HR-ICP-MS测定高纯镍金属中的微量元素杂质

高分辨电感耦合等离子体质谱(HR-ICP-MS)是目前痕量元素分析的有效手段之一。本文采用HR-ICP-MS分析高纯镍金属中的12种杂质元素。镍金属的溶解采用微波消解法,组分不需须分离富集,定容后直接上机测定。实验优选了消解用酸的种类和浓度,优化了仪器参数,并对质谱干扰进行了研究。HR-ICP-MS对各元素的检出限在1.2 ng·L~(-1)～79 ng·L~(-1)之间,高纯镍金属中各杂质元素的含量介于1.1×10~(-6)至4.66×10~(-4)之间,镍金属纯度为99.93%。     

高分辨电感耦合等离子体质谱法测定镍基单晶高温合金中36种痕量元素

基于高分辨电感耦合等离子体质谱法(HR-ICP-MS)的质谱干扰消除技术,对镍基单晶高温合金中36种痕量元素检测的质谱条件、基体干扰、质谱干扰与同位素选择进行了研究。取样品0.100 0 g,用体积比为3∶1的盐酸-硝酸混合酸10 mL、氢氟酸1 mL溶解,用水定容至250 mL。通过复杂基体质谱干扰计算判定、共存元素干扰消除,确定了待测元素的同位素和分辨模式,将镍基单晶高温合金中痕量元素准确测定的元素种类确定为36种。采用标准加入法进行定量分析,36种痕量元素的检出限(3s)为0.004～6.000μg·L^-1。方法用于分析国际标准物质,得到的测定值与认定值基本一致。方法用于镍基单晶高温合金样品分析,36种痕量元素的检出量为0.000 001 0%～0.018%。     

高分辨ICP-MS测定涂料中痕量砷形态分布的研究

为建立高分辨率电感耦合等离子体质谱法(HR-ICP-MS)测定涂料中砷化合物形态分布的分析方法,应用离子交换树脂和溶剂萃取相结合的分离技术分离涂料中As(Ⅲ)、As(Ⅴ)、MMA(甲基胂酸)、DMA(二甲基胂酸)等4种砷化合物,试液直接用HR-ICP-MS法同时测定上述4种砷化合物,在高分辨质谱测量模式下避免了大量的质谱干扰,考察了采用内标元素对基体效应的校正,应用标准加入法进行定量分析,确定了实验的最佳测定条件。结果表明,方法的检出限为0.002μg/g,样品的加标回收率为98.2%～104.2%,相对标准偏差为0.72%～2.61%。该法具有简单、快速、准确等优点,应用涂料中砷化合物的4种不同形态砷的测定,结果满意。     

环境样品中铀的HR-ICP-MS测定

高分辨电感耦合等离子体质谱法(HR-ICP-MS)是痕量元素分析的有效手段。本文采用HR-ICP-MS对环境样品(土壤、底泥、茶叶、地表水)中铀浓度和同位素比值进行了测定。土壤、底泥、茶叶样品采用微波消解法进行溶解;水样采用45μm滤膜过滤后直接测定。实验对样品制备、仪器参数设定、记忆效应消除、质量歧视效应修正等进行了探索,建立了环境样品中痕量铀浓度和同位素比值测定方法。土壤制样过程中铀的加标回收率为97.7%,铀检出限0.51ng·L~(-1)。     

