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.

Aqueous thiolated arsenic (As) species play an important role in the biogeochemical cycling of As in wetlands and hydrothermal systems. Although mine wastes such as tailings ponds and waste rock piles may harbor similarly sub-oxic and neutral to alkaline conditions that favor the formation and mobility of thio-As species, quantitative data on their existence in these systems is lacking. We conducted laboratory column experiments under contrasting redox conditions with waste rock from the Antamina mine, Peru, and processed tailings from Montague, Nova Scotia, Canada. Dissolved As concentrations between 1-7000 µg/L were recorded in drainages across these mine waste types, with up to 13 µg/L As present in thiolated form, predominantly monothioarsenate. Higher percentages of thio-As species (up to 5%) were observed in drainages from enargite-rich materials compared to arsenopyrite-bearing materials (<0.5%). The lower abundance of dissolved thio-As in the arsenopyrite-rich mine waste samples is attributed to their partially oxidized nature and reduced mineral reactivity under the experimental circumneutral drainage pH, as well as the oxidation of di- and tri-thiolated As species by dissolved Fe. Overall, our results demonstrate that aqueous thiolated As species may occur in mine wastes with different As-bearing minerals and could play an important role in governing the mobility and fate of As in these systems.