Unveiling changes in the complexation of dissolved organic matter with Pb(II) by photochemical and microbial degradation using fluorescence EEMs-PARAFAC

Dissolved organic matter (DOM) is very important in determining the speciation, behaviors, and risk of metal pollutants in aquatic ecosystems. Photochemical and microbial degradation are key processes in the cycling of DOM, yet their effects on the DOM-Pb(II) interaction remain largely unknown. This was studied by examining the complexation of river DOM with Pb(II) after degradation, using fluorescence quenching titration and excitation-emission matrices-parallel factor analysis (EEMs-PARAFAC). Three humic-like and two protein-like components were identified, with strong removals of humic-like components and decreasing average molecular weight and humification degree of DOM by photo- and photo-microbial degradation. The changes in humic-like abundance and structure resulted in notable weakening of their interaction with Pb(II). The tryptophan-like C2 was also mainly removed by photo-degradation, while the tyrosine-like C3 could be either removed or accumulated. The Pb(II)-binding of protein-like components was generally weaker but was enhanced in some degradation groups, which might be related to the lowering competition from humic-like components. The binding parameters correlated significantly with the DOM indices, which were dominated by photo-degradation for humic-like components but by seasonal variations for the tyrosine-like component. These results have implications for understanding the key mechanisms underlying the variability of the DOM-metal interaction in aquatic environments.