高分辨电感耦合等离子体质谱仪测定中亚山地冰川雪冰中超痕量元素

在超净实验条件下,利用高分辨电感耦合等离子体质谱仪直接测定雪冰样品中浓度在1ng/L~100μg/L之间的多种超痕量元素Al、Fe、Mn、Co、Cu、Zn、Sr、Sb、Cd、CsBa、Tl、Pb和Bi的实验方法进展。在测定过程中灵敏度的变化可通过监测ArAr质谱峰的变化进行校正,并建立了数学校正公式。以1%HNO3为空白溶液获得了各元素的检出限(ng/L)分别为:Al40、Mn6、Fe40、Co2.74、Cu9.6、Zn20、Sr0.03、Sb0.15、Cs0.04、Ba0.4、Tl0.07、Pb0.8和Bi0.05。利用标准参考物质SLRS-4对测试方法的准确度进行了评价。研究了在硝酸含量分别为0.5%、1%、2%和4%时雪冰中超痕量元素质谱信号强度的变化特点。测定结果发现,对于污化层样品,当硝酸的含量为1%时痕量元素的质谱信号强度最大;对于非污化层样品,痕量元素的质谱信号强度在硝酸含量为0.5%时较大,但与硝酸含量为1%时的质谱信号强度相比变化率小于10%。结合中亚山地冰川雪冰中痕量元素浓度差别大的特点,确定硝酸在样品中的含量为1%为合适的酸度。并对卓奥友峰和珠穆朗玛峰雪坑样品进行了分析方法的重复性研究。     

高流速辉光放电质谱法测定纯镍中41种痕量元素

建立了高流速辉光放电质谱法（GDMS）测定纯镍中41种痕量元素含量的分析方法。使用有证标准物质IARM 190A校正其中29种元素的相对灵敏度因子（RSF）,其他12种元素采用标准RSF。在放电电流40 mA、放电电压1000 V、气体流速400 mL/min条件下,对样品预溅射20 min后进行测定。各元素的方法定量限在0.0000001%～0.000054%之间。应用该方法分析2个纯镍样品中的41种痕量元素,测定结果与高分辨电感耦合等离子体质谱法（HR-ICP-MS）、原子荧光光谱法（AFS）、高频感应炉燃烧红外吸收法测定结果一致,当待测元素含量大于0.0001%时,结果的相对标准偏差（RSD）为0.1%～13%;当待测元素含量在0.00001%～0.0001%之间时,测定结果的RSD为0.4%～46%;当待测元素含量小于0.00001%时,测定结果的RSD为7.4%～48%。     

阴离子交换树脂分离富集/电感耦合等离子体质谱测定珊瑚中铅的同位素组成

在自制微型离子交换柱的基础上,建立了阴离子交换树脂AG1-X8分离富集珊瑚中痕量元素Pb的前处理方法,并使用高分辨电感耦合等离子体质谱(HR-ICP-MS)测定了海南橙黄滨珊瑚(porites lutea)样品中的Pb同位素比值。从全程空白值、洗脱曲线、回收率和基体分离情况等方面考察了不同洗脱剂的洗脱效果,结果表明,采用0.50 mol/L HNO3时的洗脱效果最好,方法的全程空白值为18 pg,Pb的回收率为99.6%,在洗脱过程中无拖尾现象,且能与Ca、Sr、Mg、Fe、Mn、Zn、Ba和U等珊瑚中的基体元素成功分离,对上述基体元素的去除率均能达到99.8%以上。使用该方法测得海南珊瑚样品中的207Pb/206Pb、208Pb/206Pb比值分别为0.850 5、2.087 0,相对标准偏差(RSDs,n=21)分别为0.12%和0.11%。该法质量控制良好,表明建立的AG1-X8阴离子交换树脂分离富集/HR-ICP-MS测定珊瑚中Pb的同位素组成的方法可靠,可推广应用于其它复杂样品中铅同位素组成的测定。     

电感耦合等离子体质谱测定地质样品中多种元素

用电感耦合等离子体质谱(ICP-MS)测定了地质样品中多种元素。考察了测量过程中的基体效应及质谱干扰,利用In内标,补偿由于基体效应的影响所引起的测量偏差,建立校正公式校正质谱干扰。方法的检出限为0.06~250ng/L,精密度为1.7%~3.2%,加标回收率为91%~108%,方法适于批量地质样品分析。     

