Mechanistic insights into Fe(II)-citric acid complex catalyzed CaO2 Fenton-like process for enhanced benzo[a]pyrene removal from black-odor sediment at circumneutral pH

Polycyclic aromatic hydrocarbons (PAHs) are found ubiquitously in contaminated aquatic sediments. They are difficult to degrade, particularly the high-molecular-weight PAHs (e.g., benzo[a]pyrene, BaP). In this study, CaO2 assisted with ferrous ion (Fe(II))-citric acid (CA) was applied for the first time in BaP degradation in aquatic sediment. Among the treatment processes we studied, CaO2/Fe(Ⅱ)/CA could effectively degrade BaP at circumneutral pH (7.0 ± 0.3), reaching a maximum of nearly 80% under optimal conditions (0.84 mM CaO2, 0.21 mM Fe(Ⅱ), and 0.35 mM CA in per gram of dry sediment). Contrary to some external environmental factors such as temperature, common metal ions, and natural organic matters, a certain amount of moisture content and inorganic anions (Cl-, SO42-) exhibited a positive effect on BaP degradation, which can probably be contributed to the improved mass transfer rate in the non-homogeneous sediment-water mixture and a higher level of free radicals. The degradation kinetic dominated by hydroxyl radicals included three main stages contribution ∼29.4%, ∼43.1%, and ∼2.4% to BaP degradation, respectively. Based on the theoretical calculations of density functional theory, a pathway for BaP degradation was proposed. For the treatment of actual contaminated sediment, the CaO2/Fe(II)/CA process could realize the elimination of black-odor and effective removal of PAHs from the sediment, as well as negligible ecotoxicity on benthic organisms. This study provides a reference and guidance for the use of CaO2 based Fenton-like systems in treating PAH-contaminated black-odor river sediments.