Acute toxicity of cerium to neonatal Daphnia magna: Responses of antioxidant systems, influence of environmental factors and development of a biotic ligand model

Abstract

The bioavailability of cerium (Ce) and its toxic effects on aquatic organisms are still unclear, which limits the toxicity prediction and pollution control for this element. Here, the acute toxicity of Ce to Daphnia magna neonates and the responses of the antioxidant system were investigated, and the quantitative relationships between the toxicity of Ce and environmental factors were determined. The 24 and 48 h EC50_Ce-D values based on the dissolved concentration of Ce in Daphnia magna were 60.6 and 10.9 μM, respectively, and the EC50_Ce3+ values were 23.4 and 3.73 μM, respectively. After Ce exposure at environmentally relevant concentrations (0.5-3.5 μM), significant increases in superoxide dismutase activity and malondialdehyde content were observed in Daphnia magna, while significant decreases in catalase activity and H₂O₂ content occurred. Low levels of Ce cause oxidative damage to Daphnia magna and adverse impacts on the antioxidant system; however, further molecular-based studies are needed. The addition of Ca²⁺ or Na⁺ reduced the acute toxicity of Ce to Daphnia magna. In contrast, Mg²⁺ (MgSO₄) promoted Ce toxicity, which is a new finding related to the interaction effects between cations and rare earth elements on biological ligands; however, the effects of SO₄²⁺ could not be distinguished. Complexation with organic ligands could significantly reduce the toxicity of Ce to Daphnia magna; however, complexes of Ce with citric acid and malic acid might be bioavailable to Daphnia magna. In the absence of organic ligands and competing metals, the binding constant of Ce³⁺ to Daphnia magna at toxic concentrations was 5.83. The log K values for the competitive effects of Ca²⁺ and Na⁺ were 3.73 and 2.59, respectively, while the log K value for the protective effect of fulvic acid was 3.76. These results contribute to understanding the toxicity of Ce and will help predict the toxicity of Ce in freshwater.

Keywords: Bioavailability; Chemical speciation; Ecotoxicity; Natural organic matter; Rare earth element.