The effect of water on accessory phase solubility in subaluminous and peralkaline granitic melts

The solubilities of columbite, tantalite, wolframite, rutile, zircon and hafnon were determined as a function of the water contents in peralkaline and subaluminous granite melts. All experiments were conducted at 1035 °C and 2 kbar and the water contents of the melts ranged from nominally dry to approximately 6 wt.% H₂O. Accessory phase solubilities are not affected by the water content of the peralkaline melt. By contrast, solubilities are affected by the water content of the subaluminous melt, where the solubilities of all the accessory phases examined increase with the water content of the melt, up to 2 wt.% H₂O. At higher water contents, solubilities are nearly constant. It can be concluded that water is not an important control of accessory phase solubility, although the water content will affect diffusivities of components in the melt, thus whether or not accessory phases will be present as restite material. The solubility behaviour in the subaluminous and peralkaline melts supports previous spectroscopic studies, which have observed differences in the coordination of high field strength elements in dry vs. wet subaluminous granitic glasses, but not for peralkaline granitic glasses. Lastly, the fact that wolframite solubility increases with increasing water content in the subaluminous melt suggests that tungsten dissolved as a hexavalent species.     

法国Echassieres地区石英网脉中黑钨矿及其共生矿物的固溶体研究

Echassiares石英网脉中的黑钨矿主要系钨锰矿一钨铁矿系列中的铁端员矿物一钨铁 矿，富泥但贫担，当其与妮铁矿共生时，钨铁矿可含8.91% Nb205。在该矿物中常见的元素置换 有:(1)Fe2+→Mn2+;(2)Wg6+Fe2+→Nb5+ +Fe+3 (3) 3W6+ +Fe2+ →4Nb5+。 妮铁矿呈它形，富含Ta. W,Ti。钨铁捉矿以枝状形态位于钨铁矿和妮铁矿之间，形成完整的矿物组合。Beauvoir花岗岩的侵位带入的热液交代钨铁矿是形成这种矿物组合的主要原因。同时,铅钨铁矿中的裂隙带或其边部还局部发生钨锰矿化。     

U-Pb dating of scheelite,wolframite and apatite from the Woxi Au-Sb-W deposit,western Hunan Province and their geological significanceSCIEI北大核心CSCD

沃溪矿床位于湘西雪峰隆起区的转折部位,是该区金锑钨矿床的典型代表。该矿床成矿元素及成矿期次较为复杂,各成矿阶段的形成时代长期存在争议。本次研究在对沃溪矿床详细野外调查及岩相学观察的基础上,对深部中段矿体中的白钨矿、磷灰石及浅部中段矿体中的黑钨矿开展了U-Pb同位素分析。依据本次所获年龄数据,结合观察到的矿脉交切关系、矿物共生组合等特征,本文认为沃溪矿床除了加里东期成矿作用之外,还存在燕山期成矿作用。其中,白钨矿形成相对较早,成矿年龄为149.0±12Ma、144.8±1.7Ma、139.8±6.1Ma;黑钨矿与白钨矿同时生成(或稍晚),成矿年龄为137.8±3.9Ma、134.8±5.1Ma;自然金、辉锑矿主要在白钨矿、黑钨矿形成以后通过沉淀而成,且自然金在晚阶段(125.8±5.6Ma、123.8±4.6Ma)石英-碳酸盐脉中仍有少量产出。综合已有年代学资料推测,沃溪矿床可能在经历了加里东期陆内造山成矿作用之后,还经受了燕山期伸展构造背景下深部流体不同程度的叠加改造作用。而该矿床发现的矿脉原地破裂后被后期矿物胶结等现象,则指示其矿脉的形成与液压致裂作用有关,这种作用导致矿脉反复裂开-愈合,有利于成矿元素(尤其是金)的活化迁移和再富集沉淀。     

湘南黄沙坪多金属矿床花岗斑岩的矿物化学及其对矽卡岩白钨矿成矿的指示意义

黄沙坪多金属矿床是湖南最大的铅锌生产基地,并且在与矿床内花岗斑岩接触的矽卡岩带产有隐伏的大型矽卡岩型白钨矿和中型规模的辉钼矿。钨-钼矿化的时代为晚侏罗世,与矿床内花岗斑岩侵入时代一致。然而,已有研究认为,由于该花岗斑岩规模很小,矽卡岩型白钨矿的成矿热液应来自深部岩浆房而非此花岗斑岩。为此,我们对花岗斑岩进行了仔细的镜下观测,并且对其中的副矿物和黑云母以及矽卡岩中的白钨矿进行了电子探针成分分析,应用原位LA-ICP-MS方法测定了矽卡岩中白钨矿的稀土元素含量,试图对白钨矿矿化的物质和流体来源提供确切的证据。通过研究,首次在矿床内花岗斑岩中发现了与未蚀变黑云母伴生的黑钨矿和铌铁矿,表明花岗斑岩至少在岩浆结晶作用晚期或岩浆-热液过渡阶段早期就已发生钨的矿物富集,为确定花岗斑岩是控制钨矿化的成矿岩体提供了依据。此外,发现花岗斑岩中的黑云母(属铁叶云母)含有极高的氟含量(3%),指示其应形成于富含氟的高分异岩浆。研究进一步揭示,矽卡岩中白钨矿的轻稀土元素配分模式与花岗斑岩十分一致,而重稀土元素则显著亏损,而且Eu的含量较花岗斑岩更为富集。这暗示形成白钨矿的成矿流体应直接来自花岗斑岩,即:在早期无水矽卡岩阶段,石榴子石的沉淀导致流体中的重稀土亏损而Eu相对富集;白钨矿随后再从这种流体中沉淀。此外,白钨矿的Eu含量与Sm、Gd含量具有负相关关系,表明Eu的分配是相对独立的行为,主要以Eu2+存在,从而指示沉淀白钨矿的流体具有还原的性质。结合前人的研究成果及本文所提供的新证据,我们认为,形成矽卡岩型白钨矿的钨和成矿热液应来自高分异且富F的花岗斑岩,而所需的钙则可能来自于碳酸盐围岩,即矿床内花岗斑岩应是形成钨钼矿床的物质来源,驱动热液活动的能量来源,和寻找隐伏钨矿床的重要找矿标志。     

