Dissolution Behavior of Silver Nanoparticles and Formation of Secondary Silver Nanoparticles in Municipal Wastewater by Single-Particle ICP-MS.

Ag nanoparticles (nAg) are used in various consumer products and a significant fraction is eventually discharged with municipal wastewater (WW). In this study we assessed the release of Ag from polyvinylpyrrolidone (PVP)- and citrate-coated 80 nm nAg in aerobic WW effluent and mixed liquor and the related changes in nAg size, using single particle ICP-MS (spICP-MS). The concentration of dissolved (nonparticulate) Ag in WW effluent was 0.89 ± 0.05 ppb at 168 h and was 71% lower than in deionized (DI) water, in batch reactors spiked with 5 × 10 PVP-nAg particles/mL (10 μg/L), an environmentally relevant concentration. Dissolved Ag in WW was partly reformed into ∼22 nm nAgS by inorganic sulfides and organosulfur dissolved organic carbon (DOC) after 120 h, whereas the parent nAg mean diameter decreased to 65.89 ± 0.9 nm. Reformation of nAgS from Ag also occurred in cysteine solutions but not in DI water, or humic and fulvic acid solutions. Dissolution experiments with nAg in WW mixed liquor showed qualitatively similar dissolution trends. Time-of-flight secondary ion mass spectrometry (ToF-SIMS) and X-ray photoelectron spectroscopy (XPS) analyses indicated binding of thiol- and amine-containing DOC as well as inorganic sulfides with nAg. Those WW components, as well as limited dissolved oxygen, decreased dissolution in WW.