Quantitative analysis of mass transfer during polymetamorphism in pelites of the Transangarian Yenisei Ridge

The study provides geological, structural, mineralogical, petrological, and geochronological evidence for polymetamorphic evolution of gneisses from the Garevka complex of the Yenisei Ridge. The results of the study provide significant insight into the geochemical behavior of major and trace elements in zoned garnet crystals and mineral inclusions formed during prograde and retrograde metamorphism of pelitic rocks. It was shown that the concentrations of Y and HREE in garnet decrease with increasing P and T and increase with decreasing pressure and temperature. The combined study of multicomponent chemical zoning patterns of coexisting minerals and metamorphic mineral reactions in metapelites was conducted. The results show that the main reason for a drastic increase in CaO content in garnets during collisional metamorphism is a mass exchange between garnet and plagioclase. The deviation from this trend, as indicated by the concurrent increase inthe grossular content of garnet and anorthite content of plagioclase, arises from the breakdown of epidote. The calculated metamorphic reactions, mass balance analysis, and changes in mineral chemistry during metamorphism reinforce the evidence for the isochemical character of processes with respect to most components of the system. The minimum volume of the system in which chemical exchange between reacting phases is balanced for all major and trace elements did not exceed ~ 1 mm³. The total HREE balance requires a greater reaction volume (up to ~ 8 mm ) involved in the redistribution of these elements, which provide evidence for their relatively higher mobility during metamorphism relative to other rare earth elements. The specific distribution and quite substantial mass transport of HREE are controlled by heterovalent isomorphic substitution between these elements and CaO in garnet.     

Trace element distribution in mineral inclusions in zoned garnets from eclogites of the Atbashi Range (South Tianshan)

Ion microprobe data for minerals from the eclogites of the Atbashi Range (South Tianshan) constrain the distribution of trace (Rb, Sr, Ba, Cr, V, Zr, Hf, Nb, Ta, U, Th, and Y) and rare-earth elements (REE) in zoned garnets and mineral inclusions in them. This study showed that garnets from the Atbashi eclogites are the main hosts for heavy REE; epidotes are important hosts for REE, Y, Sr, Th, and U; and omphacites are depleted in almost all trace elements compared with the bulk-rock compositions. Garnet, as well as epidote and omphacite inclusions exhibit systematic rimward depletion in a number of trace elements, which is related to the depletion of the rock matrix in these elements during crystallization. Deviations from this trend, including the enrichment of garnet rims in HREE and strong variations in the REE contents of garnets and mineral inclusions, can be explained by metamorphic reactions involving the destabilization of REE-bearing minerals. Our data suggest that the mobility of trace elements under eclogites-facies conditions is mainly controlled by the stability of certain minerals.     

Geochemistry of eclogites from the Dabie–Sulu terrane, eastern China: New insights into protoliths and trace element behaviour during UHP metamorphism

The major and trace element compositions of nine eclogites from the Dabie–Sulu ultrahigh pressure (UHP) metamorphic terrane in eastern China were determined for both whole rock and the main constituent minerals, garnet and clinopyroxene. The results indicate that the eclogite protoliths originated from a basaltic magma, which formed in a continental setting as shown by isotopic and immobile element data. Based on the garnet REE characteristics, the eclogites can be roughly divided into two groups. Group 1 has LREE enrichment with no Eu anomaly for whole rock, and smooth LREE depletion but HREE enrichment pattern for garnet, whereas group 2 shows a depletion of LREE with a pronounced positive Eu anomaly and flat HREE pattern for both whole rock and garnet. From these features, we suggest that the protoliths for group 2 are Fe–Ti–gabbros with relatively high cumulus plagioclase and Fe–Ti oxide, whereas the group 1 eclogites are probably from basalts. Therefore, the unusual garnet REE pattern observed in group 2 can be considered as an important signature for identifying gabbro protoliths for eclogites. The identification of gabbro protoliths from the eclogites in the Dabie–Sulu terrane provides evidence for Neoproterozoic rift magmatism in the northern margin of the Yangtze craton. During ultrahigh pressure metamorphism in the Dabie–Sulu terrane, LILEs (including Ba, Rb, Th, U, K) had high mobility, but REEs and HFSEs were immobile, and trace element distribution equilibrium was approached between garnet and clinopyroxene. An estimate of mass balance indicates that garnet and clinopyroxene host the majority of HREEs and Y, and clinopyroxene is a significant host for Sr, but minor and accessory minerals predominantly account for LREEs, Th, U, and Zr.     

