内蒙白云鄂博褐钇铌矿——褐铈铌矿亚族的初步研究

前言褐钇铌岩族矿物属于正铌钽酸盐矿物。矿物的化学组成可以用ABO_4的一般式来表示。在褐钇铌矿族物中存在着两个完全类质同象系列:一个是铌和钽形成的连续完全类质同象系列,即黄钇钽矿一褐钇铌矿亚族(ΣYTaO_4—ΣYNbO_4系列);另一个是钇族和铈族稀土连续完全类质同象系列,即是本文所要介绍的褐钇铌矿——褐铈铌矿亚族(ΣYNbO_4—ΣCaNbO_4系列)。     

内蒙白云鄂博西矿褐钇铌矿-褐铈铌矿族矿物的初步研究

最近,通过对内蒙白云鄂博西矿物质成份的研究,在岩心人工重砂样品中发现了褐铈铌矿、褐钇铌矿及其中间变种钇褐铈铌矿。 褐钇铌矿-褐铈铌矿族矿物的组合特征,是白云鄂博矿区所特有的。1964年在该矿区东部接触带发现了与硅镁石、金云母、铈磷灰石、方解石及烧绿石等共生的褐铈铌矿。这次钇褐铈铌矿的发现,在我国尚属首次。 本族矿物Nb_2O_5的含量高达40％以上,仅低于铌铁矿、铌钙矿、烧绿石等少数几种富铌矿     

内蒙某稀土-铌-铁矿床中稀土赋存状态分析方法的研究

内蒙某稀土-铌-铁矿床含稀土较高,以独立矿物形式存在的有独居石、各种稀土氟碳酸盐、稀土铌钛酸盐(包括易解石、黄绿石、褐铈铌矿和褐钇铌矿),稀土碳酸盐(已发现的有碳铈钠矿)和极少量的硅酸盐(如褐帘石)。此外还有相当量的稀土以类质同象存在于一些非稀土矿物中。本矿床有些稀土矿物的颗粒很细,含量又高,很难单体分离,此外,含稀土分散量的矿物又常连生和包裹这些微细的稀土矿物。用一般物理方法和岩矿手段无法使它们分开,更不能进行定量分析。因此,本文用化学方法分离和测定各类稀土矿物和     

江西崇义铁木里碱长花岗岩中铌和稀土元素的富集机制

华南是我国重要的战略性矿产资源基地,以花岗岩相关的稀有和稀土金属成矿作用而举世瞩目。其中,铌的成矿作用一般与过铝质高分异花岗岩有关,稀土元素则随岩浆演化程度增强而富集程度降低,而江西铁木里含黑云母碱长花岗岩体同时富集铌和稀土元素,矿化组合极具特色。本文在详细的矿物岩相学研究基础上,利用电子探针、飞秒激光电感耦合等离子质谱对铌和稀土矿物进行了矿物地球化学分析,借此对铁木里碱长花岗岩中铌和稀土元素的富集机制进行探讨。铁木里岩体由肉红色含黑云母碱长花岗岩(r-G)和灰白色含黑云母碱长花岗岩(g-G)组成,发育暗色包体。r-G中的铌矿物主要为岩浆期形成的铌铁金红石,稀土矿物包括岩浆期形成的硅钛铈矿、独居石、磷灰石和热液期形成的独居石和氟碳(钙)铈矿。g-G中的铌矿物包括岩浆期形成的铌铁金红石和热液期形成的铌铁金红石、易解石、铌铁矿,稀土矿物包括岩浆期磷灰石和热液期磷灰石、独居石、氟碳(钙)铈矿。暗色包体为岩浆混合成因,内含磷灰石、独居石和零星的硅钛铈矿、金红石。矿物组合特征显示,铁木里碱长花岗岩中的铌和稀土元素经过了岩浆和热液两个时期的富集。应用金红石、磷灰石、绿泥石等矿物成分特征约束了岩浆-...     

