离子交换快速分离—ICP—AES测定岩石和水系沉积物中痕量钽和铌

铌钽矿物样品经氢氟酸—硫酸分解,可以用ICP-AES直接测定试液中的铌、钽及其它元素。痕量铌可用ICP-AES直接测定,但在某些岩石和水系沉积物中钽的含量往往甚微,(1ppm左右),ICP的灵敏度不够,某些基体元素干扰又较大,因此直接测定痕量钽有困难。 秦光荣等人曾提出过在稀盐酸-酒石酸溶液中,用阳离子交换树脂柱使铌钽与其它元素分离,但流出液体积较大。本文研究了一种快速离子交换分离的新方法。样品经碱溶、浸取、过滤,沉淀及滤     

5-Br-PADAP二波长联合分光光度法同时测定矿石中铌和钽

铌、钽的显色剂很多,但由于两元素性质相近,常互相干扰,特效的光度测定方法却不多,能同时测定的更少。 5-Br-PADAP近年已成功地用于测定铌,测钽时则无法消除铌的干扰,有人     

提高光谱分析微量钽铌结果准确度研究

发射光谱法简单、快速测定矿样中微量钽铌时,主要伴生元素锡对准确测定微量钽铌有辅助作用。改进在钨、铁等元素干扰存在时,钽铌分析线对选择。与化学分析测试结果比对验证后,发现光谱分析微量钽铌准确度得到很大提高,可满足地质找矿品位0.01%的需要。     

P204萃淋树脂对地质样品中痕量铌和钽的分离富集研究及其应用

研究结果表明，P204萃淋树脂在0．5—3mol／L HCl介质吸附钽，在1—8mol／L HCl介质吸附铌，1—3mol／L HCl介质中可同时吸附铌、钽。H2SO4 H2O2溶液解脱铌，酒石酸 HCl溶液解脱钽，H2SO4 H2C2O4溶液能同时解脱铌、钽，从而建立了新的铌和钽分离富集体系。分离后的铌、钽用光度法测定。方法用于测定地质样品中的铌和钽，结果与标准值符合，其RSD(n＝7)分别＜6％和9％。     

铌钽元素分析技术新进展

铌钽是发展新兴产业所需的功能性和结构性材料,铌钽矿产是国家重点支持的战略新兴矿产资源,开展相关物料中铌钽的分析技术研究具有重要意义。由于铌和钽的物理化学性质十分相似,彼此难以分离,且易水解,加之地质样品分解困难,因此铌和钽的分析测试一直困扰着分析工作者。本文重点对铌钽元素分析中的样品前处理技术和现代分析测试技术进行综述。样品前处理是铌钽分析的关键环节,结合分析方法和样品特性,选择合理的样品分解和分离富集方法是准确测定铌钽的前提。仪器分析是现代分析测试技术的主流,电感耦合等离子体发射光谱/质谱法(ICP-OES/MS)是目前测定铌钽应用最多的方法,需要解决共存组分的干扰、基体效应和盐类影响等问题。激光剥蚀(LA)技术、X射线荧光光谱法(XRF)和中子活化分析法(NAA)采用固体进样,避免了前期样品处理的繁琐步骤和杂质的引入,是铌钽元素分析发展的方向。     

5—Br—PADAP测定矿石中的铌

作者采用5-Br-PADAP 测定铌时,加入大量酒石酸消除钽对铌的干扰,加人乙醇提高灵敏度,因此,该方法准确,操作简便、快速,能分析矿石中0.001-x%的 Nb_2O_5。     

5-Br-PADAP萃取分光光度法测定矿石中微克量铌

目前测定铌钽方法范围为几十微克,对于少量样品中痕量铌、钽难于测定。 等研究了吡啶偶氮类八种衍生物与铋的反应,并发现与二十八种金属离子(包括铌)能生成有色络合物。其后等利用5-(3,5-溴-吡啶偶氮)-2-乙氨基对甲酚研制了测定铌的方法(0—60微克)。史慧明等研究了铌与5-Br-PADAP在各种络合剂体系中的反应行为,制定了测定数十微克铌的方法。文献还试验了络合物的有机溶剂萃取。     

