中国大陆科学钻探主孔高钛与低钛榴辉岩地球化学特征对比及其对金红石成矿的指示意义

榴辉岩型金红石矿床是我国原生金红石矿床的最重要类型。本文以中国大陆科学钻探主孔0～2000m范围内揭露的榴辉岩为对象，通过对榴辉岩中TiO2与其它元素协变关系的全面分析，同时结合我国原生榴辉岩型金红石矿床TiO2的平均品位，将榴辉岩区分为高钛榴辉岩（TiO2〉2％）和低钛榴辉岩（TiO2〈2％），并据此系统对比了二类榴辉岩地球化学组成的差异。研究结果表明，高钛榴辉岩相对贫硅、贫钾、富铁，Al2O3／TiO2比值和全碱（K2O＋Na2O）含量总体偏低，Cs、Rb、Ba等大离子亲石元素和Zr、Hf等高场强元素不同程度亏损，而放射性元素Th、U则相对富集，并总体具有较低的轻重稀土比值。榴辉岩型金红石矿床的形成主要受原岩因素制约，原岩的源区组成、产出环境、起源深度、部分熔融程度和随后的结晶分异过程对Ti的初始富集均具重要影响，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。     

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。     

Geochemistry of cassiterite and wolframite from tin and tungsten quartz veins in Portugal

Cassiterite and wolframite compositions from Sn > W- and W > Sn-bearing quartz veins in Northern and Central Portugal are compared to provide evidence on fluid compositions. In Sn > W-bearing quartz veins, euhedral cassiterite shows sequences of alternating parallel darker and lighter zones. The darker zones are pleochroic, oscillatory zoned, exhibit exsolutions of columbite and ixiolite and are richer in Nb, Ta and Fe than the lighter zones which consist of nearly pure SnO₂. Cassiterite from W > Sn-bearing quartz veins is usually zoned, with homogeneous and slightly pleochroic darker zones, which are chemically similar to lighter zones. Both zones have inclusions of rutile and rare ilmenite. The darker zones of cassiterite from the former veins are richer in Nb, Ta and Fe contents and poorer in Ti than the darker and lighter zones of cassiterite from the latter veins. This is attributed to differences in the composition of magmatic hydrothermal fluids.Wolframite compositions from Sn > W- and W > Sn-bearing quartz veins do not show any significant distinction, because they precipitate from relatively similar magmatic hydrothermal fluids. In some deposits, most wolframite crystals are homogeneous, but others are heterogeneous. Inner patches, rich in a hübnerite component, rarely occur in crystals from the Filharoso and Panasqueira deposits. Zoned crystals, showing an increase in Fe and a decrease in Mn from core to rim, were found in the Vale das Gatas deposit. Complex oscillatory zoned crystals occur. In the Carris deposit, later wolframite contains inclusions of scheelite, partially replaces it and is richer in Fe and poorer in Mn than earlier wolframite. Wolframite from Sn > W-bearing quartz veins in the Argozelo deposit and W > Sn-bearing quartz veins from Vale das Gatas and Panasqueira deposits has significant Nb content. This does not depend on the Fe and Mn content of the wolframite, but W content is negatively correlated with Nb content. Only very rare single crystals of wolframite show an increase in W and a decrease in Nb from core to rim. Sn > W-bearing quartz veins contain wolframite poorer in Nb than the darker zones of cassiterite, which exsolved columbite and ixiolite. In W > Sn-bearing quartz veins from Panasqueira and Vale das Gatas, the wolframite has a higher Nb content than the cassiterite, which contains rutile inclusions enriched in Nb, because cassiterite and wolframite are derived from two distinct magmatic hydrothermal fluids of different age. The fluid responsible for wolframite precipitation will have a similar composition to that resulting from the evolution of the fluid responsible for cassiterite precipitation in the Sn > W-bearing quartz veins.     

