Characterization of nuclear fuels by ICP mass-spectrometric techniques

Isotopic analyses of radioactive materials such as irradiated nuclear fuel are of major importance for the optimization of the nuclear fuel cycle and for safeguard aspects. Among the mass-spectrometric techniques available, inductively coupled plasma mass spectrometry (ICP-MS) and thermal ionization mass spectrometry are the most frequently applied methods for nuclear applications. Because of the low detection limits, the ability to analyze the isotopic composition of the elements and the applicability of the techniques for measuring stable as well as radioactive nuclides with similar sensitivity, both mass-spectrometric techniques are an excellent amendment to classical radioactivity counting methods. The paper describes selected applications of multicollector ICP-MS in combination with chromatographic separation techniques and laser ablation for the isotopic analysis of irradiated nuclear fuels. The advantages and limitations of the selected analytical technique for the characterization of such a heterogeneous sample matrix are discussed.     

Mass spectrometric analysis of ceramic components for solid oxide fuel cells

For the determination of trace impurities in ceramic components of solid oxide fuel cells (SOFCs), some mass spectrometric methods have been applied such as spark source mass spectrometry (SSMS), laser ionization mass spectrometry (LIMS), laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS) and inductively coupled plasma mass spectrometry (ICP-MS). Due to a lack of suitable standard reference materials for quantifying of analytical results on La _x Sr _y MnO₃ cathode material a matrix-matched synthetic standard-high purity initial compounds doped with trace elements-was prepared in order to determine the relative sensitivity coefficients in SSMS and LA-ICP-MS. Radiofrequency glow discharge mass spectrometry (rf-GDMS) was developed for trace analysis and depth profiling of thick non-conducting layers. Surface analytical techniques, such as secondary ion mass spectrometry (SIMS) and sputtered neutral mass spectrometry (SNMS), were used to determine the element distribution on surfaces (homogeneity) and the surface contaminants of SOFC ceramic layers.Dedicated to Professor Dr. rer. nat. Hubertus Nickel on the occasion of his 65th birthday     

Determination of selenium and cadmium dopants in nanocomposites based on zinc and indium oxides by high resolution continuous source electrothermal atomic absorption spectrometry and inductively coupled plasma mass spectrometry

An approach is proposed to the determination of selenium and cadmium dopants in new nanocomposites based on zinc and indium oxides. The approach is based on a combination of highly efficient high resolution continuous source electrothermal atomic absorption spectrometry (ETAAS) for the analysis of suspensions and inductively coupled plasma mass spectrometry for the analysis of solutions. A procedure is developed for the determination of Se and Cd dopants and matrix components based on Zn and In in nanocomposite solutions by inductively coupled plasma mass spectrometry. Stabilizing agents for the preparation of suspensions are studied for the ETAAS analysis of powders without their decomposition. The results of determination of CdSe dopants by high resolution ETAAS are validated by inductively coupled plasma mass spectrometry.     

Estimation of the quantification uncertainty from flow injection and liquid chromatography transient signals in inductively coupled plasma mass spectrometry

The quality of the quantitative results obtained from transient signals in high-performance liquid chromatography–inductively coupled plasma mass spectrometry (HPLC–ICPMS) and flow injection–inductively coupled plasma mass spectrometry (FI–ICPMS) was investigated under multielement conditions. Quantification methods were based on multiple-point calibration by simple and weighted linear regression, and double-point calibration (measurement of the baseline and one standard). An uncertainty model, which includes the main sources of uncertainty from FI–ICPMS and HPLC–ICPMS (signal measurement, sample flow rate and injection volume), was developed to estimate peak area uncertainties and statistical weights used in weighted linear regression. The behaviour of the ICPMS instrument was characterized in order to be considered in the model, concluding that the instrument works as a concentration detector when it is used to monitorize transient signals from flow injection or chromatographic separations. Proper quantification by the three calibration methods was achieved when compared to reference materials, although the double-point calibration allowed to obtain results of the same quality as the multiple-point calibration, shortening the calibration time. Relative expanded uncertainties ranged from 10–20% for concentrations around the LOQ to 5% for concentrations higher than 100 times the LOQ.     

Determination of impurities in uranium oxide by inductively coupled plasma mass spectrometry (ICPMS) by the matrix matching method

An analytical procedure was developed to determine the concentration of some elements regarded as trace impurities in nuclear fuel using inductively coupled plasma mass spectrometry (ICPMS) associated to the matrix matching method. The assessment of this approach was carried out using a set of certified reference materials produced by the New Brunswick Laboratory (NBL). Eighteen out of the twenty-four elements in the reference materials could be easily determined. It was found that the mean values for reproducibility and accuracy were 5.0% and 15.0%. The remaining six elements provided mean values of 11.0% and 37.0%, respectively. They could not be adequately determined due to the effects of analyte signal suppression and spectral interference.     

