Rare earth elements (REE)—Minerals in the Silius fluorite vein system (Sardinia,Italy)

The Silius vein system, located in SE Sardinia (Italy) is analogous to other late- to post-Hercynian mineral systems of this type in Europe. The Silius system consists of two main veins, characterized by several generations of fluorite, calcite and quartz, with initial ribbon-like geometries, followed by breccias and cockade-like textures. In this study, aimed at investigating the REE concentrations in the Silius vein system, a REE average of ~ 800 ppm (locally ΣREE > 1500 ppm) has been observed in the carbonate gangue of the fluorite orebody. These amounts are related to the presence of the REE-bearing minerals synchysite-(Ce) and xenotime-(Y). The chemical composition of synchysite-(Ce) has been obtained by wavelength dispersive spectrometry (WDS). The average synchysite-(Ce) formula, built on the basis of (CO₃)₂F and 5 negative charges, is Ca_1.07(La_0.19,Ce_0.36,Pr_0.04,Nd_0.15,Sm_0.03,Gd_0.03,Y_0.13)(CO₃)₂F. From their geochemical characteristics, and their textural relationships with other gangue phases, it is likely that synchysite-(Ce) and xenotime-(Y) formed at the same P-T-X conditions as the other minerals of the Silius fluorite mineralization. Synchysite-(Ce) and xenotime-(Y) at Silius could be related to a local circulation phenomenon, where the REE are derived from a REE-bearing source rock in the basement of southeastern Sardinia, which has been leached by the same fluids precipitating the fluorite/calcite mineralization. REE concentrations contained in the carbonate gangue of still unexploited parts of the Silius vein deposit, as well as in dumps and tailings accumulated during past fluorite processing, could possibly represent a sub-economic by-product of the fluorite exploitation.     

Tungsten Mineralization and Mica REE Geochemistry,Huangsha,Jiangxi

The Huangsha Ag-rich tungsten deposit is genetically related to a buried granite which shows apparent vertical zoning in alteration.Greisen-type W(Mo) ores coccur at the top or the intrusive and sulfide-wolframite-quartz veins developed at the major stage of mineralization are present in low-grade metamorphic rocks in the outer-contacts.The veins exhibit a reversed zonation in the vertical section with silver concentrated in the lower part in association with sulfides.Micas,characterized by high Si and low Al.are extensively developed both in the granite and in the veins.They have similar cell parameters.belonging to 2M1 type,but those in the veins are understanding of the petrogenesis, evolution and mineralization of the granite.     

CCSD HP-UHP变质岩中磷灰石稀土元素(REE)地球化学及其示踪意义

磷灰石是一种能在UHP变质峰期稳定存在并富含稀土元素(REE)的常见副矿物,其REE组成变化可以对变质过程进行地球化学示踪。本文利用激光剥蚀等离子光谱仪(LA-ICP-MS)对中国大陆科学钻探(CCSD)钻井中及其附近出露的不同变质程度的HP-UHP变质岩(榴辉岩、角闪(片)岩和片麻岩)中的磷灰石进行了REE组成原位测定,结果显示不同围岩中磷灰石的REE组成特征及其相关系数变化很大,其球粒陨石标准化配分曲线可以分为3大类:Ⅰ.轻稀土(LREE)富集型,其REE总量(∑REE)很高,可达n×1000×10~(-6);Ⅱ.中稀土(MREE)富集型,其(La/Sm)_N<1,Eu异常变化较大;Ⅲ.重稀土(HREE)富集型,其配分曲线呈明显的左倾形式,∑REE总量很低,仅为9.228×10~(-6),且具明显的Eu负异常。磷灰石颗粒原位分析显示从边部到中心∑LREE有逐渐升高的趋势,表明了在俯冲折返的过程发生过短时增温作用,并极有可能发生过部分熔融。部分熔融过程中磷灰石中的LREE将与其它大离子半径元素一起优先释放。     

