In-situ LA-ICP-MS trace elemental analyses of magnetite: The Bayan Obo Fe-REE-Nb deposit,North China

The Bayan Obo Fe-REE-Nb deposit in northern China is the world's largest light REE deposit, and also contains considerable amounts of iron and niobium metals. Although there are numerous studies on the REE mineralization, the origin of the Fe mineralization is not well known. Laser ablation (LA) ICP-MS is used to obtain trace elements of Fe oxides in order to better understand the process involved in the formation of magnetite and hematite associated with the formation of the giant REE deposit. There are banded, disseminated and massive Fe ores with variable amounts of magnetite and hematite at Bayan Obo. Magnetite and hematite from the same ores show similar REE patterns and have similar Mg, Ti, V, Mn, Co, Ni, Zn, Ga, Sn, and Ba contents, indicating a similar origin. Magnetite grains from the banded ores have Al + Mn and Ti + V contents similar to those of banded iron formations (BIF), whereas those from the disseminated and massive ores have Al + Mn and Ti + V contents similar to those of skarn deposits and other types of magmatic-hydrothermal deposits. Magnetite grains from the banded ores with a major gangue mineral of barite have the highest REE contents and show slight moderate REE enrichment, whereas those from other types of ores show light REE enrichment, indicating two stages of REE mineralization associated with Fe mineralization. The Bayan Obo deposit had multiple sources for Fe and REEs. It is likely that sedimentary carbonates provided original REEs and were metasomatized by REE-rich hydrothermal fluids to form the giant REE deposit.     

东蒙地区夕卡岩石榴石稀土元素地球化学及其成因

东蒙地区为我国北方重要的夕卡岩型锡银铜铅锌多金属成矿区，不仅矿床发育，而且成矿种类较多，典型矿床有黄岗梁Fe（Sn）、白音诺Pb-Zn-Ag等金属和浩布高Fe（Sn）－PbZnAg（Cu）矿床。研究表明，它们都是中生代岩浆岩与本区二叠系地层相互作用的产物。本文通过对黄岗梁、白音诺和浩布高3个矿床中不同阶段的石榴石夕卡岩矿物学研究，划分出早晚两期夕卡岩石榴石矿物。早期以浅色、他形细粒、均质的钙铁榴石为主，多形成环带的核心；晚期以深色、半自形中粗粒、弱非均质的钙铝榴石为主，多构成环带的边部。同时采用ICP－MS方法对3其中石榴石比较发育的黄岗梁和浩布高2个矿床中石榴石单矿物进行了稀土元素含量的测定。结果表明，矿区早期的石榴石具有岩浆成因的特征，晚期石榴石具有热液交代成因特征，即东蒙地区既有早期岩浆阶段的岩浆型夕卡岩，又有晚期热液交代型夕卡岩的多成因认识。     

REE in fluid inclusions of quartz from gold deposits of north-eastern Russia

Inductively coupled plasma-mass spectrometry (ICP-MS) has been used to determine rare earth element concentrations in aqueous solutions extracted from fluid inclusions. Quartz has been sampled from ores of three major types of polygenic gold hydrothermal systems of North-Eastern Russia: (1) gold-quartz-sulphide (Au-Q, Nezhdaninsk); (2) gold-antimony (Au-Sb, Sarylakh) and (3) intrusion-related gold-bismuth-siderite-polysulphide (Au-Bi-Sid, Arkachan) large deposits located in terrigenous rocks of the Verkhoyansk fold belt. The total concentration of REE in the fluid inclusions is not high (up to 52 ppm). The contribution of LREE dominates in REE balance (??LREE/??HREE=7.4?C112.1). The chondrite-normalized REE patterns of inclusion fluids for the Au-Q and Au-Bi-Sid deposits are characterized by LREE enrichment with a positive or negative Eu anomaly. REE patterns for the regenerated quartz from Au-Sb deposits are characterized by pronounced differentiation between light and heavy lanthanides in fluid inclusions. Significant total REE concentration decreasing (on 1?C2 order) from early to late stages of Nezhdaninsk and Arkachan deposits is revealed. The positive correlations of total REE concentrations with Rb, Cs, Li and B contents in fluid inclusions are shown. The REE distribution in fluid inclusions can be used as indicators of the contribution of magmatic fluid in the hydrothermal system.     