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.     

Residence and redistribution of REE, Y, Zr, Th and U during granulite-facies metamorphism: behaviour of accessory and major phases in peraluminous granulites of central Spain

Accessory minerals are thought to play a key role in controlling the behaviour of certain trace elements such as REE, Y, Zr, Th and U during crustal melting processes under high-grade metamorphic conditions. Although this is probably the case at middle crustal levels, when a comparison is made with granulite-facies lower crustal levels, differences are seen in trace element behaviour between accessory minerals and some major phases. Such a comparison can be made in Central Spain where two granulite-facies terranes have equilibrated under slightly different metamorphic conditions and where lower crustal xenoliths are also found. Differences in texture and chemical composition between accessory phases found in leucosomes and leucogranites and those of melanosomes and protholiths indicate that most of the accessory minerals in melt-rich migmatites are newly crystallized. This implies that an important redistribution of trace elements occurs during the early stages of granulite-facies metamorphism. In addition, the textural position of the accessory minerals with respect to the major phases is crucial in the redistribution of trace elements when melting proceeds via biotite dehydration melting reactions. In granulitic xenoliths from lower crustal levels, the situation seems to be different, as major minerals show high concentration of certain trace elements, the distribution of which is thus controlled by reactions involving final consumption of Al-Ti-phlogopite. A marked redistribution of HREE–Y–Zr between garnet and xenotime (where present) and zircon, but also of LREE between feldspars (K-feldspar and plagioclase) and monazite, is suggested.     

华北地块东南缘中生代侵入杂岩中所含榴辉岩类包体矿物微量元素地球化学特征及其意义

华北地块东南缘中生代侵入杂岩中所含榴辉岩类包体中矿物的分析结果表明, 组成榴辉岩类包体的各矿物之间元素的分配在榴辉岩相变质阶段已经达到了化学平衡;石榴石中Al、Fe、Mn, 单斜辉石中Na、Mg、Ca, 角闪石中Na、Mg、Fe等主量元素含量与其全岩之间均呈良好的正相关, 受全岩成分制约;石榴石明显富集HREE、贫LREE, 单斜辉石相对富集LREE、MREE、贫HREE, 两者轻、重稀土含量呈相互消长的互补关系, 石榴石和单斜辉石中分别富集Y、Sr, Ga和过渡族元素Sc、Ti、V、Cr、Co等含量较高, 其含量受全岩成分控制;金红石中稀土元素的含量很少, Fe、Al、Mg、Ca、Mn、Nb、Ta、Cr和Zr含量相对较高, Rb、Sr、Ba含量极低, 部分微量元素(如Nb、Cr、Fe、V、W等)含量与其原岩有继承和对应关系;部分原生或/和退变角闪石的REE配分模式分别与单斜辉石和石榴石相似, 过渡族金属元素等的含量与石榴石、单斜辉石和全岩具有一定的相关性, 角闪石容纳Na、K、Sr、Rb、Ba等元素的能力较强, 其成分除受全岩成分的制约外, 石榴石、单斜辉石对其形成也有影响。榴辉岩类包体与其寄主中生代侵入杂岩中部分高价态/高场强元素(HFSE)和重稀土元素(HREE)呈相互消长的关系。榴辉岩的形成与扬子地块和华北地块之间的俯冲-碰撞作用有关。     

Population-wide garnet growth zoning revealed by LA-ICP-MS mapping: implications for trace element equilibration and syn-kinematic deformation during crystallisation

