Elucidation of the degradation pathways of sulfonamide antibiotics in a dielectric barrier discharge plasma system

• The degradation behavior of several sulfonamide antibiotics were characterized.
• The intermediates and byproducts formed during the plasma treatment were identified.
• The degradation pathways of the antibiotics were proposed.

The degradation of sulfonamide antibiotics, such as sulfathiazole (STZ), sulfamethazine (SMT) and sulfamethoxazole (SMZ) in water was carried out with a nonthermal dielectric barrier discharge plasma reactor operating under dry air or oxygen. In order to understand the degradation pathways of the antibiotics, the plasma-treated aqueous antibiotic solutions were characterized by various techniques such as UV–visible spectroscopy, ion chromatography, liquid chromatography coupled to a tandem mass spectrometer (LC–MS/MS), pH and electrical conductivity measurements, and total organic carbon analysis. The degradation rates of the antibiotics investigated were found to be higher with pure oxygen than with dry air, and decreased in the order: SMT > STZ > SMZ. As the degradation proceeded, the characteristic absorption peaks gradually decreased and the solution pH and conductivity increased, indicating that the antibiotics were being mineralized. The ion chromatography identified both inorganic (SO42−, NO3− and NH4+) and organic ions (acetate, formate and oxalate) as the stable degradation products. After 60-min plasma treatment with oxygen, the percentage of the S atoms transformed into SO42− was in the range of 66.9–86.4%, depending upon the type of antibiotics, while of the percentage of the N atoms transformed into NH4+ and NO3− was in the range of 15.7–33.2%. The possible degradation pathways of the antibiotics were proposed from the identified intermediate products formed during the degradation, which elucidates that the hydroxylation of the ring structures in the antibiotic molecules initiates the degradation.