Mass spectrometry of long-lived radionuclides

The capability of determining element concentrations at the trace and ultratrace level and isotope ratios is a main feature of inorganic mass spectrometry. The precise and accurate determination of isotope ratios of long-lived natural and artificial radionuclides is required, e.g. for their environmental monitoring and health control, for studying radionuclide migration, for age dating, for determining isotope ratios of radiogenic elements in the nuclear industry, for quality assurance and determination of the burn-up of fuel material in a nuclear power plant, for reprocessing plants, nuclear material accounting and radioactive waste control. Inorganic mass spectrometry, especially inductively coupled plasma mass spectrometry (ICP-MS) as the most important inorganic mass spectrometric technique today, possesses excellent sensitivity, precision and good accuracy for isotope ratio measurements and practically no restriction with respect to the ionization potential of the element investigated—therefore, thermal ionization mass spectrometry (TIMS), which has been used as the dominant analytical technique for precise isotope ratio measurements of long-lived radionuclides for many decades, is being replaced increasingly by ICP-MS. In the last few years instrumental progress in improving figures of merit for the determination of isotope ratio measurements of long-lived radionuclides in ICP-MS has been achieved by the application of a multiple ion collector device (MC-ICP-MS) and the introduction of the collision cell interface in order to dissociate disturbing argon-based molecular ions, to reduce the kinetic energy of ions and neutralize the disturbing noble gas ions (e.g. of ¹²⁹Xe⁺ for the determination of ¹²⁹I). The review describes the state of the art and the progress of different inorganic mass spectrometric techniques such as ICP-MS, laser ablation ICP-MS vs. TIMS, glow discharge mass spectrometry, secondary ion mass spectrometry, resonance ionization mass spectrometry and accelerator mass spectrometry for the determination of long-lived radionuclides in quite different materials.     

Extractive liquid-liquid spectrophotometric procedure for the determination of thiocyanate ions employing the ion pair reagent amiloride monohydrochloride

The paper describes analytical methods developed for the production date determination of uranium-based nuclear materials by the measurement of 230Th/234U isotope ratio. An improved sample preparation method for the destructive analysis involving extraction chromatographic separation with TEVA resin was applied prior to the measurement by isotope dilution inductively coupled plasma sector field mass spectrometry (ICP-SFMS). The results obtained were compared with the direct, quasi-non-destructive measurement using laser ablation ICP-SFMS technique for age determination. The advantages and limitations of both methods are discussed.     

Polynomial mass bias functions for the internal standardization of isotope ratio measurements by multi-collector inductively coupled plasma mass spectrometry

The development and application of a calibration strategy for routine isotope ratio analysis by multi-collector inductively coupled plasma mass spectrometry (ICP-MS) is described and assessed. Internal standardization was used to account for the mass dependant determinate error (mass bias). The general solution for polynomial isotope ratio mass bias functions for use with internal standardization and isotope ratio measurements by multi-collector inductively coupled plasma mass spectrometry was derived. The resulting linear isotope ratio mass bias function was demonstrated to be mathematically consistent and experimentally realistic for the analysis of acidified aqueous solutions of analyte and internal standard elements (clean solutions) by multi-collector inductively coupled plasma mass spectrometry.     

IC-ICP-MS applied to the separation and determination of traces of plutonium and uranium in aqueous leachates and acid rinse solutions of UO2 doped with Pu

It is expected that spent nuclear fuel, today mainly UO₂, may become exposed to groundwater after extended storage in a deep geologic repository. After 1000 years, the radioactivity of the fuel will be constituted essentially by α-emissions by long-lived actinides. The α-emissions play a significant role in determining the dissolution behavior of uranium, because the radiolysis of water results in the formation of oxidizing chemical species near the fuel surface. In order to study this effect, UO₂ doped with 0.1 and 10 wt.% of a strong α-emitter (namely ²³⁸Pu) was subject to leaching at room temperature (RT) in deionized water. In order to study the mechanisms of leaching in simulated conditions, very precise and accurate techniques need to be employed. In this paper, the results obtained by inductively coupled plasma mass spectrometry coupled with ion chromatography for the determination of traces of ²³⁸Pu and uranium in aqueous leachates’ solutions are illustrated.     

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.     

Determination of vanadium in petroleum and petroleum products using atomic spectrometric techniques

Vanadium is recognized worldwide as the most abundant metallic constituent in petroleum. It is causing undesired side effects in the refining process, and corrosion in oil-fired power plants. Consequently, it is the most widely determined metal in petroleum and its derivatives. This paper offers a critical review of analytical methods based on atomic spectrometric techniques, particularly flame atomic absorption spectrometry (FAAS), electrothermal atomic absorption spectrometry (ET AAS), inductively coupled plasma optical emission spectrometry (ICP OES), inductively coupled plasma mass spectrometry (ICP-MS). In addition an overview is provided of the sample pretreatment and preparation procedures for vanadium determination in petroleum and petroleum products. Also included are the most recent studies about speciation and fractionation analysis using atomic spectrometric techniques.     

