Mechanism of MnO₂ nanorods toxicity in marine microalgae Chlorella sorokiniana during long-term exposure

Due to the increasing production and use of nanomaterials (NMs), their potential toxic impacts on the environment should be considered for a safe application of NMs. In this regard, the potential hazards of MnO₂ nanorods (NRs) on the green microalgae Chlorella sorokiniana during long-term exposure were investigated. Exposure to the high concentration of MnO₂ NRs (100 and 200 mg L^-1) significantly reduced the cell number of C. sorokiniana over 20 days of the experiment. The different concentrations of MnO₂ NRs (25-200 mg L^-1) induced the remarkable increase in the chlorophyll (a+b) content of algal cells due to the shading effect of NRs. For more than 72 h, the chlorophyll content of microalgae decreased due to the aggregation of NRs and the possible effects of oxidative stress. Long-term exposure to high concentrations of NRs caused a significant decrease in the primary and secondary metabolites of microalgae, including carotenoids, phenolic compounds, proteins, lipids, and carbohydrates. Oxidative stress was one of the possible toxic mechanisms of MnO₂ NRs to microalgae validated by an increase in lipid peroxidation induced by exposure to NRs. The algal cells increased the catalase activity and the amount of extracellular polymeric substances in response to NRs toxicity. The low level of Mn ions in the culture media indicated that MnO₂ NRs dissolution was not the cause of the observed reduction in the microalgae growth. Moreover, the bulk form of MnO₂ was not involved in the toxic impact of MnO₂, which was documented by an insignificant decrease in the growth, pigment, and lipid peroxidation of C. sorokiniana. These results may provide an additional insight into the potential hazards of MnO₂ NRs on the aquatic ecosystem.