贵州遵义二叠系锰矿床中稀土元素赋存状态研究

贵州遵义地区是中国华南二叠系锰矿重要富集区之一,锰资源储量逾2亿t。通过对遵义长征、南茶及统子窝锰矿床23件岩矿石样品稀土元素组成进行测试分析,发现锰矿床普遍富集稀土元素,其中矿石∑REE总量介于326.3~1138.9×10~(-6)之间,平均538.84×10~(-6)。锰矿中凝灰岩∑REE总量最高,达到1824.5×10~(-6)。电子探针和能谱分析结果表明,锰矿中稀土元素主要以稀土独立矿物的形式存在,其中独居石、磷钇矿是最主要的稀土矿物,其以富集Ce,La和Nd为主要特征,部分矿段重稀土元素Y相对富集,指示遵义二叠系锰矿床伴生稀土组分主要以富集轻稀土元素为主要特征。     

贵州西部峨眉山玄武岩风化壳稀土元素迁移富集规律研究

通过野外地质调查、样品采集和ICP-MS分析等方法,运用地质学和地球化学理论,对贵州西部峨眉山玄武岩风化壳稀土元素迁移富集规律进行研究。研究结果表明:峨眉山玄武岩风化壳剖面垂向上,各稀土元素氧化物含量变化曲线呈"D"字型,浸出率呈上陡下缓"单齿"状曲线。在全风化-半风化层中,各稀土元素整体富集,而亚黏土层中,仅Yb,Lu,Ce三个元素富集。全风化-半风化层中,稀土元素氧化物总量变化范围847～1146×10~(-6),平均品位为973×10~(-6),浸出率变化范围15.2～45.2×10~(-2),平均浸出率为26.3×10-2。各稀土元素氧化物浸出率一般20%～70%,轻、中、重稀土氧化物总量平均浸出率分别为25.5%,33.0%及24.3%。Ce,Nd,La,Y四个元素氧化物总量及其浸出量分别平均占比稀土元素氧化物总量的76.3%和71.1%,因而,贵州西部峨眉山玄武岩风化壳型稀土资源,主要为富Ce-Nd-La-Y型。此研究结果对扩大我国稀土矿源具有重要的意义。     

吉林夹皮沟金矿带的稀土元素地球化学研究

为了解吉林夹皮沟金矿带的成矿期次,利用稀土元素的示踪性,对夹皮沟金矿带含矿石英脉、花岗岩及变质地层斜长角闪岩等21个样品进行稀土元素含量测定。测定结果表明,石英脉ΣREE=19.12×10-6～147.57×10-6,δEu=0.61～1.22,平均值0.89,具弱的负Eu异常;太古代花岗岩ΣREE=121.40×10-6～157.32×10-6,δEu=0.87～1.09;中生代花岗岩ΣREE=69.78×10-6～90.95×10-6,δEu=0.94～1.02,LREE/HREE比值分别为11.51～14.12和14.16～16.73,后者轻重稀土分馏程度略高于前者;变质围岩ΣREE=22.40×10-6～275.86×10-6,δEu=0.75～5.79,平均值2.30,具明显的正Eu异常。三者都具有轻稀土富集的平滑稀土配分模型。结合其区域地质背景、流体包裹体和稀土元素特征,得出夹皮沟金矿存在两期成矿作用,分别对应于太古代成矿花岗岩岩浆作用及中生代燕山期花岗岩岩浆作用。太古代首次富集成矿,中生代燕山期叠加成矿并扩大成矿规模,成矿时代分别为2475～2469 Ma和170～160 Ma;结合稀土特征研究及包裹体研究,成矿流体以岩浆热液流体为主,遭受轻微地层变质热液混染,中生代成矿流体混染作用更强烈。     

