Methodologies for the analysis of rare earth elements and their relevance to reference materials

India has the third largest resources of rare earth elements (REE) in the world. These resources are essentially the monazite sand present in the beaches of south-west, south-east, and mid-eastern coasts of India. Therefore, analytical methodologies for the determination of REE in sea water and high-purity materials were developed. An overview of this work and its relevance to the preparation of standard reference materials of REE in sea water, marine sediments, and high-purity materials in the future is given.     

Determination of rare earth elements in natural water samples – A review of sample separation,preconcentration and direct methodologies

This review discusses and compares the methods given for the determination of rare earth elements (REE) in natural water samples, including sea, river, lake, tap, ground and waste waters as well as Antarctic ice. Since REE are at very low concentrations in natural waters, numerous different preconcentration methods have been proposed to enable their measurement. These include liquid liquid extraction, dispersive liquid-liquid micro-extraction and solidified floating drop micro-extraction. In addition to liquid-liquid extraction methods, solid phase extraction using commercial resins, resins made in-house, silica-based exchange materials and other solid media is also discussed. These and other techniques such as precipitation/co-precipitation and flotation are compared in terms of speed, preconcentration factors achieved, precision, accuracy and limits of detection (LOD). Some papers have discussed the direct determination of REE in these sample types. Some have used specialised sample introduction systems such as ultrasonic nebulization whereas others have used a standard sample introduction system coupled with inductively coupled plasma mass spectrometry (ICP-MS) detection. These direct methods have also been discussed and compared.     

Applicability of capillary electrophoresis to the analysis of trace rare earth elements in geological samples.

This study developed a methodology to analyze trace rare earth elements (REEs) in geological materials by capillary electrophoresis (CE). Changed from dilute HNO3 into a water medium by heating, REE ions are detectable at approximately 2 ng mL(-1). In the presence of coexisting elements from geological samples, REE separations were carried out. After sample fusion with Na2O2 and interference separation with ammonium pyrrolidinedithiocarbamate chelate, REE analytes were coprecipitated with Mg(OH)2 at pH 8.5, and then prepared into a water medium for CE determination. Using the standard addition method, this protocol was validated by analyses with better than 5% precision. This method was applied to geological materials; the REE results are in consistence with their certified values. With electrokinetic injection, internal standard (IS) selected among lanthanides is a prerequisite of high-quality REE data. An approach was proposed to derive the IS content for further correcting its contribution from unknown samples.     

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 rare-earth elements in Periyar River water (Kerala, India) and seawater (Mumbai, India) using neutron activation analysis

During the present work rare earth elements (REEs) in Periyar River water and in seawater from the region of Mumbai, India, have been measured via neutron activation analysis. To separate and concentrate REEs a pre-irradiation separation approach via ion exchange was adopted. Standard addition and radiotracer studies were carried out to validate the analytical methodology including the recoveries of the separations. The measured REE concentrations in the water samples are presented and discussed. This revised version was published online in July 2006 with corrections to the Cover Date.     

Extraction chromatographic separation of Y, REE, Bi, Th, and U from the matrix suitable for their determination in pure iron and Low-Alloyed steels by ICP-MS and ICP-AES

The possibilities of tetraphenylmethylene-diphosphineoxide as stationary phase in extraction chromatography separation of REE, as well as Y, Bi, Th, and U from solutions of iron and microamounts of many other elements have been studied. The optimal conditions of separation are determined. The proposed procedure of chromatographic separation is quite applicable to the on- and off-line modes of ICP-MS and ICP-AES analyses of high-purity iron and low-alloyed steels.     

Determination of rare earth elements in Indian kimberlite using inductively coupled plasma mass spectrometer (ICP-MS)

A method has been developed for the analysis of rare earth elements (REEs) in kimberlite samples using inductively coupled plasma mass spectrometer (ICP-MS). The samples were dissolved using sodium peroxide fusion and after appropriate dilutions the solutions were analyzed using ICP-MS. The paper presents the concentration of rare-earth elements as determined by ICP-MS in eight kimberlite samples from Central India. The method was validated using certified reference materials STSD-1 and STSD-2 from Canadian Certified Reference Material Project. The method detection limit of various REEs varies from 0.12 to 1.54?mg?kg^?1. The total REE concentrations range from 418 to 726?mg?kg^?1 and fall within the interval of those reported in the literature for kimberlites. Despite the marked difference in the REE contents, all the analyzed samples show similar REE patterns that resemble those for kimberlites. In order to compare ICP-MS results, the samples were analyzed using instrumental neutron activation analysis which is a reference method for determination of REEs in geological samples.     

