Transformation of AgCl Particles under Conditions Typical of Natural Waters: Implications for Oxidant Generation

The engineered silver nanoparticles (AgNPs) used in consumer products are ultimately released to the environment either as Ag(0), silver sulfide (Ag₂S(s)), silver chloride (AgCl(s)), and/or dissolved Ag(I) complexes. Of these, AgCl(s) and Ag₂S(s) exhibit semiconducting properties and hence may have significant implications to oxidant generation and subsequent redox transformations in natural waters. In this work, we investigate the transformation and photoreactivity of AgCl(s) under simulated natural water conditions with the photoreactivity probed by measuring the oxidation of formate (HCOO^-), a simple compound with a well-defined oxidation pathway. Our results show that AgCl(s) undergoes rapid dissolution in the presence of chloride concentrations representative of seawater (ca. 0.5 M NaCl) forming dissolved Ag(I) complexes but is stable in fresh waters and slightly brackish waters (≤200 mM NaCl). We further show that under these lower salinity conditions in which AgCl(s) is stable, pH has a significant impact on the reactivity of semiconducting AgCl(s). The photoreactivity (measured as initial HCOO^- oxidation rate) of AgCl(s) is relatively constant at pH 4.0 for periods of 24 h or more; however, it decreases rapidly under alkaline conditions. The rapid transformation (or "aging") of AgCl(s) under alkaline conditions suggests that AgCl(s), potentially transported through wastewater effluent to fresh or brackish water environments, may not have a significant impact in such environments. In comparison, in situ formed AgCl(s), potentially formed as a result of the oxidation of high concentrations (≥60 μg Ag·L^-1) of Ag(0) and/or Ag₂S(s), may have significant implications to oxidant generation in natural waters. Our results further show that rapid cycling of Ag between the 0 and +I redox states in sunlit surface waters as a result of the presence of AgNP oxidants (such as H₂O₂ and organic radicals) will further enhance the rate and extent of oxidant generation by AgCl(s).