RESUMO
The objective of this work was to develop an actinide-specific monolithic support in capillary designed to immobilize precise Pu:Am ratios and its coupling to inductively coupled plasma mass spectrometry (ICP-MS) for immobilized metal affinity chromatography applications. This format offers many advantages, such as reducing the sample amount and waste production, which are of prime importance when dealing with highly active radioelements. Four organic phosphorylated-based monoliths were synthesized in situ through UV photo-polymerization in capillary and characterized. The capillary coupling to ICP-MS was set up in conventional laboratory using Th and Sm as chemical analogues of Pu and Am. A dedicated method was developed to quantify online Th and Sm amounts immobilized on the monolithic capillaries, allowing to select the best monolith candidate poly(BMEP-co-EDMA)adp. By precisely adjusting the elemental composition in the loading solutions and applying the developed quantification method, the controlled immobilization of several Th:Sm molar ratios onto the monolith was successful. Finally, the capillary ICP-MS coupling was transposed in a glove box and by applying the strategy developed to design the monolithic support using Th and Sm, the immobilization of a 10.5 ± 0.2 (RSD = 2.3%, n = 3) Pu:Am molar ratio reflecting Pu ageing over 48 years was achieved in a controlled manner on poly(BMEP-co-EDMA)adp. Hence, the new affinity capillary monolithic support was validated, with only hundred nanograms or less of engaged radioelements and can be further exploited to precisely determine differential interactions of Pu and Am with targeted biomolecules in order to better anticipate the effect of Am on Pu biodistribution.
RESUMO
Achieving precise and accurate quantification of radium (226Ra) and cesium (137Cs) by inductively coupled plasma mass spectrometry (ICP-MS) is of particular interest in the field of radiological monitoring and more widely in environmental and biological sciences. However, the accuracy and sensitivity of the quantification depend on the analytical strategy implemented. Eliminating interferences during the sample handling step and/or during the analysis step is critical since presence of matrix elements can lead to spectral and non-spectral interferences in ICP-MS. Consequently, before the ICP-MS analysis, multiple sample preparation approaches have been applied to purify and/or pre-concentrate environmental and biological samples containing radium and cesium through years, such as (co)-precipitation, solid phase extraction (SPE) or dispersive SPE (dSPE). Separation steps using liquid chromatography and capillary electrophoresis can also be useful in complement with the abovementioned sample preparation techniques. The most attractive sample handling technique remains SPE but efficiency of the extraction procedures is currently limited by sorbent specificity. Indeed, with the recent advances in ICP-MS instrumentation, it becomes indispensable to eliminate residual interferences and improve sensitivity. It is in this direction that it will be possible to meet analytical challenges, e.g. analyzing radium and cesium at concentrations below the pg L-1 range in complex matrices of small volumes, as they are found for instance in pore waters or in biological samples. Development of new innovative sorbents based for example on hybrid and nanostructured materials has been reported with the aim of enhancing sorbent specificity and/or capacity. In the present review, the performances of the different analytical approaches are discussed, followed by an overview of applications.
