Influence of humic acids of different origins on oxidation of phenol and chlorophenols by permanganate

The influences of humic acids (HAs) of different origins, including two commercial HAs, three soil HAs and one aquatic HA, on phenols oxidation by permanganate were studied. The apparent second-order rate constants of 2-chlorophenol (2-CP)/phenol oxidation by permanganate in the presence of HAs at pH 7 followed the order of commercial HA (Shanghai) > soil HAs > commercial HA (Fluka) > aquatic HA. Moreover, the commercial HA (Shanghai) could accelerate the oxidation of different chlorophenols (CP) significantly under neutral condition. The FTIR analysis demonstrated greater content of CC moieties and less amount of carboxylate, aliphatic groups and polysaccharide-like substances in soil HAs than in aqueous HA, suggesting that the increase of aromaticity in HA was beneficial to the oxidation of phenols by permanganate. The apparent second-order rate constants of 2-CP/phenol oxidation by permanganate in the presence of HAs correlated well with specific visible absorption (SVA) at 665 nm of HAs. High positive correlation coefficients (R2 > 0.75) implied that π-electrons of HA strongly influenced the reactivity of 2-CP/phenol towards permanganate oxidation, which agreed well with positive correlation between Fluorescence Regional Integration (FRI) and the apparent second-order rate constants. The π-π interaction between HAs and phenols, the steric hindrance effect and the dissociation of phenols may affect the oxidation of phenols by permanganate in the presence of HA at pH = 7.0.