5-Br-PADAP萃取分光光度法测定矿石中微克量铌

目前测定铌钽方法范围为几十微克,对于少量样品中痕量铌、钽难于测定。 等研究了吡啶偶氨类八种衍生物与铋韵反应,并发现与二十八种金属离子(包括铌)能生成有色络合物。其后等利用5-(3,5-溴-吡啶偶氮)-2-乙氨基对甲酚研制了测定铌的方法(0—60微克)。史慧明等研究了铌与5-Br-PADAP在各种络合剂体系中的反应行为,制定了测定数十微克铌的方法。文献还试验了络合物的有机溶剂萃取。     

离子交换分离——荧光分光光度法测定地质样品中痕量铌

荧光分光光度法测定痕量铌已有报导,其中文献曾报导过少数铌钽精矿样品中铌的测定,但未见广泛应用于各类地质样品中痕量铌的测定。我们在文献的基础上,进一步研究了铌在桑色素(morin)-十六烷三甲基溴化铵(CTMAB)胶束体系的荧光特性,共存元素的干扰及其用阳离子树脂交换分离的条件。实验测得本法检出限为0.27ng/ml,测定限为0.54ng/ml,比文献提高1.9倍;0.5μgNb经11次测定标准偏差为0.0125,变动系数为2.49％;标准加入回收率为:96.00—110.00％。实验结果表明:本法具有简单、灵敏、准确等特点,适合于岩石、土壤、水系沉积物等成分复杂的地质样品中痕量铌的测定。     

福建永定大坪铌钽矿床地质特征及铌钽矿物特征研究

福建永定大坪铌钽矿赋存于潜火山岩相碱长花岗斑岩内,主要有用组分为铌钽,矿石中铌钽品位达到工业指标要求。矿床具有埋藏浅和全岩矿化的特点,规模达大型以上。应用扫描电镜、电子探针、X-ray能谱分析、MLA矿物检测、光学显微镜等方法,对大坪铌钽矿中铌钽矿物特征进行了研究。研究结果表明:铌铁矿-钽铁矿类质同象系列矿物,是该矿石中钽铌主要的赋存矿物,呈自形—半自形针状、粒状、不规则状,大多为单矿物呈浸染状或其聚集体呈稀疏星点状分布于矿石中,少量细晶石含铌钽金红石。矿石中钽铌矿物粒度细小,平均粒度钽铌铁矿约80μm、细晶石约13μm、含钽铌金红石约14μm。类比宜春钽铌矿床,可能具有一定的可选性。     

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.     

二阶导数荧光光度法同时测定岩矿中铌和钽

本文研究了二阶导数荧光光度法同时测定岩矿中Nb和Ta。实验发现,在Nb(Ta)-桑色素-CTMAB荧光体系中,加入一定量乙醇,可使测定Ta的灵敏度显著提高,Ta的荧光强度与等量Nb相比约高10倍;利用二阶导数荧光光谱提高选择性,实现了Nb和Ta的同时测定。本文还采用BPR螯合树脂分离干扰元素和富集痕量Nb和Ta。方法用于地质样品分析,结果良好。     

Significance of Nb/Ta as an indicator of geochemical processes in the crust-mantle system

A mantle value of 17.5 for Nb/Ta appears well established; less well established are crustal values of 11–12, although it appears that Nb/Ta for crustal-derived melts is less than mantle Nb/Ta, demonstrating fractionation of these two elements during crustal evolution, and suggesting that Nb/Ta variation may be indicative of a particular chemical process within the crust-mantle system.

Experimental studies on silicate and carbonatitic liquids at high pressure indicate that, although silicate minerals such as garnet, amphibole and clinopyroxene do fractionate Nb and Ta, the partition coefficients (D's) for both elements are very low. Thus involvement of these minerals may explain relatively small changes in Nb/Ta, but appears inadequate to explain the crust-mantle variation. However, high-quality data for Nb, Ta may be used to provide information on mantle melting or metasomatic processes (e.g., amphibole in the source region decreases Nb/Ta in derived melts, while carbonatitic metasomatism will increase Nb/Ta in affected mantle). Titanate minerals have high D's for Nb and Ta, and do fractionate these elements (e.g., D_Nb/D_Ta rutile/liquid of 0.5–0.8), and their involvement in crystal fractionation would increase Nb/Ta in derivative liquids. In contrast, D_Nb/D_Ta for rutile/fluid is 1.25, so that rocks affected by fluid equilibrated with residual rutile will show a decrease in Nb/Ta