西太平洋海山富钴结壳稀土元素(REE)组成原位LA-ICPMS测定

利用激光剥蚀电感耦合等离子体质谱(LA-ICPMS)微区原位分析方法,对采自西太平洋海山具完整三层结构的富钴结壳样品进行了稀土元素(REE)含量测定,结果表明, 虽然均产于西太平洋海山且均具有明显的三层结构,富钴结壳化学组成受地理位置和沉积环境影响很大。绝大多数西太平洋富钴结壳具有高ΣREE、高LREE/HREE、δCe正异常和δEu基本无异常或微弱正异常的特点, 显示它们主要由正常海水沉积形成。结壳不同层圈之间REE组成有较大的区别, 其原因主要在于其形成环境和矿物组成不同。样品0327稀土元素总量(∑REE)由亮煤层到疏松层到外层逐渐升高,且亮煤层δCe和Y/Ho变化非常大,最大值分别为38.61和105.5,显示该层生长环境较为氧化且相对动荡,而样品0346中三层结构的∑REE都非常高,且变化趋势与0327正好相反,从亮煤层到致密层∑REE有降低的趋势。 亮煤层形成时海水相对较氧化的环境有利于铁锰氧化物的形成和Ce⁴⁺等稀土元素的吸附,导致其中ΣREE较疏松层和外层为高,而后期磷酸盐化导致REE元素的迁移和亏损。在结壳生长剖面上,由最外层到疏松层和亮煤层,δCe呈明显上升趋势,且变化范围趋大,说明该结壳所处的海水环境在由老至新的生长过程中由相对动荡和氧化变为相对平静和还原。     

REE Geochemistry of Loess in Xinjiang ,China

The total rare-earth element values(ΣREE)of loess in the Xinjiang region vary over a range of 128-200 ppm ,with an average of 153ppm .The average REE content of loess lies between the earth‘s crust (155ppm) and sedimentary rocks(151ppm).The Xinjiang loess,with the REE distribu-tion patterns characterized by negative slopes ,is rich in the Ce-family elements, and has a distribu-tion pattern characteristic of sedimentary rocks.The North Xinjiang loess is relatively depleted in Tb,but rich in Yb and Lu.The South Xinjiang loess is relatively rich in light rare-earth elements.This is full proof that the Xinjiang loess comes partly from weathered materials(clay rock,sandstone)in the region studied.The REE distribution patterns in the Xinjiang loess are similar to those in the precipitated dust and Aeolian sand,indicating the same material source.The REE distribution pat-terns in the Xinjiang loess are also similar to those in loess from the middle Yellow River Valley,China and Taskent,the former USSR.This implies that loesses of the three locations(Xinjiang,the mid-dle Yellow River Valley and Taskent) come from a common material source.But the REE patterns in the Xinjiang loess are different from those in wall rocks (volcanic rock,K-bearing volcanic rock).Generally ,LREE/HREE,Eu/Eu* and Ce/Ce* ratios reflect the features of parent materials of loess,indicating that the parent rocks were probably in the early stage of alkaline weathering and the weathered materials existed in an oxidation environment with basic mediums under arid-climatic conditions before transport.As a result,the migration ability of the REE is weak.     

REE Characteristics of the Lala IOCG Deposit, Sichuan, China

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元古宙铁氧化物(Cu—U─Au—REE)矿床

铁氧化物（Cu－U－Au－REE）矿床包括南澳大利亚奥林匹克坝矿床、瑞典的基鲁纳矿床、中国内蒙古的白云鄂博矿、美国密苏里东南部的铁氧化物矿床等。据围岩性质，该类矿床可分为以火成岩为容矿岩的铁氧化物矿床相以沉积岩为容矿岩两亚类．这些矿床有许多共性，也有它们自己因有特征．这类型矿床一般分布在中元古代克拉通或大陆边缘环境中，可能与裂谷有成因连系．目前深入研究这类矿床不仅有重要建论意义，而且有重要的经济意义．     

The Curves of Seven REE and Their Geological Significances of Porphyry Mo (Cu) Deposit of Chengba, Tibet

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Geochemical and mineralogical characteristics of weathered ore in the Dalucao REE deposit,Mianning–Dechang REE Belt,western Sichuan Province,southwestern China

