Grain-Scale Analysis of Solid-Phase Organic Matter and Arsenic Mobility in Mining-Impacted 1 Sediment from Sub‐Arctic Lakes, Northwest Territories, Canada

Arsenic (As) is commonly sequestered at the sediment-water interface (SWI) in mining-impacted lakes through adsorption and/or co-precipitation with authigenic iron (Fe)-(oxy)hydroxides or sulphides. The results of this study demonstrate that the accumulation of solid-phase organic matter (OM) in near-surface sediments also influences the mobility and fate of As in sub-Arctic lakes. Sediment gravity cores, sediment grab samples, and porewaters were collected from three lakes downstream of the former Tundra gold mine, Northwest Territories. Analysis of sediment using combined micro-X-ray fluorescence/diffraction, K-edge X-ray Absorption Near-Edge Structure (XANES), and organic petrography shows that As is associated with both aquatic (benthic and planktonic alginate) and terrestrially-derived OM (cutinite; funginite). Most As is hosted by fine-grained Fe-(oxy)hydroxides or sulphide minerals ( e.g., goethite, orpiment, lepidocrocite, mackinawite); however, grain-scale synchrotron-based analysis shows that As is also associated with amorphous OM. Mixed As oxidation states in porewater (median = 62 % As (V), 18 % As (III); n = 20) and sediment (median = 80 % As (-I) and (III), 19 % As (V); n = 9) indicate the presence of variable redox conditions in the near-surface sediment and suggest that post-depositional remobilization of As has occurred . Detailed characterization of As-bearing OM at and below the SWI suggests that OM plays an important role in stabilizing redox-sensitive authigenic minerals and associated As. Based on these findings, it is expected that increased concentrations of labile OM will drive post-depositional surface-enrichment of As in mining-impacted lakes and may increase or decrease As flux from sediments to overlying surface waters.