Toxicity assessment and underlying mechanisms of multiple metal organic frameworks using the green algae Chlamydomonas reinhardtii model

Metal-organic frameworks (MOFs) are an emerging class of materials which have garnered increasing attention for their utility as adsorbents and photocatalysts in water treatment. Nevertheless, the environmental risks of MOFs, especially their underlying impacts on aquatic organisms, are not fully explored. Herein, the toxicity of multiple representative MOFs was systematically assessed using a freshwater green alga (Chlamydomonas reinhardtii) model. Six typical MOFs with different metal nodes or organic linkers, including four transition metal incorporated aluminum-based porphyrin MOFs [pristine Al-PMOF, Al-PMOF (Cu), Al-PMOF (Ni), and Al-PMOF (Co)], one amine-functionalized MOF NH₂-MIL-125 (Ti), and one bimetallic Hofmann MOF (NiCo-PYZ), were successfully synthesized and characterized. All the tested MOFs significantly reduced the chlorophyll content and inhibited the algal growth, with the most toxic materials being NiCo-PYZ and Al-PMOF (Cu). Distinct toxic mechanisms were observed for the tested MOFs. Metal ion release was the primary cause for algal toxicity induced by NiCo-PYZ. The algal toxicity induced by porphyrin MOFs could be explained by the combined effects of metal ion release and nutrient adsorption, agglomeration and physical interactions, and reactive oxygen species generation. NH₂-MIL-125 (Ti) showed higher stability and more biocompatibility than the other tested MOFs. MOFs concentrations with no harmful effects to algae can be taken as the threshold values for safe use and discharge of MOFs. The ecotoxicological risks of MOFs should be considered as the applied concentrations of MOFs at mg/mL levels in environmental remediation were much higher than the no harmful effect thresholds.