电感耦合等离子体质谱（ICP-MS）法测定高纯氧化铟中铜含量的不确定度评定

对电感耦合等离子体质谱法（ICP-MS）测量高纯氧化铟中铜含量的测量不确定度进行评定。不确定度的来源主要包括分析过程中所用的天平、玻璃器皿、标准曲线、标准溶液、试液定容体积、样品消解及测量重复性等引入的不确定度分量。计算出各分量的不确定度,通过合成得到测量结果的合成不确定度、扩展不确定度及测试结果的报告形式。     

Atomic spectrometric methods for the determination of metals and metalloids in automotive fuels - A review

Gasoline, diesel, ethanol and more recently also biodiesel are the four types of fuel used for automobile, truck and other transportation vehicle. The presence of metallic and metalloid species in automotive fuels is undesirable, except in the form of additives in order to improve specific characteristics of the fuel. Metallic or metalloid elements may derive from the raw product, such as nickel and vanadium in petroleum-based fuel or phosphorus in biodiesel, or they may be introduced during production and storage, such as copper, iron, nickel and zinc in case of petroleum-based fuel and alcohol or sodium and potassium in the case of biodiesel. The most famous additive to fuel is undoubtedly lead, the use of which has been banned or drastically reduced now in many countries of the world. The problems related to the trace element content may be economic, such as fuel degradation and poisoning of automotive catalysts, and/or environmental, such as the emission of metal compounds to the atmosphere. The analytical methods that have been developed for metal and metalloid quantification in automotive fuel are reviewed in this article. The main atomic spectrometric techniques used for trace metal and metalloid determination in fuels, particularly atomic absorption spectrometry with flames, graphite furnaces and with chemical vapor generation, and inductively coupled plasma coupled with optical emission and mass spectrometry are presented, including the different sample preparation procedures proposed for these techniques.     

Determination of fission products in nuclear samples by capillary electrophoresis-inductively coupled plasma mass spectrometry (CE-ICP-MS)

Determination of fission products and of their isotopic composition is of high importance for the characterisation and complete inventory of nuclear fuels. Radiometric and mass spectrometric methods, which are currently used, enable only an incomplete determination of the fission products. Radiometric methods cannot be applied to all fission products and mass spectrometric methods are hindered by the existence of isobaric interferences, therefore a previous chemical separation is required before mass spectrometric analysis. Capillary electrophoresis (CE) has been coupled with inductively coupled plasma mass spectrometry (both ICP-QMS and ICP-SFMS). Typical detection limits of 6 ng/mL and 4 pg/mL for caesium as well as 8 ng/mL and 7 pg/mL for lanthanides have been obtained by CE-ICP-QMS and CE-ICP-SFMS, respectively. In addition to these very low detection limits, the procedures present the advantages to be fast (6 min for caesium and 13 min for lanthanides, respectively), to require a low microliter range sample volume and a nanoliter range injection volume. The radiation dose for the personnel as well as the volume of nuclear liquid wastes generated during the measurements are consequently reduced.The procedures have been applied to nuclear samples from PUREX process and leachates from MOX fuels.     

电感耦合等离子体质谱法测定固体生物质燃料中重金属

为开展重金属监测及环境保护,本文建立了电感耦合等离子体质谱法测定固体生物质燃料中重金属方法。对样品全消解酸溶法进行了实验研究,确定了微波消解酸体系和微波消解程序。采用Ge和In作为内标元素消除仪器干扰,方法线性关系良好,线性系数>0.999,检出限为0.001～0.089mg/kg。采用标准物质对方法准确性和稳定性进行验证,各元素测定值均在标准证书值范围内,相对标准偏差在0.36%～3.96%,Hg的加标平均回收率为104.7%。通过3家实验室协同实验验证了方法准确性,并给出了方法精密度。     

