Interactions of monolayer molybdenum disulfide sheets with metalloid antimony in aquatic environment: Adsorption, transformation, and joint toxicity

Abstract

The tremendous application potentiality of transitional metal dichalcogenides (TMDs), such as molybdenum disulfide (MoS2) nanosheets, will unavoidably lead to increasing release into the environment, which could influence the fate and toxicity of co-existed contaminants. The present study discovered that 59.8 % of trivalent antimony [Sb(III)] was transformed by MoS2 to pentavalent Sb [Sb(V)] in aqueous solutions under light illumination, which was due to hole oxidation on the nanosheet surfaces. A synergistic toxicity between MoS2 and Sb(III, V) to algae (Chlorella vulgaris) was observed, as demonstrated by the lower median-effect concentrations of MoS2 + Sb(III)/Sb(V) (13.1 and 20.9 mg/L, respectively) than Sb(III)/Sb(V) (38.8 and 92.5 mg/L, respectively) alone. Particularly, MoS2 at noncytotoxic doses notably increased the bioaccumulation of Sb(III, V) in algae, causing aggravated oxidative damage, photosynthetic inhibition, and structural alterations. Metabolomics indicated that oxidative stress and membrane permeabilization were primarily associated with down-regulated amino acids involved in glutathione biosynthesis and unsaturated fatty acids. MoS2 co-exposure remarkably decreased the levels of thiol antidotes (glutathione and phytochelatins) and aggravated the inhibition on energy metabolism and ATP synthesis, compromising the Sb(III, V) detoxification and efflux. Additionally, extracellular P was captured by the nanosheets, also contributing to the uptake of Sb(V). Our findings emphasized the nonignorability of TMDs even at environmental levels in affecting the ecological hazard of metalloids, providing insight into comprehensive safety assessment of TMDs.