Instrumental neutron activation analysis of carbonatites from Homa Mountain, Kenya

Twenty eight (major and trace) elements including eight rare earth elements (REEs) in African carbonatite samples were determined by instrumental neutron activation analysis. The geochemical behavior of trace elements was studied in relation to the order of carbonatite intrusion from C1 to C4 through C2 and C3 at Homa Mountain, Kenya. The enrichment of Mn, Fe, Sr, Ba, Th, U and REE is found in the sixteen carbonatites examined in this study. The general increase in the concentrations of Na, Sc, Mn, Sb, Ba, Th, U and REE occurs from C1 to C4 through C2 and C2c, but C3 carbonatite shows a different pattern. The C3 carbonatite is extraordinarily enriched in Mn, Fe and Ba and is highly enriched in Cr, As, Sb and Th. The chondrite-normalized REE distribution pattern of the C3 carbonatite is not rich in the light REE. Strong fractionation between light and heavy REEs is found in the carbonatites, and moderate fractionation in the two alkalic igneous rock samples. In order to evaluate partitioning of REEs into carbonate, oxide and other mineral fractions, a selective chemical leaching technique on carbonatites was applied and is discussed in this study. This revised version was published online in August 2006 with corrections to the Cover Date.     

白云鄂博富稀土碳酸岩的地球化学特征

重点解剖了一条距白云鄂博ＲＥＥ－Ｎｂ－Ｆｅ矿床东矿,ＮＥ方向３ｋｍ并切割白云鄂博群Ｈ１及Ｈ２岩性段的细料方解石碳解岩岩墙的岩石地球化学特征。结果表明：碳酸岩的稀土元素含量变化大,最高可达２０％（质量分数）、已构成稀土富矿石、碳酸岩的轻稀土元素高度富集,轻、重稀土元素之间发生地极度分馏,但无铕异常显示。形成这种岩石地球化学特征的可能机制为．：碳酸岩浆直接来源于岩石圈富集地幔的代程度部分熔融作用,残留     

Instrumental neutron activation analysis of carbonatites from Panda Hill and Oldoinyo-Lengai, Tanzania

Twenty nine (major and trace) elements including nine rare earth elements (REE) in African carbonatite samples were determined by instrumental neutron activation analysis (INAA). The geochemical behavior of trace elements in carbonatites, especially REE pattern (chondrite normalized), and the efficiency of neutron activation analysis compared to other methods are discussed in this study.     

Efficient recovery of rare earth elements from coal based resources: a bioleaching approach

Rare earth element (REE) resources in coal-related materials are vast. Assuming a coal production rate of 600 million short tons per year with an average REE content of 200 ppm, the potential REE resource is 120,000 tons per year, which is similar to the annual global production of REEs. Most of those resources that are associated with coal-related materials are found in association with the gangue or ash-based content from the coal ore. Under normal coal plant operation, the REEs often end up in refuse piles or tailings impoundments. In many cases, these REEs can be recovered at low cost using appropriate coal preparation, heap leaching, solvent extraction and/or selective precipitation, followed by subsequent separation and purification of individual REEs. In the present research, the processing approach uses a natural pyrite stream, which was removed during coal cleaning and used to enhance leaching. Bio-oxidation has been used commercially to accelerate leaching, and this approach has been applied to coal-based materials. The ferric ions generated from bio-oxidation oxidize sulfide minerals such as pyrite, which generates acid. Both acid and ferric ions are helpful for leaching REEs, as well as for removing residual sulfides, thereby preventing future acid mine drainage and related liabilities. It can be seen that, recovery of REEs from coal waste materials can enable coal producers to use untapped REEs resources to produce revenue and extend resource life while simultaneously reducing future environmental issues and costs.     

Determination of REEs distribution in monazite and xenotime minerals by ion chromatography and ICP-AES

Ion chromatographic techniques were investigated for the separation and the quantitative determination of some rare earth elements (REEs) in monazite and xenotime minerals. The influences of selected eluents containing complexing acids including oxalic and alpha-hydroxy isobutyric acid (alpha-HIBA) on the retention and hence the separation efficiency of REEs was studied. Different variables affecting the separation of different REEs such as pH, type, and concentration of the mobile phase were investigated. Gradient elution, using an advanced gradient pump, was controlled automatically by the Dionex AI-450 computer software. Separation of REEs was carried out using an Ion Pac CS5A column followed by a post column derivatization reaction with 4-(2-pyridylazo)resorcinol (PAR) and UV-VIS spectrophotometric detection. Mineral dissolution was carried out using sulfuric acid. A comparative evaluation of REE distribution in monazite and xenotime minerals using both ion chromatography (IC) and inductively coupled plasma atomic emission spectrometric (ICP-AES) techniques was carried out.     