Inorganic trace analysis by mass spectrometry

Mass spectrometric methods for the trace analysis of inorganic materials with their ability to provide a very sensitive multielemental analysis have been established for the determination of trace and ultratrace elements in high-purity materials (metals, semiconductors and insulators), in different technical samples (e.g. alloys, pure chemicals, ceramics, thin films, ion-implanted semiconductors), in environmental samples (waters, soils, biological and medical materials) and geological samples. Whereas such techniques as spark source mass spectrometry (SSMS), laser ionization mass spectrometry (LIMS), laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS), glow discharge mass spectrometry (GDMS), secondary ion mass spectrometry (SIMS) and inductively coupled plasma mass spectrometry (ICP-MS) have multielemental capability, other methods such as thermal ionization mass spectrometry (TIMS), accelerator mass spectrometry (AMS) and resonance ionization mass spectrometry (RIMS) have been used for sensitive mono- or oligoelemental ultratrace analysis (and precise determination of isotopic ratios) in solid samples. The limits of detection for chemical elements using these mass spectrometric techniques are in the low ng g⁻¹ concentration range. The quantification of the analytical results of mass spectrometric methods is sometimes difficult due to a lack of matrix-fitted multielement standard reference materials (SRMs) for many solid samples. Therefore, owing to the simple quantification procedure of the aqueous solution, inductively coupled plasma mass spectrometry (ICP-MS) is being increasingly used for the characterization of solid samples after sample dissolution. ICP-MS is often combined with special sample introduction equipment (e.g. flow injection, hydride generation, high performance liquid chromatography (HPLC) or electrothermal vaporization) or an off-line matrix separation and enrichment of trace impurities (especially for characterization of high-purity materials and environmental samples) is used in order to improve the detection limits of trace elements. Furthermore, the determination of chemical elements in the trace and ultratrace concentration range is often difficult and can be disturbed through mass interferences of analyte ions by molecular ions at the same nominal mass. By applying double-focusing sector field mass spectrometry at the required mass resolution—by the mass spectrometric separation of molecular ions from the analyte ions—it is often possible to overcome these interference problems. Commercial instrumental equipment, the capability (detection limits, accuracy, precision) and the analytical application fields of mass spectrometric methods for the determination of trace and ultratrace elements and for surface analysis are discussed.     

激光烧蚀-等离子体质谱结合归一定量方法原位线扫描检测石榴石多种元素

探讨了基体归一定量技术在实际应用中存在的问题.外标结合内标归一校正法避免了内标法中需要采用其它微区技术测定内标含量的繁琐步骤,可方便地用于具有环带结构等难以找到均匀分布的内标元素的地质样品的元素空间分布测定,解决了在采用直接外标法进行基体归一时,不能同时采用多外标进行校正的缺陷.激光线扫取样的最大优势是快速、省时.采用线扫的激光取样方式,结合归一定量技术,对具有环带结构的天然石榴石样品中的45种元素进行了分析测定,并与传统的激光打坑结果作对比,结果令人满意.     

电感耦合等离子体质谱(ICP-MS)及其联用技术在核工业领域的应用进展

综述了电感耦合等离子体质谱(ICP-MS)及其联用分析技术的进展,论述了其在相关核工业及环境领域中分析痕量或超痕量的放射性同位素、长寿命核素、元素形态等的应用。讨论了电感耦合等离子体质谱及联用技术的发展趋势,并对目前存在的主要问题及可能的解决方案进行了讨论。     

A theoretical adaptation of the classical isotope dilution technique for practical routine analytical determinations by means of inductively coupled plasma mass spectrometry

The classical isotope dilution approach is adapted for routine element determinations by inductively coupled plasma mass spectrometry (ICP-MS). In the approach described a calibration graph, which is curved by definition, is used as reference. This calibration graph can be derived both theoretically and practically by measuring known element concentrations. It is shown that deliberately introduced instrumental sensitivity changes are completely corrected for. The analytical consequences in terms of curvature of the calibration graph, blank determinations and detection limits are described and discussed.     

Reduction of interferences in graphite furnace atomic absorption spectrometry by multiple linear regression modelling

The multivariate effects of Na, K, Mg and Ca as nitrates on the electrothermal atomisation of manganese, cadmium and iron were studied by multiple linear regression modelling. Since the models proved to efficiently predict the effects of the considered matrix elements in a wide range of concentrations, they were applied to correct the interferences occurring in the determination of trace elements in seawater after pre-concentration of the analytes. In order to obtain a statistically significant number of samples, a large volume of the certified seawater reference materials CASS-3 and NASS-3 was treated with Chelex-100 resin; then, the chelating resin was separated from the solution, divided into several sub-samples, each of them was eluted with nitric acid and analysed by electrothermal atomic absorption spectrometry (for trace element determinations) and inductively coupled plasma optical emission spectrometry (for matrix element determinations). To minimise any other systematic error besides that due to matrix effects, accuracy of the pre-concentration step and contamination levels of the procedure were checked by inductively coupled plasma mass spectrometric measurements. Analytical results obtained by applying the multiple linear regression models were compared with those obtained with other calibration methods, such as external calibration using acid-based standards, external calibration using matrix-matched standards and the analyte addition technique. Empirical models proved to efficiently reduce interferences occurring in the analysis of real samples, allowing an improvement of accuracy better than for other calibration methods.