The expanding production of engineered nanomaterials (ENMs) can eventually cause their increased release into and presence in aquatic ecosystems, potentially threatening the health of aquatic organisms and the stability of the ecological environment. Generally, ENMs are repeatedly released into real-world aquatic environments in relatively low concentrations, potentially affecting photosynthesis in primary producers such as algae. However, knowledge regarding the effects of repeated exposure to ENMs on algal photosynthesis is still lacking. Herein, the physiological responses of the freshwater algae Chlorella vulgaris following single and repeated exposures to cerium oxide nanoparticles (CeO₂ NPs) were investigated at 10 mg/L, with a focus on photosynthesis. The results showed that repeated exposures triggered increased photosynthetic pigment contents, oxidative stress levels, decreased photosynthetic performance, and lower biomass in C. vulgaris compared to a single exposure. Photosynthesis-related genes (i.e., petA, petB, psaA, atpB, and rbcL) were found to be upregulated following repeated exposures. Particularly for petB, repeated rather than single exposure treatment significantly upregulated its expression levels by 2.92-10.24-fold compared to unexposed controls. Furthermore, increased exposure times could aggravate the interaction between CeO₂ NPs and algae, elevating 8.13%, 12.13%, and 20.51% Ce distribution on the algal cell surface or intracellularly, compared to a single exposure. This study is the first to investigate the effects of ENM exposure times on algal photosynthesis, providing new insights into the assessment of the risks these materials pose to real-world aquatic environments.

Magnetite-functionalized biochar (MBC) is a promising engineered material for remediation of antibiotic-contaminated fields. However, sorption mechanisms of ionizable organic compounds such as sulfonamide antibiotics (SAs) on MBC are still unclear. This study employed four representative SAs including sulfamethazine (SMT), sulfamerazine (SMR), sulfadiazine (SDZ), and sulfamethoxazole (SMX), to compare the difference in sorption on MBC. Results showed that the sorption capacities and affinities of the four SAs varied with their substituents, hydrophobic properties, and dissociation constants (pK_a). Synergistic effect during co-pyrolysis with Fe³⁺ enhanced the sorption performance of MBC towards SAs compared to original BC. Spectral methods confirmed structural changes of MBC such as the variance in oxygen-containing groups and defective/graphitized phases. Results of modeling pH-dependent sorption revealed that H-bonding or π-bond assisted H-bonding determined the sorption affinities and capacities of SAs. In particular, the SAs with lower pK_a were thermodynamically favorable to form H-bonding with MBC via proton exchange with water molecules. Quantum calculation results quantified the contributions of H-bonding strengths and found that the energies of H-bonding were correlated with affinities of SAs. Moreover, contributions of oxygen-containing groups instead of minerals dominated the H-bonding energies. Mechanistic insights from this study can be valuable in exploring engineered BC composites for practical application in field remediation. Graphical Abstract