Rare earth elements in supergene phosphorites

An analysis of rare earth elements in various types of supergene phosphorites established the following sequence of increasing average total contents (ppm): phosphorite from Christmas Island in the Indian Ocean, 3.89; spelean coprolitic phosphorite, 21.98; phosphorite from the weathering zone of sedimentary rocks, 27.41; phosphorite from the weathering zone of endogenous rocks, 372.32; and lacustrine coprolitic phosphorite, 461.59. Supergene phosphorites, especially the most common among them from the weathering zone of sedimentary rocks, are significantly depleted relative to marine phosphorites both in average and maximum REE contents. The REE contents of supergene phosphorites are controlled by several factors, including the REE contents in the primary rocks affected by weathering, the physicochemical conditions of phosphorite formation, the presence of a biogenic component in the phosphatogenetic system, and the structural type of the phosphorites. There is a strong positive correlation within the group of light and, in part, middle REEs (La, Ce, Nd, Sm, and Eu) and between the heavy REEs Yb and Lu, whereas the correlation between these two groups is weaker or insignificant. Gd and Tb are well correlated with the elements of both groups.     

黔中陡山沱期磷块岩成因的系统研究

黔中成磷区是中国南方陡山沱成磷期磷块岩矿床的重要组成部分。包括瓮福、开阳两个大型磷块岩矿床和若干中小型磷矿床。本文从磷的来源、沉积和富集3个方面系统地揭示了该区磷块岩的成因。稀土元素分析表明,磷可能来自同期海底火山喷发物。海洋地球化学、生物化学及磷块岩的组构研究证明,藻类生物的吸收和固定作用是磷质沉积的主要途径。磷的富集的多阶段、多因素的,经历不同的富集阶段(或方式)形成不同的磷块岩类型。     

Reconstruction of phosphate formation environments (from data on distribution of lanthanides)

The criteria for the evaluation of the REE composition of phosphorites and sedimentary rocks have been determined. These data are required to reconstruct depositional environments. Literature data on the geochemistry of some phosphorite deposits of Eurasia are considered. The REE patterns of Mesozoic phosphorites of the East European Platform are studied. On the basis of REE contents, the ratios of lanthanides and fields on the La–(Nd + Sm)–(Y + Dy), La–(Ce + Nd + Sm)–(Y + Dy), and LREE–MREE–(HREE×10) diagrams have been determined as indicators of climate and the depth and facies conditions of sedimentation.     

Duality and genetic significance of REE speciation in tourmaline from tin deposits of the Far East

The distribution of REEs and some minor elements in tourmalines of different associations and deposits of the Russian Far East is studied by the methods of ICP-MS, ICP-MS with laser ablation and scanning electron microscopy. The duality of REE speciation in tourmaline is established: in high-temperature varieties, most REEs (mainly HREEs) are incorporated in rare minerals (monazite, xenotime, zircon, and F–Ce–Y carbonate), whereas hydrothermal ores are characterized by isomorphic incorporation of LREEs in the mineral structure, as well as by a fine admixture of zircon at the expense of detrital clasts in flyschoid rocks with the zones of tourmalinization.     

贵州织金含稀土磷矿床稀土元素赋存状态研究

利用等离子质谱仪ICP-MS、扫描电镜配合能谱分析、电子探针分析方法,研究了贵州织金含磷岩系剖面稀土含量变化。结果表明,剖面上稀土含量与磷灰石含量变化呈正相关关系,说明稀土主要赋存于磷灰石矿物中;利用扫描电镜、电子探针分析方法对生物碎屑、白云石和胶磷矿进行单矿物微量元素分析研究表明,胶磷矿中稀土含量最高,生物碎屑和白云石稀土含量较低,说明织金含稀土磷矿床稀土元素赋存状态是以类质同象的形式存在于胶磷矿中;利用稀土元素化学物相分析研究同样表明只有少量的稀土元素被磷块岩中粘土矿物所吸附,大量的稀土元素以类质同相形式存在于胶磷矿中。     