法国Echassieres地区石英网脉中黑钨矿及其共生矿物的固溶体研究

Echassieres石英网脉中的黑钨矿主要系钨锰矿-钨铁矿系列中的铁端员矿物—钨铁 矿,富铌但贫钽,当其与铌铁矿共生时,钨铁矿可含8.91%Nb2O5。在该矿物中常见的元素置换有:(1)Fe2 Mn2 ;(2)W6 Fe2 Nb5 Fe3 ;(3)3W6 Fe2 4Nb5 。铌铁矿呈它形,富含Ta、W、Ti。钨铁铌矿以枝状形态位于钨铁矿和铌铁矿之间,形成完整的矿物组合。Beauvoir花岗岩的侵位带入的热液交代钨铁矿是形成这种矿物组合的主要原因。同时,沿钨铁矿中的裂隙带或其边部还局部发生锰矿化。     

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.     

Geochronology of the Narenwula W polymetallic deposit in Inner Mongolia and its implications for ore prospectingSCIEI北大核心CSCD

内蒙古那仁乌拉石英脉型钨多金属矿床是我国大兴安岭西南段近年来新发现的一个以钨为主,伴生有铋、银、锌、铜的大型矿床。然而,该区经历过多期次复杂的构造-岩浆活动,目前该矿床与区内不同期次岩浆活动的关系还不清楚,这不仅制约了对该矿床成因的认识,也阻碍了该地区钨矿找矿勘查工作的部署。本文选择区内粗粒二长花岗岩中的锆石、独居石以及石英脉型矿体中的黑钨矿、锡石开展精细的原位LA-HR-ICP-MS U-Pb年代学研究,进而构筑精细成岩成矿年代学框架。结果显示,花岗岩的锆石和独居石U-Pb年龄分别为146.2±2.2Ma和144.2±0.8Ma,二者在误差范围内一致,表明含矿花岗岩形成于晚侏罗世;主成矿期石英脉型矿石中的黑钨矿和锡石的U-Pb年龄分别为136.7±1.0Ma和137.8±1.9Ma,二者在误差范围内一致,表明该区钨锡矿化主要发生于早白垩世。由于含矿花岗岩的侵位年龄与成矿年龄之间存在超过10Myr的时差,考虑到同一岩浆-热液演化过程难以长达10Myr,表明含矿花岗岩仅仅为赋矿围岩,而与钨锡矿体无成因上的联系,并暗示区内存在与钨锡成矿有关的早白垩世隐伏的高分异花岗岩小岩体,深部具有钨锡矿找矿潜力。结合区域已有资料,本文提出那仁乌拉钨矿的形成主要受蒙古-鄂霍茨克洋闭合后的伸展过程控制,并可能受到古太平洋俯冲作用远程效应的影响。     

锡石年代学和黑钨矿微量元素对湘东鸡冠石钨矿床的成因约束

钨是我国传统的优势金属矿产,同时也是国家高新技术领域不可或缺的战略性关键矿产之一。鸡冠石矿床是近年湘东邓阜仙地区新发现的一处钨矿床,具有良好的钨锡多金属资源前景,但其成矿时代和成因尚不清楚。本文在详细的矿床地质特征观察基础上,选取鸡冠石钨矿床中黑钨矿和锡石开展原位LA-ICP-MS微量元素分析和U-Pb定年研究,并将该矿床与相邻矿床进行对比研究。结果显示:1)与黑钨矿密切共生的锡石U-Pb Tera-Wasserburg反等时线年龄为153.2±1.8Ma(MSWD=1.15),与湘东钨矿床晚侏罗世钨锡成矿时代吻合;2)鸡冠石钨矿床紧邻湘东钨矿床北组脉,且矿脉产状和形态等特征也类似;3)鸡冠石矿床中黑钨矿也与湘东钨矿床北组脉典型特征类似,黑钨矿HREE总量和标准化后的REE配分曲线与湘东钨矿床第一期黑钨矿的特征相似。黑钨矿稀土总量对比研究指示成矿流体可能是从湘东钨矿流向鸡冠石钨矿。综合鸡冠石钨矿床与湘东钨矿床紧密的时空关系以及相似的矿床特征,本文认为鸡冠石矿床为一个与晚侏罗世花岗岩有关的岩浆期后热液矿床,同时黑钨矿微量元素特征指示该矿床可能形成于一个富挥发分、低p H和高Eh的流体环境中。