New data on REE and rare-metal mineralization in pegmatites of the Slyudyanogorsk muscovite deposit in the Southern Urals

The Slyudyangorsk muscovite deposit in the southern Urals was explored and mined in 1926–1957. By the mid-1950s, 104 veins of quartz–feldspar pegmatites including 21 muscovite-bearing veins have been found. Pegmatites with giant black Y-bearing epidote crystals are crosscut by veins with giant muscovite crystals, which, in turn, are intersected by veins of two-mica–quartz–two-feldspar pegmatites with rare-metal and REE mineralization. Microprobe data on compositions of complex Ti–Ta–Nb oxides [fergusonite-(Y), samarskite-(Y), euxenite-(Y), polycrase-(Y), columbite-(Fe), pyrochlore supergroup] are characterized, as well as of uraninite, ilmenorutile, scheelite, Y-bearing epidote, certain sulfides and rock-forming minerals from the Slyudyanogorsk deposit. The morphology and interrelation of minerals indicate that they are the result of crystal growth in cavities rather than of metasomatic replacement of gneisses, as has been suggested earlier. Thus, it is more promising for rare-metal and REE minerals in the Slyudorudnik area to be found in igneous rocks (granitic muscovite–quartz–feldspar pegmatites with the Nb–Ta–Ti–Y–U–W–Mo mineralization) than in metasomatic 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.     

法国Beauvoir花岗岩中烧绿石族矿物的研究

在法国Ｂｅａｕｖｏｉｒ花岗岩中，烧绿石－细晶石族矿物是重要的铌钽矿物之一，主要出现在岩体的上部。大部分晶体为自形，白色、谈黄色或谈绿色，粒径为微米至毫米级。３０多个电子探针分析结果表明，主要成分为Ｎａ、Ｃａ、Ｕ、Ｎｂ，Ｔａ、Ｆ．从岩体的下部到上部，烧绿石族矿物的Ｎｂ／（Ｎｂ＋Ｔａ）比值呈升高的趋势。这些矿物富含铀，Ｕｏ＿２含量最高达１５．０５％，部分烧绿石和细晶石为铀烧绿石和铀细晶石；另一方面，在岩体下部，细晶石中Ｕｏ＿２含量平均为６．３％，而在岩体上部，烧绿石和细晶石中的Ｕｏ＿２平均含量为９．０％     

Geochemical diversity of minerals of the pyrochlore group

A systematic and rational nomenclature of minerals of the pyrochlore group are developed based on the results obtained by processing 671 chemical analyses of pyrochlore-group minerals from carbonatite complexes, alkali rocks, and their pegmatites, granite pegmatites, and alkali and albitized granites. The proportions of Nb, Ta, and Ti are typomorphic of pyrochlore from these four types of geological environments. The paper lists pervasive characteristics of the distribution of Na and Ca, REE, Th and U, Sr and Ba, K and Cs, Pb, Sn, Sb, and Bi in the minerals. Based on the occurrence of compositions with elevated concentrations of typomorphic elements at site B in the structure of the minerals, pyrochlore subspecies are recognized: pyrochlore, Ta-pyrochlore, Ta,Ti-pyrochlore, Zr-pyrochlore, Nb-betafite, Ta-betafite, Ti-betafite, Ti-microlite, Nb,Ti-microlite, Nb-microlite, and microlite, as well as 60 geochemically significant varieties with the predominance of certain cations at site A (REE-pyrochlore, U-pyrochlore, etc.). Aspects of a rational systematics of minerals of complicated isomorphic series are discussed.     

Dispersed mineralization in granitic rocks in the Dukat ore field,the Russian Northeast: Sources and relationship with epithermal gold-silver and silver-base-metal ores

The dispersed mineralization in the Late Cretaceous leucogranite of the Dukat ore field comprises melanocratic high-sulfide epidote-feldspar, pyroxene-feldspar and low-sulfide allanite-fluorite-feldspar inclusions in greisenized intrusions. The silver-base-metal mineralization is composed of pyrite, pyrrhotite, small particles of Pb, Zn, Sn, Ag, and Sb sulfides and oxides, their native species, and intermetallic compounds; the rare-metal mineralization consists of REE, Th, U, Ti, Zr, Nb, Ta, and W oxides, silicates, and aluminosilicates. The isotopic Nd, Sr, and Pb isotopic compositions and geochemical characteristics of the mineralized inclusions, rock-forming minerals of granitoids, hydrothermal minerals of preore metasomatic propylites and orebodies at the Dukat deposit show that their components have been taken from heterogeneous domains of the Paleozoic juvenile continental crust of the Siberian Platform.     