陕西几类重要铅锌矿床的矿物微量元素和稀土元素特征

文章将陕西铅锌矿分为海底喷气沉积型(即SEDEX型)、与海底喷气沉积-改造作用有关的类SEDEX型和MVT型3类.对马元(MVT型)、南沙沟和江坡(类SEDEX型)、铅硐山和二里河(SEDEX型)铅锌矿床中的闪锌矿等矿物进行的微量元素和稀土元素测定结果表明,3类矿床各具特点:马元铅锌矿床闪锌矿的Co、Ni、Th、Y含量较低,而Mo、Cs、Sr、Ba、T1含量较高;南沙沟和江坡铅锌矿床闪锌矿的Sn、Sb、W含量较低,而Mn、Y、Zr、In含量较高;铅硐山和二里河铅锌矿床闪锌矿的Li、Zr、CB、Ba含量较低,而W含量较高;在闪锌矿Li-Cs、Zr-In、W-Sn、∑REE-δEu、δEu-δCe散点图上,5个矿床的投点按上述3类分别集中.但铅硐山和二里河铅锌矿床与南沙沟和江坡铅锌矿床具有更多的相似性,而与马元铅锌矿床差异较大:在闪锌矿Sr-Ba、Co-Ni、Th-Y、Mo-T1散点图上,马元的投点集中于一处,而其他4个矿床的投点集中于另一处;马元闪锌矿具有十分明显的铕正异常,而南沙沟、江坡、铅硐山和二里河闪锌矿铕异常不明显,或具有负铕异常;5元素矿床闪锌矿稀土元素配分曲线均为轻稀土元素稍富集的右倾型,但马元的稀土元素总量明显低于其他4个矿床.     

Rare earth elements:A review of applications,occurrence,exploration,analysis,recycling,and environmental impact

Rare earth elements(REE)include the lanthanide series elements(La,Ce,Pr,Nd,Pm,Sm,Eu,Gd,Tb,Dy.Ho,Er,Tm,Yb,and Lu)plus Sc and Y.Currently these metals have become very critical to several modern technologies ranging from cell phones and televisions to LED light bulbs and wind turbines.This article summarizes the occurrence of these metals in the Earth’s crust,their mineralogy,different types of deposits both on land and oceans from the standpoint of the new data with more examples from the Indian subcontinent.In addition to their utility to understand the formation of the major Earth reservoirs.multi-faceted updates on the applications of REE in agriculture and medicine including new emerging ones are presented.Environmental hazards including human health issues due to REE mining and large-scale dumping of e-waste containing significant concentrations of REE are summarized.New strategies for the future supply of REE including recent developments in the extraction of REE from coal fired ash and recycling from e-waste are presented.Recent developments in individual REE separation technologies in both metallurgical and recycling operations have been highlighted.An outline of the analytical methods for their precise and accurate determinations required in all these studies,such as,Xray fluorescence spectrometry(XRF),laser induced breakdown spectroscopy(LIBS),instrumental neutron activation analysis(INAA),inductively coupled plasma optical emission spectrometry(ICP-OES),glow discharge mass spectrometry(GD-MS),inductively coupled plasma mass spectrometry(including ICP-MS,ICP-TOF-MS,HR-ICP-MS with laser ablation as well as solution nebulization)and other instrumental techniques,in different types of materials are presented.     

“海州式”磷矿床中磷灰石的矿物学研究

“海州式”磷矿床中的磷灰石主要由变质改造再活化、混合岩化交代重结晶而成，有微碳氟磷灰石、氟磷灰石两种，晶胞参数σ０＝９．３６５３－９．３８１９ｎｍ，Ｃ０＝６．８７９７－６．８９３６ｎｍ，晶体化学式为（Ｃａ５．００Ｆ３０．０２Ｓｒ０．０１ＴＲ０．０１）５．０４〔（Ｐ２．９９Ｃ０．０４）３．０３Ｏ１２〕Ｆ０．８０，（Ｃａ４．９４Ｆｅ０．０２Ｍｇ０．０２Ｓｒ０．０１ＴＲ０．０１）５．００〔（Ｐ２．９０〕     

Laser Ablation and Solution ICP-MS Determination of Rare Earth Elements in USGS BIR-1G, BHVO-2G and BCR-2G Glass Reference Materials

