Mercury isotope fractionation during aqueous photoreduction of monomethylmercury in the presence of dissolved organic matter.

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Monomethylmercury (MMHg) is a toxic pollutant that bioaccumulates in aquatic food webs. A major mechanism that limits MMHg uptake by biota is photodemethylation in surface waters. Recently, the extent of mass-independent fractionation (MIF) of Hg isotopes preserved in fish is being used to quantify this MMHg sink. Here, the effects of different types and amounts of DOM on Hg MIF during MMHg photodemethylation were investigated to assess how variable MIF enrichment factors may be with respect to changing DOM binding sites. From experiments conducted with varying amounts of reduced organic sulfur (S(red)-DOM), the extent and signature of MIF is likely dependent on whether MMHg is dominantly bound to S(red)-DOM. Similar enrichment factors were observed for low MMHg:S(red)-DOM experiments, where S(red)-DOM was in far excess of MMHg. In contrast, significantly lower and variable enrichment factors were observed for experiments with higher MMHg:S(red)-DOM ratios. Additionally the relationship between the two odd Hg isotopes that display MIF (Δ(199)Hg/Δ(201)Hg) was consistent for the low MMHg:S(red)-DOM experiments, while lower Δ(199)Hg/Δ(201)Hg relationships were observed for the higher MMHg:S(red)-DOM experiments. These results suggest that both the extent and signature of MMHg MIF are sensitive to different ligands that bind MMHg in nature.