Sulfur Species, Bonding Environment, and Metal Mobilization in Mining-Impacted Lake Sediments: Column Experiments Replicating Seasonal Anoxia and Deposition of Algal Detritus

The oxidation state of sulfur [S] is a primary control on mobility of metals in sediments impacted by legacy mining practices. Coeur d’Alene Lake of northern Idaho, USA, has been impacted by upstream legacy mining practices that deposited an estimated 75 Mt of metal(loid)- and S-rich sediments into the lake. Future lake conditions are expected to include algal blooms, which may alter S and metal remobilization during the seasonal euxinic environment. Cores of the lake sediments were exposed to anoxic and anoxic + algal detritus conditions for eight weeks at 4.5 °C through introduction of a N2 atmosphere and addition of algal detritus. At a location 2.5 cm below the sediment-water interface, anoxic conditions promoted a shift in S species to continually larger concentrations of reduced species and an associated shift in the bonding environment reflective of increased S–metal bonds. Anoxic + algal detritus conditions suppressed the increasing trend of reduced S species and induced greater release of Mn compared to the anoxic-only conditions but did not appear to enhance the release of As, Cd, or Fe. The addition of algal detritus to the sediment-water interface of these Fe- and S-rich sediments enhanced mobilization of Mn likely because of dissimilatory metal reduction where the anaerobic oxidation of the algal detritus stimulated Mn reduction. Results of the study indicate that future metal release from the lake sediments will be altered with the likely deposition of algal detritus, but the effect may not enhance the release of acutely toxic metals, such as As or Cd, or substantially impact Fe cycling in the sediments