Distinct mechanisms in the heteroaggregation of silver nanoparticles with mineral and microbial colloids

Attachment to solids is an important process for determining nanomaterial transport and their fate in environments. Here we revealed distinct behaviours in the attachment of silver nanoparticles (AgNPs) to kaolin and bacterial cells. We found preferential attachment of AgNPs to the edges of kaolin. Decreasing pH or adding metal ions promoted AgNP-kaolin attachment due to the increase of positive charge on kaolin's surfaces. Multivalent cations (Mg²⁺ and Ca²⁺) induced stronger enhancement than monovalent cations (Na⁺, K⁺ and Ag⁺), which demonstrated the positive role of electrostatic interaction in AgNP-kaolin attachment. However, the presence of metal ions inhibited AgNP binding to bacterial cells. The inhibitive effect was significantly correlated with solubility product of metal ions, which implied a chemical reaction mechanism in AgNP-cell attachment. In kaolin system, humic acid (HA) can considerably inhibit AgNP attachment and diminish the enhanced effects induced by metal ions. In contrast, in bacterial cell system, HA reduced the inhibitive effect of metal ions for AgNP adsorption, although HA itself had negligible effect on AgNP-cell attachment. Taken together, our results demonstrated the contribution of electrostatic attraction versus chemical interaction to the attachment of AgNPs to kaolin or bacterial cells, providing fundamental support to understand the attachment of nanomaterials to inorganic and organic solids in the environments.