pH Dependence of Hydroxyl Radical, Ferryl, and/or Ferric Peroxo Species Generation in the Heterogeneous Fenton Process

The heterogeneous Fenton process in the presence of Fe-containing minerals is ubiquitous in nature and widely deployed in wastewater treatment. While there have been extensive relevant studies, the dependence on pH of the nature and extent of oxidant generation and key reaction pathways remain unclear. Herein, the adsorption and decomposition of formate and H₂O₂ were quantified in the presence of ferrihydrite within the pH range of 3.0-6.0, and experiments with methyl phenyl sulfoxide were conducted to distinguish between HO^• and weaker oxidant(s) which react via oxygen atom transfer including ferryl ion ([Fe^IVO]²⁺) and/or ferric hydroperoxo intermediates (≡Fe^III(O₂H)). Both HO^• and [Fe^IVO]²⁺/≡Fe^III(O₂H) are concurrently produced on the surface over the acidic to near-neutral pH range. Despite the simultaneous formation of both oxidants, HO^• is the major oxidant responsible for substrate oxidation in the interfacial boundary layer with [Fe^IVO]²⁺/≡Fe^III(O₂H) exhibiting limited exposure to substrates. With an increase of pH, the yield of both oxidants is inhibited by the decreasing availability of surface sites due to ferrihydrite particle aggregation. Increasing pH also favors the nonradical decay of H₂O₂ as evident from the consistent oxidant production rate relative to the surface area (SSA) despite an accelerated H₂O₂ decay rate relative to SSA with pH increase.