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.     

Uranium and thorium in carbonatitic minerals from the Guli massif, Polar Siberia

This paper reports a geochemical and mineralogical study on carbonatites from the Guli massif, which hosts rare-metal mineralization. The principal carriers of radioactive elements in the carbonatites are pyrochlore-group minerals, zirconolite, and thorianite, which are described here. They are characterized by elevated concentrations (wt %) of radioactive elements: up to 17.89 UO₂ and 20.01 ThO₂ in pyrochlore, up to 6.49 UO₂ and 94.29 ThO₂ in thorianite, and up to 6.74 ThO₂ in zirconolite. The pyrochlore-group minerals, zirconolite, and thorianite from the early calcite carbonatites occur in intimate association with Ti-Zr oxides calzirtite, perovskite, and baddeleyite. Significant radioactive element fractionation in early-stage derivatives results in the depletion of the residual magmatic products in these elements. The dolomite carbonatites are reported to contain only trace amounts of pyrochlore-group minerals. It was shown that the distribution of U, Th, Nb, and Ta in the calcite and dolomite carbonatites is correlated with the evolutionary trends of pyrochlore composition. Typical schemes of isomorphic substitution are proposed for pyrochlore-group minerals and zirconolite. The pyrochlore-group minerals show an apparent evolutionary trend from U-rich towards more Th- and Ta-rich varieties, and Ba-Sr cation-deficient varieties originate during the latest stage of the evolution. The pyrochlore-group minerals, zirconolite, and thorianite may also accumulate in placers, together with gold. Because of the relative ease of extraction of the accessory minerals, the carbonatites of the Guli massif can be considered as commercial sources of radioactive raw materials.     

The origin of rutile-ilmenite aggregates (“nigrine”) in alluvial-fluvial placers of the Hagendorf pegmatite province, NE Bavaria, Germany

Summary Titanium placer deposits occur in alluvial-fluvial drainage systems which dissect Moldanubian gneisses intruded by Late Variscan pegmatites (Hagendorf province) in southern Germany. Based upon their texture (zonation, exsolution lamellae, intergrowth), microchemical data (Nb, Cr, Ta, V, Fe, W, Sn) and mineral inclusions, two major grain types of intergrown rutile and ilmenite have been established. Grains of type A are always zoned and consist of rutile cores enveloped by ilmenite containing small inclusions of wolframite. A core-rim transition zone is characterized by complex relations of rutile and ilmenite, with rutile lamellae being rich in Nb, V and Fe. Types B1 and B2 aggregates consist of ilmenite with lamellae of niobian rutile and/or ilmenorutile, and additionally have inclusions of ferrocolumbite, pyrochlore, betafite, sphalerite, pyrrhotite and Fe oxides. Such grain types featuring an intimate intergrowth of rutile and ilmenite were called nigrine. Type-C grains are quite similar in their morphological appearance but consist of W-enriched rutile devoid of mineral inclusions and reaction products. Pseudorutile and leucoxene replacing minerals of the nigrine aggregates are presumably caused by supergene alteration under fluctuating redox conditions. Phosphate and aluminum remobilized by supergene processes led to the formation of hydrous Ti-rich phases containing Al, P and Fe. High Nb and W concentrations in nigrine aggregates and in rutile type C may be taken as a marker for highly differentiated granites or pegmatites. This has implications for both, heavy-mineral-based provenance analysis and stream sediment exploration.     

