of fluid inclusion density isochores and fluid inclusion reequilibration textures with geothermobarometric data and the relative chronology of micro- and macro-scale deformation stages allow a better understanding of both the fluid and metamorphic evolution along the P–T–d path. Textural evidence for subduction towards the NE is recorded by the orientation of intragranular NE-oriented fluid inclusion planes and the presence of single, annular fluid inclusion decrepitation textures. These textures occur within quartz “foam” structures enclosed in an earlier generation of garnets with prolate geometries and rarely within recrystallized matrix quartz, and reequilibrated both in composition and density during later stages of exhumation. No fluid inclusions pertaining to the postulated ultrahigh-pressure stage for microdiamond-bearing garnet–kyanite–gneisses have yet been found. The prolate shape of garnets developed during the earliest stages of exhumation that is recorded structurally by (L  S) tectonites, which subsequently accommodated progressive ductile SW shearing and folding up to shallow crustal levels. The majority of matrix kyanite and a later generation of garnet were formed during SW-directed shear under plane-strain conditions. Fluid inclusions entrapped in quartz during this stage of deformation underwent density loss and transformed to almost pure CO₂ inclusions by preferential loss of H₂O. Those inclusions armoured within garnet retained their primary 3-phase H₂O–CO₂ compositions. Reequilibration of fluid inclusions in quartz aggregates is most likely the result of recrystallization along with stress-induced, preferential H₂O leakage along dislocations and planar lattice defects which results in the predominance of CO₂ inclusions with supercritical densities. Carbonic fluid inclusions from adjacent kyanite–corundum-bearing pegmatoids and, the presence of shear-plane-parallel fluid inclusion planes within late quartz boudin structures consisting of pure CO₂-fluid inclusions with negative crystal shapes, bear witness of the latest stage of deformation by NE-directed extensional shear.This study shows that the textures of early fluid inclusions that formed already during the prograde metamorphic path can be preserved and used to derive information about the kinematics of subduction that is difficult to obtain from other sources. The textures of early inclusions, together with later generations of unaltered primary and secondary inclusions in metamorphic index minerals that can be linked to specific deformation stages and even P–T conditions, are a welcome supplement for the reconstruction of a rather detailed P–T–d path.     

Asymmetrically zoned reaction rims: assessment of grain boundary diffusivities and growth rates related to natural diffusion-controlled mineral reactions

This study explores garnet coronas around hedenbergite, which were formed by the reaction plagioclase + hedenbergite→garnet + quartz, to derive information about diffusion paths that allowed for material redistribution during reaction progress. Whereas quartz forms disconnected single grains along the garnet/hedenbergite boundaries, garnet forms ～20‐μm‐wide continuous polycrystalline rims along former plagioclase/hedenbergite phase boundaries. Individual garnet crystals are separated by low‐angle grain boundaries, which commonly form a direct link between the reaction interfaces of the plagioclase|garnet|hedenbergite succession. Compositional variations in garnet involve: (i) an overall asymmetric compositional zoning in Ca, Fe²⁺, Fe³⁺ and Al across the garnet layer; and (ii) micron‐scale compositional variations in the near‐grain boundary regions and along plagioclase/garnet phase boundaries. These compositional variations formed during garnet rim growth. Thereby, transfer of the chemical components occurred by a combination of fast‐path diffusion along grain boundaries within the garnet rim, slow diffusion through the interior of the garnet grains, and by fast diffusion along the garnet/plagioclase and the garnet/hedenbergite phase boundaries. Numerical simulation indicates that diffusion of Ca, Al and Fe²⁺ occurred about three to four, four and six to seven orders of magnitude faster along the grain boundaries than through the interior of the garnet grains. Fast‐path diffusion along grain boundaries contributed substantially to the bulk material transfer across the growing garnet rim. Despite the contribution of fast‐path diffusion, bulk diffusion through the garnet rim was too slow to allow for chemical equilibration of the phases involved in garnet rim formation even on a micrometre scale. Based on published garnet volume diffusion data the growth interval of a 20‐μm‐wide garnet rim is estimated at ～10³–10⁴ years at the inferred reaction conditions of 760 ± 50 °C at 7.6 kbar. Using the same parameterization of the growth law, 100‐μm‐ and 1‐mm‐thick garnet rims would grow within 10⁵–10⁶ and 10⁶–10⁷ years respectively.     

