Effects of heteroaggregation with metal oxides and clays on tetracycline adsorption by graphene oxide

Multiple nanoparticles (NPs) often coexist in water with contaminants, which inevitably affect the fate and transport of coexisted contaminants and other types of nanoparticles in actual water. This research was devoted to examine the adsorption of tetracycline (TC) on graphene oxide (GO) in the presence of different amounts of model engineered and natural NPs (m-NPs), including metal oxides (ZnO and Fe2O3), clays (kaolin and montmorillonite). The experimental results proved that the existence of m-NPs greatly enhanced the TC adsorption onto GO except for that at Fe2O3/GO = 10:1 and lengthened the adsorption equilibrium time. The enhanced adsorption amount of TC with increasing m-NPs/GO ratio was primarily due to the adsorption of TC onto m-NPs. In contrast, the slightly inhibitory effects by 10:1 Fe2O3/GO could be attributed to the blockage effect on GO surface by a small amount of Fe2O3. Compared with five m-NPs/adsorbents, m-NPs/GO had the greatest promoting efficiency on TC removal. Moreover, the heteroaggregation of GO with different m-NPs was studied in aqueous phase by microscopic, spectroscopic, and computational methods. Analysis showed that the electrostatic attraction between negatively charged GO and positively charged ZnO were likely to first heteroaggregate in binary systems of GO and ZnO, while GO were prone to homoaggregate owing to electrostatic repulsion with the same negatively charged montmorillonite (or kaolin). Besides, Fe2O3 tended to first homoaggregate and then heteroaggregate with GO. In summary, this report elucidated complex interactions between GO and m-NPs, which was crucial to fundamentally understand towards a predictive framework for describing the fate and migration of GO and m-NPs in actual water.