我国稀土铌钽矿物学研究回顾与展望

作为高新技术原料用的稀土铌钽是国家发展的支柱之一, 稀土铌钽矿物学研究在与国家的技术进步同步前进。 通过研究,已经获得了我国产出的全部百余种稀土铌钽矿物的化学组成、物理性质、稀土配 分、结晶参数、共生组合和产状成因的全面系统的鉴定描述成果;发现了多种稀土铌钽新物,并提出许多新规律和新理论,建立了易解石和褐钇铌矿两个新的矿物族;确定了稀土铌钽铁锰钨的复杂氧化物的晶体结构关系;确立变生矿物学为矿物学研究的一个特殊分支,探讨了稀土次生富集的离子型稀土矿成矿机理。     

REE Minerals in the Rocks of the Katugin Rare Metal Deposit,East Transbaikalia: Behavior of Lanthanides and Y during Crystallization of an F-Saturated Agpaitic Melt

The chemical composition and origin of major REE minerals of aegirine, aegirine–arfvedsonite, arfvedsonite, and annite–riebeckite–arfvedsonite granites are studied for the Katugin Ta–Nb–Zr–Y deposit with cryolite in the southwestern part of the Aldan Shield. The REE mineralization of granites includes two types: (i) disseminated grains of pyrochlore and, to a lesser extent, other Nb–Ln oxides, Ln phosphates, and Ln–F carbonates in association with zircon, ilmenite, sphalerite, and other minerals and (ii) interstitial intergrowths of Ln fluorides.

     

In situ analyses of micas in the Yashan granite,South China: Constraints on magmatic and hydrothermal evolutions of W and Ta–Nb bearing granites

Most rare-metal granites in South China host major W deposits with few or without Ta–Nb mineralization. However, the Yashan granitic pluton, located in the Yichun area of western Jiangxi province, South China, hosts a major Nb–Ta deposit with minor W mineralization. It is thus important for understanding the diversity of W and Nb–Ta mineralization associated with rare-metal granites. The Yashan pluton consists of multi-stage intrusive units, including the protolithionite (-muscovite) granite, Li-mica granite and topaz–lepidolite granite from the early to late stages. Bulk-rock REE contents and La/Yb ratios decrease from protolithionite granite to Li-mica granite to topaz–lepidolite granite, suggesting the dominant plagioclase fractionation. This variation, together with increasing Li, Rb, Cs and Ta but decreasing Nb/Ta and Zr/Hf ratios, is consistent with the magmatic evolution. In the Yashan pluton, micas are protolithionite, muscovite, Li-mica and lepidolite, and zircons show wide concentration ranges of ZrO₂, HfO₂, UO₂, ThO₂, Y₂O₃ and P₂O₅. Compositional variations of minerals, such as increasing F, Rb and Li in mica and increasing Hf, U and P in zircon are also in concert with the magmatic evolution from protolithionite granite to Li-mica granite to topaz–lepidolite granite. The most evolved topaz–lepidolite granite has the highest bulk-rock Li, Rb, Cs, F and P contents, consistent with the highest contents of these elements and the lowest Nb/Ta ratio in mica and the lowest Zr/Hf ratio in zircon. Ta–Nb enrichment was closely related to the enrichment of volatile elements (i.e. Li, F and P) in the melt during magmatic evolution, which raised the proportion of non-bridging oxygens (NBOs) in the melt. The rims of zoned micas in the Li-mica and topaz–lepidolite granites contain lower Rb, Cs, Nb and Ta and much lower F and W than the cores and/or mantles, indicating an exotic aqueous fluid during hydrothermal evolution. Some columbite-group minerals may have formed from exotic aqueous fluids which were originally depleted in F, Rb, Cs, Nb, Ta and W, but such fluids were not responsible for Ta–Nb enrichment in the Yashan granite. The interaction of hydrothermal fluids with previously existing micas may have played an important role in leaching, concentrating and transporting W, Fe and Ti. Ta–Nb enrichment was associated with highly evolved magmas, but W mineralization is closely related to hydrothermal fluid. Thus these magmatic and hydrothermal processes explain the diversity of W and Ta–Nb mineralizations in the rare-metal granites.     

