Understanding of the mechanism of extracellular polymeric substances of aerobic granular sludge against tetracycline from the perspective of fluorescence properties

Aerobic granular sludge (AGS) exhibited an excellent removal efficiency and a high tolerance in the treatment of antibiotics wastewater. Extracellular polymeric substances (EPS) of AGS with abundant binding sites might serve as the first barrier to prevent the direct contact of antibiotics and cells, thereby keeping the stability of AGS. In this study, the investigations in the fluorescence properties and the molecular weight of AGS-EPS after interaction with tetracycline (TC) were combined to reveal the resistance mechanism of AGS-EPS against TC. The two-dimensional correlation spectroscopy (2D-COS) was utilized to analyze the interaction priority of the AGS-EPS components with TC. Results showed that TC interacted with proteins and humic acid in AGS-EPS by forming a complex through hydrogen bond and van der Waals force. Compared with humic acid, TC could preferentially interact with proteins and form more stable complexes. Moreover, the components with the larger molecular weight in AGS-EPS interact with TC prior to which with smaller molecular weight. Significantly, TC exhibited the potential of binding with the divalent cation of AGS-EPS and caused the conformation changes of the protein. Therefore, AGS-EPS could resist the TC at a certain concentration range by trapping antibiotics, while over-loaded TC would cause the instability of AGS due to the limited interaction site of AGS-EPS and the destructive effect of antibiotics on AGS-EPS. This study provided a theoretical basis for understanding the interaction mechanism between antibiotics and AGS-EPS and offered a reference for AGS to maintain the stability of granules under the threat of antibiotics.