Post-depositional redistribution of trace metals in reservoir sediments of a mining/smelting-impacted watershed (the Lot River, SW France)

Mining/smelting wastes and reservoir sediment cores from the Lot River watershed were studied using mineralogical (XRD, SEM-EDS, EMPA) and geochemical (redox dynamics, selective extractions) approaches to characterize the main carrier phases of trace metals. These two approaches permitted determining the role of post-depositional redistribution processes in sediments and their effects on the fate and mobility of trace metals. The mining/smelting wastes showed heterogeneous mineral compositions with highly variable contents of trace metals. The main trace metal-bearing phases include spinels affected by secondary processes, silicates and sulfates. The results indicate a clear change in the chemical partitioning of trace metals between the reservoir sediments upstream and downstream of the mining/smelting activities, with the downstream sediments showing a 2-fold to 5-fold greater contribution of the oxidizable fraction. This increase was ascribed to stronger post-depositional redistribution of trace metals related to intense early diagenetic processes, including dissolution of trace metal-bearing phases and precipitation of authigenic sulfide phases through organic matter (OM) mineralization. This redistribution is due to high inputs (derived from mining/smelting waste weathering) at the water-sediment interface of (i) dissolved SO4 promoting more efficient OM mineralization, and (ii) highly reactive trace metal-bearing particles. As a result, the main trace metal-bearing phases in the downstream sediments are represented by Zn- and Fe-sulfides, with minor occurrence of detrital zincian spinels, sulfates and Fe-oxyhydroxides. Sequestration of trace metals in sulfides at depth in reservoir sediments does not represent long term sequestration owing to possible resuspension of anoxic sediments by natural (floods) and/or anthropogenic (dredging, dam flush) events that might promote trace metal mobilization through sulfide oxidation. It is estimated that, during a major flood event, about 870 t of Zn, 18 t of Cd, 25 t of Pb and 17 t of Cu could be mobilized from the downstream reservoir sediments along the Lot River by resuspension-induced oxidation of sulfide phases. These amounts are equivalent to 13-fold (Cd), ∼6-fold (Zn), 4-fold (Pb) the mean annual inputs of the respective dissolved trace metals into the Gironde estuary.