Freezing Facilitates Formation of Silver Nanoparticles under Natural and Simulated Sunlight Conditions

Freezing is essential in the light-mediated transformation of organic pollutants. However, the effects of the freezing process on the reduction of Ag+ by natural organic matter (NOM) remains unclear, causing significant uncertainties in the natural formation of silver nanoparticles (AgNPs). This study investigated the sunlight-induced reduction of Ag+ by NOM under natural or controlled freezing processes. Natural (outdoor) freezing experiments demonstrated intense aggregation and precipitation of AgNPs in three aqueous media, including a NOM solution and two river water samples, under natural sunlight irradiation. Indoor experiments under simulated sunlight irradiation and controlled freezing processes showed that freezing at −20 °C and repeated freeze–thaw cycles (−20 to 4 °C) drastically accelerated the formation and growth of AgNPs compared to maintenance at 4 °C. Finally, under the natural freezing process, commercial AgNPs were found to influence the redox reduction of Ag+ probably through a reductio...