Cascading sulfur cycling in simulated oil sands pit lake water cap mesocosms transitioning from oxic to euxinic conditions

Base Mine Lake (BML), the first full-scale demonstration of oil sands tailings pit lake reclamation technology, is experiencing expansive, episodic hypolimnetic euxinia resulting in greater sulfur biogeochemical cycling within the water cap. Here, Fluid Fine Tailings (FFT)-water mesocosm experiments simulating the in situ BML summer hypolimnetic oxic-euxinic transition determined sulfur biogeochemical processes and their controlling factors. While mesocosm water caps without FFT amendments experienced limited geochemical and microbial changes during the experimental period, FFT-amended mesocosm water caps evidenced three successive stages of S speciation in ∼30 days: (S1) rising expansion of water cap euxinia from FFT to water surface; enabling (S2) rapid sulfate (SO₄^2-) reduction and sulfide production directly within the water column; fostering (S3) generation and subsequent consumption of sulfur oxidation intermediate compounds (SOI). Identified key SOI, elemental S and thiosulfate, support subsequent SOI oxidation, reduction, and/or disproportionation processes in the system. Dominant water cap microbes shifted from methanotrophs and denitrifying/iron-reducing bacteria to functionally versatile sulfur-reducing bacteria (SRB) comprising sulfate-reducing bacteria (Desulfovibrionales) and SOI-reducing/disproportionating bacteria (Campylobacterales and Desulfobulbales). The observed microbial shift is driven by decreasing [SO₄^2-] and organic aromaticity, with putative hydrocarbon-degrading bacteria providing electron donors for SRB. Comparison between unsterile and sterile water treatments further underscores the biogeochemical readiness of the in situ water cap to enhance oxidant depletion, euxinia expansion and establishment of water cap SRB communities aided by FFT migration of anaerobes. Results here identify the collective influence of FFT and water cap microbial communities on water cap euxinia expansion associated with sequential S reactions that are controlled by concentrations of oxidants, labile organic substrates and S species. This emphasizes the necessity of understanding this complex S cycling in assessing BML water cap O₂ persistence.