稀土元素在植物中的分异研究进展

有关对稀土农用的理论和实践、天然和农业生态系统中稀土的地球化学行为及稀土的增产生理过程与毒理等方面已开展了大量研究,而对稀土进入植物体内的迁移过程、分布分异现象和机制缺乏必要的了解。稀土元素在植物中的分异研究有助于“示踪”稀土元素在土壤(溶液)-植物系统中的迁移路径,进而查明控制稀土元素迁移和积累的体外和体内敏感因素。本文结合近5年的研究工作,就近年来国内外有关稀土元素在植物中的分异现象、机制及其研究意义进行了综述,并展望了此方面的研究趋势,期望能为稀土以及重金属的生物有效性研究开辟一条新思路。     

桦甸油页岩中稀土元素赋存状态研究

以吉林省桦甸油页岩为研究对象,采用电感耦合等离子质谱( ICP-MS)和化学逐级提取方法相结合,对油页岩中稀土元素的分布特征以及油页岩中稀土元素的赋存状态进行研究.结果表明,相对于中国煤,桦甸油页岩表现为轻稀土元素富集程度高于重稀土元素.油页岩中稀土元素与陆源碎屑岩关系密切,且陆源物质的供应相对比较稳定.轻重稀土间分馏...     

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。     

稀土元素超积累植物研究进展

概述了稀土元素的环境生态学特性及其超积累植物，并对稀土元素超积累植物研究的重要科学意义进行了介绍。在此基础上，详细综述了近年来稀土元素超积累植物的研究成果，包括其种属、空间地域分布，其体内稀土元素的分布、分异特征及影响因素，其吸收富集稀土元素的生理及生化机制，并展望了稀土元素超积累植物及其修复应用研究的发展前景。     

High-resolution spectra of selected rare earth elements and spectral interferences studied by inductively coupled plasma-atomic emission spectroscopy (ICP-AES)

The rare earth elements (REEs) play very important roles in industrial manufacturing, technology development and biological processes. Due to their complex emission spectra, trace levels of REEs are difficult to analyze by conventional ICP-AES techniques. The present study investigates possible spectral interferences of matrices (rare earth oxides of Ce, Pr, Nd, Sm and Dy) on the analytical lines (± 0.1 nm) of a target REE. Detailed and well-resolved spectra for selected REEs are presented, and procedures used to rectify the problem of spectral interferences caused by REE matrices are discussed. A computer-assisted system (CAS) for spectral recognition has been developed and used to assist in the study of matrix interference. To determine directly trace rare earth elements in REE matrices without sample pre-separation, the application potential is demonstrated with a one meter sequential instrument retrofitted with a 3600 grooves/mm grating.     

稀土元素日允许摄入量与农用安全性探讨

稀土农用是我国独立开创的稀土应用领域,30年来,取得了巨大的经济效益。然而,作为元素周期表中第ⅢB主族的重金属,稀土元素不是动植物的必需微量元素,其生理效应的机制还不清楚,稀土农用的安全性问题一直受到密切的关注。本文从稀土元素分析方法与人均总膳食摄入量、稀土元素毒理实验方法与日允许摄入量、稀土农用对土壤中稀土元素含量和化学形态的影响、以及稀土农用对食物中稀土元素含量影响的4个方面,对文献报道作了分析、整理和评定,结论是只要对使用的范围、剂量及施用方式进行限制,稀土农用是一种安全的农业增产方式。     

Determination of rare-earth elements by high-performance liquid chromatography/inductively-coupled plasma/atomic emission spectrometry

Liquid chromatography coupled on-line to a sequential ICP/AES system is applied for the determination of 14 rare-earth elements (REEs) in samples with widely different concentrations of REEs and matrix elements. The REEs are separated on a cation-exchanger by applying an α- hydroxyisobutyric acid gradient. The determination limits were the same as those obtained by continuous nebulization of single-element standard solutions. The chromatographic separation precludes mutual spectral interferences between the REEs. The practical value of the method developed is demonstrated by the determination of REE impurities in Specpure rare-earth oxides, by its demonstrated potential to evaluate real spectral interferences, and by the analysis of geological samples (natural phosphates) with relatively low total REE contents. The detection limits of REEs in these natural phosphates ranged between 0.005 and 0.4 μg g^?1.     

