Geochemistry of rare earth elements in oceanic phillipsites

The behavior of rare earth elements (REE) was examined in oceanic phillipsites collected from four horizons of eupelagic clay in the Southern Basin of the Pacific. The REE concentrations were determined in the >50-μm-fraction phillipsite samples by the ICP-MS method. The composition of separate phillipsite accretions was studied using the electron microprobe and secondary ion mass-spectrometry. Rare earth elements in phillipsite-only samples are related to the admixture of ferrocalcium hydroxophosphates. The analysis of separate phillipsite accretions reveals low (<0.1–18.1 ppm) REE (III) concentrations. The Ce concentration varies between 2.7 and 140 ppm. The correlation analysis shows that REE (III) are present as an admixture of iron oxyhydroxides in separate phillipsite accretions. Based on the REE (III) concentration in iron oxyhydroxides, we can identify two generations of phillipsite accretions. Massive rounded accretions (phillipsite I) are depleted in REE, while pseudorhombic (phillipsite II) accretions are enriched in REE and marked by a positive Ce anomaly. Oceanic phillipsites do not accumulate REE or inherit the REE signature of the volcaniclastic material and oceanic deep water. Hence, the REE distribution in phillipsites does not depend on the sedimentation rate and host sediment composition.     

Geochemistry and origin of rare earth elements (REEs) in the Shengli River oil shale, northern Tibet, China

The Shengli River-Changshe Mountain oil shale zone, located in the North Qiangtang depression, northern Tibet plateau, represents a potentially large marine oil shale resource in China. Twenty-eight samples including oil shale, micritic limestone and marl were collected from the Shengli River area to determine the contents and distribution patterns of rare earth elements (REEs) in marine oil shale. Oil shale samples from the Shengli River area have high ash yield (61.86–67.48%) and TOC content (8.02–13.67%) with low total sulfur (S_t,d) content (0.76–1.39%) and intermediate shale oil content (3.60–16.30%). The total rare earth element (ΣREE) content in oil shale samples is notably depleted (46.79–67.90 μg/g), approximately one third of the mean value of the North American Shale Composite (NASC), and lower than that of world-wide black shales and Chinese coals, but higher than that of world-wide coals and micritic limestone samples (29.21 μg/g) from the Shengli River area. The oil shale samples from the Shengli River area exhibit shale-like Chondrite or NASC-normalized REE patterns similar to those of micritic limestone and marl samples from this area, indicating that REEs of these different lithological samples may have been derived from a similar terrigenous source.REE contents of oil shale samples are highly positive correlated with ash yield and show a positive correlation with Fe and a weakly positive correlation with organic sulfur, and the vertical variations of REEs mainly follow those of Si, Al, K and Ti. All these facts indicate that the REE contents in oil shale seams are mainly controlled by clay minerals and, to a lesser extent, by pyrite, as well as partly associated with oil shale organic constituents. Rare earth elements in the Shengli River oil shale have originated from two sources: a felsic volcanic rock source and a clastic or/and limestone source.     

长江沉积物稀土元素的粒度效应研究

依据Stokes定律,将小于63μm的长江沉积物分成小于2、2～4、4～8、8～16、16～32、32～63μm6个粒级,采用ICP-MS法分别测试了分粒级沉积物的REE含量,结果显示:长江沉积物REE的丰度遵循元素的"粒度控制律",即随粒度变细,∑REE含量依次增高;北美页岩标准化分布曲线均呈右倾的近"W"型,轻、重稀土分馏明显,相对富集LREE,明显的Ce负异常和弱Eu亏损。对长江沉积物不同粒级样品进行X射线衍射分析和体视镜下观测,结果表明:长江沉积物随粒度增大石英和长石含量逐步增加,碳酸盐和重矿物在各个粒级中含量甚微并且随粒级变化不大;长江沉积物REE随粒度变细逐渐增加的特征主要受控于沉积物随粒度变化而变化的矿物成分,黏土粒级及细粉砂中较高的∑REE主要是黏土矿物吸附作用的结果,粗粉砂中较低的∑REE主要为长石和石英的稀释作用结果,而碳酸盐和重矿物因其较低的含量对稀土元素含量影响较小。     

