Modeling nanosilver transformations in freshwater sediments.

Silver nanoparticles (AgNPs), an effective antibacterial agent, are a significant and fast-growing application of nanotechnology in consumer goods. The toxicity of AgNPs released to surface waters during the use or disposal of AgNP-containing products will depend on the chemical transformations the nanoparticles undergo in the environment. We present a simple one-dimensional diagenetic model for predicting AgNP distribution and silver speciation in freshwater sediments. The model is calibrated to data collected from AgNP-dosed large-scale freshwater wetland mesocosms. The model predicts that AgNP sulfidation will retard nanoparticle oxidation and ion release. The resultant Ag2S-coated AgNPs are expected to persist and accumulate in sediment downstream from sources of AgNPs. Silver speciation and persistence in the sediment depend on the seasonally variable availability of organic carbon and dissolved oxygen. The half-life of typical sulfidized (85% Ag2S) AgNPs may vary from less than 10 years to over a century depending on redox conditions. No significant difference in silver speciation and distribution is observed between ≥50% Ag2S and 100% Ag2S AgNPs. Formation and efflux of toxic silver ion is reduced in eutrophic systems and maximized in oligotrophic systems.