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.

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%).