马坑铁矿床稀土元素地球化学研究

引言七十年代以来,许多研究者对马坑铁矿进行过深入的研究。关于该矿床的形成机制,特别是含矿建造中一套中一基性岩石和矿体底板岩石的成因,以及矿石的形成方式等问题,曾引起研究者们的特别关注,并开展了热烈讨论。笔者曾对该矿床的地质一地球化学特征进行了较为详细的研究,并指出它是与石炭纪海底火山活动有关的喷气-热液沉积矿床,成矿流体来源于地热对流海水与玄武岩的反应。本文是上述研究的继续和深入,目的在于为     

长江三峡巫山黄土稀土元素特征及古环境

【研究目的】巫山黄土是位于北亚热带河谷的一处代表性的粉尘堆积,具有重要的区域环境指示意义。【研究方法】本文通过系统取样,对巫山黄土的稀土元素组成特征和古气候意义进行了分析和讨论。【研究结果】结果表明：（1）巫山黄土各样品的稀土元素含量相差不大,并具有同步变化。同时轻稀土含量远远高于重稀土含量,表现为轻稀土富集,重稀土亏损;（2）巫山黄土具有从老到新∑REE逐渐减小的特点,这可能与黄土风化作用的强度不同有关;（3）剖面中不同深度样品的REE分布模式具有相似性,且特征值δCe、δEu、La/Yb、Gd/Yb和ΣREE也非常相近;（4）所有样品稀土元素配分曲线均具有负斜率,La-Eu曲线较陡,Eu-Lu曲线较平缓的特点,揭示了轻重稀土元素之间具有一定的分异作用;（5）巫山黄土δEu值分布在纵轴的0～1区间,具有明显的Eu负异常。而δCe却分布在1附近,没有表现出明显的Ce异常,表明沉积物遭受的风化作用并不强。【结论】巫山黄土并未经受较强的化学风化作用,堆积时该区的气候晚期比早期更为干冷,且在堆积过程中没有发生明显的物源改变。创新点：基于稀土元素含量揭示了巫山黄土形成过程中的气候特征及其物源的变化。     

State of rare earth elements in the rare earth deposits of Northwest Guizhou,China

We studied the states of rare earth elements in ore of the Xianglushan rare earth deposit. Rare earth ore samples were tested and examined by scanning electron microscope, electron probe, and chemical leaching. No independent rare earth minerals were detected by scanning electron microscope. Elements detected by the electronic probe for the in situ micro-zone of the sample included: O, Al, Si, Ca, Mg, Fe, Ti, K, Na, S, Cl, C, Cu, Cr, V, and Pt. Rare earth elements were not detected by electron probe. (NH4)₂SO₄, (NH₄)Cl, NaCl, and H₂SO₄ were used as reagents in chemical leaching experiments that easily leached out rare earth elements under the action of 10% reagent, indicating that the rare earth elements in ore are mainly in the ionic state rather than present as rare earth minerals.     

淮北煤田煤的稀土元素地球化学

采用仪器中子活化分析法（ＩＮＡＡ）测试了淮北煤田６、３煤层１个煤样的稀土元素含量,并探讨了稀土元素地球化学特征,得出以下认识：１１个样吕的平均ΣＲＥＥ为８１．９５３５ｕｇ／ｇ;稀土元素分布模式呈左高右低的、具Ｅｕ负异常的“Ｖ”型曲线。相关分析、聚类分析的结果表明：稀土元素与灰分、陆源碎屑的元素（Ｓｉ、Ａｌ、Ｔｉ、Ｃｒ、Ｃｏ、Ｎｉ、Ｔｈ、Ｔａ、Ｓｃ和Ｒｂ等）的关系密切,而与海相元素（Ｃａ、Ｓｒ等）关     

Geochemistry of dissolved rare earth elements in the Equatorial Pacific Ocean

Seawater samples were collected from four locations in the Equatorial Pacific Ocean during the MR02-K06 cruise of the R/V Mirai and analyzed for dissolved rare earth elements (REEs) using inductively coupled plasma mass spectrometry. According to variations of REE concentrations and Yb/La ratios, the results show that the river input of the Papua New Guinea islands may affect the compositions of REEs in the Equatorial Pacific surface water. The Yb/La values and the REE concentrations in the waters deeper than 3,000 m in the western South Pacific and the Equatorial Pacific Oceans, which represent the characteristics of Antarctic Bottom Water (AABW), demonstrate similar variation trend with depth. This result also indicates that the REEs which originated from the South Pacific Ocean have entered the North Pacific Ocean across the equator with AABW intrusion.     