河南省洛宁龙门店银铅矿稀土元素地球化学特征及地质意义

龙门店银铅矿片麻岩和中性喷出岩具有相似的稀土配分模式,轻稀土富集,曲线右倾。前者稀土总量较低,平均105.99×10~(-6),δEu=0.71~5.59,总体呈正异常;后者稀土总量略高,平均194.81×10~(-6),δEu=0.84~1.08;花岗岩稀土总量较高,平均231.06×10~(-6),具Eu负异常,混合花岗岩及辉绿岩呈正异常;矿石稀土总量相对较低,平均108.5×10~(-6),Eu正异常和负异常交替出现。岩石和矿石均有轻重稀土分异明显的特征。从片麻岩→矿石→辉绿岩→混合花岗岩→安山岩类→花岗岩,稀土元素总量递增,显示了成矿热液对岩浆岩体的淋滤萃取和对围岩的叠加改造。矿体中的Y/Ho=26.29~37.16,集中于27~31,接近陨石比值,表明矿床形成过程中应该有岩浆热液加入,体现后期岩浆热液的特征,稀土元素总量变大。燕山期岩浆热液对矿石组分有一定的改造,Eu正异常和负异常同时出现,矿石稀土元素特征体现出后期叠加岩浆流体的部分反映。结合石英、黄铁矿、方铅矿及围岩的稀土元素配分模式对比,基本确定成矿物质主要来自岩浆热液,即与蒿坪沟岩体关系密切。     

陕西汉阴黄龙金矿稀土元素地球化学特征

采用ICP-MS方法研究了陕西汉阴黄龙金矿黑色岩系中稀土元素地球化学特征和形成条件. 稀土总量在全岩和硫化物中含量为91.55～331.31×10-6 g · g-1. 轻稀土富集, 分布曲线较陡, 重稀土曲线较为平缓, 与陕西八卦庙金矿和华南黑色页岩系中的稀土元素地球化学特征相似. Eu, Ce呈负异常, 反映黑色岩系形成于干燥气候的陆棚边缘浅海的还原环境.     

深海富稀土沉积研究的若干问题

深海富稀土沉积是指稀土元素含量(包含Y)≥400×10~(-6)的一类深海沉积物,以中-重稀土富集、与钙十字沸石紧密共生而区别于其他深海沉积类型。深海富稀土沉积在太平洋和印度洋广泛分布,其稀土氧化物资源量可达1000亿t,其中重稀土资源量约为325亿t,引起了国际学术界的普遍关注。在系统总结深海富稀土沉积的调查研究历史和现状基础上,对其分布特征和规律、地球化学特征、载体矿物、富集机制、物质来源等研究进展进行了阐述,并指出了目前在稀土元素富集机制研究方面存在的几个重要问题:稀土元素的物质来源;沉积物孔隙水对于稀土元素富集的作用;钙十字沸石等共生矿物的成矿指示意义。     

氟化氢铵快速分解-电感耦合等离子体质谱(ICP-MS)法测定多金属矿中痕量稀土元素

金属矿石稀土含量测定的前处理过程中由于氢氟酸的低沸点特性,样品消解温度低,容易引发部分样品稀土含量损失,影响最终的测试结果。本文利用氟化氢铵相较氢氟酸有更高的沸点,且在加热过程中可分解产生氢氟酸的特性,采用硫酸、氟化氢铵和硝酸消解多金属矿石样品,建立了电感耦合等离子体质谱测定多金属矿中稀土元素的分析方法。该方法研究了氟化氢铵用量、消解温度和消解时间对分析结果的影响,最终选择称样量为0.0500g,氟化氢铵为300mg,消解温度为200℃,消解时间为3 h,然后配合硝酸和硫酸消解多金属矿样品。方法线性相关系数 R2均在 0.9995 以上,稀土元素的方法检出限为0.001μg/g~0.02μg/g,方法检出下限为0.004μg/g~0.08μg/g。按照实验方法测定多金属矿石的国家一级标准物质的稀土含量测定各元素结果的相对标准偏差（RSD, n=6）为0.81%~3.2%,稀土元素的方法准确度(|ΔlgC|)为0.01~0.04,分析结果与标准物质认定值一致。方法经多金属矿石国家一级标准物质验证,方法的检出限和准确度能够满足《地球化学普查规范》DZ/T 0011-2015的质量要求,方法具有操作简便、测试成本低、分析效率高、环境污染小等特点,能够满足多金属矿中痕量稀土元素的分析要求。方法有效的提高了多金属矿石样品前处理过程中的分解温度,同时避免了碱熔带来的高基体和堵塞仪器进样系统的问题,可为多金属矿石样品稀土含量的准确测定提供了可靠的方法支撑。     

