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.     

电感耦合等离子体质谱激光烧蚀固体进样技术新进展

本文简单地介绍了电感耦合等离子体质谱(LA-ICP-MS)的基本原理及装置。分别对LA-ICP-MS在飞秒激光器、紫外激光器、固液气溶胶混合进样、集合式小样品标样、原位统计分布技术上的技术新进展进行了详细的评述。     

电感耦合等离子体质谱测定富钴结壳中的稀土元素

采用封闭压力酸溶(HF+HNO3)消解样品,以Rh为内标,用电感耦合等离子体质谱测定富钴结壳中的稀土元素。用此方法对3个国家一级标准物质富钴结壳标样(GSMC-1,GSMC-2,GSMC-3)进行了多次测定,结果稀土元素的测定值与标准值相符,多次测定结果的相对标准偏差(RSD,n=5)在0.36%～4.0%之间,加标回收率为90%～106%。基于此方法,对6个富钴结壳样品进行了测定,显示富钴结壳样品中稀土元素的配分曲线与标准物质中稀土元素的配分模式一致。方法适用于富钴结壳样品的批量分析。     

微波消解-电感耦合等离子体质谱法(ICP-MS)测定板栗中的矿物元素及稀土元素[ ]

采用微波消解前处理方法,结合电感耦合等离子体质谱技术,建立了板栗中钠（Na）、钾（K）、镁（Mg）、锰（Mn）、铁（Fe）、钒（V）、钴（Co）等19种矿物元素及镧（La）、铈（Ce）、镨（Pr）、钕（Nd）、钐（Sm）、铕（Eu）、钆（Gd）、铽（Tb）、镝（Dy）、钬（Ho）、铒（Er）、铥（Tm）、镱（Yb）、镥（Lu）、钇（Y）等15种稀土元素的同时分析测定方法。该方法检出限为0.0027~0.78μg?L-1,相对标准偏差为1.4%~6.3%。通过国家标准物质GBW10019苹果的准确率实验验证,测定结果均在标准证书值范围内。实验结果表明,该方法适用于板栗中矿物元素及稀土元素的同时测定。     

A magnesium hydroxide preconcentration/matrix reduction method for the analysis of rare earth elements in water samples using laser ablation inductively coupled plasma mass spectrometry

This paper describes a simple method for simultaneous preconcentration and matrix reduction during the analysis of rare earth elements (REEs) in water samples through laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS). From a systematic investigation of the co-precipitation of REEs using magnesium hydroxide, we optimized the effects of several parameters - the pH, the amount of magnesium, the shaking time, the efficiency of Ba removal, and the sample matrix - to ensure quantitative recoveries. We employed repetitive laser ablation to remove the dried-droplet samples from the filter medium and introduce them into the ICP-MS system for determinations of REEs. The enrichment factors ranged from 8 to 88. The detection limit, at an enrichment factor of 32, ranged from 0.03 to 0.20 pg mL⁻¹. The relative standard deviations for the determination of REEs at a concentration of 1 ng mL⁻¹ when processing 40 mL sample solution were 2.0-4.8%. We applied this method to the satisfactory determination of REEs in lake water and synthetic seawater samples.     

Determination of rare earth elements in urine by electrothermal vaporization inductively coupled plasma mass spectrometry

A method was developed for the determination of rare earth elements (REEs) in urine with electrothermal vaporization inductively coupled plasma mass spectrometry (ETV-ICPMS). The undiluted sample was directly injected into the graphite tube and trifluoromethane (Freon-23) was used as chemical modifier in order to reduce the vaporization temperature and the memory effect of most of the lanthanides. The detection limits were in the range 1-10 ng/L with relative standard deviation of 3-5% at concentration levels of 1microg/L, and less than 10-15% at 100 ng/L. Two different procedures, external calibration and a standard additions method, were evaluated to measure the concentration levels of lanthanides in the urine samples and the second procedure was considered to be the best choice for calibration in this work. The level of REEs in urine of 50 healthy volunteers was in the range 5-20 ng/L, above the detection limit of ETV-ICPMS.     