Geochemistry of rare earth elements in bottom sediments of the Brazil Basin, Atlantic Ocean

The sedimentation and ore formation were studied in sediments from nine stations located in the 24°W profile in the Brazil Basin of the Atlantic Ocean. The sediments are represented by mio- and hemipelagic muds, which are variably enriched in hydrothermal iron and manganese oxyhydroxides. As compared to the sediments from other basins of the Atlantic Ocean, these rocks are marked by extremely high manganese contents (up to 1.33%) and maximal enrichment in Ce. It was shown that the positive Ce anomaly is related to the REE accumulation on iron oxyhydroxides. Influence of hydrothermal source leads to the decrease of Ce anomaly and LREE/HREE ratio. In the reduced sediments, preservation of positive Ce anomaly and/or its disappearance was observed after iron and manganese reduction. The REE contents were determined for the first time in the Ethmodiscus oozes of the Brazil Basin. Ore deposits of the Brazil Basin are represented by ferromanganese crust and ferromanganese nodules. Judging from the contents of iron, manganese, rare, and trace elements, these formations are ascribed to the sedimentation (hydrogenic) deposits. They are characterized by a notable positive Ce anomaly in the REE pattern. The extremely high Ce content (up to 96% of total REE) was discovered for the first time in the buried nodules (Mn/Fe = 0.88).     

陈家山矿煤中微量元素和稀土元素地球化学特征

通过对陈家山煤矿中下侏罗统延安组4^#主采煤层中微量元素和稀土元素的测试分析,发现煤中富集亲花岗岩的钨钼族元素W、Mo、Bi、Sn、Ba、Sr和Li,说明该区煤系形成期间的陆源碎屑主要来自花岗岩和花岗片麻岩等中、酸性岩石。4^#煤中ΣREE平均值为98.2×10^-6,稀土元素分布模式十分相似,呈左高右低的宽缓“V”型曲线,Eu负异常明显,反映出稀土元素与陆源碎屑岩关系密切,成煤期间稀土元素来源一致,陆源物质的供应相对稳定。     

白银厂铜多金属矿田微量元素和稀土元素地球化学研究

与日本黑矿及现代海底火山岩为主岩矿床相比，白银厂矿田各类矿石，尤其是块状Ｚｎ－Ｐｂ－Ｃｕ矿石具有最高的Ａｓ和Ｂｉ含量，比较高的Ｇａ、Ｃｄ和Ａｕ含量，以及较高的Ａｕ／Ａｇ和Ｃｏ／Ｎｉ比值。该矿田矿石的Ａｕ含量与闪锌矿中铁含量呈负相关关系。小铁山矿床闪锌矿与日本黑矿的闪锌矿微量元素特征很相似。矿田各类矿石ＲＥＥ型式与细碧角斑岩类岩石基体相似，这说明矿石与岩石的物质来源基本一致。研究和对比表明，火山成因     

Geochemistry of rare earth elements in micro-and macronodules from the pacific bioproductive zone

Concentrations and compositions of rare earth elements (REE) in three micronodule fractions (50–250, 250–500, and >500 μm), coexisting macronodules, and host sediments are examined. The samples were collected from three sites (Guatemala Basin, Peru Basin, and northern equatorial Pacific) located in elevated bioproductivity zones of the surficial water. The influence of micronodule size is dominant for REE compositions and subordinate for REE concentrations. For example, the Ce concentration inversely correlates with the micronodule fraction dimension and drops to the lowest value in macronodules and host sediments. The Ce decrease is generally accompanied by the Mn/Fe increase in micro- and macronodules. Hence, the role of diagenetic source of material directly correlates with the micronodule dimension. The contribution of diagenetic source is maximal for macronodules. The REE signature distinctions of micronodules and macronodules can be attributed to variations of hydrogenic iron oxyhydroxides and diagenetic (hydrothermal) iron hydroxophosphates that are the major REE carriers in ferromanganese ore deposits. The relationship and general trend in the chemistry of coexisting macronodules suggest that they can represent products of the initial stage of nodule formation.     

