title: Mercury methylation rates for geochemically relevant Hg(II) species in sediments.
abstract: Monomethylmercury (MeHg) in fish from freshwater, estuarine, and marine environments is a major global environmental issue. Mercury levels in biota are mainly controlled by the methylation of inorganic mercuric mercury (Hg(II)) to MeHg in water, sediments, and soils. There is, however, a knowledge gap concerning the mechanisms and rates of methylation of specific geochemical Hg(II) species. Such information is crucial for a better understanding of variations in MeHg concentrations among ecosystems and, in particular, for predicting the outcome of currently proposed measures to mitigate mercury emissions and reduce MeHg concentrations in fish. To fill this knowledge gap we propose an experimental approach using Hg(II) isotope tracers, with defined and geochemically important adsorbed and solid Hg(II) forms in sediments, to study MeHg formation. We report Hg(II) methylation rate constants, k(m), in estuarine sediments which span over 2 orders of magnitude depending on chemical form of added tracer: metacinnabar (β-(201)HgS(s)) < cinnabar (α-(199)HgS(s)) < Hg(II) reacted with mackinawite (≡FeS-(202)Hg(II)) < Hg(II) bonded to natural organic matter (NOM-(196)Hg(II)) < a typical aqueous tracer ((198)Hg(NO(3))(2)(aq)). We conclude that a combination of thermodynamic and kinetic effects of Hg(II) solid-phase dissolution and surface desorption control the Hg(II) methylation rate in sediments and cause the large observed differences in k(m)-values. The selection of relevant solid-phase and surface-adsorbed Hg(II) tracers will therefore be crucial to achieving biogeochemically accurate estimates of ambient Hg(II) methylation rates.
authors.affiliation: Department of Chemistry, Umeå University, SE-901 87 Umeå, Sweden.
authors.forename: Sofi
authors.initials: S
authors.lastname: Jonsson
authors.forename: Ulf
authors.initials: U
authors.lastname: Skyllberg
authors.forename: Mats B
authors.initials: MB
authors.lastname: Nilsson
authors.forename: Per-Olof
authors.initials: PO
authors.lastname: Westlund
authors.forename: Andrey
authors.initials: A
authors.lastname: Shchukarev
authors.forename: Erik
authors.initials: E
authors.lastname: Lundberg
authors.forename: Erik
authors.initials: E
authors.lastname: Björn
mesh_terms: D000327:Adsorption; D019015:Geologic Sediments; D007700:Kinetics; D008628:Mercury / Q000737:chemistry*; D008745:Methylation; D008767:Methylmercury Compounds / Q000737:chemistry*; D012995:Solubility; D013816:Thermodynamics; D014874:Water Pollutants, Chemical / Q000737:chemistry*
chemical_list: D008767:Methylmercury Compounds; D014874:Water Pollutants, Chemical; D008628:Mercury