title: Binding of mercury(II) to dissolved organic matter: the role of the mercury-to-DOM concentration ratio.
abstract: The binding of Hg(II) to dissolved organic matter (DOM; hydrophobic acids isolated from the Florida Everglades by XAD-8 resin) was measured at a wide range of Hg-to-DOM concentration ratios using an equilibrium dialysis ligand exchange method. Conditional distribution coefficients (K(DOM)') determined by this method were strongly affected by the Hg/DOM concentration ratio. At Hg/DOM ratios below approximately 1 microg of Hg/mg of DOM, we observed very strong interactions (K(DOM)' = 10(23.2+/-1.0) L kg(-1) at pH = 7.0 and I = 0.1), indicative of mercury-thiol bonds. Hg/DOM ratios above approximately 10 microg of Hg/mg of DOM, as used in most studies that have determined Hg-DOM binding constants, gave much lower K(DOM)' values (10(10.7+/-1.0) L kg(-1) at pH = 4.9-5.6 and I = 0.1), consistent with Hg binding mainly to oxygen functional groups. These results suggest that the binding of Hg to DOM under natural conditions (very low Hg/DOM ratios) is controlled by a small fraction of DOM molecules containing a reactive thiol functional group. Therefore, Hg/DOM distribution coefficients used for modeling the biogeochemical behavior of Hg in natural systems need to be determined at low Hg/DOM ratios.
authors.affiliation: U.S. Geological Survey, Water Resources Division, Boulder, Colorado 80303, USA. mhaitzer@usgs.gov
authors.forename: Markus
authors.initials: M
authors.lastname: Haitzer
authors.forename: George R
authors.initials: GR
authors.lastname: Aiken
authors.forename: Joseph N
authors.initials: JN
authors.lastname: Ryan
mesh_terms: D007700:Kinetics; D008628:Mercury / Q000737:chemistry*; D008956:Models, Chemical; D009930:Organic Chemicals; D014867:Water / Q000737:chemistry; D014873:Water Pollutants / Q000032:analysis*
chemical_list: D009930:Organic Chemicals; D014873:Water Pollutants; D014867:Water; D008628:Mercury