An electrokinetic perspective into the mechanism of divalent and trivalent cation sorption by extracellular polymeric substances of Pseudomonas fluorescens.

Extracellular polymeric substances (EPS) contain a vast number of functional groups which can provide sorption sites for heavy metal cations in solution, however, the mechanisms for the interaction of EPS with various metal cations were not well understood. In this study, the sorption potential of EPS from Pseudomonas fluorescens for different cations was investigated. The changes of electrokinetic properties that occurred on the surface of EPS once they adsorbed these cations were also studied using zeta potential measurements as a function of pH and cation concentration. The adsorption data fitted Freundlich isotherm better than Langmuir and D-R isotherms. The interactions of the cations with EPS were favourable with the separation factor Kr < 1. Under different pH conditions, the zeta potential of EPS in the different cation solution followed the order: Fe(III) (at pH ≤ 5.0) > Al(III) > Cu(II) > Mn(II) > Ni(II)≈Cd(II) > Ca(II) > EPS, while with respect to the initial cation concentration, the zeta potential of EPS was in the order: Fe(III) > Al(III) > Cu(II) > Cd(II) > Ni(II)≈Mn(II)≈Ca(II). The effect of cation sorption on the surface charge of EPS increased with pH as well as cation concentration. The thermodynamic analysis demonstrated that besides the sorption of Fe which was exothermic, all the other cations were adsorbed through an endothermic process. The ΔSads revealed that most of the cations interacted with EPS through the formation of inner-sphere complexes. The ATR-FTIR analyses confirmed that complexation occurred between the cations and functional groups on the surface of EPS. The zeta potential of EPS shifted to positive value direction due to sorption of cations on EPS, indicating that the specific interactions were involved in the sorption process. This study enhances our understanding of EPS aggregation and heavy metal bio-sorption through the electrokinetic mechanism. The results will provide useful references for immobilization of heavy metals and alleviation of Al toxicity in acidic soils.