Coprecipitation of Ti,Mo, Sn and Sb with fluorides and application to determination of B,Ti, Zr,Nb, Mo,Sn, Sb,Hf and Ta by ICP-MS

We examined the coprecipitation behavior of Ti, Mo, Sn and Sb in Ca–Al–Mg fluorides under two different fluoride forming conditions: at < 70 °C in an ultrasonic bath (denoted as the ultrasonic method) and at 245 °C using a Teflon bomb (denoted as the bomb method). In the ultrasonic method, small amounts of Ti, Mo and Sn coprecipitation were observed with 100% Ca and 100% Mg fluorides. No coprecipitation of Ti, Mo, Sn and Sb in Ca–Al–Mg fluorides occurred when the sample was decomposed by the bomb method except for 100% Ca fluoride. Based on our coprecipitation observations, we have developed a simultaneous determination method for B, Ti, Zr, Nb, Mo, Sn, Sb, Hf and Ta by Q-pole type ICP-MS (ICP-QMS) and sector field type ICP-MS (ICP-SFMS). 9–50 mg of samples with Zr–Mo–Sn–Sb–Hf spikes were decomposed by HF using the bomb method and the ultrasonic method with B spike. The sample was then evaporated and re-dissolved into 0.5 mol l^− 1 HF, followed by the removal of fluorides by centrifuging. B, Zr, Mo, Sn, Sb and Hf were measured by ID method. Nb and Ta were measured by the ID-internal standardization method, based on Nb/Mo and Ta/Mo ratios using ICP-QMS, for which pseudo-FI was developed and applied. When 100% recovery yields of Zr and Hf are expected, Nb/Zr and Ta/Hf ratios may also be used. Ti was determined by the ID-internal standardization method, based on the Ti/Nb ratio from ICP-SFMS. Only 0.053 ml sample solution was required for measurement of all 9 elements. Dilution factors of ≤ 340 were aspirated without matrix effects. To demonstrate the applicability of our method, 4 carbonaceous chondrites (Ivuna, Orgueil, Cold Bokkeveld and Allende) as well as GSJ and USGS silicate reference materials of basalts, andesites and peridotites were analyzed. Our analytical results are consistent with previous studies, and the mean reproducibility of each element is 1.0–4.6% for basalts and andesites, and 6.7–11% for peridotites except for TiO₂.     

Magmatic–hydrothermal rare-element mineralization in the Songshugang granite (northeastern Jiangxi,China): Insights from an electron-microprobe study of Nb–Ta–Zr minerals

The Songshugang granite, hidden in the Sinian metasedimentary stratum, is a highly evolved rare-element granite in northeastern Jiangxi province, South China. The samples were systematically taken from the CK-102 drill hole at the depth of 171–423 m. Four types of rocks were divided from the bottom upwards: topaz albite granite as the main body, greisen nodules, topaz K-feldspar granite and pegmatite layer. Electron-microprobe study reveals that the rare-element minerals of the Songshugang granite are very different from those of other rare-element granites. Mn^# [Mn/(Fe + Mn)] and Ta^# [Ta/(Nb + Ta)] of columbite-group minerals and Hf^# [Hf/(Zr + Hf)] of zircon are nearly constant within each type of rocks. However, back-scattered electron imaging revealed that Nb–Ta oxides and zircon of the Songshugang granite, especially those of topaz albite granite, topaz K-feldspar granite and greisen, are commonly characterized by a specific two-stage texture on the crystal scale. The early-stage Nb–Ta oxide is simply subhedral-shaped columbite-(Fe) (CGM-I) with low Mn^# (0.16–0.37) and Ta^# (0.05–0.29). Columbite-(Fe) is penetrated by the later-stage tantalite veinlets (CGM-II) or surrounded by complex Nb–Ta–Sn–W mineral assemblages, including tantalite-(Fe), wodginite (sl), cassiterite, and ferberite. Tantalite has wide range of Mn^# values (0.15–0.88) from Fe-dominance to Mn-dominance. Wodginite with Ta>Nb has large variable concentrations of W, Sn and Ti. Cassiterite and ferberite are all enriched in Nb and Ta (Nb₂O₅ + Ta₂O₅ up to 20.12 wt.% and 31.42 wt.%, respectively), with high Ta^# (>0.5). Similar to Nb–Ta oxides and Nb–Ta–Sn–W mineral assemblages, the early-stage zircon is commonly included by the later-stage zircon with sharply boundary. They have contrasting Hf contents, and HfO₂ of the later-stage zircon is up to 28.13 wt.%. Petrographic features indicate that the early-stage of columbite and zircon were formed in magmatic environment. However, the later-stage of rare-element minerals were influenced by fluxes-enriched fluids. Tantalite, together with wodginite, cassiterite, and ferberite implies a Ta-dominant media. An interstitial fluid-rich melt enriched in Ta and flux at the magmatic–hydrothermal transitional stage is currently a favored model for explaining the later-stage of rare-element mineralization.     

