Influence of extracellular polymeric substances from activated sludge on the aggregation kinetics of silver and silver sulfide nanoparticles

Extracellular polymeric substances (EPS) in activated sludge from wastewater treatment plants (WWTPs) could affect interactions between nanoparticles and alter their migration behavior. The influence mechanisms of silver nanoparticles (Ag NPs) and silver sulfide nanoparticles (Ag2S NPs) aggregated by active EPS sludge were studied in monovalent or divalent cation solutions. The aggregation behaviors of the NPs without EPS followed the Derjaguin-Landau-Verwey-Overbeek (DLVO) theory. The counterions aggravated the aggregation of both NPs, and the divalent cation had a strong neutralizing effect due to the decrease in electrostatic repulsive force. Through extended DLVO (EDLVO) model analysis, in NaNO3 and low-concentration Ca(NO3)(2) (< 10 mmol/L) solutions, EPS could alleviate the aggregation behaviors of Cit-Ag NPs and Ag2S NPs due to the enhancement of steric repulsive forces. At high concentrations of Ca(NO3)(2) (10-100 mmol/L), exopolysaccharide macromolecules could promote the aggregation of Cit-Ag NPs and Ag2S NPs by interparticle bridging. As the final transformation form of Ag NPs in water environments, Ag2S NPs had better stability, possibly due to their small van der Waals forces and their strong steric repulsive forces. It is essential to elucidate the surface mechanisms between EPS and NPs to understand the different fates of metal-based and metal-sulfide NPs in WWTP systems.