广东石人嶂钨矿床黑钨矿中铁锰比值初探

<正>黑钨矿是钨铁矿-钨锰矿完全类质同象系列的中间成员,其形成受到矿物结晶时不同的物理化学条件的影响。虽然许多学者做过很多有关的研究,如高温富锰,低温富铁的观点,与之相反的有高温富铁,低温富锰的观点,以及黑钨矿中铁锰质的含量与温度,甚至与压力、氧逸度都无关的观点等等。但对于黑钨矿中的锰铁比值研究薄弱。     

湘西沃溪矿床中黑钨矿的地质特征及微量元素地球化学

沃溪矿床位于湖南雪峰山金锑(钨)成矿带中段,是该带最大的、也是惟一发育Au-Sb-W成矿元素组合的矿床。尽管该矿的研究程度较高,但人们对该矿中重要的含钨矿物——黑钨矿的研究很少。在详细的野外地质调研基础上,对该矿黑钨矿的地质特征和微量元素进行了研究,以期揭示其矿床成因、成矿流体性质及物质来源等信息。沃溪矿床黑钨矿矿脉以顺层的含矿石英脉为主,同时发育各种节理脉;节理脉常相互交错,表现出多阶段成矿特征。矿脉中黑钨矿常与石英、碳酸盐及硫化物共生,形成具有热液充填特征的矿石构造。该矿黑钨矿的REE含量很低(1.62~4.58μg/g),明显低于南岭与花岗岩有关的黑钨矿;其HREE相对富集,并具有Eu、Sm、Gd、Tb异常及MW复合型四分组效应等特征,这可能与成矿流体的氧逸度及络合物的稳定性有关。同时,该矿黑钨矿的Y/Ho值均小于28,指示其成矿流体中以CO2-3(HCO-3)络合物为主。与南岭地区黑钨矿相比,该矿黑钨矿中Sc含量高而Nb和Ta含量很低,这可能与该区黑钨矿形成时的物理化学条件以及成矿流体对深部岩石的淋滤作用有关。沃溪矿床中黑钨矿的地质特征、化学成分及微量元素组成明显有别于南岭石英脉型黑钨矿,为其成矿作用与岩浆活动无直接成因关系提供了新的证据。     

北京密云沙厂环斑花岗岩杂岩体黑钨矿钐—钕同位素研究

鉴于缺少可直接用于同位素测年的金属矿物,许多钨矿床的成矿时代大多数是悬而未决的地质难题。本文以我国著名北京密云沙厂环斑花岗质杂岩体内产出的黑钨矿为研究对象,对钨矿床的形成年龄进行了测定,8件黑钨矿Sm-Nd同位素等时线年龄为1430±93Ma(2σ),Nd初始比值为0.510992±3(2σ)和ε_(Nd)(1430Ma)为-10.5±0.84(2σ),这是迄今在我国测定到的最老的钨矿床成矿年龄。通过对全国已有钨矿床同位素年龄数据的对比分析,并且结合它们的地质与地球化学特征,可以认为,我国最古老的钨矿床很可能形成于中元古代,而并非是古生代。另外,密云沙厂地区钨矿床的成矿作用与中元古代富矿碱性岩浆活动有关。     

赣南荡坪石英脉型黑钨矿床成矿流体研究

为揭示赣南荡坪钨矿的成矿流体特征及矿床成因,采用流体包裹体组合的研究方法,利用红外显微镜、冷热台和激光拉曼等测试手段,对黑钨矿和与其共生的石英中流体包裹体进行了系统的岩相学观察、显微测温及成分分析。结果表明,与黑钨矿形成相关的流体为中高温、中低盐度的NaCl-H_2O流体体系,与石英中流体包裹体相比,黑钨矿中包裹体的总体均一温度及盐度较高,分布范围狭窄,表明黑钨矿与共生石英中的流体包裹体形成的p-t-x条件不同。成矿流体在演化过程中的冷却作用是本矿床黑钨矿沉淀成矿的主要因素。     