Zircon U–Pb ages, Hf and O isotopes constrain the crustal architecture of the ultrahigh-pressure Dabie orogen in China

The crustal structure of the Dabie orogen was reconstructed by a combined study of U–Pb ages, Hf and O isotope compositions of zircons from granitic gneiss from North Dabie, the largest lithotectonic unit in the orogen. The results were deciphered from metamorphic history to protolith origin with respect to continental subduction and exhumation. Zircon U–Pb dating provides consistent ages of 751 ± 7 Ma for protolith crystallization, and two group ages of 213 ± 4 to 245 ± 17 Ma and 126 ± 4 to 131 ± 36 Ma for regional metamorphism. Majority of zircon Hf isotope analyses displays negative ε_Hf(t) values of − 5.1 to − 2.9 with crust Hf model ages of 1.84 to 1.99 Ga, indicating protolith origin from reworking of middle Paleoproterozoic crust. The remaining analyses exhibit positive ε_Hf(t) values of 5.3 to 14.5 with mantle Hf model ages of 0.74 to 1.11 Ga, suggesting prompt reworking of Late Mesoproterozoic to Early Neoproterozoic juvenile crust. Zircon O isotope analyses yield δ¹⁸O values of − 3.26 to 2.79‰, indicating differential involvement of meteoric water in protolith magma by remelting of hydrothermally altered low δ¹⁸O rocks. North Dabie shares the same age of Neoproterozoic low δ¹⁸O protolith with Central Dabie experiencing the Triassic UHP metamorphism, but it was significantly reworked at Early Cretaceous in association with contemporaneous magma emplacement. The Rodinia breakup at about 750 Ma would lead to not only the reworking of juvenile crust in an active rift zone for bimodal protolith of Central Dabie, but also reworking of ancient crust in an arc-continent collision zone for the North Dabie protolith. The spatial difference in the metamorphic age (Triassic vs. Cretaceous) between the northern and southern parts of North Dabie suggests intra-crustal detachment during the continental subduction. Furthermore, the Dabie orogen would have a three-layer structure prior to the Early Cretaceous magmatism: Central Dabie in the upper, North Dabie in the middle, and the source region of Cretaceous magmas in the lower.     

Zircon coronas around Fe–Ti oxides: a physical reference frame for metamorphic and metasomatic reactions

Ilmenite in coronitic gabbros from the Bamble and Kongsberg sectors, southern Norway, is surrounded by zircons ranging in diameters from a fraction of a micrometer to 10 μm across. The zircons are inert during subsequent metamorphism (amphibolite- to pumpellyite–prehnite facies) and metasomatism (scapolitization and albitization) and can be found as trails in silicates (phlogopite, talc, chlorite, amphibole, albite, and tourmaline) in the altered rocks. The trails link up to form polygons outlining the former oxide grain boundary. This 3-dimensional framework of zircons is used to (a) recognize metasomatic origin of rocks, (b) quantify the mobility of elements during mineral replacement, (c) establish the growth direction of reaction fronts and to identify the reaction mechanism as dissolution–reprecipitation. Zircon coronas on Fe–Ti oxides have been described from a number of terrains and appear to be common in mafic rocks (gabbros and granulites) providing a tool for a better understanding of metasomatic and metamorphic reactions.     

An experimental study of the grain-scale processes of peridotite melting: implications for major and trace element distribution during equilibrium and disequilibrium melting

The grain-scale processes of peridotite melting were examined at 1,340°C and 1.5 GPa using reaction couples formed by juxtaposing pre-synthesized clinopyroxenite against pre-synthesized orthopyroxenite or harzburgite in graphite and platinum-lined molybdenum capsules. Reaction between the clinopyroxene and orthopyroxene-rich aggregates produces a melt-enriched, orthopyroxene-free, olivine + clinopyroxene reactive boundary layer. Major and trace element abundance in clinopyroxene vary systematically across the reactive boundary layer with compositional trends similar to the published clinopyroxene core-to-rim compositional variations in the bulk lherzolite partial melting studies conducted at similar P–T conditions. The growth of the reactive boundary layer takes place at the expense of the orthopyroxenite or harzburgite and is consistent with grain-scale processes that involve dissolution, precipitation, reprecipitation, and diffusive exchange between the interstitial melt and surrounding crystals. An important consequence of dissolution–reprecipitation during crystal-melt interaction is the dramatic decrease in diffusive reequilibration time between coexisting minerals and melt. This effect is especially important for high charged, slow diffusing cations during peridotite melting and melt-rock reaction. Apparent clinopyroxene-melt partition coefficients for REE, Sr, Y, Ti, and Zr, measured from reprecipitated clinopyroxene and coexisting melt in the reactive boundary layer, approach their equilibrium values reported in the literature. Disequilibrium melting models based on volume diffusion in solid limited mechanism are likely to significantly underestimate the rates at which major and trace elements in residual minerals reequilibrate with their surrounding melt. Electronic supplementary material  The online version of this article (doi:) contains supplementary material, which is available to authorized users.     

