Natural Nanocolloids Mediate the Phytotoxicity of Graphene Oxide

Nanocolloids (Ncs) are ubiquitous in natural surface waters. However, the effects of Ncs on the fate and ecotoxicity of graphene oxide (GO, a popular engineered nanomaterial (ENM)) remain largely unknown. Ncs exhibit strong adsorption affinity (K_L = 1.93 L/mg) and high adsorption capacity (176.2 mg/g) for GO. After Ncs hybridization, GO nanosheets became scrolls, and the aggregation rate of GO decreased. The influence of humic acid and Ncs on GO toxicity was compared. Humic acid mitigated the phytotoxicity of GO. However, GO and GO-Ncs were found to have an envelopment effect on algal cells, and both could enter algal cells. GO-Ncs induced higher reactive oxygen species (ROS) generation, stronger DNA damage and plasmolysis, and more obvious inhibition of photosynthesis compared to GO. Proteomic analysis revealed that photosystem I- and II-related proteins (e.g., E1ZQR2 and E1ZPG5) were regulated more significantly in the GO-Ncs groups than in the GO groups. A combined proteomic and metabolomic analysis showed that inhibition of carbohydrate, fatty acid, and amino acid metabolism contributed to ROS generation. Given the high concentrations and activity of Ncs, the above results highlight the need for reconsideration of the Ncs-mediated environmental behaviors and risks of ENMs and other pollutants.