应用电子探针分析技术研究某铌-稀土矿中铌和稀土元素的赋存状态

铌是一种战略金属,在现代钢铁技术中发挥着非常重要的作用。某铌-稀土矿矿石中的Nb_2O_5平均含量达0.0855%,稀土总量(REO)含量达1.03%,接近铌矿最低工业品位要求,并伴生有稀土矿,因此查明铌和稀土的赋存状态至关重要。由于铌矿物、稀土矿物具有颗粒细小且嵌布特征复杂的特点,在偏光显微镜下不容易发现,而且定名困难,很难达到研究目的,一直是地质分析测试的难点。为查明铌和稀土元素的存在形式以及铌、稀土元素的赋存矿物,本文应用电子探针背散射图像、能谱分析及电子探针波谱定量分析技术对某铌、稀土矿矿石进行分析,主要研究铌矿物和稀土矿物的种类、嵌布关系及化学成分等特征,更准确地分析铌和稀土元素的赋存状态。结果表明:(1)铌元素主要以铌铁矿、含铌金红石的形式存在,其中铌铁矿中Nb_2O_5的平均含量为78.26%,含铌金红石中Nb_2O_5的平均含量为5.26%。(2)稀土元素主要以独居石、氟碳钙铈矿和氟碳铈矿的形式存在,其中独居石中稀土总量(REO)的平均含量为64.84%,氟碳钙铈矿中稀土总量(REO)的平均含量为57.52%,氟碳铈矿中稀土总量(REO)的平均含量为70.61%。(3)铌矿物、稀土矿物分布分散,多包裹于钾长石、方解石及黑云母等脉石矿物中。本研究实现了常规岩矿鉴定手段难以完成的矿物识别和鉴定,查明该矿床矿石中主要的铌矿物和稀土矿物的种类及特征,为后续铌-稀土矿的综合利用提供了科学依据。     

一种新产状的含铈褐钇铌矿

关于褐钇铌矿族的研究,国内外积累了不少资料。其主要产在黑云母花岗岩、花岗伟晶岩、微斜长石岩、交代变质岩、蚀变花岗岩、白岗岩及花岗岩的残坡积和冲积砂中。1979年我们在进行内蒙白云鄂博铌、稀土、铁矿床物质成分的研究时,在白云石型铌、稀土矿石中发现含铈褐钇铌矿,与该区原已发现的褐铈铌矿等矿物组成了褐钇铌矿-褐铈铌矿系列。     

辽东地区赛马矿床中首次发现独立铌钽矿物

通过扫描电镜和电子探针在赛马铌钽矿床识别出独立铌钽矿物,种类主要为铈铌钙钛矿、钙铌矿及铌钛铀矿. 该发现回答了对辽东地区是否存在独立铌钽矿物的质疑. 根据全岩Sr-Nd-Pd同位素分析结果推断该铌钽矿床的成矿过程与富集地幔有关,同时有部分地壳物质的混入.     

白云鄂博铁矿西矿区铌物相分析方法的研究

白云鄂博铁矿是我国含有稀土、铌等元素的大型综合性矿床,矿物组成复杂,已发现的各种矿物达100多种。其中铌以独立矿物形式存在的有易解石类、烧绿石、铌铁矿、钛铁金红石、褐钇铌矿、铌钙矿、包头矿等十多种;同时还存在含铌矿物,钛铁矿等;此外,还有少量铌分散于脉石矿物中,主要分散在萤石,赤(褐)铁矿、磁铁矿、稀土氟碳酸盐矿物、独居石、钠闪石、云母等矿物中。     

白云鄂博褐钇铌矿族矿物的矿物化学与矿物演化

本文在大量矿物化学资料及高温XRD研究基础上提出了褐钇铌矿族矿物的分类命名方案,详细地研究了该族矿物的化学成分、稀土和特殊稀土组成及固溶关系。发现了M-钍褐铈铌矿、T-钛褐钕铌矿、M-钕褐铈铌矿以及T-钇褐钕铌矿等一批新变种矿物。确定了褐钇铌矿族矿物在时间和空间上的分异演化序列,并讨论了主稀土和特殊稀土在演化过程中的基本行为,首次提出了褐钇铌矿族矿物水解共沉淀形成机理新模式,并确认成矿流体多阶段演化过程中因介质物理化学条件不同,稀土元素配合物呈现的稳定性差异是本族矿物时空演化的根本原因。此外,本文还呼吁对白云鄂博西矿区铕等资源进行评介和开发。     

