Spatially and time-resolved element-specific in situ corrosion investigations with an online hyphenated microcapillary flow injection inductively coupled plasma mass spectrometry set-up

A novel technique for in situ spatial, time-resolved element-specific investigations of corrosion processes is developed. The technique is based on an online hyphenation of a specially designed microflow-capillary set-up to inductively coupled plasma mass spectrometry (ICP-MS) using flow injection sample introduction. Detailed aspects of the method development, optimization of the sample microflow introduction and flow injection characteristics for the localized corrosion analysis are described. Moreover, specific challenges of the ICP-MS analysis as applied to the analysis of corrosion sample probes, e.g. high matrix load and limited sample volume, are discussed.     

Enhanced flow injection leaching of rocks by focused microwave heating with in-line monitoring of released elements by inductively coupled plasma mass spectrometry

A focused microwave digestion system was used to heat a mini-column of sample of crushed rock (hematite) during its successive leaching by repeated 250-μL injections of water, HNO₃ 1%, 10% and 30% (v/v). The mini-column was connected to the nebulizer of an inductively coupled plasma mass spectrometry instrument, which allowed a continuous monitoring of the progressive release of elements by a given leaching reagent. Quantitation of the accessible fraction of Mg, V, Cr, Mn, Co, Ni, Cu, Zn, Mo, Sb and Pb was done by calibration using 250-μL injections of standard solutions prepared in the leaching reagent matrices. Total digestion of the sample residue was also done to verify mass balance. With the exception of Mg, V and Co, where the same total amount was released with or without microwave heating, an increased release resulted from focused microwave heating, by up to an order of magnitude. Furthermore, mass balance was verified for more elements using microwave heating, presumably because of a lower relative proportion of spectroscopic interference as a result of an increased release of analytes. Using microwave energy in general resulted in the dissolution of additional phases, as evidenced by significantly different ²⁰⁸Pb/²⁰⁶Pb ratios as well as the increased release of elements with milder reagents. In fact, in the case of Pb, leaching with 30% HNO₃ was no longer necessary as all the Pb was released in the first three leaching reagents. Microwave heating could therefore be used advantageously in on-line leaching for exploration geochemistry and environmental monitoring.     

电感耦合等离子体质谱技术最新进展

对1998年以来电感耦合等离子体质谱技术（ICP－MS）的最新进展作一简要回顾。内容包括同位素比值分析、双聚焦扇形磁场高分辨ICP－MS、多接收器磁扇形等离子体质谱仪（MC－ICP－MS）、飞行时间等离子体质谱仪（ICP－TOF－MS）、“冷”等离子体及屏蔽炬技术以及动态碰撞／反应池技术等进展。     

Quantification of phosphorus in DNA using capillary electrophoresis hyphenated with inductively coupled plasma mass spectrometry

We have analyzed phosphorus in an enzymatically digested DNA molecule using capillary electrophoresis (CE) hyphenated with inductively coupled plasma mass spectrometry (ICP-MS). The DNA concentration was quantified by the phosphorus value obtained in the CE-ICP-MS analysis. The CE-ICP-MS measurement, for which the interface device AIF-01 equipped three layered nebulizer was adopted, was achieved with limited μL/min nebulizing without loss of sample in the vaporizing chamber. The samples of nucleotides and free phosphate were separated well in the CE-ICP-MS measurement, and the calibration curve (0.1-10μg/mL) of the phosphorus showed a linear (R(2)=0.999) increase in intensity. After digestion of the 100-bp double-strand DNA sample to deoxyribonucleotide-5'-monophosphates (dNMPs) by phosphodiesterase-I, phosphorus was detected by CE-ICP-MS without further purification steps. In this study, we applied two calculation schemes of DNA analysis using a dNMP concentration obtained from CE-ICP-MS. Comparative CE-ICP-MS analysis with DNA digested to dNMPs showed that the assay gave an equal value obtained from the total DNA quantification using fluorescence detection. The detection limits of the DNA sample obtained from these species and phosphorus in nucleotides using CE-ICP-MS were 3.1-26ng/mL. These LOD values were equal to the conventional fluorescence determination of DNA.     