Some Archaean gneisses appear to have high Nb/Ta, and may be a complementary component to that part of the crust which has a relatively low Nb/Ta, such as crustal-derived magmas (e.g., A- ad I-type granites and silicic volcanics). Within the crustal system pegmatites are known to have extremely high and variable Nb, Ta contents, often with low Nb/Ta. A fluid is generally considered to be involved in the generation of these rocks. Thus it is possible that fluid/melt partitioning may be the key to fractionating Nb and Ta, with preference for Ta in the fluid, and enrichment of Ta relative to Nb into the mid-upper crustal system, as the crust evolved, through upward movement of fluid.     

Mechanisms of Archean crust formation inferred from high-precision HFSE systematics in TTGs

It has been proposed that Archean tonalitic-trondhjemitic-granodioritic magmas (TTGs) formed by melting of mafic crust at high pressures. The residual mineralogy of the TTGs (either (garnet)-amphibolite or rutile-bearing eclogite) is believed to control the trace element budget of TTGs. In particular, ratios of high-field-strength elements (HFSE) can help to discriminate between the different residual lithologies. In order to place constraints on the source mineralogy of TTGs, we performed high-precision HFSE measurements by isotope dilution (Nb, Ta, Zr, Hf) together with Lu-Hf and Sm-Nd measurements on representative, ca. 3.85-2.8 Ga TTGs and related rock types from southern West Greenland, W-India and from the Superior Province. These measurements are complemented by major and trace element data for the TTGs. Texturally homogeneous early Archean (3.85-3.60 Ga old) and Mesoarchean (ca. 3.1-2.8 Ga old) TTGs have both low Ni (<11 ppm) and Cr contents (<20 ppm), indicating that there was little or no interaction with mantle peridotite during ascent. Ratios of Nb/Ta in juvenile Eoarchean TTGs range from ca. 7 to ca. 24, and in juvenile Mesoarchean TTGs from ca. 14 to ca. 27. Even higher Nb/Ta (14-42) were obtained for migmatitic TTGs and intra-crustal differentiates, most likely mirroring further fractionation of Nb from Ta as a consequence of partial melting, fluid infiltration and migmatisation. In the juvenile TTGs, positive correlations between Nb/Ta and Gd/Yb, La/Yb, Sr/Y, Zr/Sm and Zr/Nb are observed. These compositional arrays are best explained by melting of typical Isua tholeiites in both, the rutile-bearing eclogite stability field (>15 kbar, high Nb/Ta) and the garnet-amphibolite stability field (10-15 kbar, low Nb/Ta). With respect to the low end of Nb/Ta found for TTGs, there is currently some uncertainty between the available experimental datasets for amphibole. Independent of these uncertainties, the TTG compositions found here still require the presence of both endmember residues. A successful geological model for the TTGs therefore has to account for the co-occurrence of both low- and high-Nb/Ta TTGs within the same geologic terrane. An additional feature observed in the Eoarchean samples from Greenland is a systematic co-variation between Nb/Ta and initial εHf(t), which is best explained by a model where TTG-melting occured at progressively increasing pressures in a pile of tectonically thickened mafic crust. The elevated Nb/Ta in migmatitic TTGs and intra-crustal differentiates can shed further light on the role of intra-crustal differentiation processes in the global Nb/Ta cycle. Lower crustal melting processes at granulite facies conditions may generate high-Nb/Ta domains in the middle crust, whereas mid-crustal melting at amphibolite facies conditions may account for the low Nb/Ta generally observed in upper crustal rocks.     

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.     

The key role of mica during igneous concentration of tantalum

Igneous rocks with high Ta concentrations share a number of similarities such as high Ta/Nb, low Ti, LREE and Zr concentrations and granitic compositions. These features can be traced through fractionated granitic series. Formation of Ta-rich melts begins with anatexis in the presence of residual biotite, followed by magmatic crystallization of biotite and muscovite. Crystallization of biotite and muscovite increases Ta/Nb and reduces the Ti content of the melt. Titanium-bearing oxides such as rutile and titanite are enriched in Ta and have the potential to deplete Ta at early stages of fractionation. However, mica crystallization suppresses their saturation and allows Ta to increase in the melt. Saturation with respect to Ta and Nb minerals occurs at the latest stages of magmatic crystallization, and columbite can originate from recrystallization of mica. We propose a model for prediction of intrusion fertility for Ta.     