微波消解-高分辨电感耦合等离子体质谱法(HR-ICP-MS)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。本文采用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,研究了煤炭中钒、铬、锰、钴、镍、铜、镓、锗、砷、铷、锶、钇、铌、钼、镉、锡、锑、铯、钡、镧、铈、镨、钕、钐、铕、镝、钆、铽、钬、铒、镥、铪、铊、铅、钍共35种痕量金属元素在低、中、高分辨率下的质谱干扰,采用高分辨率模式测定Ge、Nd、Eu、Gd、Ho、Er、Lu,采用中分辨率模式测定Ga,采用低分辨率模式测定其余元素,建立了高分辨电感耦合等离子体质谱测定煤炭中35种痕量金属元素的方法。在优化的实验条件下,各元素标准曲线线性相关系数均在0.9999以上,检出限为0.001~0.082 μg/g。选择煤炭标准样品（SARM 20）进行方法验证,测定结果的相对标准偏差为0.27%~6.27%,测定值与标准值基本一致,标准样品中无认证值的元素进行加标回收试验,加标回收率为85.8%~116.55%。选取俄罗斯其它烟煤、澳大利亚其它烟煤、蒙古炼焦煤、印度尼西亚褐煤、俄罗斯无烟煤、印度尼西亚其它烟煤6个代表性样品进行测试,分析了不同产地煤炭的痕量金属元素含量差异。Mn、Ba、Sr以及稀土元素在6种煤炭中存在显著性差异,可为煤炭原产地溯源分析奠定基础。     

脉冲-辉光放电质谱法测量稀土合金中的关键元素

建立了脉冲-辉光放电质谱(Pulsed-GDMS)测定稀土合金中7种关键元素Mg、Fe、Cu、La、Ce、Pr、Nd的分析方法。系统考察了脉冲时间、样品均匀性、质谱仪配件(阳极帽、导流管、样品锥)、压片致密性对测量重复性的影响。对于含量在mg/g量级以上的元素,影响重复性(RSD)的最大因素是质谱仪配件的更换,不更换配件RSD3%,更换新配件RSD为2%~11%,更换重复使用的旧配件RSD为3%~21%;其次是粉末样品压片的致密性,致密样品的测量结果 RSD3%,致密性越低,测量重复性越差。采用高分辨电感耦合等离子体质谱(HR-ICP-MS)对1#稀土合金样品中的元素进行测量,以测量值为参考值对Pulsed-GDMS的测量结果进行校正,获得各元素的相对灵敏度因子,用校正后的Pulsed-GDMS对2#稀土合金样品进行测定。结果表明,对于致密样品(2#-A)的Pulsed-GDMS分析结果与HR-ICP-MS分析结果一致。在优化的条件下,实际样品测量结果的扩展不确定度可降低至3%~10%。     

高分辨电感耦合等离子体质谱(ICP-MS)法测定铁锰氧化态中57种元素

元素活动态分析作为深穿透地球化学的新方法,得到了广泛的应用。将ELEMENT XR型高分辨率等离子体质谱(HR-ICP-MS)法引入元素活动态的分析中,具有动态线性范围宽(10-12~1012)和灵敏度高的特点,使可同时测定的元素拓展至57种,大大提高了工作效率。根据实验结果结合响应面分析法,对HR-ICP-MS的主要仪器条件辅助气流量、雾化气流量和采样深度等进行了优化,确定了仪器的最佳测定条件;对铁锰氧化态的提取条件进行了系统研究:分别考察了提取时间、液固比、离心转速、提取液放置时间对提取效果的影响,确定了最佳提取条件,提取时间为24 h,液固比为15∶1,离心转速4000 r/min;在最优的测定条件和提取条件下,建立了HR-ICP-MS对铁锰氧化物结合相中57种元素的分析方法,得到了各元素的方法检出限和方法精密度,微量和痕量元素的方法检出限达到了10-9(ng/g),主量元素的检出限为10-6(mg/kg)水平,精密度为2.3%~32.5%,完全满足当前元素活动态的分析测试需要。     

Determination of trace elements in residual oil by high-resolution inductively coupled plasma mass spectrometry

An analytical method using high-resolution inductively coupled plasma mass spectrometry (HR-ICP-MS) for rapid simultaneous determination of 20 elements, including Na, Mg, Al, Ca, Ti, V, Mn, Fe, Co, Ni, Cu, Zn, Ga, As, Mo, Cd, Sn, Sb, Ba, and Pb elements, in residual oil was described. The sample was dissolved in HNO₃ by microwave digestion, and then the above 20 elements in the solution were analyzed directly by HR-ICP-MS. Most of the spectral interferences could be avoided by measuring in the high-resolution mode. The matrix effect caused by the sample-digesting solution and corrected by Sc, Rh, and Bi as the internal standard elements was studied in detail. The optimum condition of the determination was also tested and discussed. The result showed that the detection limits of the method were in the range of 0.014 to 11.6 μg L⁻¹; the relative standard deviation was less than 3.8% and recoveries in the samples were in the range of 88.4% to 108.0%. This method can be used to determine the trace elements in residual oil with the features of accurate, rapid, and convenient determination.     