The Dalucao deposit in western Sichuan Province, southwest China, is one of the largest and most extensive rare earth element (REE) deposits in the Himalayan Mianning–Dechang REE Belt. Moreover, this is the only deposit identified in the southern part of the belt. The deposit contains the No. 1, 2, and 3 orebodies. The No. 1 and 3 orebodies are hosted in two breccia pipes within syenite–carbonatite rocks that intrude a Proterozoic quartz–diorite pluton. Both breccia pipes have elliptical horizontal cross-sections at the surface, being 200–400 m long, 180–200 m wide, and extending to > 450 m depth. The No. 1 and No. 3 orebodies have total thicknesses of 55–175 m and 14–58 m, respectively. REE mineralization is associated with four brecciation events that are recorded in both pipes. The ore grades in the No. 1 and 3 orebodies are similar, with the rocks containing 1.0–4.5% rare earth oxides (REOs). The No. 1 orebody is characterized by a mineral assemblage comprising fluorite + barite + celestite + bastnäsite (i.e., Type I), whereas the No. 3 orebody is characterized by an assemblage comprising fluorite + celestite + pyrite + muscovite + bastnäsite + strontianite (i.e., Type II). Significant amounts of weathered high-grade REE ore (up to 60 wt.% of the rock mass) is mainly present in the No. 1 orebody. This is the main ore-type targeted for exploration within the Dalucao deposit, but is rarely present in other deposits in the Mianning–Dechang REE Belt.Faulting and cryptoexplosive breccia events, possibly linked to movement on the Panxi Fault, were more common in the No. 1 orebody than in the No. 3 orebody. This facilitated the introduction of ore-forming hydrothermal fluids and provided space for the precipitation of REE minerals. Based on the present results, we infer that the Dalucao deposit was the product of multiple stages of ore formation. REE minerals formed in envelopes around, or fractures within, quartz, fluorite, calcite, barite, and celestite in the brecciated ores. The main REE minerals were deposited from hydrothermal fluids within cryptoexplosive breccia, followed by weathering that increased the ore grade. Petrographic studies and X-ray powder diffraction (XRD) analyses indicate that the weathered ore contains 5–60% REE minerals (including bastnäsite, parisite, and monazite), together with gangue (quartz, barite, celestite, and fluorite), large amount of clay minerals (smectite, illite, kaolinite, and sepiolite), and relict igneous minerals (quartz, albite, and K-feldspar). The weathered samples are strongly enriched in La (up to 92,390 ppm), Ce (up to 103,500 ppm), Pr (up to 8006 ppm), and Nd (up to 16,690 ppm) compared with the unweathered brecciated ores. Conversely, Sr concentrations are significantly more enriched in the brecciated ores (up to 256,500 ppm) than in the weathered ores (generally less than 2671 ppm with one exception of 37,850 ppm) due to less celestite. Calcite is largely absent from the weathered ores (except one sample with up to 30% mode), which contrasts with the brecciated ores that contain up to 75% calcite. The effects of weathering, oxidation, loss of ions, and hydration on the brecciated ores led to the refertilization of the REEs and an increase in the grade of the ore deposit.     

REE Geochemistry of Fluorite from the Maoniuping REE Deposit, Sichuan Province, China： Implications for the Source of Ore-forming Fluids

Fluorite is one of the main gangue minerals in the Maoniuping REE deposit,Sichuan Province,China.Fluorite with different colors occurs not only within various orebodies,but also in wallrocks of the orefield.Based on REE geochemistry,fluorite in the orefield can be classified as the LREE-rich,LREE-flat and LREE-depleted types.The three types of fluorite formed at different stages from the same hydrothermal fluid source,with the LREE-rich fluorite forming at the relatively early stage,the LREE-flat fluorite in the middle,and the LREE-depleted fluorite at the latest stage.Various lines of evidence demonstrate that the variation of the REE contents of fluorite shows no relation to the color.The mineralization of the Maoniuping REE deposit is associated spatially and temporally with carbonatite-syenite magmatism and the ore-forming fluids are mainly derived from carbonatite and syenite melts.     

