Surface charge-dependent bioaccumulation dynamics of silver nanoparticles in freshwater algae

Silver nanoparticles (AgNPs) can gradually accumulate in algae to exert their toxicity; however, there is little knowledge about their bioaccumulation dynamics. For the first time, this study reports the effect of surface charge of AgNPs on their bioaccumulation dynamics in freshwater algae (Chlorella vulgaris) using biodynamic modeling. Polyethylene-coated AgNPs (PEI-AgNPs) and citrate-coated AgNPs (Cit-AgNPs) were selected as positively and negatively charged AgNPs, i.e., P-AgNPs and N-AgNPs, respectively. Their uptake and elimination dynamics were investigated at a concentration of 50% inhibition of growth rate values (EC₅₀) and 10% inhibition of growth rate values (EC₁₀). The one-component model can generally well simulate the algal uptake and elimination kinetics of N-AgNPs but not of P-AgNPs. At both concentrations, the uptake rate constants (k_u) for P-AgNPs were ∼20 times higher than that for N-AgNPs. The parameters of biphasic elimination kinetics revealed that P-AgNPs were eliminated faster than N-AgNPs during depuration compared to in subsequent processes. Compared with N-AgNPs, extended Derjaguin-Landau-Verwey-Overbeek (DLVO) theory and dark-field imaging revealed that P-AgNPs can be rapidly absorbed on the algal cell surface membrane owing to their remarkably lower energy barrier between algal cells, resulting in a faster adsorption/uptake process and aggregation of algal cells. Our results clearly demonstrate that the AgNPs exhibited surface charge-dependent bioaccumulation dynamics in algal cells. Thus, AgNP surface charge primarily influences the AgNP accumulation dynamics in algal cells.