Exposure Order to Photoaging and Humic Acids Significantly Modifies the Aggregation and Transformation of Nanoplastics in Aqueous Solutions.

The colloidal stability of nanoplastics in aqueous solutions is greatly regulated by photoaging and dissolved organic matter (DOM). However, how the exposure order to sunlight and DOM modifies the environmental behavior of nanoplastics is seldomly determined. Here, with two different exposure orders, we investigated the impact of molecular-weight (MW)-fractionated humic acids (HAs) derived from biochar and the Suwannee River, respectively, on the aggregation of poly(ethylene terephthalate) nanoplastics (PET-NPs) in mono- and divalent electrolyte solutions. For exposure pattern (i) (photoaging followed by HA coating), photoaged PET-NPs had more oxidized surfaces and exhibited 22-320% higher binding affinity to HAs (especially the higher MW fractions) than the pristine counterparts, which greatly improved the dispersion of PET-NPs. For exposure pattern (ii) (HA coating followed by photoaging), HA-PET assemblies were formed, the dispersion of which increased with increasing irradiation time and was significantly higher than that of the samples in the exposure pattern (i) at the end of the experiment. This high dispersion of photoaged HA-PET assemblies was ascribed to the extra oxidation of PET by reactive oxygen species generated in the PET-HA interfaces during photoaging. These findings highlight the "active nature" of HA-PET assemblies, which provide new insight into the reaction of HA with nanoplastics beyond adsorption in the natural environment.

Particle size of biochar significantly regulates the chemical speciation, transformation, and ecotoxicity of cadmium in biochar.

The pyrolysis of biomass containing excessive heavy metals is likely to produce heavy metal contaminated biochar (BC). Although multiple lines of evidence indicate that higher charring temperature leads to enhanced immobilization of heavy metals in BC, we find that particle size could also play a critical role in the content of heavy metals in BC and BC ecotoxicity. Here, BC derived from cadmium (Cd) enriched rice straw was prepared at different temperatures (300-600 °C) and divided into macro-, colloidal-, and nano-sized fractions, respectively. The content and chemical forms of Cd in BC fractions as well as related algal toxicity were examined. The results show that for the same temperature BC the content of Cd followed an order of colloidal-BC > macro-BC > nano-BC; and the residual fractions of Cd significantly decreased (3.47-16.08%) while that of acid soluble and reducible fractions significantly increased (4.13-16.51% and 0.24-1.71%, respectively) with decreasing particle size of BC. Consistently, colloidal-BC exhibited the highest ecotoxicity for Scenedesmus obliquus. The acid soluble fractions of Cd in macro- and colloidal-BC played a dominating role in their algal toxicity (p < 0.05). However, the ecotoxicity of nano-BC was more dependent on the total content of Cd than specific fractions probably due to the phagocytosis by algal cells. These results indicate that the chemical forms and ecotoxicity of Cd in BC could be remarkably modified by its particle size, which has profound implications for understanding the behavior and potential risk of heavy metal contaminated BC in the environment.