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。     

CCSD主孔揭示的东海超高压榴辉岩中的金红石：微量元素地球化学及其成矿意义

金红石是榴辉岩中的主要含钛副矿物。中国大陆科学钻探工程主孔100-2000m岩心样品中,金红石榴辉岩、多硅白云母榴辉岩和蓝晶石榴辉岩中都程度不等地含有金红石。金红石既可以与其它矿物一起包裹在主要变质矿物中,也可以呈粒间矿物,但在榴辉岩经受角闪岩相退变质作用过程中,金红石亦会退变为榍石。本文利用电子探针除了分析了金红石的主要元素外,还仔细测量了Nb、Cr、Zr含量。结果显示,Nb平均含量为147ppm,最高含量为670ppm,Cr的平均含量为614ppm,最高含量为3630ppm,低Nb特征(<1000ppm)显示榴辉岩原岩为镁铁质岩石;此外,三类榴辉岩也具有不同的金红石Nb、Cr地球化学特征,即金红石榴辉岩中的金红石表现为低Cr(<500ppm)、Nb变化大(0-670ppm)的特征,多硅白云母榴辉岩中的金红石以中等Cr含量(500-1200ppm)、Nb变化较大(0-480ppm)为特征,而蓝晶石榴辉岩中的金红石显著富Cr(2000-3630ppm),而Nb则非常贫乏(<140ppm)。在总共289个金红石Zr含量数据中,大部分Zr含量分布在150-240ppm之间,均值约为200ppm;利用Zacketal.(2004)提出的金红石温度计,计算得到金红石的形成温度介于690℃和7870℃之间。研究结果表明,金红石的微量元素分析是研究榴辉岩原岩特征及其钛成矿作用的实用方法之一。     

榴辉岩中金红石的矿物地球化学研究及其意义

金红石的微量元素分析在俯冲带地质作用示踪、榴辉岩原岩判别以及形成温度估算等的研究中具有重要指示作用,其U-Pb同位素和Hf同位素分析则对于确定高级变质岩的冷却时代以及探讨物质来源和壳幔作用过程具有重要意义.初步研究显示,苏鲁超高压变质地体及大陆科学钻探岩心中不同产状、不同类型的榴辉岩中的金红石具有不同的微量元素特征,对榴辉岩原岩及金红石形成温度具有很好的指示作用;3个金红石样品的Pb同位素组成在逐步淋溶分析的某个中间阶段和最后阶段均出现有相似规律的2次突变,其余阶段则相对平稳,有可能反映了金红石在其生长过程中构造环境背景的变化.进一步对金红石进行详细系统的矿物地球化学分析,有望在苏鲁地体大陆深俯冲-折返过程的地球动力学及榴辉岩型金红石矿床的研究中获得一些新的认识.     

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。     

大别山超高压榴辉岩中金红石的微量结构水

对6个大别山超高压榴辉岩中的粒间金红石进行了显微傅立叶变换红外光谱(Micro-FTIR)观察和电子探针(EMP)分析。结果显示所有金红石颗粒都在3280cm-1和3295cm-1出现强的吸收峰,少数颗粒在约3360cm-1出现较弱且宽的峰,这3组峰都是由金红石中的结构OH引起的。与高温高压合成实验结果比较发现,3280cm-1峰主要是由Ti3 H Ti4 取代引起的,3295cm-1峰可能是由Fe3 H Ti4 造成的,而约3360cm-1的峰与Mg2 取代Ti4 的电荷补偿有关。由目前认为较可靠的两个金红石红外吸收系数获得结构水的含量(质量分数)分别为:161×10-6~854×10-6和202×10-6~1075×10-6,不同的IR吸收系数导致计算的水含量相差4~5倍,因此,前人所得到的金红石高水含量可能需要重新评估。与共存的石榴石和绿辉石相似,不同样品间的金红石水含量也表现出不均一分布,指示着超高压过程中有限的流体活动和快速的板块俯冲-折返过程。     