REE and isotope (Sr,S, and Pb) geochemistry to constrain the genesis and timing of the F–(Ba–Pb–Zn) ores of the Zaghouan District (NE Tunisia)

The F–(Ba–Pb–Zn) ore deposits of the Zaghouan District, located in NE Tunisia, occur as open space fillings or stratabound orebodies, hosted in Jurassic, Cretaceous and Tertiary layers. The chondrite-normalized rare earth element (REE) patterns may be split into three groups: (i) “Normal marine” patterns characterizing the wallrock carbonates; (ii) light REE (LREE) enriched (slide-shaped) patterns with respect to heavy REE (HREE), with small negative Ce and Eu anomalies, characteristic of the early ore stages; (iii) Bell-shaped REE patterns displaying LREE depletion, as well as weak negative Ce and Eu anomalies, characterizing residual fluids of subsequent stages. The ⁸⁷Sr/⁸⁶Sr ratios (0.707654–0.708127 ± 8), show that the Sr of the epigenetic carbonates (dolomite, calcite) and ore minerals (fluorite, celestite) are more radiogenic than those of the country (Triassic, Jurassic, Cretaceous, lower Miocene) sedimentary rocks. The uniformity of this ratio, throughout the District, provides evidence for the isotopic homogeneity and, consequently, the identity of the source of the mineralizing fluids. This signature strongly suggests that the radiogenic Sr is carried by Upper Paleozoic basinal fluids.The δ³⁴S values of barite, associated to mineralizations, are close to those of the Triassic sea water (17‰). The δ³⁴S values of sulfide minerals range from − 13.6‰ to + 11.4‰, suggesting two sulfur-reduced end members (BSR/TSR) with a dominant BSR process.Taking account of the homogeneity in the Pb-isotope composition of galenas (18.833–18.954 ± 0.001, 15.679–15.700 ± 0.001 and 38.690–38.880 ± 0.004, for the ²⁰⁶Pb/²⁰⁴Pb, ²⁰⁷Pb/²⁰⁴Pb and ²⁰⁸Pb/²⁰⁴Pb ratios respectively), a single upper crustal source for base-metals is accepted. The Late Paleozoic basement seems to be the more plausible source for F–Pb–Zn concentrated in the deposits. The genesis of the Zaghouan District ore deposits is considered as the result of the Zaghouan Fault reactivation during the Late Miocene period.     

REE geochemistry of Chaohu and Longgan lakes, eastern China

The rare-earth elements （REEs） are a series of elements including lanthanides with atomic numbers from 57 to 71, as well as Y with an atomic number of 39. The REEs are commonly used as geochemical tracers in the study of many geologic processes because of their unique and chemically coherent behavior. The main purpose of this research is to understand the effect of water-particle interaction on trace metal transport, the distribution and chemical species of the REEs in water through case studies on geochemical behavior of the REEs in the Chaohu and Longgan lakes, eastern China. Concentrations of the dissolved REEs were detected by ICP-MS （Inductively Coupled Plasma-Mass Spectrometry）. Before ICP-MS measurement, REEs were concentrated from water samples by using solvent extraction and back extraction with a mixture 65% HDEHP （2-etheylhexyl hydrogen phosphate） and 35% H2MEHP （2-ehtylhexyl dihydrogen phosphate）. The results showed that the average concentrations of dissolved REEs in summer are higher than in winter for Chaohu Lake： they were 162.6 ng/kg and 86.5 ng/kg, respectively. On the country, the REE contents of winter samples were higher than those of summer water samples for Longganhu Lake： they were 111.1 ng/kg and 44.0 ng/kg, respectively. The contents of suspended particulate matter and pH are the two important factors controlling the concentrations of dissolved REE in the lakes. The contents of the REEs decrease with increasing pH in the Longgan and Chaohu lakes. The suspended particulate matter shows different sorption/desorption toward the dissolved REEs in the two water bodies. Most lake water samples have a fiat NASC-normalized REE pattern, and the others have heavy REE-enrichment patterns relative to NASC, which may imply that the dissolved REEs were mainly present in the form of fine colloids in the Chaohu and Longgan lakes.     

