Use of chelating resins and inductively coupled plasma mass spectrometry for simultaneous determination of trace and major elements in small volumes of saline water samples

For some saline environments (e.g. deeply percolating groundwater, interstitial water in marine sediments, water sample collected after several steps of fractionation) the volume of water sample available is limited. A technique is presented which enables simultaneous determination of major and trace elements after preconcentration of only 60 mL sample on chelating resins. Chelex-100 and Chelamine were used for the preconcentration of trace elements (Cd, Cu, Pb, Zn, Sc) and rare earth elements (La, Ce, Nd, Yb) from saline water before their measurement by inductively coupled plasma mass spectrometry. Retention of the major elements (Na, Ca, Mg) by the Chelamine resin was lower than by Chelex; this enabled their direct measurement in the solution after passage through the resin column. For trace metal recoveries both resins yield the same mass balance. Only Chelex resin enabled the quantitative recovery of rare earth elements. The major elements, trace metals and rare earth elements cannot be measured after passage through one resin only. The protocol proposes the initial use of Chelamine for measurement of trace and major elements and then passage the same sample through the Chelex resin for determination of the rare earth elements. The detection limit ranged from 1 to 12 pg mL(-1). At concentrations of 1 ng mL(-1) of trace metals and REE spiked in coastal water the precision for 10 replicates was in the range of 0.3-3.4% (RSD). The accuracy of the method was demonstrated by analyzing two standard reference waters, SLRS-3 and CASS-3.     

Use of chelating resins and inductively coupled plasma mass spectrometry for simultaneous determination of trace and major elements in small volumes of saline water samples

For some saline environments (e.g. deeply percolating groundwater, interstitial water in marine sediments, water sample collected after several steps of fractionation) the volume of water sample available is limited. A technique is presented which enables simultaneous determination of major and trace elements after preconcentration of only 60 mL sample on chelating resins. Chelex-100 and Chelamine were used for the preconcentration of trace elements (Cd, Cu, Pb, Zn, Sc) and rare earth elements (La, Ce, Nd, Yb) from saline water before their measurement by inductively coupled plasma mass spectrometry. Retention of the major elements (Na, Ca, Mg) by the Chelamine resin was lower than by Chelex; this enabled their direct measurement in the solution after passage through the resin column. For trace metal recoveries both resins yield the same mass balance. Only Chelex resin enabled the quantitative recovery of rare earth elements. The major elements, trace metals and rare earth elements cannot be measured after passage through one resin only. The protocol proposes the initial use of Chelamine for measurement of trace and major elements and then passage the same sample through the Chelex resin for determination of the rare earth elements. The detection limit ranged from 1 to 12 pg mL^–1. At concentrations of 1 ng mL^–1 of trace metals and REE spiked in coastal water the precision for 10 replicates was in the range of 0.3–3.4% (RSD). The accuracy of the method was demonstrated by analyzing two standard reference waters, SLRS-3 and CASS-3.     

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.     

一体化碰撞反应 (iCRC)-电感耦合等离子体质谱法测定地质样品中痕量稀土元素

钡以及轻稀土元素氧化物对中、重稀土元素的干扰一直是质谱测试中存在的问题。建立了石墨粉垫底碳酸钠-硼酸混合熔剂熔融前处理样品,以_¹⁰³Rh为内标校正,一体化碰撞反应-电感耦合等离子体质谱仪法测定地质样品中稀土元素含量的方法。探讨了碳酸钠-硼酸混合熔剂熔融前处理样品注意事项、碰撞模式下碰撞气流量和离子透镜的参数的优化、干扰校正试验等问题,采用国家标准物质GBW07403、GBW07405、GBW07427、GBW07429验证,实验结果表明,各元素线性关系良好,相关系数均大于0.999,方法检出限在0.01～0.03mg/kg之间,相对误差为0.13%～7.1%,相对标准偏差为0.79%～6.59%,测试结果与标准值相吻合。对实际样品分析,得到平滑的球粒陨石归一化的稀土元素配分曲线,证明测定结果是合理可信的。该方法熔剂用量少,过程空白低,对器皿的侵蚀小,直接加热浸取,简化了操作过程,适用于大批量地质样品中稀土元素的测定。     

Determination of Rare Earth Elements in Natural Water Samples by Rapid Sequential High-Resolution Continuum Source Flame Atomic Absorption Spectrometry (HR CS FAAS) and inductively Coupled Plasma-Mass Spectrometry (ICP-MS)

A method was developed to sequentially assay ten rare earth elements by high-resolution continuum source flame atomic absorption spectrometry. The rare earth elements Nd, Sm, Eu, Tb, Ho, Er, Tm, Yb, Y, and Sc were assayed in environmental water samples which were also analyzed by a reference inductively coupled plasma-mass spectrometry protocol. The samples did not require pretreatment or preconcentration. Interferences for the method were evaluated. Experimental parameters, including the flame composition, burner height, ionization buffers and number of pixels, were optimized. The volume necessary to run measurements in triplicate was only 15?mL per sample. The accuracy, precision and linear range were evaluated. The limits of detection ranged from 0.003 to 0.473?µg mL^?1 for the most sensitive (Yb) to the least sensitive (Tb) element.     