High Pressure Response of Rutile Polymorphs and Its Significance for Indicating the Subduction Depth of Continental Crust

α-PbO2-type TiO2 （TiO2-Ⅱ） is an important index mineral for ultrahigh-pressure metamorphism. After the discovery of a natural high-pressure phase of titanium oxide with α-PbO2- structure in omphacite from coesite-bearing eclogite at Shima in the Dabie Mountains, China, a nanoscale （〈2 nm） α-PbO2-type TiO2 has been identified through electron diffraction and high-resolution transmission electron microscopy in coesite-bearing jadeite quartzite at Shuanghe in the Dabie Mountains. The crystal structure is orthorhombic with lattice parameters a = 4.58×10-1 nm, b = 5.42×10-1 nm, c = 4.96×10-1 nm and space group Pbcn. The analysis results reveal that ruffle {011}R twin interface is a basic structural unit of α-PbO2-type TiO2. Nucleation of α-PbO2-type TiO2 lamellae is caused by the displacement of one half of the titanium cations within the {011}R twin slab. This displacement reduces the Ti-O-Ti distance and is favored by high pressure. The identification of α- PbO2-type TiO2 in coesite-bearing jadeite quartzite from Shuanghe, Dabie Mountains, provides a new and powerful evidence of ultrahigh-pressure metamorphism at 4--7 GPa, 850℃-900℃, and implies a burial of continental crustal rocks to 130-200 kilometers depth or deeper. The α-PbO2-type TiO2 may be a useful indicator of the pressure and temperature in the diamond stability field.     

榴辉岩韧性剪切变形中的流体作用及地球化学效应

韧性剪切带是在较高温条件下机械与化学作用高度耦合的系统。韧性剪切带普遍含有一种或多种流体,流体是韧性剪切变形高度局域化和剪切变形组构形成的主要影响因素。在强应变岩石中,可利用变形矿物的元素地球化学的变化特征来反演参与变形的流体的地球化学性质。苏鲁-大别超高压变质带中,多数榴辉岩经历了强烈的韧性剪切应变和流体作用,形成高度局域化、尺度不等的韧性剪切变形带,为研究在高压-超高压条件下,参与流体的性质,应变和流体相互作用提供了重要机会。样品DH-2G是一强烈剪切榴辉岩,由石榴石、绿辉石、金红石,及少量的多硅白云母、黝帘石、角闪石、斜长石、石英、锆石和磷灰石组成。在不同应变域,矿物的粒度变化明显。在类变斑晶域,石榴石粒度比剪切条带中的小2~4倍。在以下讨论中,与细粒石榴石(石榴石-I)共生的绿辉石称为绿辉石-I,与粗粒石榴石(石榴石-II)共生的绿辉石称为绿辉石-II。电子探针和原位LA-ICP-MS测试结果表明:(1)除Ni外,两类石榴石没有显著区别;(2)两类绿辉石在主量元素上也没有明显的差异,但微量元素特征,尤其是稀土元素上,存在明显的变化。与绿辉石-I相比,绿辉石-II具有以下特征:(1)轻稀土明显降低,达25~40倍左右;(2)重稀土明显富集,升高5~10倍;(3)Ni、Zn、Co、Sc、Ba、Zr、Y、Rb、Hf和HREE明显升高,而 V、Sr、U、Th、Pb和LREE明显降低;和(4)微弱的正Eu异常, Eu/Eu^*=1.04~1.45,绿辉石-I基本上没有Eu异常。并且,剪切带域金红石的Nb/Ta比值从核部(<19.0)到边部(>20.0)显著增加。岩相学、元素和温压估计研究表明:在剪切过程中不存在外来流体,流体是由无水矿物(绿辉石、石榴石、金红石等)在超高压榴辉岩折返减压过程中通过压力降低出溶结构羟基或分子水,释放出流体,流体富含V、Sr、U、Th、Pb、Zr、Nb和LREE等微量元素。这些流体显著影响深俯冲地壳的流变学性质,是迁移活动元素(LILE和LREE)及保守元素(HFSE等)的重要载体,对超高压岩片的快速折返发挥关键作用。     

Derivation of detrital rutile in the Yaoundé region from the Neoproterozoic Pan-African belt in southern Cameroon (Central Africa)