Data are reported for rare earth elements (REE) in three geological glass reference materials (BIR-1G, BHVO-2G and BCR-2G) using a UV (266 nm) laser ablation ICP-MS system and the classical (HF-HClO₄) acid decomposition method, followed by conventional nebulisation ICP-MS. External calibration of laser ablation analyses was performed using NIST SRM reference materials with internal standardisation using ²⁹Si and ⁴⁴Ca. Replicate analyses of reference basaltic glasses yielded an analytical precision of 1-5% (RSD) for all the elements by solution ICP-MS and 1-8% (RSD) by laser ablation ICP-MS. The relative differences between the REE concentrations measured by solution and laser ablation ICP-MS compared with the reference values were generally less than 11 % for most elements. The largest deviations occurred for La determined by solution ICP-MS in BIR-1G. The results of both solution and laser ablation ICP-MS agreed well, generally better than 7%, with the exception of La, Pr and Sm in BIR-1G. The measured REE laser ablation data for BIR-1G, BHVO-2G and BCR-2G agreed with the previously published data on these basaltic reference glasses, within a range of 0-10% for most elements. No significant influences were observed for the predicted spectral interferences on some REE isotopes in the analysis of basaltic glasses.     

Geochemical studies on REE and trace elements from several Cu-Au deposits along the lower Yangtze metallogenic valley, central-southern Anhui Province

The Yangtze Valley was one of the most important metallogenic regions during the Jurassic-Cretaceous period in East China, where more than 200 polymetallic Cu-Fe-Au, Mo, Zn, Pb, Ag deposits have been found. Trace elements were chemically analyzed and the relevant data were collected from literature for the Yanshanian (Mesozoic) igneous rocks which have close relationship with Cu-Au mineralization. Copper mineralization in the lower Yangtze Valley can be divided into three major types: skarn type, porphyry type and volcanic type. The porphyry type is of rare occurrence, such as the Shaxi porphyry copper deposit in the northern part of the lower Yangtze metallogenic valley. This paper focuses on the REE and trace element geochemistry of several Cu-Au deposits along the lower part of Yangtze metallogenic valley in Anhui. The results showed that there are differences in REE distribution for these four types of Cu-Au mineralization, which confine the sources of REE and trace elements as well as other mantle and transitional compatible elements. The results of both REE and trace element geochemical studies showed that these elements with different characteristics have different origins, probably representing different sources of Cu-Au deposits in the deep crust and upper mantle environments. The 40Ar/39Ar dating of one biotite sample gave an age of 131 Ma with a high level of confidence, which represents the age of formation of the Shaxi porphyrite intrusive with porphrytic Cu-Au mineralization, which is consistent with that of the majority of the adjacent acid intrusives with mass Cu-Au mineralization along the Yangtze metallogenic belt in the Yanshanian period (Mesozoic). This is the first attempt to use the high precision method to date the Shaxi porphyrite intrusive.     

A comparative study of Pleistocene phosphorites from the continental slope off western India

Two types of phosphorite recovered from the continental slope off western India are described. The first type, phosphorite 1, comprises a hard, grey nodule composed of carbonate fluorapatite (CFA) and calcite as major minerals. The phosphorite consists of light‐brown microcrystalline apatite containing a few skeletal fragments and planktonic foraminifera. Scanning electron microscope (SEM) studies show evidence of dissolution of skeletal calcite and filling of the resulting cavities by phosphate composed of ovoid to rod‐shaped apatite microparticles. Apatite also occurs as coatings on these particles. The P₂O₅ content of the phosphorite is 29%, and the CO₂ content of the CFA is about 4·5%. The rare‐earth element (REE) abundance (ΣREE=2·02 μg g^–1) is lower than in other modern phosphorites. The ⁸⁷Sr/⁸⁶Sr ratio and ?Nd value of this sample are 0·70921 and –9·9 respectively. The ¹⁴C age found through accelerator mass spectrometry (AMS) dating (18 720 ± 120 years BP) is much younger than that determined by the U‐series method (100 ka). The second type, phosphorite 2, comprises a friable, light‐brown nodule consisting of CFA as the only major mineral, with a CO₂ content of the CFA of 4·5%. In thin section, the phosphate is light brown and homogeneous, and a few bone fragments are present. The P₂O₅ content is 33%, and REE contents (ΣREE = 0·18 μg g^–1) are lower than in phosphorite 1. The age of phosphorite 2 is >300 ka. Phosphorite 1 appears to have formed during the late Pleistocene through replacement of carbonate by phosphate; phosphorite 2 is also of Pleistocene age but is much older than phosphorite 1. The initial substrate for phosphorite 2 was a fish coprolite, which was subsequently phosphatized during slow sedimentation under low‐energy conditions. Microbial mediation is evident in both phosphorites. The colour, density and P₂O₅ content of the phosphorites are found to be dependent on the nature of the initial substrates and physico‐chemical conditions during phosphatization. The CO₂ content of the CFA is not related to the precursor carbonate phase. The nature of sediments, rates of sedimentation and the time spent undergoing phosphogenesis at the sediment–water interface may control REE concentrations in phosphorites.     