古海洋环境演化对富钴结壳稀土元素富集的制约

为了探讨古海洋环境演化对海山富钴结壳稀土元素富集的制约,本次选取西太平洋Lamont海山具有多层结构富钻结壳L1作为研究对象,逐层取样分析研究,认为古海洋环境演化以及磷酸盐化作用对不同稀土元素的影响不同:Ce含量受海洋生产力水平的制约,与形成时古海洋生产力水平呈正相关关系,但受磷酸盐化影响并不显著;而磷酸盐化对富钻结壳中其他稀土元素影响存在明显差异:导致老壳层中稀土元素相对较少,而重稀土元素则相对增加.另外富钴结壳壳层在生成后可能仍然继续与周边海水发生稀土元素交换,导致壳层生成得越早,其重稀土元素相对于其他稀土元素越富集,而Eu则越亏损.     

中太平洋M海山富钴结壳稀土元素地球化学

用ICP-AES和重量法测试了中太平洋M海山不同水深范围内(1300~3000 m)25个富钴结壳样品的稀土元素和常量元素。结果显示M海山富钴结壳为水成结壳,稀土元素总量平均为2084.69μg.g-1,LREE/HREE平均为4.84,具有正的Ce异常。ΣREE(不含Ce)随水深增加而增加,而Ce和LREE/HREE比值则以文石溶跃面为界(水深2000 m)呈现不同的变化,稀土元素这些变化除了与海洋背景颗粒的吸附清扫有关外,还与稀土元素在海水中的行为有关。富钴结壳Ce虽随水深变化,但与水深关系不明显,可能反映其通量恒定。富钴结壳中Ce基本全为Ce(Ⅳ),表明氧化富集过程,这一过程受动力学因素控制。     

印度洋热液区贻贝及栖息沉积物中金属元素的特征分析

本研究采集了印度洋热液区贻贝生物及其栖息沉积物样品,分析了生物体及沉积物中常见微量元素及稀土元素的含量与分布特征,研究了生物体与沉积物金属元素的相关性,以及稀土元素的生态化学特征等.结果表明:印度洋热液区沉积物中常见微量金属主要为Fe(96.62 mg/kg)、Mn(1.143 mg/kg)和Zn(322.6 μg/kg),微量元素归一化计算得Fe含量比值高达98.15%,可获悉该热液区沉积物主要为铁矿类物质.深海贻贝中微量元素及稀土元素的分布趋势与深海沉积物中元素分布存在较好的相关性,相关性系数分别为0.991与0.996,近海贻贝中金属元素的含量及分布与深海贻贝存在差异性.深海沉积物与贻贝中轻重稀土元素均呈现分馏现象,且贻贝中富集轻稀土比较显著;从稀土配分模式可知,沉积物与贻贝中的Eu与Gd均呈现异常现象,深海沉积物和深海贻贝中Eu异常现象较为显著.深海沉积物、贻贝及近海贻贝中δEu分别为9.50、10.68和0.23,而δCe分别为2.21、2.71和4.38,表明近海贻贝中稀土元素富集来源与深海贻贝存在差异性,深海沉积物与深海贻贝稀土元素具有同源性.     

Study on distribution of elements in deep-sea Pacific polymetallic nodules via two-dimensional mapping laser ionization orthogonal time-of-flight mass spectrometry

A newly developed two-dimensional mapping high irradiance laser ionization orthogonal time-of-flight mass spectrometer (LI-O-TOFMS) has been applied for the elemental mapping of polymetallic nodules. Two polymetallic nodule standards were used to demonstrate the efficacy of LI-O-TOFMS for the standardless semiquantitative analysis and the spatial distribution of elements in a deep-sea Pacific polymetallic nodule was mapped. It was found that the two groups of elements, Mn–Ni–Cu–Fe and Co–Si–Al, show clear element-dependent spatial relationships. It is hypothesized that these spatial distributions reflect the environmental and physico-chemical conditions during the nodule formation. LI-O-TOFMS is shown to be a powerful tool in elemental analysis of polymetallic nodules, with the detection limits down to 10^− 7 g/g and a dynamic range of 7 orders of magnitude. Based on the images acquired, the contents of elements and their relationships can be revealed visually.     