微波消解-高分辨电感耦合等离子体质谱 (HR-ICP-MS)法测定煤炭中35种痕量金属元素

高分辨电感耦合等离子体质谱可以区分干扰元素和目标元素微弱的质量数差别,能解决大多数多原子、氧化物干扰问题,在煤炭痕量元素分析领域受到关注,但煤炭样品中痕量金属元素尤其是稀土元素受到的质谱干扰挑战未被系统地报道.采用HNO3-HF混酸微波消解煤炭样品,优化了消解时间、赶酸、复溶等前处理条件,研究了煤炭中V、Cr、Mn、C...     

Determination of praseodymium,neodymium and erbium in hot spring and crater lake waters by neutron activation analysis incorporating the standard addition technique

Previously undetermined three rare earth elements (REE's), Pr, Nd and Er, in acidic hot spring and crater lake waters were determined at ppb levels by neutron actavation analysis with the standard addition technique. Errors on final detemined values were 7.1–56%. Combining the present results and the results previously obtained amounts to the determination of all 14 naturally occuring REE's in the waters.     

Comparison of microconcentric and membrane-desolvation sample introduction systems for determination of low rare earth element concentrations in surface and subsurface waters using sector field inductively coupled plasma mass spectrometry

Analytical performances of a microconcentric nebulizer (MCN) and a membrane-desolvation sample introduction system (Aridus) were compared for determination of low concentrations of rare earth elements (REEs) in surface and subsurface waters using a double focusing sector field inductively coupled plasma mass spectrometer. Conventional figures of merit were employed, such as sensitivities, limits of detection (LOD), REE–O⁺ formation, matrix induced interferences, long term signal variations, and recovery from spiked sea water samples and a pristine water CRM.     

ICP-AES法直接测定金属钕、氧化钕中的稀土和非稀土杂质元素

建立了金属钕和氧化钕中24个杂质元素的高频感耦等离子体原子发射光谱直接测定的方法。配制了3组可混听多元素标准溶液，采用基体匹配法和多组分光谱拟合（MSF）技术以消除基体光谱干扰。测定元素的回收率为96．8％－104．0％，精密度为0．92（Ti)%-6.9(Ca)%.     

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

为了准确测定板栗中矿物元素和稀土元素的含量水平,采用冷冻干燥方式预处理样品,选用硝酸和过氧化氢体系微波消解样品,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。方法检出限为0.0027~0.78μg/L,相对标准偏差为1.4%~6.3%。通过国家标准物质GBW10019苹果的准确度实验验证,测定结果均在标准证书值范围内。实验结果表明,方法适用于板栗中矿物元素及稀土元素的同时测定。     

八极杆碰撞/反应池(ORS)-电感耦合等离子体质谱(ICP-MS)法测定复杂矿物中的稀土元素

对未知复杂矿物样品采用扫描电子显微镜-能谱法解析样品,确定基本成分后选择合适的样品前处理方法。实验中采用过氧化钠熔融法熔解样品,用水浸出,硝酸酸化后制备待测样品溶液。以Rh为内标,用八极杆碰撞/反应池(ORS)-电感耦合等离子体质谱(ICP-MS)法测定了复杂样品中的稀土元素。多次测定同一混合标准溶液结果的相对标准偏差(RSD,n=11)小于4%,加标回收率为90%~110%。方法适用于未知复杂矿物中稀土元素的测定。     

Polymer monolithic capillary microextraction combined on‐line with inductively coupled plasma MS for the determination of trace rare earth elements in biological samples

A rapid and sensitive method based on polymer monolithic capillary microextraction combined on‐line with microconcentric nebulization inductively coupled plasma MS has been developed for the determination of trace/ultratrace rare earth elements in biological samples. For this purpose, the iminodiacetic acid modified poly(glycidyl methacrylate‐trimethylolpropane trimethacrylate) monolithic capillary was prepared and characterized by SEM and FTIR spectroscopy. Factors affecting the extraction efficiency, such as sample pH, sample flow rate, sample/eluent volume, and coexisting ions were investigated in detail. Under the optimal conditions, the LODs for rare earth elements were in the range of 0.08 (Er) to 0.97 ng/L (Nd) with a sampling frequency of 8.5 h^?1, and the RSDs were between 1.5% (Sm) and 7.4% (Nd) (c = 20 ng/L, n = 7). The proposed method was successfully applied to the analysis of trace/ultratrace rare earth elements in human urine and serum samples, and the recoveries for the spiked samples were in the range of 82–105%. The developed method was simple, rapid, sensitive, and favorable for the analysis of trace/ultratrace rare earth elements in biological samples with limited sample volume.     