Determination of trace elements in human serum by inductively coupled plasma atomic emission spectrometry with flow injection

An analytical method for the simultaneous determination of some trace elements (Au, Fe, Mg, Li, Sr, Zn) in human serum by inductively coupled plasma atomic emission spectrometry (ICP-AES) with flow injection is described. Physical interference caused by the change of sample viscosity is discussed. When 100 μl of serum was injected, the relevant recoveries of > 99% for Li, > 98% for Cu and Mg, > 95% for Fe were obtained for an NIST SRM with R.S.D. > 1.3% using optimized flow injection parameters. The prepared lyophilized control serum for routine analysis in clinical laboratories was analyzed and verified for the validity of the technique employed in this experiment using NIST SRM 909 as a primary reference material.     

A new interface used to couple capillary electrophoresis with an inductively coupled plasma mass spectrometry for speciation analysis

In this work, a novel and high-efficiency interface has been developed in coupling CE with inductively coupled plasma MS (ICPMS). The interface completely avoids laminar flow in CE capillary caused by the suction of nebulizer, and can be easily and stably operated at room temperature with high analyte transport efficiency to ICPMS. The new interface has a liquid dead volume smaller than 5 nL, which was much smaller than those (65-2500 microL) reported previously for other interfaces. All above features led to a higher sensitivity and a better electrophoretic resolution for CE-ICPMS coupled with this new interface. With the help of this new interface, we have successfully separated and determined five species of arsenic, As(III), As(V), monomethylarsonic acid, dimethylarsinic acid and p-aminophenylarsonic acid using CE-ICPMS within 11 min with a detection limit of 0.046-0.075 ng/mL and an RSD of 2-6% (n=6).     

Elemental labelling combined with liquid chromatography inductively coupled plasma mass spectrometry for quantification of biomolecules: A review

This article reviews novel quantification concepts where elemental labelling is combined with flow injection inductively coupled plasma mass spectrometry (FI-ICP-MS) or liquid chromatography inductively coupled plasma mass spectrometry (LC–ICP-MS), and employed for quantification of biomolecules such as proteins, peptides and related molecules in challenging sample matrices. In the first sections an overview on general aspects of biomolecule quantification, as well as of labelling will be presented emphasizing the potential, which lies in such methodological approaches. In this context, ICP-MS as detector provides high sensitivity, selectivity and robustness in biological samples and offers the capability for multiplexing and isotope dilution mass spectrometry (IDMS). Fundamental methodology of elemental labelling will be highlighted and analytical, as well as biomedical applications will be presented. A special focus will lie on established applications underlining benefits and bottlenecks of such approaches for the implementation in real life analysis. Key research made in this field will be summarized and a perspective for future developments including sophisticated and innovative applications will given.     

Applications of inductively coupled plasma mass spectrometry and laser ablation inductively coupled plasma mass spectrometry in materials science

Inductively coupled plasma mass spectrometry (ICP-MS) and laser ablation ICP-MS (LA-ICP-MS) have been applied as the most important inorganic mass spectrometric techniques having multielemental capability for the characterization of solid samples in materials science. ICP-MS is used for the sensitive determination of trace and ultratrace elements in digested solutions of solid samples or of process chemicals (ultrapure water, acids and organic solutions) for the semiconductor industry with detection limits down to sub-picogram per liter levels. Whereas ICP-MS on solid samples (e.g. high-purity ceramics) sometimes requires time-consuming sample preparation for its application in materials science, and the risk of contamination is a serious drawback, a fast, direct determination of trace elements in solid materials without any sample preparation by LA-ICP-MS is possible. The detection limits for the direct analysis of solid samples by LA-ICP-MS have been determined for many elements down to the nanogram per gram range. A deterioration of detection limits was observed for elements where interferences with polyatomic ions occur. The inherent interference problem can often be solved by applying a double-focusing sector field mass spectrometer at higher mass resolution or by collision-induced reactions of polyatomic ions with a collision gas using an ICP-MS fitted with collision cell. The main problem of LA-ICP-MS is quantification if no suitable standard reference materials with a similar matrix composition are available. The calibration problem in LA-ICP-MS can be solved using on-line solution-based calibration, and different procedures, such as external calibration and standard addition, have been discussed with respect to their application in materials science. The application of isotope dilution in solution-based calibration for trace metal determination in small amounts of noble metals has been developed as a new calibration strategy. This review discusses new analytical developments and possible applications of ICP-MS and LA-ICP-MS for the quantitative determination of trace elements and in surface analysis for materials science.     