钨矿床地球化学研究进展：以黑钨矿U-Pb、Sm-Nd、Lu-Hf 同位素年代学与微量元素为例

黑钨矿是钨矿床中最主要的矿石矿物之一,对其直接开展定年研究能更有效厘定钨成矿时间。黑钨矿通常含有一定量的U且部分样品具有较高的Sm/Nd比,因而U-Pb及Sm-Nd定年方法广泛地被应用到黑钨矿矿床的定年研究中。但是受黑钨矿U-Pb及Sm-Nd定年方法以及黑钨矿样品自身的制约,U-Pb及Sm-Nd定年成功率较低或结果不理想。文章针对黑钨矿在钨矿床U-Pb年代学和Sm-Nd年代学的发展历程进行了系统的梳理与分析,探讨了黑钨矿U-Pb年代学与Sm-Nd年代学的挑战与机遇。同时结合已发表的黑钨矿Lu、Hf数据,针对黑钨矿Lu-Hf年代学的应用前景进行了评估与展望。已有数据表明,黑钨矿中Lu/Hf比值变化范围较大,有潜力作为Lu-Hf同位素定年的良好对象。文章探讨了黑钨矿用于限定钨矿床成矿时代研究中存在的问题及应对方案,旨在促进未来黑钨矿在钨矿床成矿年代学的发展。     

赣南盘古山和淘锡坑黑钨矿化学成分和晶体结构及指示意义

赣南地区是世界著名的钨矿资源产区,黑钨矿是该区钨矿中最重要的钨矿石矿物。本文以赣南盘古山和淘锡坑两个典型钨矿床中的黑钨矿作为研究对象,采用电子探针、X射线衍射等分析技术对黑钨矿的晶体结构、化学成分及其空间分布规律开展研究。结果表明,研究区黑钨矿主要属于锰钨铁矿,黑钨矿中Mn~(2+)和Fe~(2+)为类质同象的关系,因此MnO与FeO之间呈明显的负相关。在空间上x(Fe/(Mn+Fe))值有一定的变化规律,由矿脉深部到浅部,x值先变大再变小,反映出矿液的运移从下而上,随后上部矿液又有向下回流的现象;同一脉体各中段均为中间x(Fe/(Mn+Fe))值大,向两侧比值减小,说明同一中段上矿体中部黑钨矿形成温度较高,两侧黑钨矿形成温度较低。盘古山黑钨矿中Nb和Ta的含量均高于淘锡坑黑钨矿,这说明盘古山黑钨矿体比淘锡坑黑钨矿更靠近岩体。单一矿脉自下而上黑钨矿中Nb、Ta含量先是迅速变小,而后略有增大,这也说明矿液运移的复杂性。两矿区黑钨矿都具有重稀土富集左倾的"躺椅式"球粒陨石标准化配分模式。盘古山矿床黑钨矿稀土总量(ΣREEs)较高,La_N/Yb_N比值较低,轻重稀土分馏较为明显;淘锡坑矿床黑钨矿稀土总量(ΣREEs)较低,La_N/Yb_N比值范围较广,轻重稀土分馏程度有强有弱。它们都具有强烈的δEu负异常和弱的δCe负异常,说明矿床是在封闭的还原条件下形成的。将赣南盘古山、淘锡坑钨矿与广西珊瑚、江西浒坑和湖南瑶岗仙钨矿中黑钨矿的晶胞参数进行对比分析,显示产于花岗岩体内接触带的黑钨矿FeO含量较低,晶胞参数值较大;产于花岗岩体外接触带的黑钨矿FeO含量较高,晶胞参数值较小。因此,利用黑钨矿的化学成分和晶体结构的变化特征,可以指示成矿物质在空间上的运移特征,也可作为判断矿床成因的依据。研究成果对同类矿床的研究具有借鉴和启示意义。     

