The role of transformation in the risks of chemically exfoliated molybdenum disulfide nanosheets to the aquatic environment

Abstract

While the effects of environmental factors (e.g., coexisting organic macromolecules and solar irradiation) on the phase transformation and oxidative dissolution of chemically exfoliated molybdenum nanosheets (ceMoS₂) have been recognized, the effects of environmental processes on the subsequent biological impacts of ceMoS₂ are still poorly understood. In this study, the bioavailability and transitions in chemical speciation occurring during the aging process are demonstrated to be key factors causing ceMoS₂ to affect aquatic organisms. The lower survival rate of embryonic zebrafish with aged (i.e., sunlight-irradiated and dark-ambient-aged) ceMoS₂, compared to that with freshly prepared ceMoS₂, was due to the release of ionic aging products (mainly acidic Mo species) throughout the oxidative dissolution of ceMoS₂. The released soluble molybdenum interacted with natural organic matter (NOM) depending on their functionality, and this attenuated the toxicity caused by ceMoS₂ to different degrees. Toxicity triggered by aged ceMoS₂ under both dark and irradiated conditions was significantly reduced by Suwannee River NOM due to the formation of complexes with ionic Mo species, which was established by Mo K-edge X-ray absorption spectroscopy. The findings provide useful insights for comprehending the impacts of ceMoS₂ on aquatic organisms and guidance for the prevention measures necessary in the applications of MoS₂ nanosheets.

Keywords: Environmental risks; Ionic Mo species; Oxidative dissolution; Transition metal dichalcogenides.