迤纳厂矿床：一个“白云鄂博式”铁铜稀土矿床

云南武定迤纳厂铁铜稀土矿床是滇中地区具有代表性的元古宙铁铜稀土矿床之一。矿床中除了铁、铜资源外,还伴生有稀土、稀有(铌)、钇、钼、钴等组分。研究表明：稀土元素含量在条纹条带状矿石和脉状矿石中均较高,ΣREE含量分别高达(1 446.83~11 259.23)×10-6和(2 020.92~3 415.51)×10-6,尤其富集La、Ce等轻稀土元素;稀有(铌)元素主要富集在条纹条带状矿石中,含量高达(278.8~529.0)×10-6。由于矿床的矿物组成非常复杂,并且矿石中稀土、稀有(铌)矿物含量相对较少,矿物结晶粒度细小,用传统的测试技术和方法很难识别鉴定,因此矿床的矿物学特征,尤其是稀土、稀有(铌)矿物的赋存状态特征研究一直以来都较为棘手。论文应用矿物表征自动定量分析系统(AMICS),结合扫描电镜能谱仪(SEM-EDS)显微结构原位分析技术,完成了常规岩矿鉴定手段难以完成的矿物定量识别和鉴定,在矿石中发现了含量可观的氟碳钙铈矿、氟碳铈矿和少量的独居石、褐帘石、铌铁矿、褐钇铌矿、硅钍钇矿、含铌金红石等稀有稀土矿物。其中,氟碳铈矿、独居石、铌铁矿、褐钇铌矿等主要富集于条纹条带状矿石中,与铁氧化物、磷灰石、萤石、菱铁矿和早期黄铜矿、黄铁矿等紧密共生;氟碳钙铈矿、褐帘石、硅钍钇矿、含铌金红石等主要局部富集在脉状矿石中,与石英、方解石、绿泥石和晚期黄铜矿、黄铁矿等紧密共生。显然,在铁氧化物和铜硫化物成矿两个阶段均伴随有稀土成矿作用。结合前人的研究成果,笔者将主矿化期划分为铁氧化物磷灰石稀土成矿阶段(Ⅱ-1)和铜硫化物(金)稀土成矿阶段(Ⅱ-2)。其中,氟碳铈矿、独居石、铌铁矿、褐钇铌矿等主要形成于Ⅱ-1阶段,其成矿作用可能与Columbia超大陆裂谷化裂解有关;氟碳钙铈矿、褐帘石、硅钍钇矿、(含铌)金红石等则主要形成于Ⅱ-2阶段,其成矿作用可能与Rodinia超大陆裂解有关。对比研究发现,云南武定迤纳厂铁铜稀土矿床与白云鄂博超大型铌铁稀土矿床在大地构造背景、成矿元素组合、赋矿岩系、矿物组成、成矿时代、稀土来源等方面均有可对比性,初步确定云南武定迤纳厂铁铜稀土矿床是一个“白云鄂博式”矿床。     

Loparite-(Ce) from the Khibiny Alkaline Pluton,Kola Peninsula,Russia

Data on the occurrence, morphology, anatomy, composition, and formation conditions of loparite-(Ce) in the Khibiny alkaline pluton are given. Loparite-(Ce), (Na,Ce,Sr)(Ce,Th)(Ti,Nb)2O6, resulted from metasomatic alteration and assimilation of metamorphic host rocks at the contact with foyaite as well as foyaite on the contact with foidolite. This alteration was the highest in pegmatite, and albitite developed there. A decrease in temperature resulted in enrichment of the perovskite and tausonite endmembers in loparite-(Ce) owing to a decrease in the loparite and lueshite endmembers. La and Ce sharply predominate among rare earth elements in the composition of loparite-(Ce).     

