Capillary electrophoresis (CE) was hyphenated to Multi-Collector Inductively Coupled Plasma Mass Spectrometry (MC-ICP-MS) to perform isotope ratio measurements for actinides (U, Pu, Am, and Cm) and ...lanthanide fission products (Nd, Sm, Eu, and Gd) in a spent nuclear fuel sample. A capillary electrophoresis-inductively coupled plasma mass spectrometry (CE-ICP-MS) method was developed using either α-HMBA or α-HIBA as electrolytes, demonstrating the ability of alpha-hydroxycarboxylic acids to perform the concurrent separation of actinides and lanthanides in a simulated sample and a spent Mixed Oxide (MOX) fuel sample. Isotope ratios for U, Pu, Am, and Cm as well as Nd, Sm, Eu, and Gd were then determined by CE-MC-ICP-MS in two injections of approximately 30 nL of the spent MOX fuel sample. The relative standard deviations were in the per-mil range, similar to the ones obtained by two-step offline chromatography followed by Thermal Ionisation Mass Spectrometry (TIMS). The use of CE as the separation method lowered the sample quantity (in the pg range for Pu, Am, Cm and lanthanides, in the ng range for U) and waste volume production (a few hundred μL) as compared to commonly used chromatography methods. CE-MC-ICP-MS therefore makes it possible to measure multiple isotope ratios at a per-mil level of uncertainty without the need for prior offline chemical separation.
CE was hyphenated to MC-ICP-MS in a glove box to measure isotope ratios of actinides and lanthanides in spent nuclear fuel.
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•Tutorial review addressed to beginners or more experienced analysts.•Theoretical background of effects caused by organic matrices on ICP techniques.•Spatial distribution of carbon ...species and analytes in plasma.•Carbon spectroscopic and non-spectroscopic interferences in ICP.
Due to their outstanding analytical performances, inductively coupled plasma optical emission spectrometry (ICP-OES) and mass spectrometry (ICP-MS) are widely used for multi-elemental measurements and also for isotopic characterization in the case of ICP-MS. While most studies are carried out in aqueous matrices, applications involving organic/hydro-organic matrices become increasingly widespread. This kind of matrices is introduced in ICP based instruments when classical “matrix removal” approaches such as acid digestion or extraction procedures cannot be implemented. Due to the physico-chemical properties of organic/hydro-organic matrices and their associated effects on instrumentation and analytical performances, their introduction into ICP sources is particularly challenging and has become a full topic. In this framework, numerous theoretical and phenomenological studies of these effects have been performed in the past, mainly by ICP-OES, while recent literature is more focused on applications and associated instrumental developments. This tutorial review, divided in two parts, explores the rich literature related to the introduction of organic/hydro-organic matrices in ICP-OES and ICP-MS. The present Part I, provides theoretical considerations in connection with the physico-chemical properties of organic/hydro-organic matrices, in order to better understand the induced phenomena. This focal point is divided in four chapters highlighting: (i) the impact of organic/hydro-organic matrices from aerosol generation to atomization/excitation/ionization processes; (ii) the production of carbon molecular constituents and their spatial distribution in the plasma with respect to analytes repartition; (iii) the subsequent modifications of plasma fundamental properties; and (iv) the resulting spectroscopic and non spectroscopic interferences. This first part of this tutorial review is addressed either to beginners or to more experienced scientists who are interested in the analysis of organic/hydro-organic matrices by ICP sources and would like to consider the theoretical background of effects induced by such matrices.
The second part of this tutorial review will be dedicated to more practical consideration on instrumentation, such as adapted introductions devices, as well as instrumental and operating parameters optimization. The analytical strategies for elemental quantification in such matrices will also be addressed.
Precise isotopic and elemental characterization of spent nuclear fuel is a major concern for the validation of the neutronic calculation codes and waste management strategy in the nuclear industry. ...Generally, the elements of interest, particularly U and Pu which are the two major elements present in spent fuel, are purified by ion exchange or extractant resins before off-line measurements by thermal ionization mass spectrometry. The aim of the present work was to develop a new analytical approach based on capillary electrophoresis (CE) hyphenated to a multicollector inductively coupled plasma mass spectrometer (MC-ICPMS) for online isotope ratio measurements. An electrophoretic separation protocol of U, Pu, and the fraction containing fission products and minor actinides (Am and Cm) was developed using acetic acid as the electrolyte and complexing agent. The instrumentation for CE was designed to be used in a glovebox, and a laboratory-built interface was developed for hyphenation with MC-ICPMS. The separation was realized with only a few nL of a solution of spent nuclear fuel, and the reproducibilities obtained on the U and Pu isotope ratios were on the order of a few ‰ which is comparable to those obtained by thermal ionization mass spectrometry (TIMS). This innovative protocol allowed a tremendous reduction of the analyte masses from μg to ng and also a drastic reduction of the liquid waste production from mL to μL. In addition, the time of analysis was shorted by at least a factor of three. All of these improved parameters are of major interest for nuclear applications.