Determination of trace impurities in high-purity cadmium by high-resolution inductively coupled plasma mass spectrometry.

Trace impurities in high-purity cadmium were determined by high-resolution inductively coupled plasma mass spectrometry (HR-ICP-MS). To overcome some potentially problematic spectral interference, measurements were acquired in both medium and high-resolution modes. The matrix effects due to the presence of excess HCl and cadmium were evaluated. The optimum conditions for the determination were tested in this experiment and discussed. The detection limits ranged from 0.01 to 0.27 microg g-1, depending on the elements. The results for the determination of 22 trace elements in high-purity cadmium are presented.     

Trace element analysis of sediments by HR-ICP-MS using low and medium resolution and different acid digestions

For the multielement analysis of sediments (Li, Sc, V, Cr, Co, Ni, Cu, Zn, Rb, Sr, Y, Zr, Mo, Cd, Sn, Sb, Cs, Ba, lanthanides, Hf, Tl, Pb, Bi, Th, U) a dissolution with a hydrofluoric - sulfuric - nitric acid mixture, subsequent evaporation of the acids, dissolution of the residue by HCl, evaporation of the acid and redissolution of the residue by HNO₃ is a useful procedure which allows the dissolution of a wide range of mineral mixtures. An ICP-MS was used for the determination of the elements. For Cr, Ni, Cu and Zn the analysis may be complicated by the interferences of sulfur or chlorine species, which remain in the solution during dissolution. The best analytical results for these elements can be achieved in the medium resolution mode of a HR-ICP-MS. In the low resolution mode (quadrupole instrument characteristics) the determination of these elements should be performed by the isotopes of ⁵²Cr, ⁶²Ni, ⁶³Cu, ⁶⁸Zn as it was found that interferences from remaining acids are of minor importance. Received: 2 January 1997 / Revised: 17 March 1997 / Accepted: 25 March 1997     

Optimization of Sample Preparation of Carrot-Fruit Juice for Determination of Antimony,Arsenic, and Selenium by Hydride Generation-Inductively Coupled Plasma Optical Emission Spectrometry

Sample preparation procedures for the determination of As, Sb, and Se in carrot-fruit juice by hydride generation inductively coupled plasma optical emission spectrometry (HG-ICP OES) were examined. The applicability of a partial decomposition using aqua regia and simple dilution with a 2% (v/v) HNO₃ solution were tested and compared to a traditional treatment based on the wet digestion with a HNO₃/H₂O₂ mixture. The pre-reduction and hydride generation reaction conditions were evaluated. Under the optimal conditions, the hydrides were produced in the reaction of an acidified sample with NaBH₄ after pre-reduction with ascorbic acid [0.5% (m/v)] and KI [0.5% (m/v)] in 3 mol L^?1 HCl for total As and Sb, and boiling with HCl (6 mol L^?1) for total Se. The best results were obtained for the aqua regia procedure, resulting in limits of detection (LODs) between 1.2–2.4 ng g^?1 in the samples and recoveries from 90.9% to 109.1%. The method was successfully applied (without matrix effects) for the determination of As in dense mousse and pulp juice samples and for Sb in pulp juices. Standard solutions, processed in the same way as samples, were used for the calibration. Undecomposed matrix constituents strongly influenced Se; hence this element was determined using the method of standard addition. Concentrations of studied elements in analyzed products were at the trace level, that is, 6–32 ng g^?1, 4–10 ng g^?1, and 4–13 ng g^?1 for Se, As, and Sb, respectively.     