Concept of biogenic ferromanganese crust formation: coccoliths as bio-seeds in crusts from Central Atlantic Ocean (Senghor Seamount/Cape Verde)

At depths of 2,000 to 3,000 m, seamounts from the Cape Verde archipelago (Central Atlantic Ocean) are largely covered with ferromanganese crusts. Here we studied 60 to 150 mm thick crusts from the Senghor Seamount (depth: 2257.4 m). The crusts have a non lamellated texture and are covered with spherical nodules. The chemical composition shows a dominance of MnO2 (26.1%) and Fe2O3 (38.8%) with considerable amounts of Co (0.74%) and TiO2 (2.1%). Analysis by scanning electron probe microanalyzer (EPMA) revealed a well defined compositional zonation of micro-layers; the distribution pattern of Mn does not match that of Fe. Analysis by high resolution scanning electron microscopy (SEM) revealed that coccospheres/coccoliths exist in the crust material as microfossils; most of the coccospheres/coccoliths are not intact. The almost circular coccoliths belong to the type of heterococcoliths and are taxonomically related to species of the family Calcidiscaceae. By energy dispersive X-ray spectroscopic analysis an accumulation of the coccoliths in the Mn- and Fe rich micronodules was detected. Focused ion beam assisted SEM mapping highlighted that the coccoliths in the crust are Mn rich, suggesting that the calcareous material of the algal skeleton has been replaced by Mn-minerals. We conclude that a biologically induced mechanism has been involved in the formation of the crusts, collected from the Cape Verde archipelago from depths of 2,000 to 3,000 m in the mixing region between the oxygen-minimum surface zone and the oxygen-rich deep waters; the deposition process might have been triggered by chemical reactions during the dissolution of the Ca-carbonate skeletons of the coccoliths allowing Mn(II) to oxidize to Mn(IV) and in turn to deposit this element in the crust material.     

In-situ micro-analysis of platinum and rare earths in ferromanganese crusts by laser ablation-ICP-MS (LAICPMS)

A 500 mJ Nd: YAG laser coupled to an inductively coupled plasma mass spectrometer (ICPMS) has been used for the direct determination of platinum (Pt) and the rare earth elements (REE) in concentration micro-profiles through ferromanganese crusts from the South Pacific. The instrument has been calibrated with briquetted powder pellets of U.S.G.S. reference materials NOD-A-1 and NOD-P-1. Linear calibration curves including the origin have been obtained for all elements of interest. An external calibration strategy has been developed which also accounted for variations in instrument response. The precision of the LA-ICP-MS measurements in this matrix has been 4–5% for platinum and <4% for the rare earths. Platinum concentrations have varied from 150 ng g^–1 to 500 ng g^–1 through the analysed microprofile. Two major peak areas in the platinum concentration profile have correlated roughly with cerium values and with changes in the normalised REE pattern: an enrichment of Pt coincides with a pronounced positive cerium anomaly and with an enrichment of the heavy REE relative to the light REE.     

磷酸三丁酯萃淋树脂色层分离电感耦合等离子体质谱法测定富稀土样中微量铀和钍

研究了磷酸三丁酯萃淋树脂色层分离,电感耦合等离子体质谱法测定富稀土样中微量铀、钍的方法。样品经消解后,以磷酸三丁酯萃淋树脂为固定相、8 mol/L硝酸为流动相过柱分离,样品中的大部分稀土元素随流动相流出,而铀和钍则被固定相吸附,用去离子水洗脱后,再用电感耦合等离子体质谱仪测定。铀、钍的检出限分别为0.06,0.16μg/L,测定结果的相对标准偏差均小于10%(n=5),加标回收率为98%~105%。对稀土矿石标准物质进行测定,测定值与推荐值相符。该法操作简便,测定结果可靠,适于富稀土样中微量铀、钍的测定。     

快速凝固TiAl基合金稀土相显微组织的研究

利用两种不同的快速凝固方法对TiAl-RE合金中稀土相的显微组织进行了研究并与铸态组织进行对比,选择的快速凝固方法为溶体旋转法（MS）和锤钻法（HA）,试验结果表明,随着材料冷却速度的变化稀土相的显微组织发生了很大的变化,由铸态完全分布于晶粒边界之上过渡到锤砧法极细的层片和弥散分布的颗粒组织,选区电子衍射结果表明,稀土相的衍射斑点与AlCe金属间化合物一致。     