Capillary electrophoresis (CE) was hyphenated to multi-collector inductively coupled plasma mass spectrometry (MC-ICP-MS) to determine the model age of a highly enriched uranium (HEU) sample using ...the 234U/230Th radiochronometer. The use of hydroxymethylbutyric acid (HMBA) as the CE electrolyte was investigated, and a complexation stacking method was developed to increase the thorium signal obtained. The age of the material was determined by measuring the 230Th content of the HEU sample using isotope dilution in conjunction with the CE-MC-ICP-MS protocol. The CE-MC-ICP-MS protocol and a standard offline protocol using gravitational chromatography both gave results in accordance within uncertainties with the production date of the HEU sample (March 1965). Liquid waste production was only of a few microliters with the use of CE. The hyphenation of CE with MC-ICP-MS render the measurement of the age of the HEU material in less than one day possible. Obtaining results in a timely fashion is of particular importance for nuclear forensics studies.
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•A capillary electrophoresis separation of uranium and thorium was developed.•The thorium signal was increased with the use of a novel stacking method.•Capillary electrophoresis was hyphenated online with a MC-ICP-MS.•The model-age of a highly enriched uranium sample was determined with the method.•The uncertainty on the age of the uranium sample was in the percent range.
The analysis of radionuclides (RN) is of major concern in different fields like the environment, geosciences, the nuclear industry, and medical research. Inductively coupled plasma mass spectrometry ...(ICP-MS) is a valuable technique for rapid and highly sensitive analysis of RN in different types of samples. Incorporating collision-reaction cells (CRC) into ICP-MS instruments is a very attractive and elegant way to overcome spectral interferences, which affects the accuracy of measurements. This paper reviews the elemental and isotopic analysis of RN using CRC technology for different types of applications including environmental studies, the nuclear industry, forensics and biological applications. The various collision-reaction cell technologies implanted in the ICP-MS instruments, are described and discussed. The different strategies based on collision-reaction mechanisms for RN analysis described in the literature are detailed element by element, including actinides (U, Pu, Am, Cm and Np), fission products (Se, Sr, Mo, Zr, I, Cs, lanthanides) and a decay product of the uranium series (Ra).
This article reviews the elemental and isotopic analysis of radionuclides using collision-reaction cell technology in ICP-MS applications.
Online monitoring or in-situ isotopic analysis techniques in extreme environments are strategic tools in nuclear industry. A new optical method for performing isotopic analysis in solid samples at ...ambient pressure has been developed: Laser-Induced Breakdown self-Reversal Isotopic Spectrometry (LIBRIS). This method uses self-absorption of atomic or ionic resonance lines that are emitted from a non-uniform laser-induced plasma. It takes advantage of the fact that the spectral width of the absorption dip is much smaller than the spectral width of the emission line profile. Isotopic measurements were carried out on lithium samples by measuring the spectral position of the absorption dip that is shown to have a linear dependence on the 6Li isotopic abundance. Stand-off and real-time analysis can be performed without any sample preparation or pre-treatment. The effect of the laser wavelength, of the ambient gas and of the gate delay is investigated. Optimum conditions lead to a relative uncertainty of about 6% on the isotopic abundance measurement of 6Li. The influence of the spectral shifts due to Stark and Doppler effects on the performance of LIBRIS are discussed.
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•Laser Induced self-Reversal Isotopic Spectrometry (LIBRIS) is introduced for fast isotopic analysis at ambient pressure.•The wavelength of the absorption dip of a self-reversed line is linearly correlated with the isotopic abundance.•Optimized experimental conditions lead to a relative uncertainty of about 6% on the isotopic abundance of 6Li.
This tutorial review is dedicated to the analysis of organic/hydro-organic matrices by ICP techniques. A state-of-the-art focusing on sample introduction, relevant operating parameters optimization ...and analytical strategies for elemental quantification is provided.
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•Practical considerations to perform analyses in organic/hydro-organic matrices.•Description, benefits and drawbacks of recent introduction devices.•Optimization to improve plasma tolerance towards organic/hydro-organic matrices.•Analytical strategies for elemental quantification in organic/hydro-organic matrices.
Inductively coupled plasma optical emission spectrometry (ICP-OES) and mass spectrometry (ICP-MS) are increasingly used to carry out analyses in organic/hydro-organic matrices. The introduction of such matrices into ICP sources is particularly challenging and can be the cause of numerous drawbacks. This tutorial review, divided in two parts, explores the rich literature related to the introduction of organic/hydro-organic matrices in ICP sources. Part I provided theoretical considerations associated with the physico-chemical properties of such matrices, in an attempt to understand the induced phenomena. Part II of this tutorial review is dedicated to more practical considerations on instrumentation, instrumental and operating parameters, as well as analytical strategies for elemental quantification in such matrices.