四川稀土精矿的稀土元素和微量元素地球化学特征及开发利用意义

产自广东省梅州市玉水铜矿的景文矿,属于含水、重稀土-矾-铝硅酸盐矿物(简写为HREE-V-铝硅酸盐矿物),其化学结构式为Y₂Al₂V₂⁴⁺(SiO₄)₂O₄(OH)₄,该矿物在全球属首次发现,暂未开展相关研究。相对于含轻稀土矿物,含重稀土矿物在电子探针分析过程中,当被高压电子束轰击时,被激发出来的特征X射线线系繁多,线系之间分布更加密集,彼此之间相互重叠的现象也更为严重,要获得理想数据的难度很大,是亟待解决和突破的技术难题。本文对该矿物进行了精细的电子探针定量分析,获得理想的化学成分数据,为新矿物命名提供了理论数据技术支撑。通过对实验方法的探索和总结获得以下结果：①利用15kV加速电压、100nA束流对试样进行全元素扫描,以此确定出17种元素;②在定量分析过程中,对重叠峰进行了剥离;③利用仪器软件中的Zoom-Peak ID程序,选择出17种元素的分析线系、精确的峰位及上下背景值;④选取合适的标样及测试时间等定量分析条件,最终获得理想的定量分析结果(平均总量97.41wt%)。上述四条也是确保获得理想定量分析数据的关键因素。

     

Geochemistry of the rare earth elements in ferromanganese nodules from DOMES Site A,northern equatorial Pacific

The distribution of rare earth elements (REE) in ferromanganese nodules from DOMES Site A has been determined by instrumental neutron activation methods. The concentrations of the REE vary markedly. Low concentrations characterize samples from a depression (the valley), in which Quaternary sediments are thin or absent; high concentrations are found in samples from the surrounding abyssal hills (the highlands) where the Quaternary sediment section is relatively thick. Moreover, the valley nodules are strongly depleted in the light trivalent REE (LREE) and Ce compared with nodules from the highlands, some of the former showing negative Ce anomalies.The REE abundances in the nodules are strongly influenced by the REE abundances in coexisting bottom water. Some controls on the REE chemistry of bottom waters include: a) the more effective removal of the LREE relative to the HREE from seawater because of the greater degree of complexation of the latter elements with seawater ligands, b) the very efficient oxidative scavenging of Ce on particle surfaces in seawater, and c) the strong depletion of both Ce and the LREE in, or a larger benthic flux of the HREE into, the Antarctic Bottom Water (AABW) which flows through the valley. The distinctive REE chemistry of valley nodules is a function of their growth from geochemically evolved AABW. In contrast, the REE chemistry of highland nodules indicates growth from a local, less evolved seawater source.     

巢湖的稀土元素地球化学特征

采用液-液萃取法和ICP-MS测试技术对巢湖的溶解态稀土元素进行了分析。结果表明,巢湖的溶解态稀土的含量与世界淡水相当,丰水期的样品含量高于其他季节。pH值和悬浮物、胶体是控制巢湖水体中溶解态稀土含量的主要因素。巢湖的溶解态稀土的分布模式以平坦型为主,少数呈现重稀土富集。丰水期和枯水期的溶解态稀土的(La/Yb)N值从西半湖区到东半湖区呈现有规律性的逐渐增大,并且丰水期的(La/Yb)N值低于枯水期。在富营养化湖泊中,胶体和水生生物可能是造成这一现象的主要原因。     

