Multiple drivers and mechanisms of solid-water interfacial interactions in sludge dewatering: Roles of polarity and molecular structure of extracellular polymeric substances

•Water occurrence states relied on sludge viscosity and EPS water-holding ability.•EPS polarity distribution was an important factor influencing sludge viscosity.•Rigid and compact EPS matrix contributed to the release of bound water.•Disulfide bonds induced α-helix formation and polypeptide aggregation.•Carbonyl group was most sensitive to disturbance of hydrothermal temperature. Water occurrence states in sewage sludge, influenced by sludge physicochemical properties, are crucial for sludge dewaterability and have recently been regarded as a research hotspot. Here, the multifold characteristics of sludge flocs during hydrothermal treatment, including rheological properties, solid-water interfacial interactions, and the polarity distribution and molecular structure of extracellular polymeric substances (EPS), were systematically investigated, and the impact of these characteristics on sludge dewaterability was explored in depth. Hydrothermal treatment at 80 °C and 100 °C induced the conversion of free water into bound water, while an increase in temperature to 180 °C resulted in a significant decrease in bound water content, approximately 4-fold lower than at 100 °C. In addition to the conventional view of decreased sludge surface hydrophilicity at high temperatures, the decline in bound water was associated with the reduction in sludge apparent viscosity. XAD resin fractionation identified the hydrophobic/hydrophilic EPS (HPO-/HPI) ratio as an important factor determining water occurrence states. Especially, hydrolysis of HPI-related hydrophilic proteins and subsequent increase in HPO-related tryptophan-like substances played a dominant role in reducing sludge viscosity and facilitating the release of bound water. Protein conformational analysis revealed that the disruption of α-helix structures and disulfide bonds significantly reduced EPS water-holding capacity, providing strong evidence for the potential of targeting these dense structure units to enhance sludge dewaterability. These findings provide a holistic understanding of multidimensional drivers of water occurrence states in sludge, and guide directions for optimizing sludge treatment efficiency through EPS modification. [Display omitted]