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Title: Competitive exchange between divalent metal ions [Cu(II), Zn(II), Ca(II)] and Hg(II) bound to thiols and natural organic matter

Journal Article · · Journal of Hazardous Materials

Mercuric Hg(II) ion forms exceptionally strong complexes with various organic ligands, particularly thiols and dissolved organic matter (DOM) in natural water. Few studies, however, have experimentally determined whether or not the presence of base cations and transition metal ions, such as Ca(II), Cu(II), and Zn(II), would compete with Hg(II) bound to these ligands, as concentrations of these metal ions are usually orders of magnitude higher than Hg(II) in aquatic systems. Different from previous model predictions, a significant fraction of Hg(II) bound to cysteine (CYS), glutathione (GSH), or DOM was found to be competitively exchanged by Cu(II), but not by Zn(II) or Ca(II). About 20–75% of CYS-bound-Hg(II) [at 2:1 CYS:Hg(II)] and 14–40% of GSH-bound-Hg(II) [at 1:1 GSH:Hg(II)] were exchanged by Cu(II) at concentrations 1–3 orders of magnitude greater than Hg(II). Competitive exchange was also observed between Cu(II) and Hg(II) bound to DOM, albeit to a lower extent, depending on relative abundances of thiol and carboxylate functional groups on DOM and their equilibrium time with Hg(II). When complexed with ethylenediaminetetraacetate (EDTA), most Hg(II) could be exchanged by Cu(II) and Zn(II), as well as Ca(II) at increasing concentrations. Furthermore, these results shed additional light on competitive exchange reactions between Hg(II) and coexisting metal ions and have important implications in Hg(II) chemical speciation and biogeochemical transformation, particularly in contaminated environments containing relatively high concentrations of Hg(II) and metal ions.

Research Organization:
Oak Ridge National Laboratory (ORNL), Oak Ridge, TN (United States)
Sponsoring Organization:
USDOE
Grant/Contract Number:
AC05-00OR22725
OSTI ID:
1824945
Journal Information:
Journal of Hazardous Materials, Journal Name: Journal of Hazardous Materials Journal Issue: 10 Vol. 430; ISSN 0304-3894
Publisher:
ElsevierCopyright Statement
Country of Publication:
United States
Language:
English

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