Internalization of the Metal-Organic Framework MIL-101(Cr)-NH₂ by a Freshwater Alga and Transfer to Zooplankton

The common metal-organic framework (MOF) MIL-101(Cr)-NH₂ has attracted considerable attention due to its great potential applications in the environmental field. Nevertheless, its behavior and fate in aquatic systems are unknown. This study quantified and visualized the interactions of MIL-101(Cr)-NH₂ with the freshwater phytoplanktonic alga Chlamydomonas reinhardtii and its potential trophic transfer to zooplankton. The unicellular alga absorbed and accumulated the MOF by surface attachment, forming agglomerates and eventually cosettling out from water. Bioimaging revealed that MIL-101(Cr)-NH₂ was internalized by the algal cells and mainly occurred in the pyrenoid. Without algae in a freshwater system, MIL-101(Cr)-NH₂ was ingested by Daphnia magna, showing steadily increasing concentrations approaching 1-9% of dry body weight. Addition of algae substantially suppressed D. magna uptake of MIL-101(Cr)-NH₂ by 63.8-97.9%. Such inhibition could be explained by the competitive uptake of MOF by the algae and the inductive effects of algal food on MOF elimination by D. magna. The MOF (≤1 mg/L) ingested by D. magna was centered in the gut regions, whereas large MOF or algae-MOF aggregates were adsorbed onto the carapace and appendages, including the antennae, at 10 mg/L. Overall, the algae were the major targets for MIL-101(Cr)-NH₂, with nearly all algal cells settling out at 10 mg/L within 24 h. The possibility of trophic transfer of MIL-101(Cr)-NH₂ to D. magna in aquatic systems with algae present was limited due to its low accumulation potential and short retention time in D. magna.