Stability of silver nanoparticle sulfidation products

The adoption of silver nanoparticles in consumer goods has raised concerns about the potential environmental harm of their widespread use. We studied chemical transformations that Ag NPs may undergo as they pass through sulfide-rich conditions common in waste water treatment plants (WWTPs), which may limit the release of Ag⁺ from Ag NPs due to the formation of low-solubility silver sulfide (Ag₂S). However, it is uncertain whether sulfidation is complete and if sulfidized Ag NPs continue to release Ag⁺. To address these uncertainties, we monitored the reaction of Ag NPs with various levels of sulfide with an ion selective electrode and UV/visible spectrophotometry over the course of two months. We characterized the products of the sulfidation reactions with a purge-and-trap acid volatile sulfide (AVS) analysis, which served as a measure of the stability of the sulfidized products because sulfide would be readily lost to oxidation unless it is stabilized as Ag₂S. The Ag NP surface plasmon resonance (SPR) absorbance peak was initially diminished and then returned over the course of several days after reaction with limited amounts of sulfide, suggesting a dynamic system that may retain some characteristics of the pristine Ag NPs. However, ICP-MS analysis of sulfidized Ag NP suspensions over a two-month period demonstrates that sulfidation limits the release of Ag⁺ ions from nanosilver that pass through a WWTP, even when sulfide concentrations are limited relative to silver.