Subcellular and molecular localization of rare earth elements and structural characterization of yttrium bound chlorophyll a in naturally grown fern Dicranopteris dichotoma

A rare earth element (REE) hyperaccumulator, Dicranopteris dichotoma, sampled from an REE mining area in South-Jiangxi region, was chosen for analysis of 15 REEs at subcellular and molecular levels by inductively coupled plasma-mass spectrometry (ICP-MS). The sum of the concentrations of 15 REEs (∑REEs) of D. dichotoma leaf was about 0.1% dry mass. Results indicated that the ∑REEs of different subcellular fractions of D. dichotoma leaf were cell walls>organelles>the ‘soluble’ fraction (i.e., cytosol and vacuoles)>cell membranes. ICP-MS results also showed that REEs existed in chlorophylls and lutein, though REE concentrations in carotene and pheophytin were both lower than the procedural blank levels. The ∑REEs of crude lipopolysaccharide and Ribulose 1,5-bisphosphate carboxylase/oxygenase (Rubisco) obtained from D. dichotoma leaf were 1200 and 343 mg/kg, respectively. The extended X-ray absorption fine structure (EXAFS) study of D. dichotoma chlorophyll a indicated that yttrium was bound to the porphyrin ring of chlorophyll a, and one yttrium atom was surrounded by four nitrogen atoms with the average yttrium-nitrogen bond length being 0.236 nm. These data might be useful for understanding of the physiological role of REEs in hyperaccumulator D. dichotoma.     

Biogeochemistry of trace and major elements in a surface environment (volcanic rock,soil, mosses,lichens) in the S. Miguel Island,Azores, Portugal

The distribution of the chemical element during weathering of trachyandesite in S. Miguel Island (Azores, Portugal), and in mosses and lichens growing on these rocks, was studied using instrumental neutron activation analysis. A general enrichment of rare earth elements (REEs), a Ce positive anomaly (partial oxidation after primary apatite dissolution) and a Eu negative anomaly (Eu²⁺ in plagioclases/clay minerals) are observed with increasing weathering. Mosses and lichens are Ce and Eu depleted, indicating that the main REE uptake is done via absorption from REE³⁺ secondary phosphates, probably together with P (essential nutrient). Zn, Br and Sb show higher enrichment factors in lichens and mosses.     

土壤-植物体系稀土元素的分异现象

用仪器中子活化分析测定了从同一地点采集的9种不同植物根和叶中8个稀土元素（La,Ce,Nd,Sm,Eu,Tb,Yb和Lu)的含量，研究了稀土元素在植物根、叶及相应母土中的分布特征。结果表明，同一植物的根、叶和母土中稀土分布模式均有较大差异。生长在同一地点不同植物根中稀土分布模式非常相似，而叶中分布规模差别较明显。说明根对单一稀土元素的吸收主要取决于这个元素在土壤中有效态的含量，而在稀土从根到叶的运输和积累过程中出现的分异则由植物自身的结构特征决定。     

Distribution characteristics of rare earth elements in plants from a rare earth ore area

The contents of eight rare earth elements (La, Ce, Nd, Sm, Eu, Tb, Yb and Lu) in various plant species taken from a rare earth ore area were determined by instrumental neutron activation analysis. For a given plant, the REE patterns in root, leaf and host soil are different from each other. The REE distribution characteristics in roots of various species are very similar and resemble those in the surface water. The results of this study suggest that there is no significant fractionation between the REEs during their uptake by the plant roots from soil solution. However, the variation of the relative abundance of individual REE occurs in the process of transportation and deposition of REEs in plants.     