Rare metal-bearing pegmatites from the Southeastern Desert of Egypt： Geology, geochemical characteristics, and petrogenesis

The pegmatite province of the Southeastern Desert (SED) is part of a pegmatite district that extends from Egypt (extends to 1200 km2). Rare metal pegmatites are divided into (1) unzoned, Sn-mineralized; (2) zoned Li, Nb, Ta and Be-bearing; and (3) pegmatites and pegmatites containing colored, gem-quality tourmaline. The Rb/Sr data reflect a crustal origin for the rare metal pegmatites and indicate that the original SED magma was generated during the peak of regional metamorphism and predates the intrusion of post-tectonic leucogranites. These bodies developed an early border zone consisting of coarse to very coarse muscovite quartz alkali feldspar, followed by an intermediate zone of dominant quartz feldspar muscovite rock. Garnet, tourmaline, beryl, galena, pyrite, amblygonite, apatite and monazite are rare accessories in both zones. Cassiterite tends to concentrate in replacement zones and along fractures in albite quartz muscovite-rich portions. The highest concentrations of cassiterite occur in irregular greisenized zones which consist dominantly of micaceous aggregates of green Li-rich muscovite, quartz, albite and coarse-grained cassiterite. The different metasomatic post-solidification alterations include sodic and potassic metasomatism, greisenization and tourmalinization. Geochemically, the pegmatite-generating granites have a metaluminous composition, showing a differentiation trend from coarse-grained, unfractionated plagioclase-rich granite towards highly fractionated fine- to medium-grained, local albite-rich rock. Economically important ore minerals introduced by volatile-rich, rare metal-bearing fluids, either primarily or during the breakdown of the primary mineral assemblages, are niobium-tantalum oxides, Sn-oxides (cassiterite), Li-silicates (petalite, spodumene, euctyptite, and pollucite), Li-phosphates (amblygonite, montebrasite and lithopilite) and minor REE-minerals (Hf-zircon, monazite, xenotime, thorian, loparite and yttrio-fluorite). The pollucite is typically associated with spodumene, petalite, amblygonite, quartz and feldspar. The primary pollucite has Si/Al (at) ratios of 2.53-2.65 and CRK of 79.5- 82.2. Thorian loparite is essentially a member of the loparite (NaLREETi2O6)-lueshite (NaNbO3)-ThTi2O6-ThNb4O12 quaternary system with low or negligible contents of other end-member compositions. The mineral compositionally evolved from niobian loparite to niobian thorian and thorian loparite gave rise to ceriobetafite and belyankinite with high ThO2 contents. Thorian loparite is metamict or partly metamict and upon heating regains a structure close to that of synthetic loparite NaLaTi2O6.     

Crystallization of loparite in alkaline fluid-magmatic systems (from experimental and mineralogical data)

We studied loparite-containing rocks (lujaurites, juvites, foyaite-juvites, etc.) sampled from a complex of differentiated rocks and, partly, from a complex of eudialytic lujaurites of the Lovozero alkaline massif. Zoned crystals of loparite (the zoning is due to variations in Ti, Nb, REE, Sr, and Th contents) were examined by microprobing. We also carried out experimental studies of loparite formation in complex silicate–salt systems including sodium carbonate, chloride, fluoride, or sulfate at 400–1200 °C and 1–2 kbar. They show that the composition of loparites depends on the physicochemical conditions of their formation (fluid composition) and that natural loparite can crystallize in a wide range of temperatures. The produced loparite crystals are zoned as a result of variations in Ti, Nb, La, Ce, Y, Ca, and Sr contents, which is probably related to the kinetic specifics of crystallization. Their zoning is similar to that of loparites of the Lovozero massif.     

Oxide minerals in a layered kimberlite-carbonate sill from Benfontein,South Africa

The lower sill at Benfontein, South Africa, shows a high degree of magmatic sedimentation to kimberlite, oxide-carbonate, and carbonate layers. The iron-titanium oxide minerals are similar in the carbonate-rich and silicate-rich layers and are represented by titaniferous Mg-Al chromite, Mg-Al titanomagnetite, magnesian ilmenite, rutile, and perovskite. The spinel crystallization trend was toward enrichment in Mg and Ti and depletion in Cr; this trend is similar to that observed in many kimberlites. The ilmenite has Mg and Cr contents within the range observed in kimberlites and lacks the Mn enrichment observed in ilmenites from carbonatites. Perovskite in silicate-rich and carbonate-rich layers shows similar total REE contents and LREE enrichment and lacks the remarkable Nb enrichment observed in perovskite from carbonatites. These new data on the iron-titanium oxide minerals in the lower Benfontein sill do not support a genetic relationship between kimberlites and carbonatites.     