The strong partitioning of many trace elements into garnet and their slow diffusivities in both garnet and the rock matrix means that their distribution may record valuable petrogenetic information not documented by major elements in metamorphic rocks. Complex trace element growth zoning in garnet porphyroblasts from a garnet-grade metapelite from the Barrovian sequence of the Sikkim Himalaya is assessed using quantified LA-ICP-MS raster mapping coupled with X-ray micro-computed tomography. The data document systematic changes in the zoning patterns from early- to late-nucleated crystals, and also suggest that the REE+Y chemistry incorporated into garnet is dependent on persistent disequilibrium in the rock volume. There is evidence for HREE+Y diffusion haloes surrounding growing garnets and a heterogeneous HREE+Y distribution in the rock matrix. Annuli superimposed on oscillatory zoning are not consistent with formation during some rock-wide event, but are dependent on the spatial disposition of the garnet. Annuli are interpreted to reflect an integrated history of varying growth rates and the incorporation of pre-existing heterogeneities due to relatively slow matrix diffusivities. Conversely, smooth zoning of many transition metals indicate that their distribution in garnet may be controlled by equilibrium partitioning between garnet and the rock matrix. Significant rotation of garnet porphyroblasts during growth is revealed due to immobility of Cr over the duration of the crystallisation interval and overprinting of the heterogenous precursor Cr distribution. Strain rate estimates derived from this zoning are on the order of \(10^{-11}\)–\(10^{-12}\, \hbox {s}^{-1}\).     

喜马拉雅造山带新生代花岗岩中两类石榴石的地球化学特征及其在地壳深熔作用中的意义

在喜马拉雅碰撞造山带中,石榴石是变泥质岩的主要造岩矿物,也是花岗岩或淡色体的重要副矿物,保存了有关地壳深熔作用的关键信息,是揭示大型碰撞造山带中-下地壳物质的物理和化学行为的重要载体。在喜马拉雅造山带内,新生代花岗质岩石(淡色花岗岩和混合岩中的淡色体)含两类石榴石,大多数为岩浆型石榴石,自形-半自形,不含包裹体,但淡色体中含有港湾状的混合型石榴石。岩浆型石榴石具有以下地球化学特征:(1)从核部到边部,显示了典型的"振荡型"生长环带;(2)富集HREE,亏损LREE,从核部到边部,Hf、Y和HREE含量降低;(3)显著的Eu负异常;(4)相对于源岩中变质石榴石,Mn和Zn的含量显著增高。岩相学和地球化学特征都表明:变泥质岩熔融形成的熔体(淡色体)捕获了源岩的变质石榴石,熔体与石榴石反应导致大部分元素的特征被改变,只在核部保留了源岩的部分信息。同时,在花岗质熔体结晶过程中,形成少量的岩浆型石榴石。这些石榴石摄取了熔体中大量的Zn,浓度显著升高,在斜长石和锆石同步分离结晶作用的共同影响下,石榴石中Eu为明显负异常,Hf、Y和HREE浓度从核部到边部逐渐降低。上述数据和结果表明,花岗岩中石榴石的矿物化学特征记录了精细的有关花岗岩岩浆演化的重要信息。     

The trace element composition of silicate inclusions in diamonds: a review

On a global scale, peridotitic garnet inclusions in diamonds from the subcratonic lithosphere indicate an evolution from strongly sinusoidal REE_N, typical for harzburgitic garnets, to mildly sinusoidal or “normal” patterns (positive slope from LREE_N to MREE_N, fairly flat MREE_N–HREE_N), typical for lherzolitic garnets. Using the Cr-number of garnet as a proxy for the bulk rock major element composition it becomes apparent that strong LREE enrichment in garnet is restricted to highly depleted lithologies, whereas flat or positive LREE–MREE slopes are limited to less depleted rocks. For lherzolitic garnet inclusions, there is a positive relation between equilibration temperature, enrichment in MREE, HREE and other HFSE (Ti, Zr, Y), and decreasing depletion in major elements. For harzburgitic garnets, relations are not linear, but it appears that lherzolite style enrichment in MREE–HREE only occurs at temperatures above 1150–1200 °C, whereas strong enrichment in Sr is absent at these high temperatures. These observations suggest a transition from melt metasomatism (typical for the lherzolitic sources) characterized by fairly unfractionated trace and major element compositions to metasomatism by CHO fluids carrying primarily incompatible trace elements. Melt and fluid metasomatism are viewed as a compositional continuum, with residual CHO fluids resulting from primary silicate or carbonate melts in the course of fractional crystallization and equilibration with lithospheric host rocks.

Eclogitic garnet inclusions show “normal” REE_N patterns, with LREE at about 1× and HREE at about 30× chondritic abundance. Clinopyroxenes approximately mirror the garnet patterns, being enriched in LREE and having chondritic HREE abundances. Positive and negative Eu anomalies are observed for both garnet and clinopyroxene inclusions. Such anomalies are strong evidence for crustal precursors for the eclogitic diamond sources. The trace element composition of an “average eclogitic diamond source” based on garnet and clinopyroxene inclusions is consistent with derivation from former oceanic crust that lost about 10% of a partial melt in the garnet stability field and that subsequently experienced only minor reenrichment in the most incompatible trace elements. Based on individual diamonds, this simplistic picture becomes more complex, with evidence for both strong enrichment and depletion in LREE.