Determination of rare earth elements in environmental matrices by sector-field inductively coupled plasma mass spectrometry

In the framework of an international certification campaign, sector-field inductively coupled plasma mass spectrometry (sector-field ICP–MS) was used for the accurate determination of the rare earth elements in five candidate reference materials: aquatic plant, calcareous soil, mussel tissue, river sediment, and tuna muscle. All samples were taken into solution by use of microwave-assisted or mixed microwave-assisted / open beaker acid digestion. Subsequently, the samples were appropriately diluted and subjected to ICP–MS analysis. Except for Sc, all the elements involved were determined at low mass resolution (R = 300). For Sc, application of a higher resolution setting (R = 3000) was required to separate the analyte signal from those of several molecular ions which gave rise to spectral overlap at low mass resolution. Some of the heavier REE can also suffer from spectral overlap attributed to the occurrence of oxide ions (MO⁺) of the lighter REE and Ba. This spectral overlap could be successfully overcome by mathematical correction. Matrix effects were overcome by use of two carefully selected internal standards, such that external calibration could be used. On each occasion, a geological reference material was analyzed as a quality-control sample and the reliability of all results obtained was additionally checked by means of chondrite normalization. For tuna muscle the content of all REE was below the limit of detection. For calcareous soil and river sediment, low to sub μg g^–1 values were observed, whereas the REE content of aquatic plant and mussel tissue was considerably lower (low to sub ng g^–1). Overall, the results obtained were in excellent agreement with the average values, calculated on the basis of all “accepted” values, obtained in different laboratories using different techniques.     

Determination of ultra-trace rare earth elements in chondritic meteorites by inductively coupled plasma mass spectrometry

A method for the direct determination of ultra-trace rare earth elements (REE) in seven Chinese chondritic meteorites by inductively coupled plasma mass spectrometry (ICP-MS) was developed. Samples were digested with a mixture of HF+HNO₃ acids in Teflon pressure bomb. The accuracy and precision of the method were assessed by the analysis of four standard reference materials including one chondrite (Allende) and three basalts (BCR-1, BHVO-1 and W-2), the results obtained in this study agree quite well with the recommended values. The reproducibilities (expressed as RSD) of samples were less than 5%.     

Determination of rare earth elements in environmental matrices by sector-field inductively coupled plasma mass spectrometry

In the framework of an international certification campaign, sector-field inductively coupled plasma mass spectrometry (sector-field ICP-MS) was used for the accurate determination of the rare earth elements in five candidate reference materials: aquatic plant, calcareous soil, mussel tissue, river sediment, and tuna muscle. All samples were taken into solution by use of microwave-assisted or mixed microwave-assisted / open beaker acid digestion. Subsequently, the samples were appropriately diluted and subjected to ICP-MS analysis. Except for Sc, all the elements involved were determined at low mass resolution (R = 300). For Sc, application of a higher resolution setting (R = 3,000) was required to separate the analyte signal from those of several molecular ions which gave rise to spectral overlap at low mass resolution. Some of the heavier REE can also suffer from spectral overlap attributed to the occurrence of oxide ions (MO+) of the lighter REE and Ba. This spectral overlap could be successfully overcome by mathematical correction. Matrix effects were overcome by use of two carefully selected internal standards, such that external calibration could be used. On each occasion, a geological reference material was analyzed as a quality-control sample and the reliability of all results obtained was additionally checked by means of chondrite normalization. For tuna muscle the content of all REE was below the limit of detection. For calcareous soil and river sediment, low to sub microg g(-1) values were observed, whereas the REE content of aquatic plant and mussel tissue was considerably lower (low to sub ng g(-1)). Overall, the results obtained were in excellent agreement with the average values, calculated on the basis of all "accepted" values, obtained in different laboratories using different techniques.     

