内蒙古大石寨地区稀土元素的区域分布特征

总结了内蒙古大石寨地区1∶25万区域地球化学调查获得的1点/4km2的水系沉积物组合样品中的La、Ce、Pr、Nd、Sm、Eu、Gd、Tb、Dy、Ho、Er、Tm、Yb、Lu、Y等15种稀土元素的区域地球化学分布特征。稀土元素分布与研究区中部的黑云母花岗岩密切相关,轻稀土主要分布在该岩体外围的二叠系地层中,重稀土主要分布在该岩体上方。该岩体上方和外围地层的稀土元素分布、稀土元素总量、轻重稀土比及δCe、δEu、(La/Sm)N、(La/Tb)N、(La/Lu)N、(Ce/Yb)N、(Gd/Lu)N等稀土元素分馏特征的差异明显。利用区域地球化学调查水系沉积物样品中的稀土元素含量,可获得研究区可靠的稀土元素区域地球化学分布特征,也可反映研究区地质特点,并为区域地球化学异常解译提供参考资料。     

Rare earth element composition of Paleogene vertebrate fossils from Toadstool Geologic Park,Nebraska, USA

Fossil bones and teeth from terrestrial environments encode unique rare earth and trace element (REE and TE) signatures as a function of redox conditions, pH, concentrations of complexing ligands, and water-colloid interactions. This signature is set early in the fossilization process and serves as a paleoenvironmental and paleoclimatic proxy. These signatures can also be used to interpret temporal and spatial averaging within vertebrate accumulations, and can help relocate displaced fossil bones back into stratigraphic context. Rare earth elements in vertebrate fossils from upper Eocene and Oligocene strata of Toadstool Geologic Park, northwestern Nebraska, record mixing and evolution of Paleogene vadose or groundwaters and variations in paleoenvironments. REE signatures indicate that HREE-enriched alkaline groundwater reacted with LREE- and MREE-enriched sediments to produce 3-component mixtures. REE signatures become increasingly LREE- and MREE-enriched toward the top of the studied section as the paleoenvironment became cooler and drier, suggesting that REE signatures may be climate proxies. Time series analysis suggests that REE ratios are influenced by cycles of ca. 1050, 800, 570, 440, and 225 ka, similar to some previously determined Milankovitch astronomical and climate periodicities.     

REE Compositions of Lower Ordovician Dolomites in Central and North Tarim Basin, NW China: A Potential REE Proxy for Ancient Seawater

Rare earth dement compositions of Lower Ordovician dolomites in the Central and Northern Tarim Basin are studied. Most dolomite samples are more or less contaminated by clay minerals. Their rare earth element compositions have been consequently changed, showing both seawater-like and non-seawater-like features. The clay contamination should be disposed before the REE data are used. Through ICP-MS and ICP-AES analyses, the REE features are well documented. The clay contamination is quantitatively determined by microscopic investigation, trace elements and REE contents. The dolomites, at least in the Tarim Basin, are thought to be pure when their total LREE contents are less than 3x10-6. Through comparison, the pure dolomites show similarities in REE patterns but differences in REE contents with co-existing pure limestone, which indicates that dolomitization may slightly change the REE compositions. Nevertheless, whatever the change is, the pure dolomites may act as a potential REE proxy for Ordovician seawater, which would be significant for ancient massive dolomite strata that lack limestone.     

REE Compositions of Lower Ordovician Dolomites in Central and North Tarim Basin, NW China： A Potential REE Proxy for Ancient Seawater

Rare earth element compositions of Lower Ordovician dolomites in the Central and Northern Tarim Basin are studied. Most dolomite samples are more or less contaminated by clay minerals. Their rare earth element compositions have been consequently changed, showing both seawater-like and non-seawater-like features. The clay contamination should be disposed before the REE data are used. Through ICP-MS and ICP-AES analyses, the REE features are well documented. The clay contamination is quantitatively determined by microscopic investigation, trace elements and REE contents. The dolomites, at least in the Tarim Basin, are thought to be pure when their total LREE contents are less than 3×10^-6. Through comparison, the pure dolomites show similarities in REE patterns but differences in REE contents with co-existing pure limestone, which indicates that dolomitization may slightly change the REE compositions. Nevertheless, whatever the change is, the pure dolomites may act as a potential REE proxy for Ordovician seawater, which would be significant for ancient massive dolomite strata that lack limestone.     