Direct determination of rare earth impurities in high purity erbium oxide dissolved in nitric acid by inductively coupled plasma mass spectrometry

A novel method was developed for the direct determination of trace quantities of rare earth elements (REEs) in high purity erbium oxide dissolved in nitric acid by inductively coupled plasma mass spectrometry (ICP-MS) in this work. The mass spectra overlap interferences arose from Er matrix on the neighbouring and monoisotopic analytes of ¹⁶⁵Ho(100) and ¹⁶⁹Tm(100) were eliminated by adjusting instrumental peak resolution value from 0.7 to 0.3 amu. The matrix suppression effect of Er on the ion peak signals of REEs impurities was effectively compensated with spiking In as internal standard element. The limit of quantitation (LOQ) of REEs impurities was from 0.0090 to 0.025 μg g⁻¹, the recoveries of spiked sample for REEs were found to be in the range of 90.3-107% through using the proposed method and relative standard deviation (R.S.D.) varied between 2.5% and 6.7%. The novel methodology had been found to be suitable for the direct determination of trace REEs impurities in 99.999-99.9999% high purity Er₂O₃ and the results obtained from this method keep in good agreement with that acquired from high resolution ICP-MS.     

高分辨电感耦合等离子体磁质谱法测定含铜不锈钢中痕量磷

作者通过试验,用电感耦合等离子体磁质谱(HR-ICP-MS)测定含铜不锈钢中磷含量时,采用高分辨率模式,选择分辨率为4000,在此条件下磷峰可与干扰双原子分子或离子的峰分开。又通过以含铁基的磷标准溶液优化了气体流量和离子透镜的参数,使磷的信号值提高至3×105cps。而加入45Sc作为内标元素又可显著提高测定的稳定性。分别用不锈钢样品和纯铁粉作基体,加入标准溶液制作标准曲线。结果表明:两种方法的线性均较好,分别测得实际样品的结果及其相对标准偏差也基本一致。但两种方法的检出限(3s)不同,前者为1.0μg·g^-1,后者为0.18μg·g^-1。所提出方法的样品处理过程如下:称取样品0.10g置于消解罐中,加入盐酸溶液2mL及硝酸溶液1mL,待剧烈反应缓解时,将消解罐加盖并置于微波消解仪中,于100℃消解10min,升温至200℃继续消解20min。冷却后将溶液转移至100 mL石英容量瓶中,加入0.2mg·L^-1钪内标溶液1mL,加水至刻度,摇匀。此溶液在仪器工作条件下进行HR-ICP-MS测定。对含磷51μg·g^-1的含铜不锈钢,按本方法测定所得结果的相对标准偏差(n=10)小于4%。应用本方法分析了7种标准物质或已知样品(包括低合金钢、含铜不锈钢、高温合金),并同时用ICP-AES进行校对分析。结果表明,本方法与ICP-AES的测定结果基本一致。但本方法的结果与标准物质的认定值更接近,而且对低含量磷(9μg·g^-1)也可很好测定。     

Application of iminodiacetate chelating resin muromac A-1 in on-line preconcentration and inductively coupled plasma optical emission spectroscopy determination of trace elements in natural waters

On-line system incorporating a microcolumn of Muromac A-1 resin was used for the developing of method for preconcentration of trace elements followed by inductively coupled plasma (ICP) atomic emission spectrometry determination. A chelating type ion exchange resin has been characterized regarding the sorption and subsequent elution of 24 elements, aiming to their preconcentration from water samples of different origins. The effect of column conditioning, pH and flow rate during the preconcentration step, and the nature of the acid medium employed for desorption of the retained elements were investigated. A sample (pH 5) is pumped through the column at 3 ml min⁻¹ and sequentially eluted directly to the ICP with 3 M HNO₃/HCl mixtures. In order to remove residual matrix elements from the column after sample loading a short buffer wash was found to be necessary. The effectiveness of the matrix separation process was illustrated. The procedure was validated by analyzing several simple matrices, Standard River water sample as well as artificial seawater. Proposed method can be applied for simultaneous determination of In, Tl, Ti, Y, Cd, Co, Cu and Ni in seawater and for multielement trace analysis of river water. Recovery at 1 μg l⁻¹ level for the determination of investigated 24 elements in pure water ranged from 93.1 to 96% except for Pd (82.2%) and Pb (88.1%). For the same concentration level for seawater analysis recovery was between 81.9 and 95.6% except for Hg (38.2%).     