电感耦合等离子体质谱法测定三水铝土矿中的15种有效稀土元素

建立电感耦合等离子体质谱法测定三水铝土矿中15种有效稀土元素的分析方法。参考三水铝土矿中有效铝的概念,提出了有效稀土元素的概念,并对三水铝土矿中稀土元素的回收利用的可行性进行了评价。模拟低温拜耳法生产氧化铝的工艺,对三水铝土矿中稀土元素溶出过程中的氢氧化钠浓度、溶出温度及时间等条件进行了试验,采用90 g/L氢氧化钠结合微波消解技术对三水铝土矿进行分解,用ICP-MS法测定有效稀土元素,有效稀土元素测定结果的相对标准偏差为0.92%~7.40%(n=7),回收率为98.6%~101.2%。该方法可用于测定三水铝土矿中有效稀土元素,能够对三水铝土矿中稀土元素的回收利用价值进行评价。     

Determination of rare earth elements in tomato plants by inductively coupled plasma mass spectrometry techniques

In recent years identification of the geographical origin of food has grown more important as consumers have become interested in knowing the provenance of the food that they purchase and eat. Certification schemes and labels have thus been developed to protect consumers and genuine producers from the improper use of popular brand names or renowned geographical origins. As the tomato is one of the major components of what is considered to be the healthy Mediterranean diet, it is important to be able to determine the geographical origin of tomatoes and tomato‐based products such as tomato sauce. The aim of this work is to develop an analytical method to determine rare earth elements (RRE) for the control of the geographic origin of tomatoes. The content of REE in tomato plant samples collected from an agricultural area in Piacenza, Italy, was determined, using four different digestion procedures with and without HF. Microwave dissolution with HNO₃ + H₂O₂ proved to be the most suitable digestion procedure. Inductively coupled plasma quadrupole mass spectrometry (ICPQMS) and inductively coupled plasma sector field plasma mass spectrometry (ICPSFMS) instruments, both coupled with a desolvation system, were used to determine the REE in tomato plants in two different laboratories. A matched calibration curve method was used for the quantification of the analytes. The detection limits (MDLs) of the method ranged from 0.03 ng g^?1 for Ho, Tm, and Lu to 2 ng g^?1 for La and Ce. The precision, in terms of relative standard deviation on six replicates, was good, with values ranging, on average, from 6.0% for LREE (light rare earth elements) to 16.5% for HREE (heavy rare earth elements). These detection limits allowed the determination of the very low concentrations of REE present in tomato berries. For the concentrations of REE in tomato plants, the following trend was observed: roots > leaves > stems > berries. Copyright © 2009 John Wiley & Sons, Ltd.     

银菊珍珠胶囊中稀土元素的电感耦合等离子体质谱分析

建立了一种电感耦合等离子体质谱法测定银菊珍珠胶囊中稀土元素的方法。利用该方法分析了国家一级灌木枝叶标准物质（GBW 07603）和国际柑橘叶标准物质（NIST1572）中的稀土元素,结果与标准值一致。该方法已被用于分析银菊珍珠肢囊样品中的稀土元素。     

Nuclear forensic analysis with laser ablation inductively coupled plasma mass spectrometry in CMX-6

Journal of Radioanalytical and Nuclear Chemistry - The 6th Collaborative Materials Exercise, CMX-6, was organized by the Nuclear Forensic International Technical Working Group in 2018 and 2019. Two...     

Quantitative analysis of original and powdered rocks and mineral inclusions by laser ablation inductively coupled plasma mass spectrometry

Direct analysis of rocks by laser ablation inductively coupled plasma mass spectrometry is described. Both powdered standard rocks and the original rocks were analysed and the results agreed with each other in spite of the difference in the surface states. Microprobe analysis of biotite in granite JG1 was also done directly with a focused laser beam and the results obtained were very close to the solution values given by the conventional aqueous method using biotite separated from an original rock. For quantitative analysis, the measured signal intensity was normalized either by the ablated weight or the barium signal intensity. Forty-two major and minor elements (two of them being used as internal standards) in twelve standard rocks fromt the igneous rock series of the Geological Survey of Japan were determined successfully.     

Determination of trace elements in steel by laser ablation inductively coupled plasma mass spectrometry.

