Morphology, structure, and composition of sulfidized silver nanoparticles and their aggregation dynamics in river...

The sulfidized form represents an environmentally relevant transformation state of silver nanoparticles (Ag-NPs) released into natural systems via wastewater route. However, the detailed characterization of sulfidized silver nanoparticles (S-Ag-NPs) is missing and their colloidal stability in aquatic systems is only insufficiently studied. The aim of this study was to systematically evaluate the surface properties, morphology, structure, composition, as well as aggregation dynamics of S-Ag-NPs in synthetic and natural river water. The S-Ag-NPs were prepared by sulfidation of citrate-coated silver nanoparticles (Cit-Ag-NPs). The sulfidation of Ag-NPs was accompanied by the formation of fiber-like Ag₂S nano-bridges, Ag⁰-Ag₂S core-shell structures, and hollow regions. In contrast to the published literature, the nano-bridges were thinner (2-9 nm) and longer (up to 60 nm), they formed at higher S^2-/Ag molar ratio (2.041), and the formation of the core-shell structures was observed even in the absence of natural organic matter (NOM). Furthermore, we observed selective sulfidation of nanoparticles which can induce the hot spots for the release of toxic Ag⁺ ions. The critical coagulation concentration (CCC) of Ca²⁺ determined for S-Ag-NPs in reconstituted river water was 2.47 ± 0.23 mmol/L and thus higher than the CCC obtained for Cit-Ag-NPs in our earlier study revealing higher colloidal stability of S-Ag-NPs. In natural river water, S-Ag-NPs were also colloidally more stable compared to the Cit-Ag-NPs. Furthermore, the stabilizing effect of NOM was much higher for S-Ag-NPs than for Cit-Ag-NPs. For S-Ag-NPs stabilized by a low amount of citrate, we expect longer residence times in the water phase of rivers and thus higher risk for aquatic organisms. In contrast to this, the pristine Cit-Ag-NPs are expected to be accumulated faster in the sediments representing higher risk for benthic organisms. This study contributes to better understanding of environmental fate and effects of Ag-NPs released via wastewater route.