Two important issues are addressed in this part: the first concerns the instrumentation and optimization of instrumental and operating parameters, pointing out (i) the description, benefits and drawbacks of different kinds of nebulization and desolvation devices and the impact of more specific instrumental parameters such as the injector characteristics and the material used for the cone; and, (ii) the optimization of operating parameters, for both ICP-OES and ICP-MS. Even if it is at the margin of this tutorial review, Electrothermal Vaporization and Laser Ablation will also be shortly described. The second issue is devoted to the analytical strategies for elemental quantification in such matrices, with particular insight into the isotope dilution technique, particularly used in speciation analysis by ICP-coupled separation techniques.
The high-precision isotopic characterization of actinides and fission products in nuclear samples is fundamental for various applications such as the management of spent nuclear fuel or the ...validation of neutronic calculation codes. However multi-elemental isotope ratio measurements by mass spectrometric techniques are hampered by the presence of both spectral and non-spectral interferences as complex sample matrices are encountered in such topics, but also due to the lack of high precision mass spectrometers able to cover the entire mass spectrum. This work describes a new LC-MC-ICPMS approach allowing simultaneous high-precision and multi-elemental isotope ratio measurements of four fission products of interest for nuclear issues (Nd, Sm, Eu, Gd) within a single elution run. Variable motorized Faraday cup configurations were successively used during a specifically designed elution procedure in order to take into account the non-natural Nd, Sm, Eu, Gd isotopic compositions encountered in irradiated nuclear samples. This new method, involving the relevant isotopic reference standard injection timings for on-line mass bias corrections, was validated by the analysis of a simulated fission product fraction from a 235U-irradiated target. Reproducibilities better than 2‰ (k=2), comparable to those obtained by off-line measurements and the classic sample-standard bracketing mass bias correction approach, were obtained for all isotope ratios, except those involving isotopes with a transient signal peak apex lower than 100mV, for which the reproducibilities were comprised between 2‰ and 6‰.
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•New hyphenated method between LC and MC-ICPMS.•Multi-elemental isotopic measurements by cup configuration switch during LC elution.•High precision isotopic measurements in nuclear fuel samples.•Comparison of data treatment methods for transient signals.
Accurate measurements of neodymium isotope ratios in irradiated nuclear fuel samples are fundamental for the validation of neutronic calculation codes, in particular for burn-up qualification. To ...prevent possible spectral and non-spectral interferences, neodymium is generally purified from the complex sample matrices prior to measurements by mass spectrometric techniques. This work describes the on-line coupling of ion exchange chromatography with multi-collector inductively coupled plasma mass spectrometry for Nd isotope ratio measurements. In the first part of the paper, the causes of the isotope ratio drifts traditionally observed during transient signal acquisitions are investigated. Both mass-dependent isotopic fractionation on the chromatographic column and distinct time lags between amplifier responses of the Faraday cup configuration were shown to be the main phenomena involved in the observed isotope ratio drifts. In the second part, we present a new approach for mass bias correction called “Intra Injection Sample-Standard Bracketing (IISSB)” based on direct “on-line” injection of the standard via the chromatographic system before and after the analyte. This new method, particularly adapted to analysis of nuclear materials, was validated by on-line measurements on a simulated sample representative of fission products present in an irradiated uranium material. Reproducibilities obtained by IISSB were found to be comparable with those found in off-line measurements and classical sample-standard bracketing technique for mass bias correction on all Nd isotope ratios.
The low abundance cerium-144 radionuclide is one of the significant contributors to the decay heat from spent nuclear fuel for cooling times of less than ten years after nuclear reactor discharge. ...The accurate quantification of the 144Ce content (or 144Ce/238U) in irradiated nuclear fuel is necessary to validate and extend the neutronic calculation codes as well as to improve the short-term nuclear waste management strategies. In order to quantify the 144Ce/238U atomic ratios at low uncertainty, we developed a new analytical technique based on double spike isotope dilution associated with mass spectrometry. This includes (1) the chemical elimination of the major neodymium-144 isobaric interference by two steps of liquid chromatography prior to isotope analysis by Thermal Ionization Mass Spectrometry (TIMS) using both total evaporation and sequential methods, and (2) the preparation and use of an in-house double spike solution, using a mixture of a natural Ce solution with a 233U-enriched solution. This new approach was applied for the first time on two Mixed Oxide (MOx) spent nuclear fuel samples and allowed the determination of 144Ce/238U atomic ratios ranging from 35 × 10−6 to 59 × 10−6 with a relative expanded uncertainty of measurement of around 1% at a 95% confidence level.
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