皖北九顶山组灰岩稀土元素地球化学特征及对古海水的制约

采集皖北新元古代九顶山组灰岩进行了系统的岩石学和稀土地球化学分析,研究了灰岩中稀土元素的来源,并对海水的稀土配分模式进行反演,结果表明:灰岩中稀土元素主要受控于古海洋,基本不受陆源物质影响;灰岩样品中稀土含量很低,平均为8.54×10-6,轻重稀土分异明显,为正常浅海沉积;海水稀土配分模式与灰岩相似,为重稀土亏损,灰岩和海水的Y/Ho、Y/Dy值呈正相关;海水具有较高的Y/Ho比、Ce负异常,且海水的δEuNASC值小于1,表明了新元古代海水与现代海水的稀土元素特征基本相似。     

Economically viable rare earth element deposits along beach placers of Andhra Pradesh,eastern coast of India

A comprehensive study was carried out in order to determine the radioelement and rare earth element (REE) concentrations in beach placer deposits at selected locations along the eastern coast of Andhra Pradesh in India. This was done to evaluate the economic value of these deposits. The findings of this study suggest that high Th and low K concentrations delineate the prospective regions having REE deposits. The beach placers, in general, can be characterized by high thorium and moderate uranium concentrations. The concentrations of REEs vary in the following order: Ce > La> Nd > Pr > Sm > Gd > Dy. Rapid in situ thorium prospectivity coupled with laboratory-based techniques like ICP-MS, as proposed in this study, would help in the identification of prospective REE sources along the coastal placers. The development of indigenous resources of light rare earth elements (LREEs), medium rare earth elements (MREEs), and heavy rare earth elements (HREEs) would decrease the dependence on imports, which have a strategic hold on the production and supply of the REEs, globally.     

若尔盖铀矿田方解石稀土元素与碳氧同位素地球化学特征及其意义

方解石是若尔盖铀矿田与成矿最为密切的脉石矿物之一。方解石的REE地球化学特征研究表明,产于地层中的方解石、矿区中的方解石和含矿方解石具有明显不同的稀土元素组成特征,分别具有轻稀土富集右倾型、重稀土富集左倾型和相对平坦型的3种稀土配分模式。其中产于地层中的方解石明显继承了地层中岩石的稀土元素特征,而含矿方解石表现出与矿石稀土元素相似的特征。碳氧同位素显示地层中的方解石为海洋沉积碳酸盐岩的碳氧同位素组成特征;矿区方解石脉、含矿方解石脉的碳同位素组成明显表现为地幔来源的特点;而矿区方解石脉的氧同位素组成具明显的深部来源特征,含矿方解石脉的氧同位素组成表明在成矿过程中有大气降水的混入。若尔盖铀矿田的方解石主要为热液成因,其矿床成因类型属于典型的热液矿床,成矿流体主要来源于地幔。     

高岭石和埃洛石-7Å对稀土元素吸附特征的实验研究

针对赣南风化淋积型稀土矿中稀土元素的分异现象,通过研究该稀土矿的主要矿物成分——高岭石和埃洛石-7的矿物特征及其在不同条件下的吸附特征,探讨了该类型稀土矿的成矿机制和稀土元素分异机理。高岭石和埃洛石-7吸附稀土元素的能力受体系p H值以及金属阳离子钾、钠的的影响,且埃洛石-7吸附稀土元素的能力高于高岭石。横向对比实验结果表明当体系中赋存有K+时,两种粘土矿物对稀土元素的吸附呈现出分化趋势,其中高岭石主要吸附中-重稀土元素,埃洛石-7反之,因此风化淋积型稀土矿风化过程中释放出的K+可能会使高岭石和埃洛石-7呈现出差异吸附特征,进而反过来影响稀土矿中稀土元素的配分。     

黔西北天桥铅锌矿床热液方解石C、O同位素和REE地球化学

利用连续流动质谱和电感耦合等离子体质谱(ICP-MS)对黔西北天桥铅锌矿床原生矿石中脉石矿物热液方解石C、O同位素组成和稀土元素含量进行了分析,结果表明热液方解石C、O同位素组成相对均一,不同标高方解石C、O同位素组成不具明显差别,其δ13CPDB和δ18OSMOW分别为-3.4‰～-5.3‰和14.7‰～19.5‰,在δ13CPDB-δ18OSMOW图上介于原始碳酸岩与海相碳酸盐岩之间。热液方解石总稀土元素含量较低(ΣREE=6.80×10-6～49.1×10-6),表现为轻稀土富集、Eu负异常的"M"型,其Eu/Eu*变化范围为0.30～0.55,与硫化物具有相似的稀土配分模式。根据热液方解石与蚀变围岩、远矿围岩及不同时代地层碳酸盐岩的C、O同位素组成和REE含量特征对比结果,结合前人研究成果,认为该矿床成矿流体具"多来源混合"特征,其中围岩碳酸盐岩为成矿流体提供了主要的C和REE来源,地层中膏岩海相硫酸盐岩为成矿流体提供了主要的S来源,而成矿流体中的水则主要为变质基底昆阳群等提供的变质水,并受到大气降水的影响。     