A rapid quantitative analysis of the trace elements in steel by laser ablation inductively coupled plasma mass spectrometry is described. The conditions for laser ablation and normalization methods to improve the analytical precision are given. The optimum conditions for laser ablation were achieved when the ion yield was a maximum at the focus position in the fixed Q pulse mode, and above the focus position in the Q-switched pulse mode. It was found that the fixed Q pulse mode was most suitable for the determination of trace metal elements in steel, and that the Q-switched pulse mode was most suitable for both non-metallic elements and elements with a high boiling-point. In order to improve the analytical precision for those elements with a strong background intensity, normalization methods with both the matrix ion, 57Fe+, and 38Ar+ are proposed.     

Determination of trace elements in geological samples by laser ablation inductively coupled plasma mass spectrometry

Laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS) was applied for the sensitive multi-element analysis of traces and ultra-traces in geological samples. In order to prepare homogeneous targets the powdered geological samples were melted together with a lithium-borate mixture (90% Li₂B₄O₇, 10% LiBO₂) in a muffle furnace at 1050 °C. The quantification of the analysis results was carried out using the BCR-2G and BM standard reference material (SRM). The experimentally determined relative sensitivity coefficients (RSC) for both SRMs vary between 0.2 and 3 for most of the elements, whereas the relative standard deviation (RSD) of the determination (N = 3) of the concentration was 5–20%. The analysis results of LA-ICP-MS for various geological samples are in agreement with those of other methods. Received 31 March 1999 / Revised: 26 May 1999 / Accepted: 31 May 1999     

激光剥蚀-电感耦合等离子体质谱法测定多晶硅中杂质元素

采用激光剥蚀固体进样技术结合电感耦合等离子体质谱法测定了多晶硅中的元素B、Cu和Zn。考察了该三种杂质元素在多晶硅样品不同深度层面和同一深度层面的分布情况;尝试了采用硅基体信号归一化的方法计算了测定元素的含量。结果表明,杂质元素B、Cu和Zn在多晶硅材料中分布均匀,且测定结果与辉光放电质谱法的测定结果相吻合。这一方法可用于判别多晶硅表面的污染情况,以及杂质元素在多晶硅材料内部分布的均匀性。     

Determination of trace elements in geological samples by laser ablation inductively coupled plasma mass spectrometry

Laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS) was applied for the sensitive multi-element analysis of traces and ultra-traces in geological samples. In order to prepare homogeneous targets the powdered geological samples were melted together with a lithium-borate mixture (90% Li₂B₄O₇, 10% LiBO₂) in a muffle furnace at 1050?°C. The quantification of the analysis results was carried out using the BCR-2G and BM standard reference material (SRM). The experimentally determined relative sensitivity coefficients (RSC) for both SRMs vary between 0.2 and 3 for most of the elements, whereas the relative standard deviation (RSD) of the determination (N = 3) of the concentration was 5–20%. The analysis results of LA-ICP-MS for various geological samples are in agreement with those of other methods.     

Determination of rare earth elements in seawater by on-line column preconcentration inductively coupled plasma mass spectrometry

A home made column of commercially available iminodiacetate resin, Muromac A-1 (50–100 mesh) was used to concentrate rare earth elements (REEs) (15 elements: Y, La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, and Lu) in seawater. An automated low pressure flow analysis method with on-line column preconcentration/inductively coupled plasma mass spectrometry (ICP-MS) is described for the determination of REEs in seawater. Sample solutions (adjusted to pH of 3.0) passed through the column. After washing the column with water, the adsorbed elements were subsequently eluted into the plasma with 0.7 M nitric acid. Calibration curves were accomplished by means of purified artificial seawater with a sample loading time of 120 s. Detection limits (DLs) of the on-line column preconcentration/ICP-MS by eight replicate operations were between 0.040 and 0.251 pg ml⁻¹ for REEs in the artificial seawater. The precision was less than 8.9% for REEs and one sample can be processed in 7 min using a 7 ml of sample. The proposed method was applied to determine REEs in coastal seawater of Hiroshima Bay, Japan.