Extraterrestrial ~3He in marine polymetallic nodules: a potential method for measuring growth rate of nodules

The comparative measurements of helium isotope compositions between marine poly-metallic nodules and their surrounding sediments, their magnetic fractions and bulk from C-C Zoneof the East Pacific Basin are reported. The ~4He content and ~3He/~4He ratio of polymetallic nodulesand their surrounding sediments are extremely high; the ~3He, ~4He concentrations and most~3He/~4He ratios of magnetic fractions in nodules and sediments are apparently higher than those inbulk. The helium isotope data points of nodules and sediments are all distributed along or closelyto the mixing curve of the interplanetary dust particles (IDPs) and the terrigenous sediments in thechart of ~3He-~3He/~4He. In the same sampling site, the ~3He/~4He ratios of nodules and their surround-ing sediments are very similar, and the changes of both ratios are synchronous. It shows that thehigh ~3He/~4He ratios in nodules and sediments may all result from IDPs. So, if the flux of extrater-restrial ~3He into the nodules and sediments is constant, the growth rate of polymetallic nodules andthe sedimentation rate of sediments can be independently calculated according to the concentra-tion of extraterrestrial ~3He in nodules and sediments.     

电荷注入检测器电感耦合等离子体光谱仪的稀土元素分析性能

研究了电荷注入检测器电感耦合等离子体发射光谱（ＣＩＤ－ＩＣＰＥＳ）测定稀土元素的分析性能。结果表明,在稀土元素常用谱线波段内（２６０～４４０ｎｍ）光谱背影发射强度低于４０ＣＰＳ（计数／秒）,ＲＳＤ〈０．６％。研究了谱线强度和相对标准偏差的关系,当谱线强度高于５ＣＰＳ时,对于任何稀土元素谱线的ＲＳＤ均低于０．６％。谱线强度降低时,ＲＳＤ逐渐增大。文中给出了稀土元素常用分析谱线的强度值、线背比、背影等     

微量稀土对工业纯铝中杂质相的变质行为

采用SE,EDAX,TEM他稀土对工业纯铝中富Fe(Si)杂质相的变质作用及机制,结果表明：富铈混合稀土（RE）是一种有效变质剂,可使铝中杂质相由粗大长针（条）状或骨骼变细小的团球状或短棒状,且分布均均匀,提高了材料的力学性能（尤其是塑性）,其变质机制主要是因稀土在固／液界面前前沿的富集,导致了稀土进入杂质相形成（AlFeSiRE)的复杂化合物,或吸附在杂质相表面阻碍其长大,但过量稀土易导致第二相数量增多,降低材料塑性,其加入量应小于 0．07％（质量分数）。     

Extraterrestrial3 He in marine polymetallic nodules: A potential method for measuring growth rate of nodules

The comparative measurements of helium isotope compositions between marine polymetallic nodules and their surrounding sediments, their magnetic fractions and bulk from C-C Zone of the East Pacific Basin are reported. The⁴He content and³He/⁴He ratio of polymetallic nodules and their surrounding sediments are extremely high; the³He,⁴ He concentrations and most³He/⁴He ratios of magnetic fractions in nodules and sediments are apparently higher than those in bulk. The helium isotope data points of nodules and sediments are all distributed along or closely to the mixing curve of the interplanetary dust particles (IDPs) and the terrigenous sediments in the chart of³He-³He/⁴He. In the same sampling site, the³He/⁴He ratios of nodules and their surrounding sediments are very similar, and the changes of both ratios are synchronous. It shows that the high³He/⁴He ratios in nodules and sediments may all result from IDPs. So, if the flux of extraterrestrial³He into the nodules and sediments is constant, the growth rate of polymetallic nodules and the sedimentation rate of sediments can be independently calculated according to the concentra-tion of extraterrestrial³He in nodules and sediments.

     

黔西南卡林型金矿床稀土元素地球化学特征

分析了黔西南地区板其、、丫他及戈塘等卡林型金矿床的(La/Yb)N、(La/Sm)N、∑REE及LREE/HREE等稀土元素的含量及参数特征.结果表明,该区金矿床相对富集LREE;该区戈塘金矿具有明显的MREE富集及正Eu异常的特点,表明成矿热液应该是一种还原性流体,来源于深部或至少经历过对富含斜长石源区的水-岩反应矿...