Ofloxacin (OFL) is a commonly used antibiotic and is widely present in various water bodies. Indirect photodegradation is crucial for the transformation and fate of antibiotics in surface water, which largely depends on the structure and composition of dissolved organic matter (DOM). Nevertheless, knowledge about the optical characteristics of diverse DOM polar fractions as well as the relationship with indirect photodegradation of antibiotics is still scarce. In this study, XAD-8 in combination with anion and cation exchange resins was used to separate DOM into six polar fractions: hydrophilic acid (HIA), hydrophilic basic (HIB), hydrophilic neutral (HIN), hydrophobic acid (HOA), hydrophobic basic (HOB) and hydrophobic neutral (HON). UV–vis and fluorescence spectroscopy were applied to analyze DOM polar fractions and explore their impact on OFL indirect photodegradation. The results showed that indirect photodegradation was the primary photodegradation route of OFL when the irradiation wavelength was greater than 320 nm, triple-state excited DOM (3DOM*) was the main reactive intermediates (RIs) that affected the indirect photodegradation of OFL. Excitation-emission matrix spectroscopy combined with parallel factor analysis (EEMs-PARAFAC) and correlation analysis demonstrated that terrestrial humic-like substances could yield generous RIs to facilitate OFL indirect photodegradation. The HIB and HOA fractions of SRNOM contained large aromaticity and humification degree and more terrestrial humic-like substances, thus exhibiting greater OFL indirect photodegradation rates. The HOA and HOB fractions of FA had abundant terrestrial humic-like substances and contributed more to OFL indirect photodegradation. This study helped us understand the effect of DOM structural characteristics on the OFL indirect photodegradation.
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