Fluctuating redox conditions accelerate the electron storage and transfer in magnetite and production of dark hydroxyl radicals.

Magnetite (Fe3O4), known as a geo-battery that can store and transfer electrons, often co-occurs with sulfide in subsurface environments with fluctuating redox conditions. However, little is known about how fluctuating redox conditions (e.g., sulfidation-oxidation) affect the electron storage and transfer in Fe3O4 that was associated with the production of dark hydroxyl radicals (⋅OH) and the oxidation of dissolved organic matter (DOM). This study revealed that Fe3O4 sulfidated by sulfide (S-Fe3O4) at neutral pH exhibited higher ⋅OH production upon oxygenation than Fe3O4, in which the cumulative ⋅OH concentration increased with increasing initial S/Fe ratio (≤ 0.50), sulfidation duration and number of sulfidation-oxidation cycle. X-ray photoelectron spectroscopy and wet-chemical analyses of Fe and S species of S-Fe3O4 showed that sulfidation enables electron storage in Fe3O4 by increasing both structural and surface Fe(II). Sulfide was converted into S0, acid volatile sulfur (AVS), and chromium-reducible sulfur (CRS) during Fe3O4 sulfidation. S-Fe3O4 with lower AVS/CRS ratio exhibited higher reactivity to produce ⋅OH, indicating the important role of CRS in transferring electrons from Fe(II) to O2. Based on quenching experiments and electron paramagnetic resonance analysis, a one-step two-electron transfer mechanism was proposed for O2 reduction during S-Fe3O4 oxygenation, and surface-bound rather than free ⋅OH were identified as the primary reactive oxygen species. The ⋅OH from S-Fe3O4 oxygenation was shown to be efficient in degradation of DOM. Overall, these results suggested that sulfidation-oxidation can accelerate the electron storage and transfer in Fe3O4 for dark ⋅OH production, having an important impact on the carbon cycling in subsurface environments.