Estimation of platinum in environmental water samples with solid phase extraction technique using inductively coupled plasma mass spectrometry

A solid phase extraction technique for the determination of platinum(IV) at trace levels by inductively coupled plasma mass spectromA solid phase extraction technique for the determination of platinum(IV) at trace levels by inductively coupled plasma mass spectrometry (ICP-MS) was developed. The method was based on retention of platinum in a sample on silica gel modified with aminepropyl groups. The retention of platinum(IV) from the sample solution and the recovery of platinum with 1.0 mol L⁻¹ thiourea solution were quantitative. The relative standard deviation (RSD) was calculated as 5% (n = 7) at the 10 ng L⁻¹ level. The enrichment factor was found to be (50-fold) for 250 mL of water sample. Under optimum conditions, the method detection limit (MDL) was found to be 1 ng L⁻¹ for platinum in water matrices. Recoveries of Pt from spike addition to atmospheric water samples were quantitative (80–95%). The present method was used for the determination of platinum in precipitation, throughfall and runoff water samples.      

电感耦合等离子体质谱(ICP-MS)法测定锆钛矿中的铪

锆钛矿组成成分复杂,存在耐高温的锆、钛化合物,不易分解,且铪以类质同象进入锆矿物,导致锆钛矿中的铪含量不均,因此完全分解锆钛矿并准确测定其中含量不同的铪成为一个难题。本文建立了碳酸钠-硼砂高温熔融,以178Hf为分析同位素及50 ng/mL185Re为内标,使用电感耦合等离子体质谱法（ICP-MS）测定锆钛矿中铪的新方法,可准确锆钛矿中含量不均的铪。实验研究了锆钛矿成分及其熔融方法,结果表明碳酸钠-硼砂高温熔融效果最好,可完全溶解耐高温难分解的锆钛矿,当碳酸钠-硼砂质量配比为2:1时熔融效果最佳。电感耦合等离子体质谱法具有检出限低、灵敏度高、线性范围宽等优势,可用于测定锆钛矿中含量不均的铪,ICP-MS蠕动泵转速为45 rpm、雾化流量为1.06 L/min时雾化效率最优。在选定的实验条件下,HfO2质谱强度与其质量浓度在0.01～250 ng/mL范围内呈良好的线性关系,相关系数为0.9997,背景等效浓度为0.029 ng/mL,方法检出限为0.0032 ng/mL。按实验方法对中国国家标准物质中的HfO2进行测定,测定值与认定值一致,相对标准偏差在1.6%~3.2%之间。按实验方法对锆钛矿样品中的HfO2进行测定并进行加标回收率实验,测定结果的相对标准偏差（RSDs,n=9）在0.9～3.4%之间,加标回收率在96%～106%之间,满足国家地质矿产行业标准DZ/T 0130—2006的要求。     

电感耦合等离子体质谱法测定血液和精液中的硼

采用HNO3-H2O2和氨水-甘露醇两种方法处理样品,电感耦合等离子体质谱法（ICP-MS）测定血液和精液中的硼。Be作内标补偿基体效应,并用标准加入法验证了方法的可靠性,标准加入法与外标法测定结果相吻合。在测定B的同时,还可进行Cr、Cu、Cd、Ba、Sr、Mn、Co、Tl、Li、Pb、Zn、Sc、Ti、V、As等多元素测定。两种样品处理方法的测定值呈显著正相关（r=0.99919）。方法检出限为0．11ng／mL（氨水-甘露醇法）,0.06ng／mL（HNO3-H2O2）。已用于测定某硼矿区血液和精液样品中的硼。     

Slurry sampling flow injection chemical vapor generation inductively coupled plasma mass spectrometry for the determination of trace Ge,As, Cd,Sb, Hg and Bi in cosmetic lotions

