Extracellular polymeric substances (EPS) are important components of activated sludge, whose content and composition have important effects on the macro-physical properties of sludge. In this study, the response of EPS in sludge to temperature (-40-200 °C) was systematically investigated using XAD resin fractionation, variable-temperature infrared spectra (VTIS) and two-dimensional correlation spectroscopy (2D-COS). The relationships between the molecular structure of EPS and the macro-physical properties (rheological property and dewatering performance) of waste activated sludge (WAS) at varying temperature were also established. During the freezing treatment, the solubilization of biopolymers and destruction of the hydrophilic functional groups (hydroxy, amino and carboxyl) resulted in the production of small organic matters, which enhanced EPS hydrophobicity and reduced electrostatic repulsion of sludge, and subsequent dewaterability improvement. For the hydrothermal treatment, the EPS transformation showed a two-stages reaction including stage I (70-120 °C) and stage II (>120 °C). Stage I (70-120 °C), a plenty of hydrophilic functional groups (hydroxy, amino and carboxyl) in EPS were exposed via the solubilization of biopolymers, which enhanced electrostatic repulsion of sludge and EPS hydrophilicity, and subsequence in deterioration of sludge dewaterability and fluidity. However, at stage II (>120 °C), the high temperature caused hydrolyzation of macromolecular organic matters in completely, in which the secondary structure of the protein was destroyed, causing the peptide chain to unfold. In addition, the reduction of α-helix and β-sheet content and intensified Maillard reaction decreased electrostatic repulsion of sludge, thus resulted in the improvement of sludge dewaterability and fluidity. This study enriched the theoretical basis of the optimal control of sludge treatment based on temperature regulation.
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