Major and Trace Element Characteristics of Apatites in Granitoids from Central Kazakhstan: Implications for Petrogenesis and Mineralization

This paper presents abundances of major and trace elements of apatites in granitic rocks associated with different types of ore deposits in Central Kazakhstan on the basis of electron probe microanalysis and laser ablation inductively coupled plasma mass spectrometry. Our results demonstrate that the concentrations and ratios of elements in apatites from different granitoid rocks show distinct features, and are sensitive to magma evolution, petrogenetic and metallogenetic processes. Apatites in the rocks associated with Mo‐W deposits have high content of F and MnO, low content of Cl, which may be indicative of sedimentary sources, while apatites from a Pb‐Zn deposit show relatively high content of Cl and low F content, which possibly suggest a high water content. In these apatites, Sr contents decrease, while Mn and Y contents increase with magma evolution. This relationship reflects that these elements in apatites are related with the degree of magmatic differentiation. Four types of REE patterns in apatites are identified. Type 1 character of highest (La/Yb)_N in apatites of Aktogai porphyry Cu‐Mo deposit, Sayak‐I skarn Cu deposit and Akzhal skarn Pb‐Zn depposit is likely produced by the crystallization of heavy REE‐enriched minerals. Type 2 character of upward‐convex light REE in apatite of Aktogai porphyries likely results from La‐enriched mineral crystallization. Type 3 feature of Nd depletion in apatites of East Kounrad and Zhanet deposits both from Mo‐W deposits primarily inherits the character of host‐rock. Type 4 apatites of Aktogai deposit and Akshatau W‐Mo deposit with wide range of REE contents may suggest that apatites crystallize under a wide temperature range. Three types of apatite with distinct redox states are identified based on Eu anomaly. The Aktogai apatite with slight negative Eu anomaly displays the most oxidized state of the magma, and the apatites of other samples at Aktogai, East Kounrad and Akzhal with moderate negative Eu anomaly show moderate oxidizing condition of these rocks, while the remaining apatites with strong En anomaly indicate a moderate reductive state of these rocks.     

埃迪卡拉纪全球成磷事件沉积地球化学模型探讨:以扬子板块不同相区陡山沱组含磷岩层研究为实例

埃迪卡拉纪是地球第二次大规模成磷时期,全球各大陆均有这次成磷事件的记录。目前对于该时期成磷事件的形成 尚未有广泛接受的地球化学模型解释。而磷酸盐的沉积受海水氧化还原条件的控制,因此通过该时期磷块岩沉积与海水氧 化还原条件演变之间关系的研究可为全球大规模成磷事件的沉积地球化学模型建立提供验证。文章通过对扬子板块埃迪卡 拉纪不同相区磷块岩中碳酸盐组分稀土元素分析,结果表明磷块岩形成时底层海水处于次氧化-接近氧化的不稳定状态, 氧化还原界面沿浅海-大陆架呈现动态变化的特征,为磷块岩的大规模形成提供最佳沉积地球化学条件。合适的海水化学 条件及丰富的磷质来源,大大增加了磷块岩沉积的空间和机会,导致了地质历史时期第二次全球规模成磷发生。     

贵州修文小山坝铝土矿中稀土元素地球化学特征

前人已经积累了大量贵州铝土矿的研究成果,但关于铝土矿与其中稀土元素的关系至今不清。本研究以修文小山坝铝土矿为例,通过ICP-MS分析测试,研究了矿石和围岩的稀土元素组成。结果表明,矿石中稀土配分模式为轻稀土富集向右倾斜型,具明显Eu负异常,与下寒武统娄山关群含泥质白云岩稀土特征参数和配分模式相似,指出该矿床成矿物质来源以下寒武统娄山关群含泥质白云岩为主,在相对氧化环境下经风化作用成矿。矿床中稀土元素主要富集于矿体及其周围,与Al2O3含量具正相关关系。矿石中稀土元素含量大多达到或超过综合利用标准,具有巨大的潜在经济价值。     