Trace element data for sublithospheric inclusions in diamonds are less abundant. REE in majoritic garnets indicate source compositions that range from being similar to lithospheric eclogitic sources to strongly LREE enriched. Lower mantle sources, assessed based on CaSi–perovskite as the principal host for REE, are not primitive in composition but show moderate to strong LREE enrichment. The bulk rock LREE_N–HREE_N slope cannot be determined from CaSi–perovskites alone, as garnet may be present in these shallow lower mantle sources and then would act as an important host for HREE. Positive and negative Eu anomalies are widespread in CaSi–perovskites and negative anomalies have also been observed for a majoritic garnet and a coexisting clinopyroxene inclusion. This suggests that sublithospheric diamond sources may be linked to old oceanic slabs, possibly because only former crustal rocks can provide the redox gradients necessary for diamond precipitation in an otherwise reduced sublithospheric mantle.     

西藏松多榴辉岩的矿物原位微量元素地球化学研究

对松多榴辉岩中单矿物进行的LA-ICP-MS原位微区微量元素分析研究结果表明,石榴石主要富集中、重稀土元素和Y,同时具有高丰度的Sc、V、Cr和Co等元素;绿辉石中的微量元素以中稀土元素、Sr、Sc、V、Cr、Co、Ni和Ti为主,含有一定量的Zr、Hf等。石榴石、绿辉石、角闪石和绿帘石中均显示轻稀土元素亏损的特点,表明在退变质过程中没有发生明显的富轻稀土元素的外来流体交代作用,因而其微量元素矿物地球化学的某些特点不同于苏鲁地区的榴辉岩。石榴石变斑晶中某些元素(如Ti、Zr)的分带性暗示了榴辉岩在紧随峰期变质之后的折返过程中发生了降压增温过程。榴辉岩主要变质矿物中微量元素的分配显然受到矿物主量元素的分配所控制,如MgO在石榴石和绿辉石之间的分配对Ni、Co、Ti分配的控制以及CaO的分配对Sr、Y、REE分配的控制等。退变质过程中矿物的形成或分解以及物理化学条件的改变都可以引起矿物间微量元素的重新分配。由绿辉石退变质而形成的角闪石,较之原先的绿辉石,其微量元素配分曲线总体特征会发生变化,但元素总体丰度相近,某些元素特点相似,又反映了绿辉石和角闪石之间的成生联系。金红石是Ti、Nb、Ta、Zr、Hf的主要赋存矿物,而与之共生的绿帘石所表现出来的高场强元素的亏损特征表明了金红石的存在所带来的影响。     

北秦岭松树沟榴辉岩的确定及其地质意义

松树沟石榴石角闪岩(榴闪岩)呈透镜状产于松树沟超镁铁岩旁侧的斜长角闪岩中,一直以来被认为是形成于接触交代变质或麻粒岩相变质过程。详细岩相学及矿物元素分析,在榴闪岩的基质矿物、石榴石幔部及锆石包体中发现残留的绿辉石,而且石榴石也保存了明显的进变质主、微量元素成分环带,表明松树沟榴闪岩为榴辉岩退变质的产物,至少经历了从角闪岩相到榴辉岩相再到角闪岩相的三阶段顺时针PT演化过程。锆石定年结果得到榴辉岩的变质年龄为500±8Ma,原岩结晶时代为796±16Ma,与秦岭岩群北侧官坡超高压榴辉岩的变质年龄和原岩年龄完全一致,也与北秦岭区域高压-超高压变质时代和原岩的结晶时代一致。表明松树沟榴辉岩与北秦岭造山带已发现的高压-超高压变质岩石一起都应是古生代大陆深俯冲作用的结果,而松树沟超镁铁岩可能是俯冲的大陆板片在折返过程中携带的俯冲隧道中的交代地幔岩。     

Prograde metamorphic sequence of REE minerals in pelitic rocks of the Central Alps: implications for allanite–monazite–xenotime phase relations from 250 to 610 °C

