Mechanistic insights into a novel nitrilotriacetic acid-Fe⁰ and CaO₂ process for efficient anaerobic digestion sludge dewatering at near-neutral pH

Traditional Fenton or Fenton-like oxidation has been widely studied for waste activated sludge dewaterability. However, the narrow pH range (2.0–4.0) and the instabilities of Fe²⁺ and H₂O₂ have hindered its commercial application. Owing to the high alkalinity of anaerobic digestion (AD) sludge, traditional Fenton or Fenton-like oxidation is economically unfeasible for its dewatering. In this study, we successfully demonstrated a novel and feasible method that used nitrilotriacetic acid (NTA)-Fe⁰ combined with CaO₂ (NTA-Fe⁰/CaO₂) at near-neutral pH (∼6.0) (a slight pH adjustment) in which capillary suction time ratio (CST₀/CST) and centrifuged weight reduction (CWR) improved by 6 folds and 42.98 ± 0.37%, respectively, under the optimal conditions. The presence of NTA accelerated the Fe⁰ corrosion, Fe²⁺ stability and turnover between Fe²⁺ and Fe³⁺. As such, Fe⁰ could effectively catalyze CaO₂ to produce hydroxyl radicals (•OH) under near-neutral conditions. Accordingly, various molecular weight hydrophilic compounds in different extracellular polymeric substances fractions were significantly reduced after treatment. The hydrophilic functional groups especially protein molecules were largely reduced. Consequently, the viscosity of sludge and particle size effectively decreased, while the release of bound water, surface charge, flocculation, and flowability of sludge were improved. The cost-benefit analysis further demonstrated the NTA-Fe⁰/CaO₂ treatment has high reusability and stability and is also more economical over the FeCl₃/CaO and Fenton's reagent/CaO treatments. In summary, the NTA-Fe⁰/CaO₂ process is a cost-effective and practically feasible technology for improving AD sludge dewaterability.