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。     

四川小金-理县一带铌钽矿成矿预测研究

四川小金-理县一带发育有燕山期和印支期两期花岗岩,存在稀有金属化探异常,已发现多处稀有金属矿(化)点,具有较好的铌钽成矿地质条件.该区内Nb、Ta具有印支期和燕山期两期成矿模式,前者富Ta,后者富Nb.岩体化学成分上以富碱为特征,Nb、Ta与Ti、Na、K相关性较好.通过对区域地质、区域地球物理、地球化学特征和已知矿床矿点的对比,研究了含矿岩体的岩石化学、岩石地球化学特征.在此基础上划分出4个铌钽找矿远景区,预测了资源远景储量(334)为Ta2O5 200～500t,Nb2O5 300～600t.     

Nb/Ta fractionation observed in eclogites from the Chinese Continental Scientific Drilling Project

This paper reports detailed analyses of Nb and Ta concentrations of 19 eclogite samples and their principal mineral constituents from the main drill hole of the Chinese Continental Scientific Drilling Project (CCSD) and nearby outcrops. We observe highly fractionated and overall suprachondritic Nb/Ta values in minerals, e.g., rutile (4.8–87), titanite (12–62) and amphibole (2.0–67). Amphiboles in amphibolites (retrograded from eclogite) can be classified into two groups: a low Nb/Ta group that bears higher Al contents and is thus of higher pressure origin, and a high Nb/Ta, lower pressure group. The former group was likely formed during subduction; the latter may have formed during exhumation in the presence of rutile and titanite. The significant Nb/Ta fractionation in rutile and other minerals may reflect early dehydration of the subducted slab at shallow depths before the formation of rutile, which occurs at depths ≥50 km. The dehydration, with amphiboles existing as the main Nb–Ta-bearing phase, would lead to Nb/Ta fractionation, i.e., forming subchondritic Nb/Ta ratios in the released fluids and, complementarily, suprachondritic Nb/Ta ratios in the residual phases. While a large proportion of the fluids may escape from the slab to the mantle wedge, considerable amounts of the fluids can be retained in hydrous minerals within the descending slab, thus forming hydrated cold eclogites with subchondritic Nb/Ta characteristics. As subduction continues to depths over 50 km, rutile appears and consequently controls the Nb–Ta budget. In the presence of rutile, melting of the hydrated cold eclogites with very low Nb/Ta ratios would form magmas with negative Nb, Ta anomalies and subchondritic Nb/Ta. Further dehydration of the continuously descending slab results in even more fractionated Nb/Ta ratios in subsequently released fluids and residues, providing a feasible explanation for the large Nb/Ta variation observed in the modern arc magmas and residual eclogites.     

Nb–Ta fractionation by partial melting at the titanite–rutile transition

During the evolution of the Earth, distinct geochemical reservoirs with different Nb/Ta ratios have developed. Archean granitoids of the tonalite–trondhjemite–granodiorite (TTG) suite, which represent the Earth’s early continental crust, show larger Nb/Ta variations than any other Earth reservoir. This implies that significant Nb–Ta fractionation must have occurred during early crust formation, while the underlying mechanism behind is still unclear. Here, we present a new model on how Nb may be fractionated from Ta during partial melting of subducted oceanic crust. Our data show that Nb/Ta ratios in melts derived from rutile- and titanite-bearing eclogite are largely controlled by the modal relative abundances of rutile and titanite in the source. High modal ratios of titanite over rutile generate melts with very high Nb/Ta (>60), whereas low modal titanite/rutile produces melts with much lower Nb/Ta (≤30). Very low Nb/Ta (<16) occur when all Ti-phases are consumed at very high degrees of melting. As the modal ratio of titanite to rutile is a function of pressure, the Nb/Ta of melts is a function of melting depth. Our new model helps to explain the extreme variation of Nb/Ta observed in many TTGs and thus how Nb and Ta were fractionated during the early evolution of the Earth. Furthermore, the model also indicates that simple one-stage melting models for mafic crust are not sufficient to explain the formation of TTGs.