Kinetics and mechanisms of flumequine degradation by sulfate radical based AOP in different water samples containing inorganic anions

Abstract

Many studies have reported that hydroxyl radical (HO˙) driven advanced oxidation processes (AOPs) could degrade fluoroquinolones (FQs) antibiotics effectively. Compared with HO˙, sulfate radical (SO₄˙⁻) shows a similar oxidation capacity but a longer half-life. SO₄˙⁻ could cause chain reactions and resulted in the generation of halogen radicals and carbonate radicals from the main anions in sea water including Cl⁻, Br⁻ and HCO₃⁻. However, few studies were focused on the degradation of FQs in marine aquaculture water and seawater, as well as the bioaccumulation of transformation products. As a typical member of FQs, flumequine (FLU) was degraded by UV/peroxodisulfate (PDS) AOPs in synthetic fresh water, marine aquaculture water and seawater. The reaction rate constants in the three water samples were 0.0348 min⁻¹, 0.0179 min⁻¹ and 0.0098 min⁻¹, respectively. The reason was attributed to the inhibition of the anions as they could consume SO₄˙⁻ and initiate the quenching reaction of free radicals. When the pH value increased from 5 to 9, the reaction rate decreased from 0.0197 min⁻¹ to 0.0066 min⁻¹. The energy difference between HOMO and LUMO of FLU was calculated to be 8.07 eV indicating that FLU was a stable compound. The atoms on quinolone ring of FLU with high negative charge would be more vulnerable to attack by free radicals through electrophilic reactions. Two possible degradation pathways of FLU were inferred according to the degradation products. Preliminary bioaccumulation analysis of transformation products by the EPI suite software proved that the values of log K_ow and log BCF of the final product P100 were less than those of FLU and the intermediates.