夕卡岩中黑钨矿床形成的地质地球化学特征

柿竹园钨矿床,钨元素在夕卡岩中不仅可以形成白钨矿床,而且还可以形成黑钨矿床,两者均具有相当大的规模,构成黑、白钨矿复合型矿床,这在文献中却少先例.因此,探讨夕卡岩中黑钨矿形成的地质地球化学特征,对进一步研究黑钨矿的成矿理论和普查找矿工作等均具有一定的意义. 区域地质概况矿田位于东坡-月枚复式向斜北段扬起部位.矿区内泥盆系余田桥组地层广泛发育.矿区的西北侧沿褶皱、断裂的交汇处有斑状黑云母花岗岩侵入,接触带上形成不连续的“周边状”夕卡岩,     

南岭热液型钨矿(主要成矿区)成矿温度初测及其分析

一、前言我国南岭钨矿,在世界上素负盛名,已有五十多年的开采和研究历史,但具体研究成矿温度的工作至今还很少。本文拟就主要成矿区钨矿成矿温度及有关问题作一初步探讨。关于热液矿床成矿温度的划分,一般认为:500-300℃为高温热液;300-200℃为中温;200-50℃属低温。在实际工作中,鉴定成矿温度的标志常常是依据矿物的共生组合,其次是近矿的围岩蚀变类型及矿脉矿石结构构造等等。目前,利用矿物母液包裹体测     

微量元素地质温度计

研究表明,矿物、矿石、岩石中微量元素的种类、丰度、分配和比值等,与温度、压力有简单的热力学关系,与其它成岩成矿的环境变量有密切的相关性,因而可以作为各种成岩成矿作用的灵敏的地球化学指示剂. 众所周知,成岩成矿的物理化学条件是综合性的,微量元素用作各种成因条件的指示剂也是多方面的.本文着重阐述微量元素作为地质温度计的可能性和应用问题. 由于温度对成岩成矿作用所起的重大影响,     

赣中大王山钨多金属矿床流体包裹体及 H-O-S 同位素特征

为确定赣中大王山钨多金属矿床成因类型及地质特征, 笔者对主成矿期石英和硫化矿物进行了流体包裹体、H-O-S 同位素研究。 结合野外矿体产出形态, 可以将研究区划分出3 期成矿作用, 早期以矿囊状为特征, 与围岩无明显的蚀变现象, 主成矿期为大脉状, 与围岩发生云英岩化, 成矿晚期可见含矿石英晶洞。 主成矿期包裹体岩相学和显微测温结果显示： 石英中主要发育气液二相包裹体、富气相包裹体、CO₂三相包裹体和气-液-固三相包裹体 ; 包裹体均一温度为 180 ℃ ～280 ℃（峰值为190 ℃ ～210 ℃）, 盐度为7.86% ～20.22% NaCl_eqv （峰值为11%～17% NaCl_eqv ）, 结合前人对赣中石英脉型黑钨矿中的黑钨矿测温结果, 推测大王山形成于中温、中高盐度;石英包裹体δD_V-SMOW 值介于- 93.1‰～-72.5‰, δ¹⁸O_H2O 值介于0.9‰～3.4‰, 石英包裹体的温度-盐度关系图显示成矿流体混入了低温、低盐度的流体相;δ³⁴S 值介于-1.3‰～+1.9‰之间, 表明成矿物质硫源主要来自深源岩浆。 结合前人研究显示, 黑钨矿较石英早结晶, 成矿流体以岩浆水为主, 大气降水参与成矿, 硫源与深部岩浆有关。 赋矿碱长花岗岩中见有W-Mo 多金属矿囊和细晶岩、伟晶岩脉, 其成岩时间和成矿时间一致。 指示了大王山钨多金属与围岩碱长花岗岩具有一定的亲源性, 并且岩浆-流体液态不混溶作用是导致W-Mo 多金属矿沉淀的主因。     

迁安紫苏花岗岩的稀土元素地球化学

迁安断块隆起或称迁安花岗岩片麻岩穹隆是冀东高级变质地体的一个重要组成部分,它的四周为大型古断裂所切割,仅在西侧保留了边缘褶皱束,在褶皱束内有同构造的或构造后的纵向断裂(钱祥麟,1981)。本文讨论的紫苏花岗岩,大致沿西部边缘褶皱束的纵向断裂分布。     

Regional and local variations in the composition of the wolframite series from SW Japan and possible factors controlling compositional variations