Submicroscopic accessory minerals overprinting clay mineral REE patterns (celadonite–glauconite group examples)

Samples of glauconite, representing different stages of glauconitisation, as well as different formation environments, were analysed for rare earth elements (REE) and other trace elements using a combination of bulk sample and spatially-resolved in situ techniques. The results indicate that the high-sensitivity, spatially-resolved technique of laser ablation-inductively coupled plasma-mass spectrometry (LA-ICP-MS) produces values up to two orders of magnitude lower than the bulk sample analyses. This suggests that submicroscopic rare earth element-bearing phases are distributed within the glauconite aggregates comprising the bulk samples. Analytical scanning electron microscopy (ASEM) revealed the presence of micrometre-sized grains of apatite and pore filling precipitates of an unidentified (REE, Ca)-phosphate (approximate composition Ca_0.3–0.4(Ce_0.4La_0.1–0.2Nd_0.1)PO₄) in some glauconite grains.The inherent REE concentrations of the glauconite aggregates (i.e., glauconite crystallites without accidental mechanical inclusions or authigenic, not layer silicate mineral precipitates) was found to be relatively low (e.g., typically less than 100 ppm), and this value decreased with increasing glauconitisation (smectite–mica transformation through a series of recrystallisation processes). These results suggest that the REEs substitute for Ca in the interlayer space of the layer silicate structure and, therefore, the REE content decreases as Ca is progressively removed from the interlayer (smectite–mica transition).LA-ICP-MS, when combined with electron probe microanalysis (EPMA) or ASEM, offers an opportunity to exclude submicroscopic accessory minerals from glauconite trace element analyses, and so produces reliable trace element data for the respective minerals which host those elements.These results illustrate that accessory minerals are difficult to eliminate from clay samples, and that care needs to be taken in the interpretation of clay mineral REE distributions, irrespective of the aggregation state of the studied clay (i.e., whether finely dispersed within the sedimentary rock, or forming millimetre-sized aggregates). Model calculations showed that authigenic apatite associated with the studied green marine clays tends to have higher REE content than “bioapatites”, the total REE content being above 10 000 ppm.     

REE丰度结构类型

REE燕式曲线丰度结构与REE地球化学特征的相互关系研究为基础，引入丰度坐标系（双对数坐标系），在这种准四维坐标系中一个点定量表示相应的一条燕式曲线的总形态的基础上对REE丰度结构进行系统科学分类，便于对大量样品数据进行定量地球化学研究。     

Alteration of Syenite in Syenite-Carbonatite Complex with Regards to the REE Mineralization in Dalucao REE Deposit, Sichuan Province

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黄河沉积物中稀土元素(REE)组成的粒度效应*

依据Stokes颗粒沉降原理将黄河利津水文站和汊河清八站的表层沉积物分别提取为<2μm,2~4μm,4~8μm,8~16μm,16~32μm和32~63μm的6个粒级,采用ICP-MS法对各个粒级沉积物的15个稀土元素进行测试。结果表明:黄河沉积物两个样品REE含量随粒度增大的变化趋势有细微差别,但总体随粒度大小呈"高—低—高"的不对称马鞍型分布,其中最高REE含量和最低REE含量分别位于<4μm的粘土粒级和4~16μm细粉砂粒级中; 各粒级沉积物经北美页岩标准化后,REE的配分模式一致,呈平缓的右倾型,相对富集轻稀土,明显的Eu正异常和Ce负异常。对各个粒级样品进行X射线衍射分析及体视镜下观测,石英含量随粒级增大而增加, 长石在8~16μm中含量最高,在16~32μm中,碳酸岩含量最高,随着粒级增大,重矿物含量逐渐增加,黄河沉积物REE随粒度的变化特征与粘土矿物对其吸附及流域碎屑沉积物不同粒级的矿物成分密切相关。     

REE Geochemical Characteristics of Two Granite-Derived Weathering Profiles, Guangxi, South China: Implications for the Formation of the Ion Adsorption Type REE Deposit

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REE Geochemistry in the Weathered Crust of Granites, Longnan Area,Jiangxi Province

Warm and humid climate and gentle hilly topography have provided favourable conditions for the devel-opment of the weathering crust of the granite intrusions in the Longnan area, Jiangxi Province. REE is mostlyconcentrated in an adsorption state in clay in the wholly weathered zone. The rare-earth minerals enriched inthe parent rocks provided the source material for the REE enrichment. Exchangeable REE accounts for48-86%. Extraction experiments and stable isotopic study of clay minerals suggest that the downward infiltra-tion of meteoric water and increasing gradient of pH values have played an important role in the enrichment ofREE during the progressive weathering. Slight fractionation of individual REE can not change their distribu-tion patterns in the profiles. which are inherited from the parent rocks.