Determination of trace impurities in high purity copper using sector-field ICP-MS: continuous nebulization, flow injection analysis and laser ablation

High resolution inductively coupled plasma mass spectrometry (HR-ICP-MS) was applied for multielement-determination in high-purity copper (approx. 99.99%). The samples were introduced into the instrument by three different introduction systems, which were studied with respect to high accuracy, low detection limits and fast analysis: continuous nebulization (CN), flow injection analysis (FIA) and laser ablation (LA). The trueness of the applied method was checked by the analysis of high-purity copper reference material (BCR Cu074). All values obtained for this CRM using CN were in the range of the stated uncertainty for the 9 elements determined: Ag, As, Bi, Cr, Fe, Ni, Pb, Sb, and Sn with contents in the range of 0.5–13 μg/g. Another approach for checking the trueness of the method was to compare the results obtained by this method characterizing the purity of a 4N (99.99% copper content) copper material with those obtained by application of electrothermal atomic absorption spectrometry (ET-AAS) and inductively coupled plasma optical emission spectrometry (ICP-OES). For further characterizing, the concentrations of 49 elements were found in this material below detection limits of HR-ICP-MS in the range of low μg/kg and sub μg/kg. The combination of HR-ICP-MS and a flow injection analysis system (FIAS) improved the robustness of the system in regard to high matrix concentrations. Therefore, matrix concentrations up to 4 g/L could be used for liquid analysis and detection limits were lowered by a factor of 2–5. A calibration method for bulk analysis with laser ablation was developed with doped copper powder as pressed pellets for calibration standards. This method proved to be an excellent fast semi-quantitative method, which was less time consuming in comparison with the analysis of liquids. After application of correction factors the deviation between the results obtained by laser ablation and by analysis of liquids was ≈ 15% for most elements. The method offered the possibility to check for potential losses of analytes occurring during the wet chemical operations. Received: 23 November 1998 / Revised: 25 February 1999 / Accepted: 2 March 1999     

Determination of trace impurities in high purity copper using sector-field ICP-MS: continuous nebulization, flow injection analysis and laser ablation

High resolution inductively coupled plasma mass spectrometry (HR-ICP-MS) was applied for multielement-determination in high-purity copper (approx. 99.99%). The samples were introduced into the instrument by three different introduction systems, which were studied with respect to high accuracy, low detection limits and fast analysis: continuous nebulization (CN), flow injection analysis (FIA) and laser ablation (LA). The trueness of the applied method was checked by the analysis of high-purity copper reference material (BCR Cu074). All values obtained for this CRM using CN were in the range of the stated uncertainty for the 9 elements determined: Ag, As, Bi, Cr, Fe, Ni, Pb, Sb, and Sn with contents in the range of 0.5–13 μg/g. Another approach for checking the trueness of the method was to compare the results obtained by this method characterizing the purity of a 4N (99.99% copper content) copper material with those obtained by application of electrothermal atomic absorption spectrometry (ET-AAS) and inductively coupled plasma optical emission spectrometry (ICP-OES). For further characterizing, the concentrations of 49 elements were found in this material below detection limits of HR-ICP-MS in the range of low μg/kg and sub μg/kg. The combination of HR-ICP-MS and a flow injection analysis system (FIAS) improved the robustness of the system in regard to high matrix concentrations. Therefore, matrix concentrations up to 4 g/L could be used for liquid analysis and detection limits were lowered by a factor of 2–5. A calibration method for bulk analysis with laser ablation was developed with doped copper powder as pressed pellets for calibration standards. This method proved to be an excellent fast semi-quantitative method, which was less time consuming in comparison with the analysis of liquids. After application of correction factors the deviation between the results obtained by laser ablation and by analysis of liquids was ≈ 15% for most elements. The method offered the possibility to check for potential losses of analytes occurring during the wet chemical operations. Received: 23 November 1998 / Revised: 25 February 1999 / Accepted: 2 March 1999