A slurry sampling inductively coupled plasma mass spectrometry (ICP-MS) method has been developed for the determination of Ge, As, Cd, Sb, Hg and Bi in cosmetic lotions using flow injection (FI) vapor generation (VG) as the sample introduction system. A slurry containing 2% m/v lotion, 2% m/v thiourea, 0.05% m/v l-cysteine, 0.5 μg mL⁻¹ Co(II), 0.1% m/v Triton X-100 and 1.2% v/v HCl was injected into a VG-ICP-MS system for the determination of Ge, As, Cd, Sb, Hg and Bi without dissolution and mineralization. Because the sensitivities of the analytes in the slurry and that of aqueous solution were quite different, an isotope dilution method and a standard addition method were used for the determination. This method has been validated by the determination of Ge, As, Cd, Sb, Hg and Bi in GBW09305 Cosmetic (Cream) reference material. The method was also applied for the determination of Ge, As, Cd, Sb, Hg and Bi in three cosmetic lotion samples obtained locally. The analysis results of the reference material agreed with the certified value and/or ETV-ICP-MS results. The detection limit estimated from the standard addition curve was 0.025, 0.1, 0.2, 0.1, 0.15, and 0.03 ng  g⁻¹ for Ge, As, Cd, Sb, Hg and Bi, respectively, in original cosmetic lotion sample.     

Analysis of nickel-niobium alloys by inductively coupled plasma optical emission spectrometry

Inductively coupled plasma optical emission spectrometry (ICP-OES) was applied to the analysis of major and minor elements of Ni-Nb alloys obtained by aluminothermic reduction process. Digestion of samples was made using a mixture of HF+HNO₃. Minor and trace elements were determined without matrix separation. The precision for all constituents was <3%. Recoveries for the analyte-spiked samples were 95%.     

Determination of As,Cd, Pb,and Hg in urine using inductively coupled plasma mass spectrometry with the direct injection high efficiency nebulizer

The application of the large-bore direct injection high efficiency nebulizer (LB-DIHEN) for the determination of arsenic (As), cadmium (Cd), lead (Pb), and mercury (Hg) in urine by inductively coupled plasma mass spectrometry (ICP-MS) is described. The LB-DIHEN is compared with the standard method using a concentric pneumatic nebulizer and cyclonic spray chamber. In addition to the toxicological significance of As, Cd, Pb, and Hg, these elements represent a cross-section of analytical issues including spectral interferences (e.g., ⁴⁰Ar³⁵Cl⁺ on ⁷⁵As⁺ and ⁹⁸Mo¹⁶O⁺ on ¹¹⁴Cd⁺) and memory effects (Hg). In this study, the low sample consumption of the LB-DIHEN is used to reduce the volume of urine needed for analysis, and to reduce the volume of final diluted sample required for analysis. Eliminating the spray chamber and reducing the dead volume of the nebulizer reduces memory effects, especially for analytes such as Hg. The Dynamic Reaction Cell (DRC) is used in this study to attenuate the background level of ArCl⁺ in spite of the increase in the solvent load and, in turn, the urine matrix (chloride) delivered to the plasma by the LB-DIHEN. This is the first report on coupling the LB-DIHEN to a standard autosampler for unattended sample analysis. The robustness of direct injection nebulization for routine analysis and the issues associated with automation of the sample introduction process are discussed. Although the figures of merit (sensitivity, limit of detection, and precision) determined for both nebulizers are slightly poorer for the LB-DIHEN than for the concentric pneumatic nebulizer, there is not a clinically significant difference between the results for both sample introduction systems. The accuracy of results is assessed using archived urine materials that are circulated by several different proficiency testing (PT) programs and external quality assessment schemes (EQAS). Results obtained using the LB-DIHEN were within the acceptable range established by a consensus pool generated using different methods, none of which are likely to be using direct injection nebulization. Internal quality control sample results obtained using the LB-DIHEN were compared to those obtained using the conventional nebulizer. Reported results were similar for both nebulizers. Thus, these results show that the LB-DIHEN is certainly feasible for the analysis of urine specimens.     

Lead determination in whole blood by laser ablation coupled with inductively coupled plasma mass spectrometry

This work describes a simple procedure for blood lead level determination. The proposed method requires little sample pretreatment and subsequent direct analysis of a dried blood spot on a filter membrane using laser ablation coupled with inductively coupled plasma mass spectrometry (LA-ICP-MS). In general, LA-ICP-MS studies are somewhat limited by the lack of matrix-matched standards for calibration purposes. Here we describe aqueous standard calibration and matrix-matched calibration methods. This method was validated by analysis of the reference materials. With the matrix-matched calibration method, the recovery ranged from 97.8% to 112.8%, while the aqueous standard calibration method ranged 90.4% to 122.4%. The lower detection limit was estimated as 0.1 ng mL⁻¹. The determination precision, expressed as the relative standard deviation (RSD), was not worse than 10% for all results. A sample throughput of approximately 5 min per sample made it possible to rapidly screen a large number of samples.     