The regional and local variations in the composition of the wolframite series associated with the ilmeniteseries and magnetite-series granitoids in the Inner Zone of SW Japan were investigated using X-ray diffraction and microprobe analyses. It is concluded that the variation in Mn/Fe ratios in the source materials (granitic magmas in most cases) is the dominant factor controlling the regional variation in the wolframite compositions, while, as exemplified by the Kaneuchi mine, Kyoto Prefecture, the wallrock chemistry and pH of ore fluids are responsible for the local variation within a single vein system. Within a fresh euhedral crystal from the mine, only slight compositional variation of less than 3 mole% MnWO₄ is found in the form of oscillatory zoning. This study, combined with the fluid inclusion research, indicates that the wolframite compositions (Mn/Fe ratios) cannot be used as a geothermometer.     

Compositional characteristics of wolframite in tin deposits,Dupangling, Guangxi

Statistical data on major, trace and rare-earth elements in wolframite from the quartz vein-and greisen-type tin deposits in the Dupangling orefield reveal: (1) The components in wolframite can be divided into two relatively independent groups: the WO₃-Nb-Ta-Sc-REE group, in which WO₃ is negatively correlated with the others and the FeO-MnO-Sn group, in which MnO is negatively correlated with the other two; (2) In general, REE fractionation is not significant, reflected mainly by the separation of Eu from other REE’s. LREE and HREE increase or decrease simultaneously, with HREE being more variable; (3) Nb, Ta, Sc, REE substitute for W, and Sn may enter into wolframite lattice accompanied by Fe-Mn substitution; (4) In contrast to wolframite in quartz veins, which is poor in REE, Nb, Ta and Sc and has highδ Eu values and LREE / HREE and Nb/Ta ratios, wolframite in greisen is rich in REE, Nb, Ta, Sc and has lowδ Eu values and LREE/HREE and Nb/Ta ratios; and (5) The contents and ratios of trace elements and REE partitioning parameters of wolframite can be used as guide for prospecting.     

Über den transport von Wolfram und den Absatz von Wolfram-Doppel-Oxiden in fluiden wässrigen LösungenThe transport of tungsten and the deposition of tungsten double oxides in fluid,aqueous solutions

The transportation of W in aqueous gas-phases at and above 500°C is examined using thermodynamic data. The transport of W is possible as fluoride and oxifluoride. The deposition of wolframite continues with decreasing temperature and pressure. The stabilities of wolframates in hydrothermal solutions are examined for temperatures up to 300°C with Eh-pH-diagrams, exchange reactions of wolframite with oxides, sulfides and dissolved ions. Fe₂WO₆ becomes stable against Fe₂O₃ + WO₃ above 126°C. At 300°C its range of stability begins at high pO₂ which is not realised in hydrothennal endogenous solutions. In consequence of the very low Gibbs energies of MgWO₄, CaWO₄ and BaWO₄, the minerals MgWO₄ and BaWO₄ should be more important than wolframite, if Mg and Ba coexist in solution together with W. Co and Ni also should be found as trace elements in wolframite, if Co and Ni were in solution in sufficiently high concentrations together with W.     

模糊综合评判在铀矿成矿预测中的应用

本文介绍了模糊综合评判法在铀矿成矿预测中的应用。该法可定量地分析预测区的地质信息,综合多种成矿因素的作用,以达到分析预测区成矿远景的目的。其步骤是:将整个预测区划分为若干子区单元,作为评判对象;根据预测区的特殊性及地质成矿过程的一般性,确定出影响成矿的主要因素,组成评判因素集;计算每个子区单元在每个因素上对“成矿”的隶属度,确定评判矩阵;选用加权平均等3个评判函数,用二次评判的方法进行模糊综合评判,得到评判结果,最后对评判结果择优,划分出三级成矿远景区。     

Physicochemical study of the hubnerite-ferberite (MnWO4-FeWO4) zonal distribution in wolframite (Mn X Fe(1−X)WO4) deposits

