Toxicity and activity inhibition of metal-organic framework MOF-199 to nitrogen-fixing bacterium Azotobacter vinelandii

Metal-organic framework (MOF) materials with fantastic properties have found important applications in various areas. Learning the lessons from plastics and microplastics, it is urgent to investigate the environmental impacts of emerging materials to avoid potential pollution. However, the environmental toxicity and risks of MOF materials are seldom reported. Herein, we studied the toxicity and activity inhibition of MOF-199 to nitrogen-fixing bacterium Azotobacter vinelandii. MOF-199 significantly suppressed the growth of A. vinelandii and led to cell death at 40 mg/L. MOF-199 penetrated the cell wall and induced the shrinking of bacterial cells. MOF-199 reduced the nitrogen fixation activity of A. vinelandii at 40 mg/L by decreasing the gene nifH levels and inhibiting the CaMg-ATPase activity, which was further confirmed by the changes in oxidative phosphorylation related genes. Complete growth inhibition and activity loss of A. vinelandii occurred at 60 mg/L of MOF-199. The toxicological mechanism of MOF-199 to A. vinelandii was assigned to the oxidative stress, which occurred at 20 mg/L and higher. Both Cu release and particulates themselves contributed to the toxicity of MOF-199 to A. vinelandii. These findings highlighted the environmental hazards and risks of MOF materials to nitrogen-fixing bacteria and nitrogen fixation in the biogeochemical cycle.