Review of melting experiments on carbonated eclogite and peridotite: insights into mantle metasomatism

Experimental studies on the partial melting of eclogite and peridotite provide important clues on mantle metasomatism. Here, we review results from some of the recent experiments and show that melting of carbonated eclogite and peridotite can produce carbonatitic to carbonated silicate melt, in which carbonates melt preferentially before Ti oxides and silicates. Low-degree melting results in carbonatitic melt coexisting with Ti oxides and silicates. This process also leads to the fractionation between some high-field strength elements (Nb, Ta, Zr, Hf, and HREE) and highly incompatible elements (U and Th) in the melt. When Ti oxides are nearly exhausted in eclogite, extremely high TiO₂ contents (e.g. 19 wt.%) are present in the melt with marked concentration of Nb and Ta. These results help to explain the features of carbonatitic metasomatism and the Nb–Ta spike in oceanic island basalts as identified in experimental studies. These studies also explain the reducing conditions that stabilize diamond in the deep mantle (>150 km) as well as the occurrence of diamond at different depths reported in various studies. Melting in such a reduced mantle can happen through redox reaction between diamond, pyroxene, and olivine, in which the initial liquid is a carbonated silicate melt. However, the theoretical oxygen fugacity (fO₂) in the asthenosphere is much lower than that predicted by the reaction and requires elevated fO₂, which can be caused by the addition of relatively oxidized materials from the lower mantle, deep asthenospheric material, and various recycled components. A combination of these processes generates locally oxidized domains in the deep mantle.     

Evolution of chemical composition of pyrochlore group minerals from phoscorites and carbonatites of the Khibina alkaline massif

Phoscorites and carbonatites of the Khibina alkaline massif, Russia contain three minerals of the pyrochlore group. They are, in order of crystallization: uranpyrochlore and pyrochlore in the phoscorites, and pyrochlore and bariopyrochlore in late calcite carbonatites. Early calcite carbonatites also contain uranpyrochlore and pyrochlore, but they are xenocrysts derived from the phoscorites. Alteration of the pyrochlore group minerals led to increasing U, Ti and water contents and decreasing Na, Ca, Nb and F contents. Crystallization of zoned uranpyrochlore to pyrochlore crystals in the phoscorites is explained by the experiments of Ryabchikov and Hamilton (1993, 1994) on the interaction of carbonate-phosphate melts with mantle peridotites.     

