Anaerobic pyrite oxidation in a naturally occurring pyrite-rich sediment under preload surcharge

Pyrite undergoes oxidation when exposed to aqueous oxygen to produce acidic leachate with high concentrations of H⁺, SO₄^2-, and Fe³⁺. The oxidation mechanism is currently ascribed to contact between the mineral and aqueous oxygen. Consequently, management of acidic leachate from acid sulfate soils and acid mine drainage is focused on the prevention of contact between the sediment and aqueous oxygen through the surface. Intriguing though is the fact that in aquatic sediments, redox processes occur in sequence with the oxidizing agents. Among the common oxidants in aquatic sediments are O₂, [Formula: see text], Mn, and Fe, in the order of efficiency. Consequently, following the depletion of oxygen in pyrite-rich sediment, it would be expected that [Formula: see text], followed by Mn and then Fe, would continue the oxidation process. However, evidence of anaerobic pyrite oxidation in a naturally occurring pyrite-rich sediment is limited. Few studies have investigated the process in aquatic systems but mostly in laboratory experimental set ups. In this study, pyrite oxidation in a naturally occurring pyrite-rich sediment was investigated. A section of the sediment was covered with surface surcharge, in the form of compacted fill. The section of the sediment outside the surcharged area was preserved and used as control experiment. Solid phase soil and porewater samples were subjected to elemental, mineralogical, and microbial analyses. The results show excess accumulation of sulfate and sulfide in the anoxic zones of the original sediment and beneath the surcharge, accompanied by the disappearance of [Formula: see text], Mn, and Fe in the anoxic zones, indicating electron transfers between donors and acceptors, with pyrite as the most likely electron donor. The study outcome poses a significant challenge to the use of surface cover for the management of acidic leachate from pyrite oxidation, particularly, in areas rich in [Formula: see text], MnO^-₂, or Fe.