Interaction of Titanium Minerals and Their Melts with Diamond-Forming Media (Experiments at 7–8 GPa)

Melting relations in the multicomponent diamond-forming systems of the upper mantle with a boundary of K–Na–Mg–Fe–Ca carbonate, phases of the model peridotite and eclogite, carbon, and titanium minerals from kimberlite (ilmenite FeTiO₃, perovskite CaTiO₃, and rutile TiO₂) were studied experimentally at 7–8 GPa and 1600–1650°C. Perovskite reacts with the formation of rutile in the diamond-forming silicate–carbonate melts. We discovered liquid immiscibility between melts of titanium minerals, on the one hand, and carbonate–carbon, peridotite–carbonate–carbon, and eclogite–carbonate–carbon diamond-forming melts, on the other. The solubility of titanium mineral in diamond-forming melts is negligible independent of their concentration in the experimental systems. Growth melts retain high diamond-forming efficiency. In general, the experimental results are evident for the xenogenic nature of titanium minerals in inclusions in diamond and, therefore, in diamond-forming melts. It is shown that the physicochemical factors that may correlate the diamond content with the concentration of Ti in kimberlite do not occur during the diamond genesis in silicate–carbonate–carbon parental melts containing titanium minerals and their melts.     

Chemical evolution and petrogenetic implications of loparite in the layered,agpaitic Lovozero complex,Kola Peninsula,Russia

Summary Lovozero, the largest of the world’s layered peralkaline intrusions, includes gigantic deposits of Nb + REE-loparite ore. Loparite, (Na,Ce,Ca)₂(Ti,Nb)₂O₆, became a cumulus phase after crystallisation of about 35% of the ‘Differentiated Complex’, and its compositional evolution has been investigated through a 2.35 km section of the intrusion. The composition of the cumulus loparite changes systematically upwards through the intrusion with an increase in Na, Sr, Nb and Th and decrease in REE and Ti. This main trend of loparite evolution records differentiation of the peralkaline magma through crystallisation of 1600 m of the intrusion. The formation of the loparite ores was the result of several factors including the chemical evolution of the highly alkaline magma and mechanical accumulation of loparite at the base of a convecting unit. At later stages of evolution, when concentrations of alkalis and volatiles reached very high levels, loparite reacted with the residual melt to form a variety of minerals including barytolamprophyllite, lomonosovite, steenstrupine-(Ce), vuonnemite, nordite, nenadkevichite, REE, Sr-rich apatite, vitusite-(Ce), mosandrite, monazite-(Ce), cerite and Ba, Si-rich belovite. The absence of loparite ore in the “Eudialyte complex” is likely to be a result of the wide crystallisation field of lamprophyllite, which here became a cumulus phase. Received November 6, 2000; revised version accepted January 18, 2001     

Exsolution intergrowths of titanian ferrocolumbite and niobian rutile from the Weinebene Spodumene Pegmatites,Carinthia, Austria

Summary Titanian ferrocolumbite is a rare accessory mineral in the spodumene-bearing pegmatites at Weinebene, Carinthia, Austria. It contains abundant exsolved niobian rutile and scarce inclusions of cassiterite that may be primary. The titanian ferrocolumbite is relatively homogeneous with Mn/(Mn + Fe) 0.24–0.33, Ta/(Ta + Nb) 0.09–0.13 (atomic ratios) and 0.47–0.88 Ti per 12 cations (2.7–5.0 wt.% TiO₂). Natural specimens are considerably disordered but become more ordered on heating. Niobian rutile has Mn/(Mn + Fe) 0.00–0.04 and Ta/(Ta + Nb) 0.26–0.38; it concentrates Fe, Ta, Ti and Sn relative to the Mn- and Nb-enriched ferrocolumbite. The overall scarcity of Nb, Ta-oxide minerals in the spodumene-bearing pegmatites of southern Ostalpen conforms to their general features ranking them with the albite-spodumene type of rare-element pegmatites.With 4 Figures     

