Graphene layers are potential candidates in a large number of applications. However, little is known about their ecotoxicological risks largely as a result of a lack of quantification techniques in complex environmental matrices. In this study, graphene was synthesized by means of graphitization and exfoliation of sandwich-like FePO4/dodecylamine hybrid nanosheets, and (14)C was incorporated in the synthesis. (14)C-labeled graphene was spiked to artificial freshwater and the uptake and depuration of graphene by Daphnia magna were assessed. After exposure for 24 h to a 250 μg/L solution of graphene, the graphene concentration in the organism was nearly 1% of the organism dry mass. These organisms excreted the graphene to clean artificial freshwater and achieved roughly constant body burdens after 24 h depuration periods regardless of the initial graphene exposure concentration. Addition of algae and humic acid to water during the depuration period resulted in release of a significant fraction (>90%) of the accumulated graphene, but some still remained in the organism. Accumulated graphene in adult Daphnia was likely transferred to the neonates. The uptake and elimination results provided here support the environmental risk assessment of graphene and the graphene quantification method is a powerful tool for additional studies.

The exciting commercial application potential of graphene materials may inevitably lead to their increasing release into the environment where they may pose ecological risks. This study focused on using carbon-14 labeled few-layer graphene (FLG) to determine whether the size of graphene plays a role in its uptake, depuration and biodistribution in adult zebrafish. After 48 h exposure to larger FLG (L-FLG) at 250 μg/L, the amount of graphene in the organism was close to 48 mg/kg fish dry mass, which was more than 170-fold greater than the body burden of those exposed to the same concentration of smaller FLG (S-FLG). The amount of uptake for both L-FLG and S-FLG increased by a factor of 2.5 and 16, respectively, when natural organic matter (NOM) was added in the exposure suspension. While the L-FLG mainly accumulated in the gut of adult zebrafish, the S-FLG was found in both the gut and liver after exposure with or without NOM. Strikingly, the S-FLG was able to pass through the intestinal wall and enter the intestinal epithelial cells and blood. The presence of NOM increased the quantity of S-FLG in these cells. Exposure to L-FLG or S-FLG also had a significantly different impact on the intestinal microbial community structure.

Summary Covalent organic frameworks (COFs) are a new type of crystalline porous polymers known for chemical stability, excellent structural regularity, robust framework, and inherent porosity, making them promising materials for capturing various types of pollutants from aqueous solutions. This review thoroughly presents the recent progress and advances of COFs and COF-based materials as superior adsorbents for the efficient removal of toxic heavy metal ions, radionuclides, and organic pollutants. Information about the interaction mechanisms between various pollutants and COF-based materials are summarized from the macroscopic and microscopic standpoints, including batch experiments, theoretical calculations, and advanced spectroscopy analysis. The adsorption properties of various COF-based materials are assessed and compared with other widely used adsorbents. Several commonly used strategies to enhance COF-based materials’ adsorption performance and the relationship between structural property and sorption ability are also discussed. Finally, a summary and perspective on the opportunities and challenges of COFs and COF-based materials are proposed to provide some inspiring information on designing and fabricating COFs and COF-based materials for environmental pollution management.

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