On-line solid phase extraction CZE for the simultaneous determination of lanthanum and gadolinium at picogram per liter levels

A non-specific on-line method is presented for the extraction and preconcentration of two rare earth elements using a microcartridge containing C18-derivatized silica particles prior to their analysis by CZE. The microcartridge, named analyte concentrator, was coupled on-line to the inlet of the separation capillary (fused-silica (FS) capillary, 75 mm id x 12 cm from the inlet to the microcartidge and 37 cm from the microcartridge to the detector). The reversed-phase sorbent quantitatively retained gadolinium (Gd) and lanthanum (La) as 2-(5-bromo-2-pyridylazo)-5-diethylaminophenol complexes in the presence of non-ionic micelles of polyethylene glycol tert-octylphenyl ether, enabling sample clean-up and concentration enhancement with minimum sample handling. The rare earth elements chelates were released from the sorbent with methanol and then analyzed by CZE with diode array detection. A background electrolyte of 20 mM sodium tetraborate containing 8% ACN, pH 9.0, was found to be optimal for the separation of metal chelates. The concentration limits of detection were lowered to picogram per liter levels (20 pg/L for La and 80 pg/L for Gd). A 1000-fold improvement in concentration sensitivity for La- and Gd-2-(5-bromo-2-pyridylazo)-5-diethylaminophenol complexes with respect to CZE without preconcentration was reached.Fil: Vizioli, Nora Matilde. Consejo Nacional de Investigaciones Científicas y Técnicas; Argentina. Universidad de Buenos Aires; ArgentinaFil: Gil, Raul Andres. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - San Luis. Instituto de Química de San Luis. Universidad Nacional de San Luis. Facultad de Química, Bioquímica y Farmacia. Instituto de Química de San Luis; ArgentinaFil: Martinez, Luis Dante. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - San Luis. Instituto de Química de San Luis. Universidad Nacional de San Luis. Facultad de Química, Bioquímica y Farmacia. Instituto de Química de San Luis; ArgentinaFil: Silva, María Fernanda. Universidad Nacional de Cuyo. Facultad de Ciencias Agrarias; Argentina. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Mendoza; Argentin