Alteration of bioaccumulation mechanisms of Cu by microalgae in the presence of natural fulvic acids

The impact of natural fulvic acids (FAs) on the toxicity and bioaccumulation of Cu by Chlorella pyrenoidosa was studied. FAs extracted from Taihu Lake were separated into three fractions using dialysis bags: F1 (<500 Da), F2 (500-1000 Da) and F3 (>1000 Da). The results showed that the F3 fraction with a larger molecular weight contained less acidic groups and unsaturated aliphatic structures than F1 and F2, and it showed stronger alleviation of the toxicity of Cu to algae. In the presence of F1∼F3, the bioaccumulation curve of Cu in algae intersected with the straight line in the binary system of Cu-algae at approximately 5.3 × 10^-3－6.0 × 10^-3 mM of Cu equilibrium concentration, showing an inhibition of bioaccumulation of Cu in lower concentrations but an enhancement in higher Cu concentrations. The ratio of {Cu}_ads/{Cu}_int was used to clarify the transformation mechanism on adsorption; the transition interval occurred at a ratio of 3.5-4.4. This ratio indicated a shift from a mechanism of slow trending to equilibrium to a mechanism with rapid increase, which may be due to the bridging action of Cu to form a ternary complex of FA-Cu-algae and the occurrence of multilayer adsorption. The promotion order of F1> F3> F2 was consistent with percentages of the carboxyl group in total acidic functional groups in the FAs. This research is helpful for improving the accuracy of present models for the prediction of heavy metal risks in aqueous environments.