赣南稀土精矿粉配制的稀土溶液反射波谱特征研究

赣南离子吸附型稀土矿是我国重要的稀土资源,本文运用美国ASD FieldSpec-3便携式地物波谱仪,对赣南寻乌稀土矿区稀土精矿粉配置的25个稀土溶液样品进行波谱测试,获取了不同稀土含量的波谱特征,结果表明溶解在水体中的稀土元素在可见光-近红外574 nm、790 nm、736 nm、520 nm、861 nm、443 nm等波段具有多个明显的稀土特征吸收谷及若干次级的稀土特征吸收谷;通过与15种稀土单元素波谱特征对比分析,可见这些吸收特征主要由一种或几种稀土单元素引起;随着稀土浓度的降低,这些吸收特征逐渐减弱甚至消失。这一研究进一步加深了对我国赣南稀土溶液波谱特征的认识,同时为赣南稀土元素的高光谱遥感研究奠定了理论基础。     

滇西陇川营盘山离子吸附型稀土矿稀土元素分布特征

滇西陇川地区广泛分布着白垩纪至古近纪中酸性花岗岩,以邦棍尖山为代表的岩体花岗岩稀土含量较高,经复杂的风化淋滤作用,岩体中的稀土元素在风化壳中迁移、富集成矿,陇川营盘山稀土矿即为近年新发现的该类型矿产地之一。为研究新发现的营盘山稀土矿稀土元素分布特征、富集规律及稀土配分特征,利用电感耦合等离子体质谱仪(ICP-MS)分析成矿母岩及其风化壳不同风化程度样品稀土分量,结果表明:风化壳各层位稀土元素分布特征相比母岩具有明显的继承性,随风化程度升高,轻重稀土分馏程度升高,轻稀土在全风化层上部相对富集,且随风化程度升高轻稀土富集程度升高,而重稀土的富集程度则逐渐减弱,Gd是风化壳富集能力最强的元素,Dy富集能力最弱,Ce富集在近地表,重稀土具有更强的向下迁移能力。同时,研究发现该稀土矿床的稀土配分特征为低钇、铕,富镧、铈、钕。     

麦哲伦海山群MK海山富钴结壳稀土元素的赋存相态

利用ICP-OES和ICP-MS,分析了麦哲伦海山群西北端MK海山2 170 m水深的MKD23B-3号富钴结壳样品,获得了其剖面上主元素、稀土元素（REE）和Y含量数据,并基于元素含量间的线性相关关系,研究了REE和Y的赋存相态。结果显示:该样品剖面从基岩到表面可划分为5层,第Ⅰ、Ⅱ层为磷酸盐化壳层,第Ⅲ、Ⅳ、Ⅴ层为未磷酸盐化壳层。在未磷酸盐化壳层中,REE和Y主要赋存在δ-MnO₂相中;而在磷酸盐化壳层中,REE和Y除了赋存在Fe、Mn氧化物相中外,主要赋存在独立于碳氟磷灰石（CFA）的矿物相态中,可能为稀土的磷酸盐。并提出利用磷酸盐中REE/Y 估算富钴结壳磷酸盐化壳层次生稀土的方法,据此估算了MK海山富钴结壳磷酸盐化壳层次生稀土的量。在该样品中,次生稀土占稀土总量的42%~88%,近一半以上的稀土是次生的,磷酸盐化作用对于REE和Y的次生富集具有显著的贡献;因此解读磷酸盐化富钴结壳的稀土元素（特别是Nd同位素）古海洋记录必须排除次生稀土元素的干扰。     