松树岗钽铌钨锡矿床石英脉的矿物学研究——云母和黑钨矿成分对热液成矿过程的制约

矿石矿物和脉石矿物的成分演化蕴含了热液成矿过程的详细信息。本文基于岩相学观察,从云母和黑钨矿着手,利用电子探针和LA-ICP-MS分析技术,对赣东北松树岗Ta-Nb-W-Sn矿床的浅部热液成矿过程开展了研究。结果表明,松树岗矿床浅部的钨锡矿体的石英脉,从早到晚,由深至浅,可以划分为黑钨矿石英脉、锡石石英脉、硫化物石英脉和贫矿石英脉。4类石英脉中都含有早期的铁锂云母和晚期的白云母与铁的氧化物集合体,深部早期脉中的云母以铁锂云母为主,而浅部晚期脉中的云母以白云母为主。与早期铁锂云母相比,晚期白云母具有明显较低的Ti、Na、Rb、Cs、W、Nb、Zn、Li_2O含量和明显较高的Pb、Cu、B含量。从深部早期脉到浅部晚期脉,云母成分存在如下演化趋势:Ti、Na、W、Nb含量降低,Pb、Zn、Cu、Li_2O、B含量增高。不同深度的黑钨矿石英脉中含有两种不同成分的黑钨矿,属同一期演化早晚形成。相对于热液流体早期沉淀的黑钨矿,晚期黑钨矿具有明显较低的Nb、Ta、Zr、Hf、Ti、Sn、U、In、Sc含量和明显较高的Mo含量和Fe O/MnO值。云母和黑钨矿主微量元素成分的演化揭示了在松树岗矿床浅部的热液成矿早期以岩浆热液为主,晚期由于水岩反应的加强有较多围岩物质贡献。     

初论铌、钽和钨的成矿作用：实验研究

针对目前没有关于Ｗ和Ｎｂ、Ｔａ的成矿作用与富氟钠长花岗岩成因关系的统一认识和实验证据的缺乏，我们完成了Ｗ、Ｎｂ、Ｔａ在流体和熔体中分配的一些实验。本研究旨在借助实验结果解释Ｗ、Ｎｂ、Ｔａ矿床的成因联系及它们成矿的可能机制。实验结果表明：在钠长石花岗岩熔体结晶过程中发生了Ｎｂ、Ｔａ和Ｗ的明显分离；钨倾向于在流体中分布，而Ｎｂ、Ｔａ则具有向硅酸盐熔体分配的趋势，在岩浆结晶晚期以独立矿物形式存在。这些实验结果与野外地质观察到的结果一致。     

Natural and experimental constraints on formation of the continental crust based on niobium–tantalum fractionation

Fractionation between Nb and Ta, elements generally regarded as geochemical ‘identical twins’, is a key to deciphering the formation of the continental crust (CC). Here we show that Nb/Ta of rutile grains in eclogitic rocks from the Chinese Continental Scientific Drilling (CCSD) project are remarkably heterogeneous but overall subchondritic at core depths of 100–700 m, and are less variable and mainly suprachondritic at core depths of 700–3025 m, indicating clear Nb/Ta fractionation across a subducted slab. To understand the potential mechanism of Nb/Ta fractionation within the subducted plate, we analysed by laser ablation ICPMS a thermal migration experiment in which a wet andesite was placed in a large thermal gradient (300°C/cm with ends ranging from 950–350°C) at 0.5Gpa. Results show that Nb, Ta and Ti, driven by the thermal gradient, preferentially migrate by diffusion through supercritical fluids into the cooler end of the experiment (at 650–350°C). Due to contrasting Nb and Ta thermal migration patterns, dramatic fractionation between Nb, Ta, and Ti took place in the cooler end. Experimental results are consistent with the measured Nb, Ta in rutile from CCSD drillhole samples. We consider that major fractionation between Nb, Ta must occur before rutile appears, most likely during the prograde blueschist to amphibole–eclogite transformation, when Ti is also mobile. Before rutile appears, partitioning between Ti‐rich dominant minerals such as amphiboles and fluids in the hotter region where dehydration preferentially occurs, produces Nb–Ta–Ti‐rich fluids with subchondritic Nb/Ta, and dehydration residues with suprachondritic Nb/Ta. Meanwhile, owing to evolution of the thermal gradient within the subducting slab, thermal migration of Nb, Ta, and Ti in aqueous fluids result in Nb, Ta, and Ti enrichment in the cooler region and depletion in the hotter region. As a result of high‐pressure metamorphism, hydrous rutile‐rich eclogites with overall subchondritic Nb/Ta form in the cooler region, whereas relatively anhydrous rutile‐poor eclogites with suprachondritic Nb/Ta form in the hotter region. Subsequently, partial melting of hydrous rutile‐rich eclogites with initial subchondritic Nb/Ta at deeper levels transfers overall subchondritic Nb/Ta coupled with Nb, Ta, and Ti depletion characteristics to the CC, leaving dry rutile‐poor eclogites with suprachondritic Nb/Ta and rutile‐rich residual eclogites with overall, heterogeneous subchondritic Nb/Ta as a complementary reservoir to the CC.     