大别—苏鲁超高压榴辉岩中富Si金红石的地球化学意义

本文对大别—苏鲁造山带的超高压榴辉岩中的富Si金红石进行了地球化学研究。通过对双河、东海等地区的金红石进行详细的岩相学以及激光剥蚀电感耦合等离子体质谱(LA-ICP-MS)微量元素分析,结果显示不同地区、不同赋存状态(粒间颗粒和包裹体)的金红石均含有高达400×10~(-6)以上的Si。金红石中富含Si的现象普遍存在于大别—苏鲁不同地区的超高压变质岩中。纳米离子探针(NanoSIMS)面扫描分析显示,金红石中的Si均匀分布于金红石颗粒内部而非包裹体。这与前人报道的金红石中富含Si可能是硅酸盐包裹体所致这一结论不一致。据此,推测金红石中一定量的Si可能是以6次配位的形式存在,替代Ti的位置。这种类质同象置换通常在地壳范围的温、压条件下是不可能完成的,而陆壳物质深俯冲产生的高温、高压环境是Si进于金红石晶格的有利条件。因此,富Si金红石可能发展成为一种新的示踪超高压变质作用矿物学标准。同时,这一研究对揭示地球深部Si的赋存形态和指示陆壳物质俯冲深度具有重要的意义。     

柴北缘鱼卡榴辉岩型金红石矿床金红石矿物学、元素地球化学及成因

鱼卡金红石矿床是青海省境内发现的第一个超大型榴辉岩型金红石矿床。笔者在总结前人基础资料及详细野外地质矿产调查的基础上,通过榴辉岩岩石学及金红石矿物学研究,利用LA-ICP-MS法对该矿床中的金红石进行原位微量元素分析等。结果表明:金红石赋存状态主要有五种,即包裹结构、粒间结构、串珠状结构、退变残余结构、丝缕状出溶结构,其中以粒间和串珠状赋存状态产出时,含矿性最好。同时,变质阶段的差异、流体活动的强弱将影响金红石的赋存状态。流体活动越弱时,野外表现为榴辉岩的新鲜程度越高、且少或不发育长英质脉体、矿物越自形,则越有利于形成粒间和串珠状金红石富矿;折返过程中流体或熔体作用过强、野外表现为广泛发育长英质脉体、榴辉岩中矿物呈他形产出时,则金红石已经退变为钛铁矿和榍石。总结前人的地球化学和年龄数据表明:富集地幔源区、演化程度高、陆壳混染程度低的富钛基性原岩是鱼卡榴辉岩型金红石矿床主要物质来源,高压(超高压)变质作用促进了钛的进一步富集成矿,成矿年代集中在440～430Ma。金红石锆温度计显示的成矿温度主要在570～671℃之间,金红石中高场强元素Ti、Nb、Ta、Zr、Hf等富集,表明其可能形成于俯冲带环境。这些成因认识等将为柴北缘成矿带榴辉岩型金红石矿床的进一步找矿工作部署、勘查评价及突破提供了重要的理论支撑与借鉴。     

大别—苏鲁超高压榴辉岩中高钛石榴子石的成分特征及其与金红石包裹体的成因联系

石榴子石是榴辉岩中的基本造岩矿物。本文对苏鲁地体中的毛北榴辉岩和大别地体中的双河榴辉岩中的石榴子石进行了研究。结果显示,石榴子石都表现出中心“富”钛特征,即石榴子石颗粒的中心部位的TiO₂含量（0.10%~0.50%）明显高于正常榴辉岩中石榴子石的钛含量(TiO₂ 一般<0.1%)。另外,在石榴子石中心部位含有大量金红石及其它钛矿物包裹体,其定向分布特征揭示其出溶成因模式。计算结果显示,出溶金红石的原始石榴子石大约含1.7% TiO₂,揭示其超深源特征。此外,在石榴子石中发现了一颗TiO₂含量达8%~9%的钙铝榴石,具超深源成因特征。因此,本文认为超钛钙铝榴石也是超高压变质作用的标志矿物。     

