Anthony Nonell

Introduction of organic/hydro-organic matrices in inductively coupled plasma optical emission spectrometry and mass spectrometry: A tutorial review. Part II. Practical considerations

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.

Multi-elemental Gd, Eu, Sm, Nd isotope ratio measurements by liquid chromatography coupled to MC-ICPMS with variable Faraday cup configurations during elution

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‰.

Simple separation and characterization of lanthanide–polyaminocarboxylic acid complexes by HILIC ESI-MS

The separation and characterization of lanthanide (Ln) complexes bearing ethylenediaminetetraacetic acid (EDTA) and diethylenetriaminepentaacetic acid (DTPA), species of concern in advanced nuclear fuel treatment processes, were investigated by hydrophilic interaction liquid chromatography (HILIC) coupled with electrospray ionization mass spectrometry (ESI-MS). Selectivity properties of stationary phases with different polar functions (cross-linked diol, cyano, zwitterionic and amide) towards the Ln (Er, Eu, Gd, Nd)–EDTA/DTPA complexes were assessed. Only amide bonded stationary phases allowed simple separation of the complexes in isocratic mode, while the other stationary phases did not provide sufficient selectivity, leading to the co-elution of the complexes whatever the mobile phase composition. The chromatographic properties of two amide-based columns with different surface characteristics (XBridge and TSK Gel) were probed with a set of lanthanide complexes under identical conditions. The column giving the best performances was selected for further retention mechanism study. The effect of several parameters, such as the acetonitrile (ACN) content (40–80%) and ammonium acetate concentration (5–20 mmol L−1) was studied on the retention of the lanthanide complexes. The results showed that electrostatic interactions did not significantly affect their elution, while the adsorption mechanism was found to be predominant for ACN percentages higher than 55%. In the final step, faster HPLC conditions were applied by using an amide column packed with sub-2 μm particles (Acquity). More efficient separation of the lanthanide complexes, and decreases in analysis time, solvent consumption and generated effluent volumes, were obtained. Such an approach could lead to the development of greener analytical methods than conventional chromatographic separations, which is of prime concern for the study of radioactive samples.

A new procedure for high precision isotope ratio determinations of U, Cu and Zn at nanogram levels in cultured human cells: What are the limiting factors?

The monitoring of isotopic fractionations in in vitro cultured human cell samples is a very promising and under-exploited tool to help identify the metabolic processes leading to disease-induced isotopic fractionations or decipher metabolic pathways of toxic metals in these samples. One of the limitations is that the analytes are often present at small amounts, ranging from tens to hundreds of ng, thus making challenging low-uncertainty isotope ratio determinations. Here we present a new procedure for U, Cu and Zn purification and isotope ratio determinations in cultured human neuron-like cells exposed to natural U. A thorough study of the influence of the limiting factors impacting the uncertainty of δ238U, δ66Zn and δ65Cu is also carried out. These factors include the signal intensity, which determines the within-day measurement reproducibility, the procedural blank correction and the matrix effects, which determine the accuracy of the mass bias correction models. Given the small Cu and U amounts in the cell samples, 15-30 and 20ng respectively, a highly efficient sample introduction system was employed in order to improve the analyte transport to the plasma and, hence, the signal intensity. With this device, the procedural blanks became the main uncertainty source of δ238U and δ65Cu values, accounting over 65% of the overall uncertainty. The matrix effects gave rise to inaccuracies in the mass bias correction models for samples finally dissolved in the minimal volumes required for the analysis, 100-150µL, leading to biases for U and Cu. We will show how these biases can be cancelled out by dissolving the samples in volumes of at least 300µL for Cu and 450µL for U. Using our procedure, expanded uncertainties (k = 2) of around 0.35‰ for δ238U and 0.15‰ for δ66Zn and δ65Cu could be obtained. The analytical approach presented in this work is also applicable to other biological microsamples and can be extended to other elements and applications.

Accurate measurements of 129I concentration by isotope dilution using MC-ICPMS for half-life determination

Abstract Determining the 129I concentration, a long-lived radionuclide present in spent nuclear fuel, is a major issue for nuclear waste disposal purpose. 129I also has to be measured in numerous environmental, nuclear and biological samples. To be able to accurately determine the 129I concentration, an analytical method based on the use of a multicollector-inductively coupled plasma mass spectrometer (MC-ICPMS) combined with an isotope dilution technique using an 127I spike, was developed. First, the influence of different media (HNO3, NaOH and TMAH) on natural 127I signal intensity and stability and on memory effects was studied. Then an analytical procedure was developed by taking into account the correction of blanks and interferences. Tellurium was chosen for instrumental mass bias correction, as no certified standards with suitable 127I/129I ratio are available. Finally, the results, reproducibility and uncertainties obtained for the 129I concentration determined by isotope dilution with a 127I spike are presented and discussed. The final expanded relative uncertainty obtained for the iodine-129 concentration was lower than 0.7% (ku2009=u20091). This precise 129I determination in association with further activity measurements of this nuclide on the same sample will render it possible to determine a new value of the 129I half-life with a reduced uncertainty (0.76%, ku2009=u20091).