The distribution of REE minerals in metasedimentary rocks was investigated to gain insight into the stability of allanite, monazite and xenotime in metapelites. Samples were collected in the central Swiss Alps, along a well‐established metamorphic field gradient that record conditions from very low grade metamorphism (250 °C) to the lower amphibolite facies (～600 °C). In the Alpine metapelites investigated, mass balance calculations show that LREE are mainly transferred between monazite and allanite during the course of prograde metamorphism. At very low grade metamorphism, detrital monazite grains (mostly Variscan in age) have two distinct populations in terms of LREE and MREE compositions. Newly formed monazite crystallized during low‐grade metamorphism (<440 °C); these are enriched in La, but depleted in Th and Y, compared with inherited grains. Upon the appearance of chloritoid (～440–450 °C, thermometry based on chlorite–choritoid and carbonaceous material), monazite is consumed, and MREE and LREE are taken up preferentially in two distinct zones of allanite distinguishable by EMPA and X‐ray mapping. Prior to garnet growth, allanite acquires two growth zones of clinozoisite: a first one rich in HREE + Y and a second one containing low REE contents. Following garnet growth, close to the chloritoid–out zone boundary (～556–580 °C, based on phase equilibrium calculations), allanite and its rims are partially to totally replaced by monazite and xenotime, both associated with plagioclase (± biotite ± staurolite ± kyanite ± quartz). In these samples, epidote relics are located in the matrix or as inclusions in garnet, and these preserve their characteristic chemical and textural growth zoning, indicating that they did not experience re‐equilibration following their prograde formation. Hence, the partial breakdown of allanite to monazite offers the attractive possibility to obtain in situ ages, representing two distinct crystallization stages. In addition, the complex REE + Y and Th zoning pattern of allanite and monazite are essential monitors of crystallization conditions at relatively low metamorphic grade.     

REE concentrations of garnet and omphacite in eclogites from the Dabie Mountain, central China

Distributions of the rare-earth elements (REE) in omphacite and garnet and REE behaviors during metamorphic processes were discussed. The REE concentrations of garnet and omphacite in six eclogite samples from the Dabie Mountain, central China, were measured by inductively coupled plasma-mass spectrometry (ICP-MS). The correlation of δEu ratios between garnet and omphacite indicated that chemical equilibrium of REE distribution between garnet and omphacite could be achieved during ultra-high pressure (UHP) metamorphism. Most of the partition coefficients (Kd=CiOmp/CiGrt) of light rare-earth elements (LREE) are higher than 1. However the partition coefficients of heavy rare-earth elements (HREE) are lower than 1. This indicated that the LREE inclined to occupy site M2 in omphacite, but the HREEs tended to occupy eightfold coordinated site in garnet during the eclogite formation. The REE geochemistry of the eclogites indicated that LREE could be partially lost during the prograde metamorphic process of protolith, but be introduced into the rocks during the symplectite formation. LREE are more active than HREE during the UHP metamorphism. The results are favorable to highlighting the REE behavior and evolution of UHP metamorphic rocks.     

Redistribution of trace elements during prograde metamorphism from lawsonite blueschist to eclogite facies; implications for deep subduction-zone processes

The transfer of fluid and elements from subducting crust to the overlying mantle wedge is a fundamental process affecting arc magmatism and the chemical differentiation of the Earth. While the production of fluid by breakdown of hydrous minerals is well understood, the liberation of trace elements remains generally unconstrained. In this paper, we evaluate the behaviour of trace elements during prograde metamorphism and dehydration using samples of high-pressure, low-temperature metamorphic rocks from New Caledonia. Samples examined include mafic and pelitic rock-types that range in grade from lawsonite blueschist to eclogite facies, and represent typical lithologies of subducting crust. Under lawsonite blueschist facies conditions, the low temperatures of metamorphism inhibit equilibrium partitioning between metamorphic minerals and allow for the persistence of igneous and detrital minerals. Despite this, the most important hosts for trace-elements include lawsonite, (REE, Pb, Sr), titanite (REE, Nb, Ta), allanite (LREE, U, Th), phengite (LILE) and zircon (Zr, Hf). At epidote blueschist to eclogite facies conditions, trace-element equilibrium may be attained and epidote (REE, Sr, Th, U, Pb), garnet (HREE), rutile (Nb, Ta), phengite (LILE) and zircon (Zr, Hf) are the major trace-element hosts. Chlorite, albite, amphibole and omphacite contain very low concentrations of the investigated trace elements. The comparison of mineral trace-element data and bulk-rock data at different metamorphic grades indicates that trace elements are not liberated in significant quantities by prograde metamorphism up to eclogite facies. Combining our mineral trace-element data with established phase equilibria, we show that the trace elements considered are retained by newly-formed major and accessory minerals during mineral breakdown reactions to depths of up to 150 km. In contrast, significant volumes of fluid are released by dehydration reactions. Therefore, there is a decoupling of fluid release and trace element release in subducting slabs. We suggest that the flux of trace elements from the slab is not simply linked to mineral breakdown, but results from complex fluid-rock interactions and fluid-assisted partial melting in the slab.Electronic Supplementary Material Supplementary material is available in the online version of this article at http://dx.doi.org/10.1007/s00410-003-0495-5.Editorial responsibility: J. Hoefs     