苏鲁榴辉岩型金红石矿床研究进展

文章对苏鲁榴辉岩型金红石矿床的研究进展进行了简单综述。苏鲁超高压变质带金红石矿床的勘探可追溯到20世纪50年代末，近年来找矿工作取得重要进展，已查明金红石矿床总储量达数千万吨。矿床属典型的榴辉岩型金红石矿床，与超高压变质作用关系密切。金红石在榴辉岩中最主要也最具工业价值的赋存方式是呈粒间颗粒充填于主矿物绿辉石和石榴石之间，金红石中的微量元素与其寄主榴辉岩的类型和产状有明显的相关性，并且可反映其形成温度，因此在苏鲁超高压变质榴辉岩和金红石矿床的研究中具有重要价值。富钛基性原岩是榴辉岩型金红石矿床形成的物质基础，高压区域变质作用是这类矿床形成的必要条件。     

Rutile to Titanite Transformation in Eclogites and its Geochemical Consequences: An Example from the Sumdo Eclogite, Tibet

The formation of titanite coronae after rutile is common in retrograde high-to ultrahigh-pressure meta-mafic rocks, which provides a good opportunity to address the geochemical behavior of HFSE in crustal environments. In the Sumdo eclogite, titanite occurs either as a corona around rutile grains or as semi-continuous veins cross-cutting the major foliation, whereas rutile grains occur either as inclusions in garnet or omphacite or as a relict core surrounded by titanite. Textural relationships ...     

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.     

大别-苏鲁超高压变质带榴辉岩部分熔融的证据——微量元素和铅同位素

俯冲玄武质洋壳的部分熔融作用是一种重要的大陆生长作用，但是陆壳物质在俯冲过程中能否发生部分熔融缺少直接的证据。笔者利用已有的微量元素分配系数，讨论了岛弧玄武岩在脱水和部分熔融2种过程中微量元素行为和铅同位素演化的差异。Pb在2种过程中都属于不相容元素，但在脱水过程中其不相容性明显高于Rb、Ba、Th、U，而在熔融过程中则低于上述元素，在ω(Rb)/ω(Pb)-ω(Rb)、ω（Ba)/ω(Pb)-ω(Ba)、ω（Th)/ω(Pb)-ω(Th)、ω（U）／ω(Pb)-ω(U)相关图上2种过程的演化方向差别明显。此外，Pb和Th、U的相容性的差异也使得石榴石和绿辉石的单矿物铅同位素在2种过程中明显不同。在此基础上，结合大别－苏鲁榴辉岩的实测数据，认为大别－苏鲁榴辉岩可能部分是岛弧玄武岩部分熔融后的残余体，部分为单纯脱水的产物。大陆玄武质岩石在俯冲过程中也可能发生部分熔融作用。     

大别山榴辉岩氢氧同位素组成及其地球动力学意义

碧溪岭榴辉岩石至少经历了５个阶段的变质作用，矿物对氧同位素地质测温结果与通过岩石学方法计算的温度吻合得非常好，表明碧溪岭榴辉岩体中大部分同位素体系接近或达到平衡，且退变质作用未明显破坏这种平衡，榴辉岩全岩δ＾１８Ｏ为３‰～５‰指示其母岩玄武岩曾与地表水在变质作用之前发生过一定程度的交换作用。     

