Novel insights into the multistep chlorination of silver nanoparticles in aquatic environments

Due to the increasing applications, silver nanoparticles (AgNPs) are inevitably released into the environments and are subjected to various transformations. Chloride ion (Cl^-) is a common and abundant anion with a wide range of concentration in aquatic environments and exhibits a strong affinity for silver. The results indicate that AgNPs experienced multistep chlorination, which was dependent on the concentration of Cl^- in a non-linear manner. The dissolution of AgNPs was accelerated at Cl/Ag ratio of 1 and the intensive etching effect of Cl^- contributed to the significant morphology changes of AgNPs. The dissolved Ag⁺ quickly precipitated with Cl^- to form an amorphous and passivating AgCl(s) layer on the surface of AgNPs, thus the dissolution rate of AgNPs decreased at higher Cl/Ag ratios (100 and 1000). As the Cl/Ag ratio further increased to 10,000, the overall transformation rate increased remarkably due to the complexation of Cl^- with AgCl(s) to form soluble AgCl_x^(x-1)- species, which was verified by the reaction of AgCl nanoparticles with Cl^-. Besides, several environmental factors (electrolytes, surfactants and natural organic matter) affected AgNPs dissolution and the following chlorination. These results will expand the understanding of the environmental fate and potential risks of AgNPs in natural chloride-rich waters.