川西甲基卡锂资源富集区根系土壤重金属含量水平及时空分布特征

锂能源金属的战略地位不断提高,与锂矿床及锂金属相关的研究也在不断跟进,锂矿区土壤重金属污染近年来持续受到关注,其含量分布情况值得深入研究。本文对亚洲最大的锂矿区——川西甲基卡根系土壤环境进行重金属含量监测,调查和评价锂矿区土壤重金属含量水平及其安全性。2016—2018年于川西甲基卡锂资源富集区采集根系土壤样品68件,采用电感耦合等离子体质谱法(ICP-MS)测定根系土壤Cd、As、Pb、Cr、Cu、Ni、Zn含量。测试结果表明,甲基卡矿区根系土壤Cd、As、Pb、Cr、Cu、Ni、Zn含量平均值分别为0.13、15.31、25.47、60.57、16.12、23.59、66.83mg/kg,与2018年8月最新颁布的农用地土壤标准对比,无一超标,均低于风险筛选值及管制值。常见矿床的尾矿库区土壤一般存在严重的重金属污染,而甲基卡尾矿库土壤重金属含量均低于环境标准限值,且矿业活动停止的三年期间尾矿库区根系土壤中Cd、As、Cr含量明显呈逐年下降趋势。本研究认为,选矿厂房及尾矿库周边根系土壤重金属由于人为源的存在有一定的富集现象,但不构成危害,废弃物对环境污染小。     

Geochemical and mineralogical characteristics of recent clastic sediments from lower Godavari river: Implications of source rock weathering

The major, trace and rare earth elements geochemistry and clay mineral compositions in the river bed sediments from lower reaches of Godavari river suggest that they are derived from weathering of felsic rocks. Trace and rare earth elemental compositions indicate evidence of sedimentary sorting during transportation and deposition. Lower concentrations of transition elements, such as V, Ni and Cr imply enrichment of felsic minerals in these bed sediments. The REE pattern in lower Godavari sediments is influenced by the degree of source rock weathering. The light rare earth elements (LREE) content are indicating greater fractionation compared to the heavy rare earth elements (HREE). A striking relationship is observed between TiO₂ and gZREE content suggesting a strong control by LREE-enriched titaniferous minerals on REE chemistry. Shale-normalized REE pattern demonstrate a positive Eu anomaly, suggesting weathering of feldspar and their secondary products, which are enriched in Eu. Chondrite-normalised REE pattern is characteristic of felsic volcanic, granites and gnessic source rocks. Trace elemental compositions in sediments located near urban areas suggest influence of anthropogenic activity. Chemical Index of Alteration (CIA) is high (avg. 65.76), suggesting a moderate chemical weathering environment. X-ray diffraction analysis of clay fraction shows predominance of clay minerals that are formed because of the chemical weathering of felsic rocks.     

碱熔沉淀分离-电感耦合等离子体质谱法测定伴生重晶石稀土矿中的稀土元素

采用电感耦合等离子体质谱法(ICP-MS)测定伴生重晶石轻稀土矿中的稀土元素时,Ba以及轻稀土元素La、Ce、Pr、Nd、Sm等对中重稀土造成严重的质谱重叠干扰,因此在保证矿石完全消解的同时,若能选择合适的前处理方法实现目标元素与基体的有效分离,将有利于减少质谱干扰。本文采用过氧化钠-碳酸钠熔融分解伴生重晶石的稀土矿样品,熔融物用三乙醇胺溶液提取,将沉淀过滤去除硅、铁、锰、铝等大量基体元素,而稀土元素与钡、锶、钙等留存于沉淀中,沉淀经盐酸溶解后再用氨水进行二次沉淀,将稀土元素与伴生的高含量钡、锶、钙等元素分离,分离率超过96%,从而极大地降低了由钡的氧化物和氢氧化物对~(153)Eu等元素质量数的质谱干扰。轻稀土元素对中重稀土元素的干扰则通过测定高浓度的单元素标准溶液在m/z 138～175处的表观浓度来计算干扰校正系数,对干扰量进行扣除校正。该方法通过稀土矿石标准物质GBW07187、GBW07188验证,测定值与认定值的相对误差10%;应用于伴生重晶石稀土矿石实际样品分析,相对标准偏差(RSD,n=12)为0.5%～4.6%,证明了本方法可用于分析高钡矿石中的稀土元素。     

