Effects of photo-irradiation on mercury binding to dissolved organic matter: Insights from FT-IR and synchronous fluorescence two-dimensional correlation spectroscopy

The binding interactions between Hg and dissolved organic matter (DOM) affect the fate and transport of Hg in the aquatic environment. Here, we investigate the effects of photo-irradiation on the binding characteristics of dissolved organic matter with Hg(II) using FT-IR and synchronous fluorescence two-dimensional correlation spectroscopy (2D-COS). Results showed that the binding of Hg(II) onto humic acid (HA) followed the order of humic-like fraction > fulvic-like fraction > protein-like fraction and photo-irradiation did not affect this order. The binding affinity of each site within the fluorescent fraction was affected by the photoreaction patterns. Pre irradiation of HA before Hg(II) binding changed its structures and binding ability. UV irradiation showed a more obvious effect on Hg(II)-HA complexes than solar irradiation, and UV irradiation enhanced the reactivity of aromatic groups of HA. The amine or amide N-H of HA played a leading role in binding with Hg(II) in the dark, whereas the aromatic amine C-N became dominant after UV irradiation. In fulvic acid (FA), the aromatic hydrogen C-H played a leading role in Hg(II) binding in the dark, but solar irradiation promoted the binding ability of polysaccharide C-O and the carboxyl C=O became dominant after UV irradiation. The response sensitivity of the fulvic-like fraction to Hg(II) was higher than that of the protein-like fraction in FA. Multiple types of sites binding to Hg(II) were verified in the fulvic-like fraction and protein-like fraction of FA. These findings provide new insight into photo-induced structural changes of DOM upon Hg binding.