Aggregation and Dissolution of 4 nm ZnO Nanoparticles in Aqueous Environments: Influence of pH, Ionic Strength, Size, and Adsorption of Humic Acid

Metal oxide nanoparticles are used in a wide range of commercial products, leading to an increased interest in the behavior of these materials in the aquatic environment. The current study focuses on the stability of some of the smallest ZnO nanomaterials, 4 +/- 1 nm in diameter nanoparticles, in aqueous solutions as a function of pH and ionic strength as well as upon the adsorption of humic acid. Measurements of nanoparticle aggregation due to attractive particle-particle interactions show that ionic strength, pH, and adsorption of humic acid affect the aggregation of ZnO nanoparticles in aqueous solutions, which are consistent with the trends expected from Derjaguin-Landau-Verwey-Overbeek (DLVO) theory. Measurements of nanoparticle dissolution at both low and high pH show that zinc ions can be released into the aqueous phase and that humic acid under certain, but not all, conditions can increase Zn2+(aq) concentrations. Comparison of the dissolution of ZnO nanoparticles of different nanoparticle diameters, including those near IS and 240 nm, shows that the smallest nanoparticles dissolve more readily. Although qualitatively this enhancement in dissolution can be predicted by classical thermodynamics, quantitatively it does not describe the dissolution behavior very well.