沂水青龙峪超镁铁质岩石和基性麻粒岩的锆石SHRIMP U-Pb定年

本文主要对沂水青龙峪出露的超镁铁质岩石和基性麻粒岩进行了锆石SHRIMP U-Pb定年研究。超镁铁质岩石以捕掳体形式存在于沂水杂岩中,不发育鬣刺结构,氧化物组成具有超镁铁质科马提岩的高MgO、富CaO、低SiO2、TiO2、K2O和Na2O含量特征;矿物组合以单斜辉石+橄榄石±斜方辉石+铬铁矿为主;变质矿物以角闪石+蛇纹石化为特征;该岩石以稀土元素总含量(∑REE)低、LREE/HREE=3.35～4.40及Ce和Eu负异常为特征。微量元素组成以Ba、Nb、Zr负异常和Nd、Sm正异常为特征。根据锆石SHRIMP U-Pb定年法对该超镁铁质岩石中捕获的早期岩浆结晶锆石和新生的变质锆石进行的研究,年龄值分别为2657～2702Ma和2551～2585Ma,表明该超镁铁质岩石形成年龄为2585～2657Ma。基性麻粒岩的氧化物组成特征表明其属高Mg的洋岛拉斑玄武岩,麻粒岩相——高角闪岩相变质作用与新太古代的深熔和岩浆侵入作用有关,矿物组合以紫苏辉石+单斜辉石±角闪石+斜长石±石榴子石为特征;晚期蚀变作用与辉长岩墙、辉绿岩脉及石英闪长岩买的侵入有关,矿物组合以滑石化+绢云母化+绿泥石化为特征;稀土元素组成以轻重稀土元素无分异和无Eu异常为特征;微量元素组成以Nb、Zr、P、Ti负异常和Sr、K正异常为特征;锆石SHRIMP U-Pb定年结果表明麻粒岩相——角闪岩相变质作用年龄为2498.4±7.6Ma,导致麻粒岩相——角闪岩相变质的深熔和岩浆结晶年龄为2551±24Ma,晚期蚀变作用的年龄分别为2231～2235Ma和1850±19Ma。     

Diamond precipitation and mantle metasomatism – evidence from the trace element chemistry of silicate inclusions in diamonds from Akwatia, Ghana

Trace element concentrations in the four principal peridotitic silicate phases (garnet, olivine, orthopyroxene, clinopyroxene) included in diamonds from Akwatia (Birim Field, Ghana) were determined using SIMS. Incompatible trace elements are hosted in garnet and clinopyroxene except for Sr which is equally distributed between orthopyroxene and garnet in harzburgitic paragenesis diamonds. The separation between lherzolitic and harzburgitic inclusion parageneses, which is commonly made using compositional fields for garnets in a CaO versus Cr₂O₃ diagram, is also apparent from the Ti and Sr contents in both olivine and garnet. Titanium is much higher in the lherzolitic and Sr in the harzburgitic inclusions. Chondrite normalised REE patterns of lherzolitic garnets are enriched (10–20 times chondrite) in HREE (La_N/Yb_N = 0.02–0.06) while harzburgitic garnets have sinusoidal REE_N patterns, with the highest concentrations for Ce and Nd (2–8 times chondritic) and a minimum at Ho (0.2–0.7 times chondritic). Clinopyroxene inclusions show negative slopes with La enrichment 10–100 times chondritic and low Lu (0.1–1 times chondritic). Both a lherzolitic and a harzburgitic garnet with very high knorringite contents (14 and 21 wt% Cr₂O₃ respectively) could be readily distinguished from other garnets of their parageneses by much higher levels of LREE enrichment. The REE patterns for calculated melt compositions from lherzolitic garnet inclusions fall into the compositional field for kimberlitic-lamproitic and carbonatitic melts. Much more strongly fractionated REE patterns calculated from harzburgitic garnets, and low concentrations in Ti, Y, Zr, and Hf, differ significantly from known alkaline and carbonatitic melts and require a different agent. Equilibration temperatures for harzburgitic inclusions are generally below the C-H-O solidus of their paragenesis, those of lherzolitic inclusions are above. Crystallisation of harzburgitic diamonds from CO₂-bearing melts or fluids may thus be excluded. Diamond inclusion chemistry and mineralogy also is inconsistent with known examples of metasomatism by H₂O-rich melts. We therefore favour diamond precipitation by oxidation of CH₄-rich fluids with highly fractionated trace element patterns which are possibly due to “chromatographic” fractionation processes. Received: 27 January 1996 / Accepted: 5 May 1997     

