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

Yaoling Zhang, Lijie Zhang, Xujun Liang, Quanying Wang, Xiangping Yin, Eric M. Pierce, Baohua Gu

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10 Scopus citations


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. 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.

Original languageEnglish (US)
Article number127388
JournalJournal of Hazardous Materials
StatePublished - Feb 15 2022
Externally publishedYes

All Science Journal Classification (ASJC) codes

  • Environmental Engineering
  • Environmental Chemistry
  • Waste Management and Disposal
  • Pollution
  • Health, Toxicology and Mutagenesis


  • Biogeochemical cycling
  • Competitive exchange
  • Mercury
  • Organic ligands
  • Transition metals


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