辉光放电质谱法测定高纯材料中痕量硫杂质

准确测定并控制材料中杂质元素含量是发挥高纯材料性能不可或缺的环节。辉光放电质谱法(GDMS)是准确、快速、高灵敏分析高纯材料中痕量及超痕量硫的理想方法。对GDMS分析高纯铜和镍基高温合金中痕量硫的质谱干扰进行了讨论,优化了放电电流和放电电压,采用多种标准物质对硫的相对灵敏度因子(RSF)进行了校准和验证,并与二次离子质谱法(SIMS)进行分析结果比对,验证了GDMS定量分析结果的准确性和可靠性。     

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.     

Cyanex 923 as the extractant in a rare earth element impurity analysis of high-purity cerium oxide.

In this work, the feasibility of employing Cyanex 923 as an extractant into the non-cerium REE (rare earth elements) impurity analysis of high-purity cerium oxide was investigated. Through investigations on the choice of the extraction medium, the optimium extraction acidity, matrix Ce4+ effect on the non-cerium REE ion extraction, the optimium extractant concentration and suitable extracting time, and oscillation strengh, it was found that when the phase ratio was at 1:1 and the acicidity was about 2% H2SO4, by gently shaking by hand for about 2 min, 10 mL of 30% Cyanex 923 could not extract even for a 20 ng amount of non-cerium REE3+ ions. However, the extraction efficiency for Ce4+ of 100 mg total amount under the same conditions was about 96%, indicating that a 25-fold preconcentration factor could be achieved. Thus, it was concluded that Cyanex 923 could be used in a REE impurity analysis of 99.9999% or so pure cerium oxide for primary sepapation to elimilate matrix-induced interferences encountered in an ICP-MS (inductively coupled plasma mass spectroscopy) determination.     

Recent developments of radioanalytical methods at the IBR-2 pulsed fast reactor

Experience in the application of radioanalytical methods, including NAA, at the IBR-2 pulsed fast reactor is reviewed. Details of the instruments dedicated to neutron activation analysis and radiography studies are reported. Applications of resonance neutrons to environmental monitoring, studying of water ecosystems, analysis of geological samples in oil extraction regions, and investigation of high-purity materials are exemplified.     

高纯硅溶胶成分标准物质稳定性研究

考察了高纯硅溶胶成分标准物质研制过程中影响稳定性的因素。根据高纯硅溶胶的物理化学性质,研究了影响高纯硅溶胶稳定的pH值、粒度分布、电解质等主要因素。提出了保持高纯硅溶胶稳定的措施,解决了高纯硅溶胶成分标准物质的稳定性问题,使标准物质稳定保存1年以上。     

Thermal characterization and kinetic analysis of nesquehonite,hydromagnesite, and brucite,using TG–DTG and DSC techniques

Nesquehonite, hydromagnesite, and brucite are important precursors for the preparation of high-purity magnesia (MgO) using magnesium resources from salt lake as raw materials. In this paper, TG–DTG and DSC were used to investigate the thermal decomposition behaviors of the three precursors. Decomposition kinetic parameters at each stage were evaluated based on the TG data using the iso-conversional method. Decomposition mechanisms were determined using the master-plots method. The decomposition temperature range, heat absorption, and kinetic parameters of the three phases were then compared. The most probable mechanism of each stage from the perspective of crystal structure was found to be consistent with the calculation results from the master-plots method. Results led to the conclusion that nesquehonite is the most appropriate precursor for the preparation of high-purity MgO. Further studies on precursor selection and calcining condition selection for the preparation of MgO using bischofite will benefit from this research.     

Systematic Investigations of Plastic Vials Concerning Their Suitability for Ultratrace Anion Analysis in High-Purity Industrial Applications

Ultratrace anion analysis in high-purity industrial applications is done using commercially available plastic vials to store the eluted liquid samples. Plastic vials are manufactured with materials containing several additives. Such additives might potentially release anionic contaminants, thus degrading the blank quality and determination limits (DL). The durability and thermal stability of several materials was found to be a function of anionic species. Fluorinated materials showed the best results for the majority of anions with the exception of fluoride. For the selective analysis of fluoride, polypropylene was found to be the best vial material, together with glass. Cold water extraction showed better results compared to hot water extraction. Over a long observation period, hot water extraction did not at all improve the performance, indicating that this type of supposedly efficient cleaning of the plastic containers to render them less prone to contaminant release does not hold true.     

