Contribution, Composition, and Structure of EPS by In Vivo Exposure to Elucidate the Mechanisms of Nanoparticle-Enhanced Bioremediation to Metals

Bacterial extracellular polymeric substances (EPS) have been recently found to contribute most for metal removal in nanoenhanced bioremediation. However, the mechanism by which NPs affect EPS-metal interactions is not fully known. Here, Halomonas sp. was employed to explore the role of EPS after in vivo exposure to Cd/Pb and polyvinylpyrrolidone (PVP) coated iron oxide nanoparticles (IONPs, 20 mg L^-1) for 72 h. Cd-IONPs produced the highest concentrations of EPS proteins (136.3 mg L^-1), while Cd induced the most production of polysaccharides (241.0 mg L^-1). IONPs increased protein/polysaccharides ratio from 0.2 (Cd) to 1.2 (Cd-IONPs). The increased protein favors the formation of protein coronas on IONPs surface, which would promote Cd adsorption during NP-metal-EPS interaction. FTIR analysis indicated that the coexistence of Cd and IONPs interacted with proteins more strongly than with polysaccharides. Glycosyl monomer analyses suggested mannose and glucose as target sugars for EPS complexation with metals, and IONPs reduced metal-induced changes in monosaccharide profiles. Protein secondary structures changed in all treatments, but we could not distinguish stresses induced by metals from those by IONPs. These findings provide greater understanding of the role of EPS in NP-metal-EPS interaction, providing a better underpinning knowledge for the application of NP-enhanced bioremediation.