Multi-elemental Nd, Sm, Eu, Gd isotope ratio measurements by stop-flow isotachophoresis coupled to MC-ICPMS

In this study, a new analytical procedure based on isotachophoresis (ITP) coupled to a multi collector inductively coupled plasma mass spectrometer named Stop-Flow-ITP-MC-ICPMS is developed for exhaustive and high-precision multi-elemental isotopic characterization. We demonstrate that Stop-Flow-ITP makes it possible to stop the analytes migration several times for a duration compatible with the detector configuration changes without losing the separation performance. With this procedure, isotope ratio measurements of four lanthanides of interest for nuclear applications (Nd, Sm, Eu and Gd) were obtained with a reproducibility better than 0.4% in a single analysis with only 20ng of each element. A nebulization interface between ITP and MC-ICPMS composed of a dual inlet spray chamber and a multiple flow stream valve made it possible to perform isotopic reference standard injections for on-line mass bias correction by the sample standard bracketing approach. The flexibility of the Stop-Flow-ITP-MC-ICPMS procedure opens the way to online determination of isotope ratio measurements of multiple analytes present in a sample in a single analysis.

Evaluation of superficially and fully porous particles for HILIC separation of lanthanide–polyaminocarboxylic species and simultaneous coupling to ESIMS and ICPMS

In this work, amide-bonded columns packed with fully porous particles (FPP) and superficially porous particles (SPP) were evaluated to separate lanthanide–polyaminocarboxylic species by hydrophilic interaction liquid chromatography (HILIC), using two model samples of interest in nuclear and other industrial applications. We assessed the gains achieved by reducing the dimensions of the columns along with the size of the FPPs to sub-2 μm and by using sub-3 μm SPP-packed columns. The FPP-packed Acquity column (100 × 2.1 mm; 1.7 μm) performed better than the SPP-packed Accucore column (150 × 2.1 mm; 2.6 μm), with a separation that was two times more efficient and three times shorter, while generating around 30% less in effluent volumes. This column was also coupled simultaneously to electrospray ionisation mass spectrometry (ESIMS) and inductively coupled plasma mass spectrometry (ICPMS). The instrumental set-up was performed in a conventional laboratory, by taking into account the geometrical constraints existing in the laboratory dedicated to radioelement analysis. Furthermore, separation of the series of lanthanide (Ln) species was demonstrated for the first time thanks to the separation mode of hydrophilic interaction liquid chromatography.

The half-life of 129I

The radionuclide 129I is a long-lived fission product that decays to 129Xe by beta-particle emission. It is an important tracer in geological and biological processes and is considered one of the most important radionuclides to be assessed in studies of global circulation. It is also one of the major contributors to radiation dose from nuclear waste in a deep geological repository. Its half-life has been obtained by a combination of activity and mass concentration measurements in the frame of a cooperation of 6 European metrology institutes. The value obtained for the half-life of 129I is 16.14 (12) ×u202f106 a, in good agreement with recommended data but with a significant improvement in the uncertainty.

Precise U and Pu isotope ratio measurements in nuclear samples by hyphenating capillary electrophoresis and MC-ICPMS

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.

Neodymium isotope ratio measurements by CE-MC-ICPMS: investigation of isotopic fractionation and evaluation of analytical performances

Precise isotope ratio measurements in the nuclear field often require hyphenation of separation techniques with multicollector inductively coupled plasma mass spectrometry (MC-ICPMS). Among these separation techniques, electrokinetic methods are very interesting as they use the lowest sample volumes and produce the least amount of radioactive waste. The objectives of this study were to evaluate the performances when coupling electrokinetic techniques with MC-ICPMS for measuring isotope ratios of Nd, an element of interest for nuclear purposes. During data acquisition along the elution peak, an isotope ratio drift was observed and studied. In order to discriminate the drift induced by the MC-ICPMS detectors, the raw data of the isotope signals were corrected by taking into account the difference of time response of the Faraday cup amplifiers. An isotopic mass-dependent fractionation induced by the electrokinetic separation was then highlighted. Some of the parameters were modified (i.e., the length of the capillary and the external pressure) to evaluate their impact on the amplitude of fractionation. Finally, the measurement performances were evaluated for all the isotope ratios. The reproducibility obtained was lower than 0.2‰ regardless of the considered Nd isotope ratio with only 0.5 ng of injected Nd.