Impacts of Select Organic Ligands on the Colloidal Stability, Dissolution Dynamics, and Toxicity of Silver Nanoparticles

Key understanding of potential transformations that may occur on silver nanoparticle (AgNP) surface upon interaction with naturally ubiquitous organic ligands (e.g., −SH (thoil), humic acid, or −COO (carboxylate)) is limited. Herein we investigated how dissolved organic carbon (DOC), −SH (in cysteine, a well-known Ag⁺ chelating agent), and −COO (in trolox, a well-known antioxidant) could alter the colloidal stability, dissolution rate, and toxicity of citrate-functionalized AgNPs (citrate–AgNPs) against a keystone crustacean Daphnia magna. Cysteine, DOC, or trolox amendment of citrate–AgNPs differentially modified particle size, surface properties (charge, plasmonic spectra), and ion release dynamics, thereby attenuating (with cysteine or trolox) or promoting (with DOC) AgNP toxicity. Except with DOC amendment, the combined toxicity of AgNPs and released Ag under cysteine or trolox amendment was lower than of AgNO₃ alone. The results of this study show that citrate–AgNP toxicity can be associated with oxidative stress, ion release, and the organism biology. Our evidence suggests that specific organic ligands available in the receiving waters can differentially surface modify AgNPs and alter their environmental persistence (changing dissolution dynamics) and subsequently the toxicity; hence, we caveat to generalize that surface modified nanoparticles upon environmental release may not be toxic to receptor organisms.