Geochemical constraints of the eclogite and granulite facies metamorphism as recognized in the Raobazhai complex from North Dabie Shan,China

A combined study of major and trace elements, fluid inclusions and oxygen isotopes has been carried out on garnet pyroxenite from the Raobazhai complex in the North Dabie Terrane (NDT). Well‐preserved compositional zoning with Na decreasing and Ca and Mg increasing from the core to rim of pyroxene in the garnet pyroxenite indicates eclogite facies metamorphism at the peak metamorphic stage and subsequent granulite facies metamorphism during uplift. A P–T path with substantial heating (from c. 750 to 900 °C) after the maximum pressure reveals a different uplift history compared with most other eclogites in the South Dabie Terrane (SDT). Fluid inclusion data can be correlated with the metamorphic grade: the fluid regime during the peak metamorphism (eclogite facies) was dominated by N₂‐bearing NaCl‐rich solutions, whereas it changed into CO₂‐dominated fluids during the granulite facies retrograde metamorphism. At a late retrograde metamorphic stage, probably after amphibolite facies metamorphism, some external low‐salinity fluids were involved. In situ UV‐laser oxygen isotope analysis was undertaken on a 7 mm garnet, and impure pyroxene, amphibole and plagioclase. The nearly homogeneous oxygen isotopic composition (δ¹⁸O_VSMOW = c. 6.7‰) in the garnet porphyroblast indicates closed fluid system conditions during garnet growth. However, isotopic fractionations between retrograde phases (amphibole and plagioclase) and garnet show an oxygen isotopic disequilibrium, indicating retrograde fluid–rock interactions. Unusual MORB‐like rare earth element (REE) patterns for whole rock of the garnet pyroxenite contrast with most ultra‐high‐pressure (UHP) eclogites in the Dabie‐Sulu area. However, the age‐corrected initial ε_Nd(t) is ? 2.9, which indicates that the protolith of the garnet pyroxenite was derived from an enriched mantle rather than from a MORB source. Combined with the present data of oxygen isotopic compositions and the characteristic N₂ content in the fluid inclusions, we suggest that the protolith of the garnet pyroxenite from Raobazhai formed in an enriched mantle fragment, which has been exposed to the surface prior to the Triassic metamorphism.     

