Use of sequential extraction and mercury stable isotope analysis to assess remobilization of sediment-bound legacy mercury

The goal of this project was to assess how anthropogenic legacy mercury (Hg) retained in streambed sediment may be remobilized to stream water. To do this, we performed sequential extractions and Hg isotope analyses on streambed sediment collected along the length of East Fork Poplar Creek, a point-source contaminated stream in Oak Ridge, Tennessee, USA. Legacy Hg within streambed sediment appears to have been isotopically fractionated by equilibrium isotope effects driven by isotope exchange between co-existing Hg(0) and Hg(ii) species, potentially over-printing fractionation patterns that would have been imparted by kinetic redox reactions. Weakly-bound and recalcitrant sediment Hg pools were isotopically similar to one another, suggesting that small amounts of recalcitrant Hg may be released and then rapidly and weakly re-adsorbed onto the sediment. This weakly-bound Hg pool appears to contribute dissolved Hg to the hyporheic pore water, which may subsequently enter the surface flow. The isotopic composition of the organically-bound sediment Hg pools, as well as biofilm and suspended particulates, converged with that of the weakly-bound and recalcitrant sediment Hg pools along the flow path. This appears to be indicative of both physical mixing with streambed sediment and the transfer of weakly-bound sediment Hg into biofilm and suspended particulates, followed by re-incorporation into the organically-bound sediment Hg pool. Overall, these results provide evidence that legacy Hg in the streambed is remobilized, enters the stream water as dissolved Hg, and may be incorporated into streambed biofilm, which constitutes a basal resource within the stream ecosystem.