滇东寒武系磷矿成因新见解——风暴成矿模式初探

近年来,随着风暴流和风暴岩的新理论、新概念的不断引入,在分析沉积环境、沉积成矿作用时,不断提出了许多新思路,也不断地冲击和修正以往的传统认识,作者于1986年随同成都地矿所寒武系磷矿专题组对滇东一带包括昆阳梅树村、海口、鸣矣河、晋宁王家湾、二街、八街、安宁白登、江川清水沟、宜良大滴水、寻甸先锋等矿区的磷矿进行了详细的研究,在下寒武统中谊村段及其相当的地层中发现了多层磷质风暴沉积物。本文拟概略介绍磷质风暴沉积物的标志、特征、剖面结构并初步探讨磷矿富集与风暴事件关系的沉积演化模式。     

新疆阿尔泰可可托海3号伟晶岩脉磷灰石矿物中稀土元素“四分组效应”及其意义

新疆阿尔泰可可托海3号伟晶岩脉磷灰石矿物中稀土元素（REE）和其他微量元素的ICP－MS分析结果表明，Y／Ho,Zr/Hf和Nb/Ta明显偏离球粒陨石中对应的比值，并存在显著的REE“四分组效应”，REE“四分组效应”量化特征参数TE3，4主要与Y／Ho,Nb/Ta分异程度有关，与δEu负异常演化程度相一致，锰铝榴石也呈现REE“四分组效应”和Y／Ho,Nb/Ta显著分异，指示REE“四分组效应”是形成伟晶岩熔体的一个基本特征，并不是由富LREE矿物（如独居石）和富HREE矿物（如四榴子石）结晶引起的残余熔体REE含量的异常变化，其机制可能是富F，B和P的过铝质窝本与含水流体间相互作用，REE在流体相／熔体相的分配受温度，压力和流体相组成复合控制的综合结果。     

Metavolcanic host rocks,mineralization, and gossans of the Shaib al Tair and Rabathan volcanogenic massive sulphide deposits of the Wadi Bidah Mineral District,Saudi Arabia

The Wadi Bidah Mineral District of Saudi Arabia contains more than 16 small outcropping stratabound volcanogenic Cu–Zn–(Pb) ± Au-bearing massive sulphide deposits and associated zones of hydrothermal alteration. Here, we use major and trace element analyses of massive sulphides, gossans, and hydrothermally altered and least altered metamorphosed host rock (schist) from two of the deposits (Shaib al Tair and Rabathan) to interpret the geochemical and petrological evolution of the host rocks and gossanization of the mineralization. Tectonic interpretations utilize high-field-strength elements, including the rare earth elements (REE), because they are relatively immobile during hydrothermal alteration, low-grade metamorphism, and supergene weathering and therefore are useful in constraining the source, composition, and physicochemical parameters of the primary igneous rocks, the mineralizing hydrothermal fluid and subsequent supergene weathering processes. Positive Eu anomalies in some of the massive sulphide samples are consistent with a high temperature (>250°C) hydrothermal origin, consistent with the Cu contents (up to 2 wt.%) of the massive sulphides. The REE profiles of the gossans are topologically similar to nearby hydrothermally altered felsic schists (light REE (LREE)-enriched to concave-up REE profiles, with or without positive Eu anomalies) suggesting that the REE experienced little fractionation during metamorphism or supergene weathering. Hydrothermally altered rocks (now schists) close to the massive sulphide deposits have high base metals and Ba contents and have concave-up REE patterns, in contrast to the least altered host rocks, consistent with greater mobility of the middle REE compared to the light and heavy REE during hydrothermal alteration. The gossans are interpreted to represent relict massive sulphides that have undergone supergene weathering; ‘chert’ beds within these massive sulphide deposits may be leached wall-rock gossans that experienced silicification and Pb–Ba–Fe enrichment from acidic groundwaters generated during gossan formation.