Chemical speciation of chromium in sea water : Part 1. Effect of Naturally Occurring Organic Materials on the Complex Formation of Chromium(III)

The effect of naturally occurring organic materials on the coprecipitation behaviour of trivalent chromium is studied to estimate the relative abundance of organic-bound chromium in sea water. Some amino acids and polyhydric organic acids can bind chromium(III) under the conditions prevalent in natural sea water. Some of the chromium(III) in sea water therefore probably occurs in organic species.     

铱基催化剂在酸性析氧反应中的研究进展

降低对化石能源依赖,实现无碳能源需要构建以可再生能源(如太阳能、风能等)为主体的能源框架.氢气是无碳能源框架下的一种较为理想的能源载体,而电解水制氢技术能够有效制备环境友好的高纯氢气.其中,质子交换膜基(PEM)电解水技术相较碱性电解技术能够实现更高的质子导电性、电解效率、响应速度以及产物气体分离能力,展现出较高的应用...     

三重四极杆电感耦合等离子体质谱(ICP-MS)法测定氧化铕中13种稀土杂质元素

稀土杂质元素直接影响高纯单金属稀土材料的整体性能,是高科技领域许多材料的重要组成部分。通过考察最佳的消解酸量、温度、时间、氧气反应气流量、稀释气流量,建立了基于三重四极杆电感耦合等离子体质谱仪(ICP-MS/MS)直接测定氧化铕中13种稀土杂质元素分析方法。该方法采用0.1%基体直接进样,可以很大程度提高前处理分析效率。利用碰撞模式测定氧化铕稀土中的Y、La、Pr、Nd、Sm、Gd、Tb、Dy、Ho、Er、Yb、Lu元素,氧气质量转移模式测定氧化铕中的Tm,两种模式结合可以有效去除多原子干扰,实现氧化铕的稳定测试分析。通过对氧化铕标准物质（GBW02902）直接测定分析,结果表明,在碰撞和氧气质量转移模式下,各元素线性相关系数（r）均大于 0.9999,方法检出限为0.001~0.023 mg/kg,测试精密度优于1.99%,13种元素的测试值都在认定值的不确定度范围之内。该分析方法操作简单,测试稳定,效率高,为实验室进行氧化铕材料中REE杂质的准确测试分析提供思路和借鉴。     

Flame photometric determination of potassium in sea water and marine organisms

A convenient flame photometric procedure for determining potassium in sea water and biological materials is described. Factors affecting the intensity of the spectral line emitted by potassium ions were studied. The major constituents of sea water showed no spectral interference on the potassium analysis. Chloride ions and sulphuric acid gave a negative radiation interference while sodium ions showed a positive effect. The “internal standard addition” procedure was used for eliminating the effect of these interfering constituents.An average potassium/chlorinity ratio of 0.538 was obtained for the Pacific coastal water with potassium concentration being expressed in mg-atom. The applicability of this procedure for the détermination of potassium in biological materials was also demonstrated.     

Development of certified reference materials of high-purity volatile organic compounds: purity assay by the freezing-point depression method

For accurate measurement of concentrations of substances by instrumental analysis, reliable calibration standards are needed. In Japan, national reference materials are supplied under the national standards dissemination system named the Japan Calibration Service System (JCSS). In JCSS, calibration standards for the analysis of environmental pollutants are supplied. For the traceability to the SI of reference materials for calibration in JCSS, the National Metrology Institute of Japan (NMIJ) is developing high-purity reference materials of volatile organic compounds (VOCs) as NMIJ CRMs. The freezing-point depression method, which has potential as a primary method of measurement, is employed for the determination of property value. In this paper, a development scheme of certified reference materials of high-purity VOCs is described. Presented at BERM-11, October 2007, Tsukuba, Japan.     

REDOX VARIATIONS OF THE ANCIENT OCEAN IN THE WESTERN MARGIN OF THE TARIM BASIN——THE EVIDENCE FROM Ce ANOMALIES OF MARINE SHELL FOSSILS

Two episodes of paleoredox fluctuation variation are indicated in some localities in thelate Cretaceous--early Tertiary ocean of western Tarim recorded by REE distribution patterns,Ce anomalies, and Th/U ratios from systematic studies on the chemical composition, withspecial reference to REE and 20 trace elements, based on 11 marine shell fossils occurringin the Upper Cretaceous--Lower Tertiary strata of the western Tarim Basin, Xinjiang. Thefactors Controlling the redox fluctuation may be probably caused by shifting places ofsurface runoff put into the sea as a result of transgression and regression.