茶叶和蔬菜中铅的同位素稀释电感耦合等离子体质谱的测定

采用同位素稀释电感耦合等离子体质谱(ID-ICP-MS)法测定了铅的含量,通过对茶叶标准物质(GBW-07605)中铅的测定,考察了方法的准确度和精密度,比较了同位素稀释法与普通外标定量法的测定结果。在5mLHNO3～0.5mLHF～1mLH2O2的消解体系中,ID-ICP-MS法测量茶叶中铅的回收率可达97.7%,相对标准偏差(RSD)小于1.2%。实验对市售的12种茶叶和10种蔬菜中Pb进行测定,铅含量符合相应国家标准的样品分别占总样品数的83%和90%。该法适合于植物样品中微量铅的测定。     

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。     

Application of inductively coupled plasma sector field mass spectrometry for low-level environmental americium-241 analysis

An improved and novel sample preparation method for ²⁴¹Am analysis by inductively coupled plasma sector field mass spectrometry has been developed. The procedure involves a selective CaF₂ pre-concentration followed by an extraction chromatographic separation using TRU™ resin. The achieved absolute detection limit of 0.86 fg (0.11 mBq) is comparable to that of alpha spectrometry (0.1 mBq) and suitable for low-level environmental measurements. Analysis of different kinds of environmental standard reference materials (IAEA-384 - Fangataufa lagoon sediment, IAEA-385 - Irish Sea sediment and IAEA-308 - Mixed seaweed from the Mediterranean Sea) and alpha spectrometry were used to validate the procedure. The chemical recovery of sample preparation ranged between 72 and 94%. The results obtained are in good agreement with reference values and those measured by alpha spectrometry. The proposed method offers a rapid and less labor-intensive possibility for environmental ²⁴¹Am analysis than the conventionally applied radioanalytical techniques.     

Rapid isolation of plutonium in environmental solid samples using sequential injection anion exchange chromatography followed by detection with inductively coupled plasma mass spectrometry

This paper reports an automated analytical method for rapid determination of plutonium isotopes (²³⁹Pu and ²⁴⁰Pu) in environmental solid extracts. Anion exchange chromatographic columns were incorporated in a sequential injection (SI) system to undertake the automated separation of plutonium from matrix and interfering elements. The analytical results most distinctly demonstrated that the crosslinkage of the anion exchanger is a key parameter controlling the separation efficiency. AG 1-×4 type resin was selected as the most suitable sorbent material for analyte separation. Investigation of column size effect upon the separation efficiency revealed that small-sized (2 mL) columns sufficed to handle up to 50 g of environmental soil samples. Under the optimum conditions, chemical yields of plutonium exceeded 90% and the decontamination factors for uranium, thorium and lead ranged from 10³ to 10⁴. The determination of plutonium isotopes in three standard/certified reference materials (IAEA-375 soil, IAEA-135 sediment and NIST-4359 seaweed) and two reference samples (Irish Sea sediment and Danish soil) revealed a good agreement with reference/certified values. The SI column-separation method is straightforward and less labor intensive as compared with batch-wise anion exchange chromatographic procedures. Besides, the automated method features low consumption of ion-exchanger and reagents for column washing and elution, with the consequent decrease in the generation of acidic waste, thus bearing green chemical credentials.     

Element-tagged immunoassay with inductively coupled plasma mass spectrometry for multianalyte detection

The multianalyte immunoassay approach is currently attracting increasing attention due to its high sample throughput, short assay time, low sample consumption and reduced overall cost per assay. This paper reviews progress in the field of multianalyte immunoassays using inductively coupled plasma mass spectrometry, as well as applications of this approach in different fields. Examples related to the combination of protein microarray technology with the multitag approach of the immunoassay ICP-MS method and to the use of ICP-MS in the field of imaging are described. A novel strategy that involves tagging antibodies for ICP-MS detection in sensitive multitag bioassays is also presented. Finally, the outlook for this promising technique is discussed.