A thermochemical approach to the problem of zonal structure in metallogenetics involving the use of Ellingham diagrams and minimization of free energy (ΔG) agrees closely with the “normal” zonal structure as defined by Fersman (1934). This approach is applied to the hubnerite-ferberite (MnWO₄-FeWO₄) solid solution in order to elucidate the repartition law of the Mn/Fe ratio in wolframite (Mn _X Fe_(1?X)WO₄). The study requires experimental determination of thermodynamical data, such as enthalpy ΔH of the solid solution, which is obtained using a high-temperature calorimetric method developed for this purpose. The calculation leads to an equation which gives the Mn molar value of wolframite with respect to temperature and the Mn/Fe ratio of the mineralizing solution. It is theoretically demonstrated that a high manganese content in wolframite is connected with high deposition temperature, but the decrease of the Mn/Fe ratio is a consequence of the decrease of the Mn/Fe ratio in the mineralizing solution, as can be observed in the Borralha deposit from which the geochemical study has been made. Conversely, a rapid lowering of the temperature of deposition leads to an increase of the Mn/Fe ratio in wolframite. Consequently, this ratio cannot be used as a geologic thermometer, but rather as an indicator of the position of the source of the mineralization.     

一些常见铀矿物的红外吸收光谱特征

作者对我国产出的41种常见的铀矿物进行了红外光谱分析,并收集了国外已有资料,综合了10类53种铀矿物的红外吸收光谱特征。     

Fluid Inclusion Studies of Ore and Gangue Minerals from the Piaotang Tungsten Deposit, Southern Jiangxi Province, China

The Piaotang deposit is one of the largest vein-type W-polymetallic deposits in southern Jiangxi Province, South China. The coexistence of wolframite and cassiterite is an important feature of the deposit. Based on detailed petrographic observations, microthermometry of fluid inclusions in wolframite, cassiterite and intergrown quartz was undertaken. The inclusions in wolframite were observed by infrared microscope, while those in cassiterite and quartz were observed in visible light. The fluid inclusions in wolframite can be divided into two types: aqueous inclusions with a large vapor-phase proportion and aqueous inclusions with a small vapor-phase ratio. The homogenization temperature (Th) of inclusions in wolframite with large vapor-phase ratios ranged from 280°C to 390°C, with salinity ranging from 3.1 to 7.2 wt% NaCl eq. In contrast, the Th values of inclusions with small vapor-phase ratios ranged from 216°C to 264°C, with salinity values ranging from 3.5 to 9.3 wt% NaCl eq. Th values of primary inclusions in cassiterite ranged from 316°C to 380°C, with salinity ranging from 5.4 to 9.3 wt% NaCl eq. Th values for primary fluid inclusions in quartz ranged from 162°C to 309°C, with salinity values ranging from 1.2 to 6.7 wt% NaCl eq. The results show that the formation conditions of wolframite, cassiterite and intergrown quartz are not uniform. The evolutionary processes of fluids related to these three kinds of minerals are also significantly different. Intergrown quartz cannot provide the depositional conditions of wolframite and cassiterite. The fluids related to tungsten mineralization for the NaCl-H2O system had a medium-to-high temperature and low salinity, while the fluids related to tin mineralization for the NaCl-H2O system had a high temperature and medium-to-low salinity. The results of this study suggest that fluid cooling is the main mechanism for the precipitation of tungsten and tin.     

白钨矿精矿中黑钨矿的物相分析

白钨矿精矿中黑钨矿的物相分析,与黑钨矿中少量白钨矿的物相分析一样,都是由于两者的含量相差过于悬殊,很艰找到合适的选择性溶剂和条件,得到较为满意的分析结果,所以至今仍为国内外尚未过关的课题.本文应用新的选择性溶剂-结晶氯化铝,它比以往使用的那一种选择性溶剂对白钨矿的溶出率要大,采取适当措施后黑钨矿的溶出率可以降低得很小,并且对钨矿中的一些常见共生的含钙矿物能同时全部除去,在此基础上测定残渣中的钨(黑钨矿和残剩少量白钨矿的和)和钙(白钨矿的钙),钙的含量按CaWO_4固定组成换算成白钨矿的钨,差减即得黑钨矿的钨.