北秦岭造山带西段早古生代榴辉岩相变质岩石的发现及其地质意义SCIEI北大核心CSCD

西秦岭地处中国中央造山系东西转换衔接部位,随着东秦岭以及祁连、柴北缘和东昆仑早古生代高压-超高压变质岩石的陆续发现和深入研究,西秦岭造山带变质作用研究吸引了大家的普遍关注。本文在大范围野外地质调查基础上,在北秦岭造山带西段天水南部的秦岭岩群长英质片麻岩中发现了一套石榴子石斜长角闪岩(榴闪岩),并开展了详细的锆石形貌和内部结构、微区微量元素和U-Th-Pb同位素研究。CL图像显示榴闪岩锆石普遍具有核-幔-边或核-边结构,部分存在原岩残留锆石。定年结果得到榴闪岩原岩残留锆石年龄为710±52Ma,同时得到497±3Ma、452±3Ma和423±7Ma三期变质年龄。其中497±3Ma变质年龄来自锆石核部并显示出轻稀土亏损、重稀土平坦且没有明显负Eu异常的稀土配分曲线特征,表明该时期的矿物组合中有石榴子石但没有斜长石,与榴辉岩相变质锆石特征一致;452±3Ma变质年龄来自锆石幔部或边部,对应测点重稀土元素的分异加大,并出现弱的负Eu异常,说明此时石榴子石被消耗且出现少量斜长石;423±7Ma变质年龄来自锆石的最边部,对应稀土配分曲线表现出更明显的负Eu异常和更大的重稀土元素分异特征,指示此时岩石中石榴子石含量更少,斜长石含量更多。上述结果表明该榴闪岩可能经历了~500Ma的榴辉岩相变质作用,并在~450Ma和~420Ma叠加了两期退变质改造。天水地区榴闪岩无论是其野外产状,还是变质锆石的形貌和内部结构、稀土配分曲线特征及其所记录的原岩和三期变质年龄都与北秦岭造山带东段大陆俯冲型高压-超高压变质榴辉岩近乎一致,指示早古生代时期,北秦岭造山带西段与东段经历了相似的大陆(深)俯冲和折返过程,它们共同构成一条统一的早古生代高压-超高压变质岩带。     

Trace element zoning in garnet from the Kwoiek Area,British Columbia: disequilibrium partitioning during garnet growth?

Trace element zoning in garnets from two contact-metamorphosed rocks from the Kwoiek area, British Columbia (Hollister 1969a), was measured with an ion microprobe. Zoning profiles have three distinct parts with chemical breaks defined by co-variation of major and trace elements. Important features of the trace element zoning profiles are: (1) roughly bell-shaped zoning profiles for Y and the HREEs, (2) an abrupt increase in Ti at a point midway through each garnet with inflections in the zoning profiles of other elements (Li, Na, Cr, V, Y, Zr, and the HREE), and (3) irregular Cr and V profiles. Unlike Mn zoning, the zoning profiles of most other trace elements cannot be easily modeled using simple Rayleigh fractionation models. Ti activity in the two samples is buffered by phase relations with ilmenite. Garnets from a continuously heated contact metamorphic environment should display continuous Ti zoning profiles if equilibrium was maintained and provided the Ti buffering assemblage did not change during garnet growth. The irregular Ti profiles suggest disequilibrium behavior. Several elements (Cr, V) may indicate breakdown of a phase enriched in trace elements during metamorphism. The source for the mass excess of these elements is probably the refractory cores of ilmenite grains. Either differing matrix transport rates of trace lements or interface kinetic controlled segregation could explain the unusual trace element behavior at the element inflection point. The preferred explanation involves segregation of elements at the interface of the garnet that were trapped during episodes of rapid garnet growth.     

The Rare Earth Elements and Uranium in Garnets from the Beinn an Dubhaich Aureole, Skye, Scotland, UK: Constraints on Processes in a Dynamic Hydrothermal System

Garnets from skarns in the Beinn an Dubhaich granite aureole,Isle of Skye, Scotland, have a large range of concentrationsof uranium (0·2–358 ppm) and the rare earth elements(REE) (23–4724 ppm). Variations in these concentrationscorrelate with major element zonation within the garnets, andwith changes in the shape of REE patterns. Typical patternsin most garnets display light REE (LREE) enrichment, flat heavyREE (HREE) distribution and a negative Eu anomaly. These patternsare interpreted to represent equilibrium trace element exchangebetween pre-existing pyroxene, hydrothermal fluid and calcicgarnets. Iron-rich zones are characterized by positive Eu anomaliesand an increase in the abundance of the LREE relative to theHREE. These patterns are interpreted as resulting from changesin REE speciation related to the introduction of externallybuffered fluid to the skarn system. Relatively Fe-poor zonesshow strongly HREE-enriched patterns with negative Eu anomaliesand in some instances depletions in Y relative to Ho and Dy,which are interpreted as resulting from surface sorption ofthe REE during rapid, disequilibrium garnet growth. Strong correlationsbetween U abundance and the REE patterns indicate that the sameprocesses have affected U distribution. Both types of patterncan be modified by the effects of closed-system crystallizationon REE abundance in the fluid, and changes in fluid major elementchemistry. KEY WORDS: fractionation; garnet; hydrothermal; rare earth elements; skarn