Direct Quantification of Major and Trace Elements in Geological Samples by Time-of-Flight Mass Spectrometry with a Pulsed Glow Discharge

A method has been developed for the determination of 24 elements (As, B, Ce, Co, Dy, Fe, K, La, Lu, Mg, Mn, Na, Nb, Nd, P, Pr, Rb, S, Sb, Si, Sm, Th, Ti, and U) in ore samples by pulsed direct current glow discharge time-of-flight mass spectrometry (PGD-TOF-MS). Sample treatment consisted of pressing the powdered samples into 10?mm diameter aluminum tablets. Quantification was performed using relative sensitivity factors with iron as the normalization element. PGD-TOFMS has low spectral interferences and low limits of detection and provides the quantification of the wide range of elements with a single method instead of a combination of several techniques. The limits of detection of the designed method were in the range 2–4?×?10^?6 mass %, depending on the element. The designed procedure was validated by the analysis of standard reference materials. The obtained results showed adequate repeatability (6–9% relative standard deviation), demonstrating high efficiency of the glow discharge mass spectrometry for the direct analysis of geological samples. The designed method requires a minimal sample pretreatment and is applicable for the determination of wide range of elements of the periodic table (e.g., metals, nonmetals, and rare earth elements) in a single analytical procedure without sample dissolution with adequate accuracy, sensitivity, and repeatability. The designed approach may replace the complex techniques that are normally required for this task.     

电感耦合等离子体质谱分析莲子芯茶中的稀土元素

建立了一种压力密闭消解电感耦合等离子体质谱法测定莲子芯茶中Y、La、Ce、Pr、Nd、Sm、Eu、Gd、Tb、Dy、Ho、Er、Tm、Yb、Lu等15种稀土元素的方法。用该方法分析国家标准物质中的稀土元素,分析结果与标准值一致,并用该方法对莲子芯茶实际样品进行了分析。     

茶叶中稀土元素的萃取分离-ICP-AES法测定

采用1-苯基-3-甲基-4-苯甲酰基-5-吡唑酮(PMBP)苯溶液萃取分离-ICP-AES法同时测定茶叶中15种稀土元素,消除了基体的干扰,并对样品前处理方法、萃取分离条件进行了考查.方法回收率为: 92.3%～112%,相对标准偏差＜2.5%.在最佳工作条件下,测定了茶叶标准物质(GBW07605)中稀土元素,结果与标准值吻合.     

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.     

Mapping of rare earth elements in nuclear waste glass–ceramic using micro laser-induced breakdown spectroscopy

A micro-LIBS system was set up based on a quadruple Nd:YAG laser at 266 nm coupled with a microscope. Elemental mapping was performed on a Mo-rich glass–ceramic sample containing CaMoO₄ crystallites hundreds of microns in length and about 25 μm in section diameter. The topography of single-shot laser-induced craters was characterized using an atomic force microscope (AFM), which revealed a crater size less than 7 μm. Mappings of Mo, Ca, Sr, Al, Fe, Zr and rare earth elements such as Eu, Nd, Pr and La were undertaken. Laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS) was conducted to validate the micro-LIBS analysis. Principal components analysis calculation was used to investigate the correlation of elements in the two phases of glass–ceramic. Correlation between Ca, Sr, rare earth elements and Mo indicates their preferential incorporation into the calcium molybdate crystalline phase. Anti-correlation between Fe, Zr, Al and Mo revealed their affinity to the glass phase.     

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。     

弱酸阳离子交换纤维柱富集-电感耦合等离子体原子发射光谱法测定水样中的稀土

提出了聚丙烯基弱酸性阳离子交换纤维柱富集痕量稀土元素,1.0 mol/L HCl溶液作为洗脱剂,电感耦合等离子体原子发射光谱法测定水样中稀土元素的方法。在优化的试验条件下,弱酸性阳离子交换纤维对La、Nd、Eu、Gd、Er和Yb的吸附容量分别为86.5,98.2,98.7,99.2,84.9,91.5 mg/g;La、...     

Selective preconcentration of rare earth elements by substoichiometric precipitation of calcium oxalate and its application to the neutron activation analysis of biological material

A preconcentration method for trace amounts of rare earth elements (REs) based on the substoichiometric precipitation of calcium oxalate was developed. RE(III) was quantitatively coprecipitated with calcium oxalate which had been precipitated from the calcium of a macrocomponent in a biological sample by addition of a substoichiometric amount of oxalate. In this way high selectivity for RE(III) from other elements was achieved. The method was applied to the neutron activation analysis of a biological sample (NBS SRM 1572 Citrus Leaves), and Sc, La, Ce, Pf, Nd, Sm, Eu, Th, Dy, Ho, Yb and Lu were determined with a relative standard deviation of less than 5%.