太古宙TTG的Nb/Ta变化特征: 对“Nb-Ta悖论”的启示

英云闪长岩-奥长花岗岩-花岗闪长岩（TTG）是地球早期大陆地壳最重要的组成部分。TTG的Nb/Ta比值变化不仅与它的成因相关,而且与早期构造环境和地壳分异过程关系紧密。本文选择阴山地块出露的TTG片麻岩及下地壳斜长角闪岩/麻粒岩包体作为研究对象,开展了寄主花岗闪长岩和同源镁铁质包体中的角闪石和黑云母的原位微区矿物的微量元素分析工作,以及TTG与非同源斜长角闪岩包体的全岩主微量元素分析工作。矿物化学研究结果表明,花岗闪长岩和同源镁铁质包体的角闪石具有相似的Mg^#值,但是两者具有明显不同的Nb/Ta比值。镁铁质包体中的角闪石更富Cr、Ta,Nb/Ta比值为30~50;TTG岩石中的角闪石Cr和Ta含量偏低,但具有更高的Nb/Ta比值（38~70）。TTG和镁铁质包体中的角闪石Cr含量与Nb/Ta具有较好的负相关关系。全岩地球化学分析结果揭示,TTG片麻岩的具有高Nb/Ta比值（13~65,平均值31）,斜长角闪岩和麻粒岩包体具有变化的Nb/Ta比值（10~56）。太古宙绿岩带中玄武质岩石的Nb/Ta平均值为~15,阴山地块斜长角闪岩和麻粒岩包体具有高的Nb/Ta比值,反映了这些代表基性下地壳的岩石经历了部分熔融作用或后期的交代作用,使其Nb/Ta比值发生改变。研究区具有高Nb/Ta比值的TTG可能来源于高Nb/Ta比值基性下地壳部分熔融,并继承了源区高Nb/Ta比值的特征。通过本文研究揭示,高Nb/Ta比值的TTG并非一定形成于俯冲带洋壳榴辉岩相部分熔融,下地壳富角闪石和黑云母的岩石部分熔融是形成高Nb/Ta比值TTG的一种重要途径。

     

SiO2 Solubility in Rutile at High Temperature and High Pressure

Silicon-bearing rutile has been found in chromitite from the Luobusa (罗布莎) ophiolite, Tibet. However, the extent of SiO2 solubility in rutile and the nature of its origin are still unclear. At high pressure, SiO2 takes a rutile structure with Si in 6-fold coordination. Thus, high pressures may enhance its solubility in rutile because of possible isovalent exchange in the oetabedral site. In this study, we report new experimental results on SiO2 solubility in rutile up to 23 GPa and 2 000 ℃. Starting materials were mixtures of powdered pure rutile and pure quartz, with compositions of (Ti0.5Si0.5)O2,(Ti0.93Si0.07)O2, and (Ti0.75Si0.25)O2. The mixtures were loaded into either platinum capsules (for a 10/5 assembly) or rhenium capsules (for an 8/3 assembly). The experiments were carried out using multi-anvil high-pressure apparatus with a rhenium resistance heater. Sample temperatures were measured with a W5%Re-W26%Re thermoeouple and were controlled within ±1 ℃ of the set temperature. TiO2-rich and SiO2-rich phases were produced in all the quenched samples. Microprobe analyses of the phases show that the solubility of SiO2 in rutile increases with increasing pressure, from 1.5 wt.% SiO2 at 10 GPa to 3.8 wt.% SiO2 at 23 GPa at a temperature of 1 800 ℃. The solubility also increases with increasing temperature from 0.5 wt.% SiO2 at 1 500 ℃ to 4.5 wt.% SiO2 at 2 000 ℃ at a pressure of 18 GPa. On the other hand, the solubility of TiO2 in coesite or stishovite is very limited, with an average of 0.6 wt.% TiO2 over the experimental P-T ranges. Temperature has a much larger effect on the solubility of SiO2 in rutile than pressure. At high pressure, the melting point of SiO2 is defmitely higher than that of TiO2 and the eutectic point moves towards SiO2 in the TiO2-SiO2 system. Lower oxygen fugacity decreases the solubility of SiO2 in rutile, whereas water has little effect on the solubility. Our experimental data are extremely useful for determining the depth of origin of the SiO2-bearing ruffle found in nature.     