ICP-MS Measurement of Trace and Rare Earth Elements in Beach Placer-Deposit Soils of Odisha,East Coast of India,to Estimate Natural Enhancement of Elements in the Environment

Inductively coupled plasma mass spectrometry (ICP-MS) has been used to measure the concentration of trace and rare earth elements (REEs) in soils. Geochemical certified reference materials such as JLk-1, JB-1, and JB-3 were used for the validation of the analytical method. The measured values were in good agreement with the certified values for all the elements and were within 10% analytical error. Beach placer deposits of soils mainly from Odisha, on the east coast of India, have been selected to study selected trace and rare earth elements (REEs), to estimate enrichment factor (EF) and geoaccumulation index (I_geo) in the natural environment. Enrichment factor (EF) and geoaccumulation index (I_geo) results showed that Cr, Mn, Fe, Co, Zn, Y, Zr, Cd and U were significantly enriched, and Th was extremely enriched. The total content of REEs (ƩREEs) ranged from 101.3 to 12,911.3 µg g⁻¹, with an average 2431.1 µg g⁻¹ which was higher than the average crustal value of ΣREEs. A high concentration of Th and light REEs were strongly correlated, which confirmed soil enrichment with monazite minerals. High ratios of light REEs (LREEs)/heavy REEs (HREEs) with a strong negative Eu anomaly revealed a felsic origin. The comparison of the chondrite normalized REE patterns of soil with hinterland rocks such as granite, charnockite, khondalite and migmatite suggested that enhancement of trace and REEs are of natural origin.     

电感耦合等离子体质谱(ICP-MS)法测定高钨基体样品中稀土元素的含量

准确测定钨矿和钨酸盐晶体等高钨基体样品中稀土元素的含量有助于开展矿床地球化学特征研究及钨酸盐激光晶体材料的制备和性质研究。在高钨基体样品电感耦合等离子体质谱法（ICP-MS）分析时,为了考察高钨及高含量阳离子等基体组成对分析结果的影响,实验针对Na2WO4、CaWO4、NaY(WO4)2、MnWO4和(Fe,Mn)WO4等高钨基体样品,采用硝酸和氢氟酸高压密闭消解,加入稀土元素并用2% HNO3溶液稀释定容配制成稀土元素浓度为1 ng·g-1的基体匹配标准溶液;同时,直接用2% HNO3溶液配制稀土元素浓度相同的非基体匹配标准溶液以对比系统考察两种基体溶液中稀土元素的相对灵敏度系数（RSC）差异。结果显示,基体匹配溶液与2% HNO3溶液中稀土元素的RSC相对偏差基本小于15%,表明基体效应的影响可以忽略不计。进而,为了准确测定常见高钨基体样品中稀土元素的含量,实验建立了基于ICP-MS的高钨基体样品中稀土元素准确定量分析方法,该方法线性关系好（R2 ? 0.9997）,检出限低（0.5 ~ 27.9 pg·g-1）,准确度理想（相对误差-6.25 ~ 10.74%）。采用该方法测定了钨酸钙单晶实际样品中稀土元素的含量并将其与基体匹配法的测定结果进行比对,结果显示两者相对偏差为0.80 ~ 12.75%,说明本文所建立的分析方法可靠,能用于定量测定高钨基体样品中稀土元素的含量。     

Correlation between terbium and the other rare earth element contents in fern leaves

The lanthanides (REEs) in 142 fern leaves collected from 9 sampling sites in Japan were analyzed by instrumental neutron activation analysis. Between two REEs a strong positive correlation was found in the logarithmic scattering diagram with correlation and regression coefficients close to unity, suggesting neither selective accumulation by plants nor different availability from soil between the two elements. However, between Tb and the other REEs the relationship showed two lines with the same correlation coefficient. This suggested that there must be a difference in the availability of REEs or in their absorption characteristics by plants. Further analysis revealed that the splitting was due to some difference in the environmental factors where the fern grew. However, the amount of REE in the soil collected together with the corresponding fern did not reflect the REE concentration in the fern leaves.     

Rare earth elements distribution in clay zones of sedimentary formation, Pondicherry, south India

Concentrations of five rare earth elements (REE) were measured in clay samples of a deep bore hole comprising major aquifers of Pondicherry region, south India in order to investigate the geochemical variations among various litho-units. Clay samples from Cretaceous formation show distinct gray to black color whereas Tertiary deposits have clays with color varying from pale yellow to brown to gray. All measured REEs exhibit lower concentrations than Upper Continental Crust (UCC) average values. Large variations in REEs contents were observed in different sedimentary formations (Tertiary and Cretaceous). Chondrite normalized ratio of La/Lu and Eu/Eu* indicate that the clays are derived from weathering of felsic rock and possibly under humid climate. All the samples showed positive Eu anomaly in North American Shale Composite (NASC) normalized plot which shows plagioclase feldspar as the major contributor to these clays. Positive Eu anomaly is also an indication of reduced condition of the formation.