Silver release from silver nanoparticles in natural waters

Silver nanoparticles (AgNPs) are used increasingly in consumer products for their antimicrobial properties. This increased use raises ecological concern because of the release of AgNPs into the environment. Once released, zero-valent silver may be oxidized to Ag+ and the cation liberated or it may persist as AgNPs. The chemical form of Ag has implications for its toxicity; it is therefore crucial to characterize the persistence of AgNPs to predict their ecotoxicological potential. In this study, we evaluated the release of Ag from AgNPs of various sizes exposed to river and lake water for up to 4 months. Several AgNP-capping agents were also considered: polyvinylpyrrolidone (PVP), tannic acid (Tan), and citric acid (Cit). We observed a striking difference between 5, 10, and 50 nm AgNPs, with the latter being more resistant to dissolution in oxic water on a mass basis. However, the difference decreased when Ag was surface-area-normalized, suggesting an important role of the surface area in determining Ag loss. We propose that rapid initial Ag+ release was attributable to desorption of Ag+ from nanoparticle surfaces. We also observed that PVP- and Tan-AgNPs are more prone to Ag+ release than Cit-AgNPs. In addition, it is likely that oxidative dissolution also occurs but at a slower rate. This study clearly shows that small AgNPs (5 nm, PVP and Tan) dissolve rapidly and almost completely, while larger AgNPs (50 nm) have the potential to persist for an extended period of time and could serve as a continuous source of Ag ions.