白云岩风化剖面元素地球化学特征:对黔中九架炉组“三稀金属”富集机制的启示

黔中早石炭世九架炉组铝土矿含矿岩系富集Ti、Li、Sc、V、Ga、Nb、Ta、Zr、Hf、Th和稀土(REEs)等"三稀金属",具有成为独立矿床或伴生资源的潜力。这些元素大部分与九架炉组共有同一母岩,且富集程度受母岩的成分和风化作用控制。本研究选取九架炉组母岩乌当娄山关群白云岩和纳雍牛蹄塘组泥质白云岩的现代风化剖面为研究对象,研究元素在风化作用过程中的迁移特征及分布规律,进而为九架炉组微量元素的富集机制提供启示。研究获得以下认识:1)依据剖面结构、ZrHf、Nb-Ta、Y-Ho二元图特征及REE配分曲线和Eu/Eu*值的相似性表明研究区土层主要来源于基底或母岩的风化; 2)白云岩风化成土过程中Si、Fe、Cr、As、Sb、Ti、Nb、Ta、Zr、Hf、Th、REEs等元素化学性质相对稳定,富集程度较高,而Ca、Mg、Na、K、Sr、P、Mo、Cd等元素化学性质活泼,容易淋失亏损; 3)纳雍剖面REEs~(3+)和Ca~(2+)半径差与REEs富集系数相关性良好,表明碳酸盐岩风化过程中,含钙矿物磷灰石是稀土元素分配的重要控制因素; 4)九架炉组的母岩也是Ti、Li、Sc、V、Ga、Nb、Ta、Zr、Hf、Th等微量元素的主要物质来源,母岩风化过程中,这些微量元素首先在副矿物、黏土矿物、铝矿物及磷灰石等矿物相中初步富集,之后随风化碎屑物一起沉积形成微量元素超常富集地层; 5)纳雍剖面地表和地下水提供了部分P、Be、Zn、Sb、Pb、Y及REEs来源,指示水体迁入作用也是九架炉组REEs富集的重要原因。研究表明黔中九架炉组微量元素的来源较复杂,风化-沉积过程中,化学性质稳定的元素残留在风化碎屑物中并被搬运-沉积在负地形中,而化学性质活泼的元素首先被带入水体,在沉积-成岩过程中特定条件下发生二次富集作用(例如次生矿物的形成及吸附)形成微量元素富集的地层。     

Determination of Ge, As, Se and Te in Silicate Samples Using Isotope Dilution-Internal Standardisation Octopole Reaction Cell ICP-QMS by Normal Sample Nebulisation

A method for the determination of Ge, As, Se and Te in silicate samples using isotope dilution-internal standardisation (ID-IS) octopole reaction cell (ORC) ICP-QMS by normal sample nebulisation was developed. The method does not involve either hydride generation or ion exchange. Germanium, Se and Te were determined by isotope dilution (ID), and As was determined by ID-IS. A silicate sample with an added Ge-Se-Te spike was digested with an HF-HNO₃-HBr mixture, dried, re-dissolved with HF and the supernatant liquid was directly aspirated into an ORC-ICP-QMS instrument with He or H₂ gas. No matrix effects were observed down to a dilution factor (DF) of ∼ 70 for Ge, Se and Te and DF of ∼ 1000 for As, which resulted in 3s detection limits in silicates of 2, 1, 0.1 and 4 ng g⁻¹, respectively. Advantages of the method are the simple sample introduction as well as a capability of determining S, Ti, Zr, Nb, Mo, Sn, Sb, Hf and Ta by ID-IS-ICP-QMS/SFMS from the same solution. Furthermore, the total sample solution consumption was only 0.253 ml with DF = 2000. Therefore, only a 0.13 mg test portion was required. To demonstrate the applicability of this technique, Ge, As, Se and Te in eight silicate reference materials were determined, as well as S, Ti, Zr, Nb, Mo, Sn, Sb, Hf and Ta in four carbonaceous chondrites.