title: Binding of HgII to high-affinity sites on bacteria inhibits reduction to Hg0 by mixed FeII/III phases.
abstract: Magnetite and green rust have been shown to reduce aqueous Hg(II) to Hg(0). In this study, we tested the ability of magnetite and green rust to reduce Hg(II) sorbed to 2 g · L(-1) of biomass (Bacillus subtilis), at high (50 μM) and low (5 μM) Hg loadings and at pH 6.5 and 5.0. At high Hg:biomass loading, where Hg(II) binding to biomass is predominantly through carboxyl functional groups, Hg L(III)-edge X-ray absorption spectroscopy showed reduction of Hg(II) to Hg(0) by magnetite. Reduction occurred within 2 h and 2 d at pH 6.5 and 5.0, respectively. At low Hg:biomass loading, where Hg(II) binds to biomass via sulfhydryl functional groups, Hg(II) was not reduced by magnetite at pH 6.5 or 5.0 after 2 months of reaction. Green rust, which is generally a stronger reductant than magnetite, reduced about 20% of the total Hg(II) bound to biomass via sulfhydryl groups to Hg(0) in 2 d. These results suggest that Hg(II) binding to carboxyl groups does not significantly inhibit the reduction of Hg(II) by magnetite. However, the binding of Hg(II) to biomass via sulfhydryl groups severely inhibits the ability of mixed Fe(II/III) phases like magnetite and green rust to reduce Hg(II) to Hg(0). The mobility of heavy metal contaminants in aquatic and terrestrial environments is greatly influenced by their speciation, especially their oxidation state. In the case of Hg, reduction of Hg(II) to Hg(0) can increase Hg mobility because of the volatility of Hg(0). Since Hg is typically present in aquatic and terrestrial systems at low concentrations, binding of Hg(II) to high-affinity sites on bacteria could have important implications for the potential reduction of Hg(II) to Hg(0) and the overall mobility of Hg in biostimulated subsurface environments.
authors.affiliation: Biosciences Division, Argonne National Laboratory, Argonne, Illinois 60439, United States. bmishra@anl.gov
authors.forename: Bhoopesh
authors.initials: B
authors.lastname: Mishra
authors.forename: Edward J
authors.initials: EJ
authors.lastname: O'Loughlin
authors.forename: Maxim I
authors.initials: MI
authors.lastname: Boyanov
authors.forename: Kenneth M
authors.initials: KM
authors.lastname: Kemner
mesh_terms: D000327:Adsorption; D001412:Bacillus subtilis / Q000737:chemistry*; D001665:Binding Sites; D018533:Biomass; D052203:Ferrosoferric Oxide / Q000737:chemistry*; D008628:Mercury / Q000737:chemistry*; D010084:Oxidation-Reduction; D019163:Reducing Agents / Q000737:chemistry*
chemical_list: D019163:Reducing Agents; D008628:Mercury; D052203:Ferrosoferric Oxide