UC Santa Barbara

The concentration of silver nanoparticles (nano-Ag) in aqueous media influences the kinetics of ion release; hence, the transformation and stability of nano-Ag are also influenced. The stability, dissolution and further transformation of nano-Ag in aqueous media at predicted environmental concentrations (PECs) ≤ μg/L may differ from that reported at higher concentrations. Analytical techniques characterizing nanoparticles (NPs) at μg/L have advantages and limitations, including an inherent bias based on theoretical and analytical considerations, as well as the matrix effects. In this work, we applied nanoparticle tracking analysis (NTA), single particle ICP-MS (sp-ICP-MS), and localized surface plasmon resonance (LSPR) analysis to study the stability and dissolution of nano-Ag with different nominal sizes (20, 40, 80 and 100 nm) at PECs in synthetic wastewater (SWW). The influence of the main wastewater constituents, such as organic matter, Cl^-, S^2-, PO₄^3- and NH₄⁺, on the stability and dissolution of nano-Ag (40 nm) at PECs was also determined. Diagrams of the predominant species of silver exposed to major ligands were generated using MINTEQ. After 5 h in SWW, 20 nm nano-Ag dissolved 19.27% and 40 nm nano-Ag dissolved 14.8%. Aggregates of Ag particles were clearly noted for 80 and 100 nm nano-Ag after 5 h of exposure to SWW. Aggregates size also ranged very similar for both techniques, NTA and sp-ICP-MS, 29-211 nm and 38-241 for NTA and 48-210 and 50-220 nm, for sp-ICP-MS, respectively. Monodispersed size distribution (22-85 nm) and low dissolution (up to 5.1%) of nano-Ag at PECs were observed in presence of organic matter (5-800 μg/L) and PO₄^3- (9.5-47.5 mg/L), while precipitation and higher dissolution (up to 74.9%) were observed in media containing either Cl^- (0.07-10.64 g/L), S^2- (0.32-32.1 mg/L) or NH₄⁺ (36-90 mg/L), respectively. Speciation diagrams predict the formation of Ag₂S_(s) and AgCl_(s), and soluble species such as AgCl_x^(x-1)-, AgNH₃⁺ and Ag(NH₃)²⁺ when Ag⁺ at PECs in wastewater. The NTA and sp-ICP-MS were suitable techniques for sizing nano-Ag in wastewater at PECs at experimented nominal sizes. sp-ICP-MS was also useful to quantify the coexistence of Ag⁺ and nano-Ag. The LSPR analysis served to determine the relative persistence of original nano-Ag at PECs in the wastewater during the first 5 h after spiking.