华北地区中生代玄武岩高Nb/Ta值对地壳岩石再循环的直接记录

为揭示中国东部中生代大规模岩石圈减薄作用的深部地幔地球化学响应,对华北东部5个地区的中生代玄武岩进行了ICP-MS分析。结果表明,119~125 Ma玄武岩不仅具显著分异的稀土元素组成(La/Yb=35~60)、岛弧玄武岩型微量元素分布特征,且具高Ni(210×10-6~510×10-6)和Cr(510×10-6~1400×10-6)含量、高Mg#(71~78),以及系统高于球粒陨石的Nb/Ta值[19.9±1.0(1σ),n=16];而100 Ma碱锅玄武岩具有与球粒陨石(17.6)接近的Nb/Ta值[17.3±0.2(1σ)]。再循环地壳岩石在金红石稳定域内以榴辉岩为残余的部分熔融体 地幔橄榄岩反应,不仅使地幔岩石熔点降低、获得高Nb/Ta值及石榴子石特征,而且橄榄石向辉石的转变反应使Ni和Cr在交代地幔中的总分配系数显著降低。受熔体交代地幔橄榄岩的部分熔融可合理解释119~125 Ma玄武岩的上述地球化学特征,玄武岩Nb/Ta值应是对岩石圈减薄过程中地壳物质返回地幔后熔融产生硅质熔(流)体对上覆地幔交代的直接地球化学记录。     

Origins of Xenolithic Eclogites and Pyroxenites from the Central Slave Craton, Canada

Major- and trace-element and Sr–Nd–Hf isotopic compositionsof garnet and clinopyroxene in kimberlite-borne eclogite andpyroxenite xenoliths were used to establish their origins andevolution in the subcontinental lithospheric mantle beneaththe central Slave Craton, Canada. The majority of eclogitescan be assigned to three groups (high-Mg, high-Ca or low-Mgeclogites) that have distinct trace-element patterns. Althoughpost-formation metasomatism involving high field strength element(HFSE) and light rare earth element (LREE) addition has partiallyobscured the primary compositional features of the high-Mg andhigh-Ca eclogites, trace-element features, such as unfractionatedmiddle REE (MREE) to heavy REE (HREE) patterns suggestive ofgarnet-free residues and low Zr/Sm consistent with plagioclaseaccumulation, could indicate a subduction origin from a broadlygabbroic protolith. In this scenario, the low REE and smallpositive Eu anomalies of the high-Mg eclogites suggest moreprimitive, plagioclase-rich protoliths, whereas the high-Caeclogites are proposed to have more evolved protoliths withhigher (normative) clinopyroxene/plagioclase ratios plus trappedmelt, consistent with their lower Mg-numbers, higher REE andabsence of Eu anomalies. In contrast, the subchondritic Zr/Hfand positive slope in the HREE of the low-Mg eclogites are similarto Archaean second-stage melts and point to a previously depletedsource for their precursors. Low ratios of fluid-mobile to lessfluid-mobile elements and of LREE to HREE are consistent withdehydration and partial melt loss for some eclogites. The trace-elementcharacteristics of the different eclogite types translate intolower _Nd for high-Mg eclogites than for low-Mg eclogites. Withinthe low-Mg group, samples that show evidence for metasomaticenrichment in LREE and HFSE have lower _Nd and _Hf than a samplethat was apparently not enriched, pointing to long-term evolutionat their respective parent–daughter ratios. Garnet andclinopyroxene in pyroxenites show different major-element relationshipsfrom those in eclogites, such as an opposite CaO–Na₂Otrend and the presence of a CaO–Cr₂O₃ trend, independentof whether or not opx is part of the assemblage. Therefore,these two rock types are probably not related by fractionationprocesses. The presence of opx in about half of the samplesprecludes direct crystallization from eclogite-derived melts.They probably formed from hybridized melts that reacted withthe peridotitic mantle. KEY WORDS: eclogites; pyroxenite xenoliths; mantle xenoliths; eclogite trace elements; eclogite Sr isotopes; eclogite Hf isotopes; eclogite Nd isotopes     

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

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