Textural evolution of perovskite in the Afrikanda alkaline–ultramafic complex,Kola Peninsula,Russia

Perovskite is a common accessory mineral in a variety of mafic and ultramafic rocks, but perovskite deposits are rare and studies of perovskite ore deposits are correspondingly scarce. Perovskite is a key rock-forming mineral and reaches exceptionally high concentrations in olivinites, diverse clinopyroxenites and silicocarbonatites in the Afrikanda alkaline–ultramafic complex (Kola Peninsula, NW Russia). Across these lithologies, we classify perovskite into three types (T1–T3) based on crystal morphology, inclusion abundance, composition, and zonation. Perovskite in olivinites and some clinopyroxenites is represented by fine-grained, equigranular, monomineralic clusters and networks (T1). In contrast, perovskite in other clinopyroxenites and some silicocarbonatites has fine- to coarse-grained interlocked (T2) and massive (T3) textures. Electron backscatter diffraction reveals that some T1 and T2 perovskite grains in the olivinites and clinopyroxenites are composed of multiple subgrains and may represent stages of crystal rotation, coalescence and amalgamation. We propose that in the olivinites and clinopyroxenites, these processes result in the transformation of clusters and networks of fine-grained perovskite crystals (T1) to mosaics of more coarse-grained (T2) and massive perovskite (T3). This interpretation suggests that sub-solidus processes can lead to the development of coarse-grained and massive perovskite. A combination of characteristic features identified in the Afrikanda perovskite (equigranular crystal mosaics, interlocked irregular-shaped grains, and massive zones) is observed in other oxide ore deposits, particularly in layered intrusions of chromitites and intrusion-hosted magnetite deposits and suggests that the same amalgamation processes may be responsible for some of the coarse-grained and massive textures observed in oxide deposits worldwide.     

THE GEOCHEMISTRY OF TANTALUM AND NIOBIUM

Ta and Nb are associated in nature. Both are oxyphile and are related geochemically to Fe, Mn, Ti, rare earths U, Th, Zr, W, Sn, Bi, and Sb. Both accompany the alkali metals,especially Na and Li. Their close relationship explains their isomorphism in mineral-forming processes. Zr, W, and Sn entrain Ta and Nb in the crystal lattices of their minerals in limited amounts. The concentration of Ta and Nb increases in the course of magma evolution from ultrabasic to alkalic. Nb predominates over Ta in the main kinds of rocks by from 5:1 to 17:1. Only in granite pegmatites is Ta dominant. In granitic rocks Ta and Nb are associated with Fe, Mn, Bi, Sb, W, and Sn. In granosyenitic complexes they form complex minerals with Ti, rare earths of the Y subgroup, U, and Th. Concentrations of Ta and Nb in granitic and granosyenitic complexes increase toward the end of the magmatic and pegmatitic processes, and afterward diminish toward the end of the pneumatolytic-hydrothermal processes. In alkalic complexes Ta and Nb are associated with Ti, rare earths of the Ce group, and Th. Concentrations of Ta and Ni in alkalic massifs are caused by magmatic differentiation. In alkalic ultrabasic complexes, in magmatic and pegmatitic processes, Ta and Nb do not form independent minerals but enter into minerals of Ti and Fe, i. e. perovskite, titanomagnitite, and pyroxenes. --M. Russell.     

钙钛矿-锶钛矿-钠镧钛矿体系化合物晶体化学的研究概况

钙钛矿—锶钛矿—钠镧钛矿三元系是钙钛矿族矿物的典型代表。常温常压下CaTiO3为Pbnm结构，但随温度增高可分别相变为I4／mcm和Pm3m结构；SrTiO3的稳定结构是Pm3m14／mcm相；Na／2Ln1／2TiO3的结构则随Ln代表的元素种类不同而有所差异。三个端员组分在压力下的结构变化均没有明确的结论。在三个二元系中，只有CaTiO3—SrTiO3体系研究较深入，并已给出了T-X相图。本从样品的合成实验及高温和高压原位测量等方面展望钙钛矿型化合物的晶体化学研究及其意义。