Fabrication of functional group-rich monoliths for magnetic field-assisted in-tube solid phase microextraction of inorganic selenium species in water samples followed by online chromatographic determination

Abstract

Efficient separation and enrichment is a crucial step in the analysis of Se(IV) and Se(VI). In the present study, for the first time, online monolith-based magnetic field-assisted in-tube solid phase microextraction (MFA/IT-SPME) was applied to capture inorganic selenium species in water samples. To this aim, porous monoliths mixed with magnetic nanoparticles were synthesized in a silica capillary and employed as a microextraction column (MEC) for MFA/IT-SPME. After that, a magnetic coil utilized to induce variable magnetic fields in adsorption and desorption steps was entwined around the MEC. Se(IV) was coordinated with o-phenylenediamine to form a coordination compound that was infused onto the MEC to be captured. Results evidenced that application of magnetic field during the extraction procedure assisted the capture of the Se(IV)–OPA complex, with an enhancement in the extraction efficiency from 83% to 97%. Under the optimized conditions, MFA/IT-SPME was online combined with HPLC equipped with a diode array detector (DAD) to perform quantification of Se(IV) and Se(VI) in environmental water samples. Total inorganic Se was quantified after pre-reduction of Se(VI) to Se(IV) prior to applying the established approach, and a subtraction method was adopted to calculate the Se(VI) and Se(IV) contents. The limit of detection for Se(IV) was as low as 0.012 μg L⁻¹. The reliability of the suggested method was investigated by assaying Se(IV) and Se(VI) species in real-life water samples with satisfactory recoveries (81.1%–116%) and repeatability (RSDs below 9%).