Transformation of silver ions to silver nanoparticles mediated by humic acid under dark conditions at ambient temperature

Abstract

The conversion of silver materials in environments would impact their toxicity and risk. Previous studies have reported that silver ions (Ag+) could be reduced to silver nanoparticles (AgNPs) by natural organic matters (NOM) under sunlight or heating conditions. However, whether such reaction could occur in darkness at ambient temperature and the transformation mechanism were unclear. This study found that Ag+ at environmentally relevant concentrations (as low as 1 μg/L) could be reduced to AgNPs by Suwannee River humic acid (SRHA) in darkness at 30 °C. The reaction mechanism probed by X-ray absorption fine structure spectroscopy revealed that Ag+ was first bound to the carboxylic groups of SRHA to form Ag+-SRHA ligands, which were then reduced to metallic Ag. The increase of pH (6–9) and the coexistence of formate, acetate, carbonate, and sulfate promoted the formation of AgNPs. Besides, the formed AgNPs would coalesce to large aggregates under acidic conditions or in the presence of sulfate. These results suggest that the dark transformation of Ag+ to AgNPs mediated by NOM could occur in environments and are important for the better understanding of the natural origin of AgNPs.