Si diffusion in zircon

Self-diffusion of Si under anhydrous conditions at 1 atm has been measured in natural zircon. The source of diffusant for experiments was a mixture of ZrO₂ and ³⁰Si-enriched SiO₂ in 1:1 molar proportions; experiments were run in crimped Pt capsules in 1-atm furnaces. ³⁰Si profiles were measured with both Rutherford backscattering spectrometry (RBS) and nuclear reaction analysis with the resonant nuclear reaction ³⁰Si(p,γ)³¹P. For Si diffusion normal to c over the temperature range 1,350–1,550°C, we obtain an Arrhenius relation D = 5.8 exp(−702 ± 54 kJ mol⁻¹/RT) m² s⁻¹ for the NRA measurements, which agrees within uncertainty with an Arrhenius relation determined from the RBS measurements [62 exp(−738 ± 61 kJ mol⁻¹/RT) m² s⁻¹]. Diffusion of Si parallel to c appears slightly faster, but agrees within experimental uncertainty at most temperatures with diffusivities for Si normal to c. Diffusion of Si in zircon is similar to that of Ti, but about an order of magnitude faster than diffusion of Hf and two orders of magnitude faster than diffusion of U and Th. Si diffusion is, however, many orders of magnitude slower than oxygen diffusion under both dry and hydrothermal conditions, with the difference increasing with decreasing temperature because of the larger activation energy for Si diffusion. If we consider Hf as a proxy for Zr, given its similar charge and size, we can rank the diffusivities of the major constituents in zircon as follows: D _Zr < D _Si << D _{O, dry} < D _{O, ‘wet’}.     

钱二块铀矿床采铀注液结垢趋势的理论分析与预测

用离子系数矩阵法对钱二块铀矿床地浸采铀试验注液中存在的独立离子反应进行了确定,由溶度积规则及反应平衡原理,借助Matlab编程,估算出了钱二块铀矿床地浸采铀试验注液可能会生成的沉淀物种类及数量,为防治结垢提供了一定的理论依据.     

海藻硫酸多糖911对小鼠脾淋巴细胞增殖反应及对细胞产生IL—2作用的影响

本文以~3H—TdR掺入法观察911对小鼠脾淋巴细胞增殖反应的影响并用CTLL细胞检测了其对IL—2的作用。体外实验结果表明,911对小鼠脾淋巴细胞增殖反应有明显的增强作用,以0.5μg/ml的浓度效果最为明显,相对增殖指数RPI可达200％;体内实验则以5mg/kg体重ip,连续7d效果最好,相对增殖指数RPI可达176％;911用药组小鼠IL—2的产生量均高于对照组,以5mg/kg和10mg/kg效果最好。以上实验证明,这一多糖是一种有希望的新免疫调节药物。     

尼罗罗非鱼对不同颜色定置网片的反应特性

本文初步研究了尼罗罗非鱼对红、黄、绿、蓝、青灰色定置网片反应特性,并探讨了该鱼对青灰色网片的适应特性。结果表明:绿色网片对罗非鱼的阻拦作用最大,青灰色网片次之,红、黄色网片再次,蓝色网片最小。罗非鱼对青灰色网片具明显的适应现象,它们完成整个适应过程所需的实验重复次数约为7次。     

地浸采铀浸出液氧化沉淀法除铁研究

在氧化沉淀法去除铁的过程中,氧化反应分别在自然曝气、充气和除钙的条件下进行,对照结果进行分析,得出最佳的除铁配方,同时还着重对氧化反应速率及其影响因素（pH,Eh等）进行了探索性研究,为以后试验提供了一定的依据。