Rutile, as an important component in alluvial or eluvial heavy mineral deposits, is known in southern Cameroon. These deposits are underlain by the Neoproterozoic low- to high-grade Yaoundé Group. Geochemical, thermometric, fluid inclusion and Pb isotopic studies of the rutile from alluvial and eluvial concentrates and from medium-grade micaschist from the nearby Yaoundé region permit the following conclusions: (1) alluvial and eluvial rutile of the Yaoundé region are derived from the degradation of metapelites, metamafic rocks and pegmatites of the nearby Yaoundé Group; (2) rutile in the Yaoundé Group formed during the Pan-African metamorphism, or was inherited as detrital rutile from a 900 Ma source. The study also shows that the rutile can be used to trace the history of the Pan-African belt north of the Congo craton.     

金红石中锆含量温度计及其微量元素地球化学特征

Zack et al.(2004a)、Watson et al.(2006)以及Tomkins et al.(2007)(在2GPa条件下)的金红石中锆含量温度计计算结果显示,徐淮地区中生代侵入杂岩所含榴辉岩类包体所经历的榴辉岩相变质的温度范围分别为776～1099℃(平均898℃)、663～923℃(平均750℃)和714～981℃(平均804℃),这些温度结果可能并非榴辉岩相峰期变质温度;其角闪岩相退变质作用过程中保存的温度范围分别为555～777℃(平均697℃)、541～663℃(平均6170C)和588～714℃(平均667℃),这些结果不能代表角闪岩相退变质再平衡后的温度,而只能代表角闪岩相退变质作用过程中某-阶段的温度.微量元素地球化学特征研究表明,榴辉岩类包体所含金红石中的某些微量元素(如Nb、Ta、Cr、Fe、V等)含量与其原岩有继承和对应关系,其原岩主要为镁铁质岩石;榴辉岩类包体与其寄主岩石中部分高价态/高场强元素(HFSE)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.     

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。     

钛的地球化学性质与成矿

钛由于其高强度和抗腐蚀性特征,在航空航天、医药、手机等领域得到越来越广泛的应用,是二十世纪的战略金属元素。在自然界中,钛铁矿、钛磁铁矿和金红石是最具经济价值的含钛矿物。钛最初被认为是变质过程中最不活泼的金属元素之一,随着越来越多的证据显示钛可以在特定条件下进入变质热液流体中发生活动迁移。高压变质脉体中金红石和磷灰石作为共生矿物存在,这可能为富F溶液对钛迁移富集的影响,当氟磷灰石从富F流体中结晶沉淀时K_2TiF_6络合物分解,钛在其中的溶解度降低进而结晶沉淀出金红石,而这一富集迁移沉淀机制很可能是变质型金红石矿床变质富集的机制。在岩浆矿床中,钛常作为伴生元素赋存于磁铁矿床中。一般认为部分熔融程度、挥发分含量和成矿岩浆温度等决定了含钛矿或高钛岩体的形成,本文认为富金红石的再循环洋壳或者富钛沉积矿床重熔是岩浆型钛矿床的重要成矿物质来源。沉积型钛矿床的形成与区域地质、地理和水动力学有关,它们常在被动大陆边缘,以高风化、高品位钛源岩为后盾通过风化、剥蚀和海侵等主要形成在沿海岸带特别是南北纬30°低纬度地区。总之富钛源区、起源深度、部分熔融温度和程度、陆壳混染程度、挥发分、流体成分、风化剥蚀能力等决定了钛矿化成功与否。     

俯冲-碰撞和高压、超高压变质带中的金红石研究进展

金红石是高级变质岩和热液矿床中广为展布的一种矿物。目前,金红石在俯冲—碰撞和高压—超高压变质带中研究包括以下4个方面：①金红石在俯冲—碰撞带中的作用;②金红石同质多象变体;③金红石的U Pb定年;④金红石对源区的示踪。第一方面的研究一直是最近10余年来研究的主题之一,而后3个方面的研究尚处于起步阶段,上述研究对认识俯冲—碰撞过程中埃达克岩的成因和特征,对超高压大陆深俯冲深度及形成岩石温压条件的限定,对重塑超高压或高级变质地体峰期变质事例年龄,对赋存金红石岩石的源区示踪具有重要的意义。