The colloidal stability of silver nanoparticles (AgNPs) in natural aquatic environments influences their transport and environmental persistence, while their dissolution to Ag+ influences their toxicity to organisms. Here, we characterize the colloidal stability, dissolution behavior, and toxicity of two industrially relevant classes of AgNPs (i.e., AgNPs stabilized by citrate or polyvinylpyrrolidone) after exposure to natural organic matter (NOM, i.e., Suwannee River Humic and Fulvic Acid Standards and Pony Lake Fulvic Acid Reference). We show that NOM interaction with the nanoparticle surface depends on (i) the NOM’s chemical composition, where sulfur- and nitrogen-rich NOM more significantly increases colloidal stability, and (ii) the affinity of the capping agent for the AgNP surface, where nanoparticles with loosely bound capping agents are more effectively stabilized by NOM. Adsorption of NOM is shown to have little effect on AgNP dissolution under most experimental conditions, the exception being when the NOM is rich in sulfur and nitrogen. Similarly, the toxicity of AgNPs to a bacterial model (Shewanella oneidensis MR-1) decreases most significantly in the presence of sulfur- and nitrogen-rich NOM. Our data suggest that the rate of AgNP aggregation and dissolution in aquatic environments containing NOM will depend on the chemical composition of the NOM, and that the toxicity of AgNPs to aquatic microorganisms is controlled primarily by the extent of nanoparticle dissolution.

The widespread application of silver in consumer products and the resulting contamination of natural environments with silver raise questions about the toxicity of Ag+ in the ecosystem. Natural organic matter, NOM, which is abundant in water supplies, soil, and sediments, can form stable complexes with Ag+, altering its bioavailability and toxicity. Herein, the extent and kinetics of Ag+ binding to NOM, matrix effects on Ag+ binding to NOM, and the effect of NOM on Ag+ toxicity to Shewanella oneidensis MR-1 (assessed by the BacLight viability assay) were quantitatively studied with fluorous-phase Ag+ ion-selective electrodes (ISEs). Our findings show fast kinetics of Ag+ and NOM binding, weak Ag+ binding for Suwannee River humic acid, fulvic acid, and aquatic NOM, and stronger Ag+ binding for Pony Lake fulvic acid and Pahokee Peat humic acid. We quantified the effects of matrix components and pH on Ag+ binding to NOM, showing that the extent of binding greatly depends on the environmental conditions. The effect of NOM on the toxicity of Ag+ does not correlate with the extent of Ag+ binding to NOM, and other forms of silver, such as Ag+ reduced by NOM, are critical for understanding the effect of NOM on Ag+ toxicity. This work also shows that fluorous-phase Ag+ ISEs are effective tools for studying Ag+ binding to NOM because they can be used in a time-resolved manner to monitor the activity of Ag+ in situ with high selectivity and without the need for extensive sample preparation.