浙东南离子吸附型稀土矿床成矿规律与找矿方向探讨

离子吸附型稀土矿(以下简称iRee)主要分布于我国南岭地区,浙江省虽不在南岭五省之内,但经过浙江省地勘单位三十多年的不断探索,在浙东南地区陆续发现了数个稀土矿及多个成矿远景区,填补了浙江省该类型稀土矿的找矿空白。为探究浙东南iRee矿床地质特征、成矿影响因素以及稀土元素运移、赋存规律,圈定成矿远景区,本文对区内出露的花岗斑岩型iRee,火山岩型iRee以及变质岩型iRee进行系统采样,通过岩相学、岩石地球化学等方法对各类iRee剖面进行对比研究。分析结果表明,荷地花岗斑岩的平均∑REE为271.39×10^-6,凝灰岩围岩平均∑REE为253.36×10^-6,大柘片麻岩∑REE约为517.21×10^-6,而南岭含矿岩体的平均∑REE约为289×10^-6,表明浙东南地区iRee矿床具有较好的成矿母岩条件。此外,通过对原岩中各矿物稀土元素含量的测定,查明了稀土元素主要赋存在独立的稀土矿物及少量的副矿物中,是主要的成矿物质来源;通过风化壳剖面的对比,发现稀土元素地球化学特征主要继承原岩性质,而外生作用条件使得稀土元素发生次生富集。在此工作基础上,结合前人研究成果,初步总结了区内离子吸附型稀土矿矿床成矿规律,并讨论下一步找矿方向。     

The development of acidic groundwaters in coal-bearing strata: Part I. Rare earth element fingerprinting

This study examines the rare earth element (REE) pattern of acidic mine discharges in the Durham basin (NE England) as a means of fingerprinting their sources and understanding the water-rock interactions Although whole rock compositions proved to be unhelpful, mimicking acid mine water generation in a series of selective leachates of the coal and coal-bearing strata gave REE patterns similar to those measured in the emergent waters. REE ratios and anomalies were used as indicators of specific interactions in the development of acidic groundwater. The implications of the findings for the classification and evolution of acid mine discharges are discussed.     

深海沉积物中的稀土矿产资源研究进展

近年发现,太平洋和印度洋的深海盆地中存在大量富含稀土的深海沉积物。主要类型为多金属软泥、沸石黏土和远洋黏土,其中的全稀土含量(∑REY,∑REE+Y)为400×10-6~2000×10-6,最高可达6600×10-6,重稀土含量(HREE)已达到或超过中国南方离子吸附型矿床的重稀土品位两倍以上,是潜在的新型稀土资源,具有重要的经济价值。目前不少学者对富稀土的深海沉积物进行了大量地球化学及部分矿物学的工作,认为多金属软泥中的稀土元素多赋存于与海底热液作用有关的铁锰氧化物和氢氧化物中,而沸石黏土和远洋黏土中稀土元素的富集则与磷酸盐的混入密切相关,其稀土元素主要存在于与磷灰石成分相当的生物鱼骨屑中。深海黏土的北美页岩标准化稀土配分模式与海水相似,表明其中的稀土元素主要来自于海水,REY富集成矿可能主要受控于磷灰石早期成岩阶段,期间稀土元素未发生分异。尽管近些年对深海沉积物中的稀土元素研究取得了不少成果,但是,对于沉积物中的稀土富集机制及影响因素等问题仍然需要更加深入的研究。作为稀土资源大国,为了争取我国在国际海底稀土资源竞争中的话语权,维护中国的稀土利益,中国应加紧开展相关的稀土资源勘查和潜力评价。     

鄂尔多斯盆地北缘延安组2号煤层稀土元素异常原因及其地质意义

鄂尔多斯盆地北缘延安组2号煤层稀土元素的异常原因一直存在着争议,以2号煤发育较完整的榆林大海则煤矿为例,运用电感耦合等离子质谱（ICP-MS）、扫描电子显微镜（SEM）等方法,分析煤及夹矸中稀土元素（REE）含量及其矿物学特征,并揭示稀土元素异常原因。结果显示:煤中总稀土元素（∑REE）含量为3.71~46.21 μg/g,轻稀土元素（LREE,La-Eu）比重稀土元素（HREE,Gd-Lu）更富集;稀土元素标准化配分模式图显示少数样品为Eu正异常;稀土元素含量较高的样品和拥有Eu正异常的样品主要分布在与夹矸距离较近的煤层中,表明煤中稀土元素分布受到了夹矸的影响;在夹矸中发现很多晶型较好的锆石、磷灰石、透长石及锐钛矿,这些矿物是在聚煤过程中接受火山物质的直接证据。综合认为,鄂尔多斯盆地延安组2号煤沉积期,盆地周缘存在一次火山活动,火山灰降落覆盖在泥炭沼泽之上,影响了聚煤作用,致使煤中稀土元素分布异常。研究结果解释了鄂尔多斯盆地北缘的煤中稀土元素异常原因,为研究区煤的加工利用方式提供参考。