Species selective concentration and determination of nano-selenium and inorganic selenium species in environmental waters by micropore membrane filtration and ICP-MS.

Accurate quantification of nano-selenium (nSe) and other ionic Se species in aquatic environments is a prerequisite for reliable estimation of their potential hazards. In this study, a micropore membrane filtration-based method followed by ICP-MS analysis was proposed for the selective concentration and determination of nSe in the water column. Polyvinylidene fluoride (PVDF) and nylon micropore filtration membranes were proven to efficiently capture nSe under optimal conditions (retention > 91.0 ± 0.87%). At the same time, ionic selenite and selenate could escape from the membranes, realizing the isolation of nSe and ionic Se species. The interference of dissolved organic matter (DOM) during separation can be resolved by adding Ca(II) ions, which can induce the formation of DOM aggregates by cation bridging effects. nSe retained on PVDF membranes could be effectively eluted with FL-70 (a powerful alkaline surfactant) aqueous solutions (0.5%, m/v) while maintaining the original size and morphology. Although nSe trapped on nylon membranes could not be easily eluted, quantification can also be achieved after membrane digestion. Speciation of ionic selenite and selenate in the filtrate was further conducted with an anion exchange column by using HPLC coupled with ICP-MS. The developed method was used to analyze Se species in six real water samples. Spiking experiments showed that the recoveries of nSe ranged from 70.2 ± 2.7% to 85.8 ± 1.3% at a spike level of 0.2 µg/L, and the recoveries of Se(IV) and Se(VI) ranged from 83.6 ± 0.5% to 101 ± 1% at a spike level of 0.55 µg/L, verifying the feasibility for the analysis of environmental water samples. This work provides possibilities to investigate the transformation and potential risks of nSe in the environment.