Quantification of Heteroaggregation between Citrate-Stabilized Gold Nanoparticles and Hematite Colloids

Collisions with and attachment to natural colloids (heteroaggregation) is likely to influence significantly the fate, transport, and toxicity of engineered nanoparticles (ENPs). This study investigated heteroaggregation between hematite (α-Fe2O3) colloids and citrate-capped gold nanoparticles (Cit-AuNPs) using a novel approach involving time-resolved dynamic light scattering and parallel experiments designed to quantify nanoparticle attachment and heteroaggregate surface charge. Experiments were performed in low ionic strength synthetic water at environmentally relevant pH in the presence and absence of Suwannee River Natural Organic Matter (SRNOM). In the absence of SRNOM at pH values where Cit-AuNPs and hematite are oppositely charged, attachment efficiencies are high and Cit-AuNPs are capable of destabilizing hematite following an "electrostatic patch" mechanism. Furthermore, maximum observed surface coverages were far below those predicted by geometry alone, a fact predicted by the random sequential adsorption (RSA) model that has significant implications for the estimation of heteroaggregate attachment efficiencies. At pH values where both particles are negative or in the presence of small amounts of SRNOM, attachment was minimal. Calculated attachment efficiencies using the measured surface coverages corroborate these findings. The calculation of attachment efficiencies and the identification of mechanisms governing heteroaggregation represents an important step toward predicting the transport, fate, and toxicity of ENPs in the environment.