Dynamic responses and adsorption mechanisms of Chlamydomonas reinhardtii extracellular polymeric substances under Cd, Cu, Pb, and Zn exposure.

Extracellular polymeric substances (EPS) can effectively attenuate heavy metal mobility in aquatic ecosystems and reduce metal toxicity to cells. However, a systematic study of microalgae EPS responses and their adsorption behaviors, characteristics, and mechanisms under different heavy metal exposures has not been performed. In this study, EPS extracted from Chlamydomonas reinhardtii CC-125 was analyzed for compositional changes (monosaccharides and proteins) under Cd, Cu, Pb, and Zn treatments. The EPS adsorption capacities and mechanisms for the four metal ions were also investigated. Cd (10 mg/L), Cu (5 mg/L), and Zn (5 mg/L) exposure induced changes in the microalgal EPS composition and structure, and a protein/polysaccharide ratio of greater than 1 was found. This result indicated the crucial role of proteins in stress resistance. In contrast, Pb stress resulted in an increase of 532.64% and 117.48% in proteins and polysaccharides, respectively, with galactose and glucose playing key roles in this process. A fluorescence analysis revealed that Cd/Pb exposure reduced the tryptophan and tyrosine levels in the EPS, while Cu/Zn only weakened tryptophan. As a biosorbent, the adsorption capacity of the EPS for the four metals followed the order of Pb > Cd > Cu > Zn. The fluorescence quenching titration results revealed that fluorescent compounds in the EPS had the strongest complexation ability with Pb (logK: 8.16 × 10), followed by Cu (logK: 1.79 × 10), while their abilities for Cd and Zn were weaker. A spectroscopic analysis indicated that the primary functional groups involved in EPS binding with Pb/Cd and Cd/Zn were protein carboxyl groups (C=O/O-C=O) and glycosidic bonds (C-OH/C-O-C), respectively. This study elucidates the response strategies and adsorption mechanisms of the C. reinhardtii EPS to different metals and provides a basis for environmental heavy metal pollution bioremediation.