An automatic flow assembly for on-line dynamic fractionation of trace level concentrations of mercury in environmental solids with high organic load

A hybrid and compact flow system for automatic assessment of trace level concentrations of bioaccessible mercury in different phases of environmental solid samples with high organic load is described for the first time. It integrates dynamic sequential extraction with on-line digestion of the extracts and atomic fluorescence spectrometric detection of their total bioaccessible mercury concentration. Four extractants (i.e. deionized water, HNO₃ solution, KOH solution and solution containing both Na₂S and KOH) are applied sequentially to a solid sample packed in a column to release four bioaccessible Hg fractions (i.e. water soluble, exchangeable, organic matter associated, and sulphide bound Hg). Important advantages of the newly developed on-line method compared to its batch-wise counterpart include significant reduction in the time for acquisition of the dynamic extraction data (e.g. duration of 14 h versus 120 h for the batch-wise method), evaluation of the kinetics of release of the bioaccessible mercury fractions, and minimization of matrix interferences and potential re-adsorption of the extracted mercury species. The trueness of the method was assessed by applying it to two reference materials with relatively high organic matter content (river sediment AGAL-10 and biosoil AGAL-12). The sums of the Hg concentrations in the four bioaccessible fractions and the residual fraction of the two reference materials were found to differ from the corresponding certified values by only 1.8% and 3.8%, respectively. - Highlights: • An automatic sequential extraction procedure for Hg in complex solid samples. • It involves online digestion of non-labile Hg forms in the extracts. • S²⁻ is removed from the 4th fraction by acidification, oxidation and N₂ purging. • The procedure was validated with sediment and biosoil reference materials.