Dans ce travail, des méthodes d’analyses de spéciation exhaustive de lanthanides (Ln), en présence d'acides polyaminocarboxyliques (EDTA, DTPA) utilisés comme agents de desextraction dans les procédés de traitement de combustibles nucléaires usés, ont été développées par couplage simultané HILIC-ESIMS/ICPMS. Pour réduire les volumes d’effluents chromatographiques tout en maintenant des séparations efficaces et rapides, les performances de colonnes remplies de particules entièrement poreuses (FPP) et de particules superficiellement poreuses (SPP) ont été évaluées, aboutissant à la sélection de la technologie FPP de diamètre sub-2-µm. Selon la composition des échantillons, le couplage HILIC-ESIMS peut s'avérer suffisant pour des études de spéciation exhaustive, nécessitant l'évaluation du potentiel de l'ESIMS pour la mesure de composition isotopique d'éléments. Des méthodes de mesure de rapports isotopiques du natSm complexé à l'EDTA ont alors été développées avec deux types d’ESIMS, en introduisant directement l'échantillon. Une méthode de déconvolution a ensuite été développée pour déterminer les rapports isotopiques du natSm. L'approche a été validée avec un complexe de Sm enrichi en 147Sm et 149Sm. L'étape ultérieure a consisté à déterminer les rapports isotopiques du Sm avec le couplage simultané, en appliquant plusieurs méthodes de traitements de signaux transitoires. Des méthodes de quantification par étalonnage externe et par dilution isotopique spécifique ont été ensuite développées avec ce même complexe. Les développements réalisés avec le Sm pourront être étendus à d'autres lanthanides et aux actinides. / In this work, analysis methods of lanthanide (Ln) comprehensive speciation, in the presence of polyaminocarboxylic acids (EDTA, DTPA) used as back extraction agents in spent nuclear fuel treatment processes, were developed by simultaneous coupling HILIC-ESIMS/ICPMS. To reduce chromatographic effluent volumes while maintaining efficient and rapid separations, the performances of columns packed with fully porous particles (FPP) and superficially porous particles (SPP) were evaluated, resulting in the selection of the sub-2-µm FPP technology. Depending on the sample composition, HILIC-ESIMS coupling may be sufficient for comprehensive speciation studies, requiring assessment of the ESIMS potential for isotopic composition measurement of elements. The isotopic ratio measurement methods of natSm complexed with EDTA were then developed with two types of ESIMS, directly introducing the sample. A deconvolution method was then developed to determine the natSm isotope ratios. The approach was validated with Sm complex enriched in 147Sm and 149Sm. The next step was to determine the Sm isotopic ratios with the simultaneous coupling, by applying several methods of transient signal processing. Quantification methods by external calibration and specific isotopic dilution were then developed with this same complex. The developments carried out with Sm may be extended to other lanthanides and actinides.

Essa dissertação de mestrado descreve o desenvolvimento de hardwares de colunas para cromatografia líquida capilar. O processo de desenvolvimentos desses dispositivos é descrito gradativamente e os pontos fortes e as limitações de cada modelo de hardware são discutidos. O melhor modelo de hardware desenvolvido apresentou produção simples, fácil conexão ao sistema cromatográfico e resistência a pressões superiores a 900 bar. Sucessivamente ao estabelecimento de um modelo de hardware apropriado, os efeitos dos materiais do hardware na eficiência das colunas foram avaliados. Poucos estudos relatam a influência do hardware nas separações em escala capilar, de forma que essa dissertação contribui para o preenchimento dessa lacuna. Capilares de aço inoxidável e sílica fundida e frits de aço inoxidável e fibra de vidro foram avaliados. Colunas com eficiências superiores a 100.000 pratos por metro foram produzidas. / This master\'s dissertation describes the development of hardware for capillary liquid chromatography columns. The development process of the devices is described gradually and the strengths and limitations of each model of hardware are discussed. The best-developed hardware model presented easy production, practice connection to the chromatographic system and resistance to pressures greater than 900 bar. After the establishment of an appropriate hardware model, the effects of hardware materials on the efficiency of the columns were evaluated. Few studies report the influence of the hardware on capillary scale separations; therefore, this dissertation contributes to fill this gap. Capillaries of stainless steel and fused silica and frits of stainless steel and glass fiber were evaluated. Columns with efficiencies greater than 100,000 plates per meter were produced.

Essa dissertação de mestrado descreve o desenvolvimento de hardwares de colunas para cromatografia líquida capilar. O processo de desenvolvimentos desses dispositivos é descrito gradativamente e os pontos fortes e as limitações de cada modelo de hardware são discutidos. O melhor modelo de hardware desenvolvido apresentou produção simples, fácil conexão ao sistema cromatográfico e resistência a pressões superiores a 900 bar. Sucessivamente ao estabelecimento de um modelo de hardware apropriado, os efeitos dos materiais do hardware na eficiência das colunas foram avaliados. Poucos estudos relatam a influência do hardware nas separações em escala capilar, de forma que essa dissertação contribui para o preenchimento dessa lacuna. Capilares de aço inoxidável e sílica fundida e frits de aço inoxidável e fibra de vidro foram avaliados. Colunas com eficiências superiores a 100.000 pratos por metro foram produzidas. / This master\'s dissertation describes the development of hardware for capillary liquid chromatography columns. The development process of the devices is described gradually and the strengths and limitations of each model of hardware are discussed. The best-developed hardware model presented easy production, practice connection to the chromatographic system and resistance to pressures greater than 900 bar. After the establishment of an appropriate hardware model, the effects of hardware materials on the efficiency of the columns were evaluated. Few studies report the influence of the hardware on capillary scale separations; therefore, this dissertation contributes to fill this gap. Capillaries of stainless steel and fused silica and frits of stainless steel and glass fiber were evaluated. Columns with efficiencies greater than 100,000 plates per meter were produced.