title: Thermodynamic Modeling of the Solubility and Chemical Speciation of Mercury and Methylmercury Driven by Organic Thiols and Micromolar Sulfide Concentrations in Boreal Wetland Soils.
abstract: Boreal wetlands have been identified as environments in which inorganic divalent mercury (HgII) is transformed to methylmercury (MeHg) by anaerobic microbes. In order to understand this transformation and the mobility and transport of HgIIand MeHg, factors and conditions in control of the solubility and chemical speciation of HgIIand MeHg need to be clarified. Here we explore the ability of thermodynamic models to simulate measured solubility of HgIIand MeHg in different types of boreal wetland soils. With the input of measured concentrations of MeHg, sulfide, eight low molecular mass thiols and thiol groups associated with natural organic matter (NOM), as determined by sulfur K-edge X-ray absorption near-edge structure (XANES) spectroscopy and Hg LIII-edge extended X-ray absorption fine structure spectroscopy (EXAFS), the model could accurately predict porewater concentrations of MeHg in the wetlands. A similar model for HgIIsuccessfully predicted the average level of its concentration in the porewaters, but the variability among samples, driven mainly by the concentration of aqueous inorganic sulfide, was predicted to be larger than measurements. The smaller than predicted variability in HgIIsolubility is discussed in light of possible formation of colloidal HgS(s) passing the 0.22 μm filters used to define the aqueous phase. The chemical speciation of the solid/adsorbed and aqueous phases were dominated by NOM associated thiol complexes for MeHg and by an equal contribution from NOM associated thiols and HgS(s) for HgII.
authors.affiliation: Department of Chemistry, Umeå University , SE-901 87 Umeå, Sweden.
authors.forename: Van
authors.initials: V
authors.lastname: Liem-Nguyen
authors.affiliation: Department of Forest Ecology and Management, Swedish University of Agricultural Sciences , SE-901 83 Umeå, Sweden.
authors.forename: Ulf
authors.identifier: 0000-0001-6939-8799
authors.initials: U
authors.lastname: Skyllberg
authors.affiliation: Department of Chemistry, Umeå University , SE-901 87 Umeå, Sweden.
authors.forename: Erik
authors.identifier: 0000-0001-9570-8738
authors.initials: E
authors.lastname: Björn
mesh_terms: D008628:Mercury; D008767:Methylmercury Compounds / Q000737:chemistry; D012987:Soil; D012995:Solubility; D013438:Sulfhydryl Compounds / Q000737:chemistry; D013440:Sulfides / Q000737:chemistry; D013816:Thermodynamics; D014874:Water Pollutants, Chemical; D053833:Wetlands
chemical_list: D008767:Methylmercury Compounds; D012987:Soil; D013438:Sulfhydryl Compounds; D013440:Sulfides; D014874:Water Pollutants, Chemical; D008628:Mercury