长江三峡地区成冰纪-埃迪卡拉纪转换时期微量元素和稀土元素地球化学特征

通过微量元素和稀土元素地球化学分析,对长江三峡地区陡山沱组层型剖面--田家园子剖面成冰系南沱组顶部和埃迪卡拉系陡山沱组下部102个岩石样品进行了地球化学研究。重点分析了氧化还原敏感元素(Zn,Co,U,Mo,Ni,V)的富集特征,并探讨其可能成因机制以及三峡地区成冰纪-埃迪卡拉纪转换时期的水体特征。结果表明:在南沱组顶部仅Zn和Co富集;在盖帽白云岩下部,氧化还原敏感元素均富集,而在盖帽白云岩上部,除Zn和V外,其他氧化还原敏感元素均亏损;在陡山沱组Ⅱ段下部,氧化还原敏感元素由最初的亏损,逐渐变为较稳定的富集。在陡山沱组下部,出现2次明显的富集峰值,分别出现在剖面的0.4m处(盖帽白云岩中间)和6.5m处(陡山沱组Ⅱ段下部)。整个剖面大部分样品具有Eu的轻微正异常(Eu/Eu^*＜1.6), 而在剖面0.4m和6.5m处,Eu具有明显的正异常,结合稀土配分类型、Y/Ho值、La异常、Ce异常等指标,推测这2次异常均可能受到深海热液流的影响,而缺氧海水的上涌造成水体缺氧,导致这些元素出现富集峰值。U/Th、V/(V+Ni)以及稀土元素指标综合指示,三峡地区南沱组顶部冰碛岩应为氧化环境下的沉积物;随着冰川消融,冰融淡水注入古海洋,陡山沱组盖帽碳酸盐的沉积受冰融淡水的影响,深部缺氧海水的上涌使沉积水体经历氧化-缺氧-氧化的转变,海水的分层性较强;而陡山沱组Ⅱ段下部沉积环境以分层性较弱的弱氧化环境为主。     

黔西北香炉山稀土矿的稀土元素赋存状态

以香炉山稀土矿床为研究对象,研究矿石中稀土元素赋存状态。采用扫描电镜、电子探针及化学浸取实验方法,对稀土矿石样品进行测试分析和浸取实验。扫描电镜未扫描出独立的稀土矿物,电子探针对样品原位微区探测出的元素有:O、Al、Si、Ca、Mg、Fe、Ti、K、Na、S、Cl、C、Cu、Cr、V、Pt,未探测到稀土元素。采用10%的(NH_4)_2SO_4、(NH4)Cl、NaCl和H_2SO_4化学试剂,室内常温常压,浸取24 h,结果显示,矿石中稀土元素容易被浸取,浸出率较高,为11.47%～24.00%,说明矿石中稀土元素的赋存状态为离子态存在,而不是稀土矿物。     

Geochemistry and biogeochemistry of rare earth elements in a surface environment (soil and plant) in South China

Plants and soils derived from different kinds of parent materials in South China were collected for analyses of rare earth elements (REEs) by inductively coupled plasma-mass spectrometry (ICP-MS). The distribution patterns and transportation characteristics of REEs in the soil–plant system were studied. The results show that geochemical characteristics of REEs depend on the types of soils, soils derived from granite being the highest in REE concentration. In a soil profile, REE concentrations are higher in B and C horizons than those in A horizon, with Eu negative anomaly and Ce positive anomaly. Plants of different genera growing in the same sampling site have quite similar REE distribution pattern, but plants of the same genera growing in different soils show considerable variation in characteristics of REEs. The patterns of the different parts of plant resemble each other, but the slope of the patterns becomes different. REEs have fractionated when they were transported and migrated from soil to plant root, stem and leaf, revealing that heavy REEs are relatively less available. REEs distributions in plants are influenced by the soil they grow in and also characterized by their individual biogeochemical characteristics. Biological absorption coefficients indicate difference of REE absorption capacity of plants. Electronic supplementary material  The online version of this article (doi:) contains supplementary material, which is available to authorized users.     

Concentrations of rare earth elements in topsoil from East China

Fifty topsoil samples collected from 12 different regions of East China have been analyzed for rare earth elements (REEs). The average REE concentrations of the 50 topsoil samples are much higher than world average and are characterized by LREE-enrichment, HREE-depletion, Eu-depletion and Ce-enrichment. However, the REE concentration is not strongly affected by the climate of the sampling site; it is controlled mainly by parent materials. The plot of Ce/Eu against Eu/Sm is proved to be useful to distinguish different parent materials of topsoil. Each element in the 50 topsoil has a good correlation with its neighboring element. Seven of the 13 values are above 0.987.