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A molecular level understanding of the thermodynamics and kinetics of the chemical bonding between mercury, Hg(II), and natural organic matter (NOM) associated thiol functional groups (NOM-RSH) is required if bioavailability and transformation processes of Hg in the environment are to be fully understood. This study provides the thermodynamic stability of the Hg(NOM-RS) structure using a robust method in which cysteine (Cys) served as a competing ligand to NOM (Suwannee River 2R101N sample) associated RSH groups. The concentration of the latter was quantified to be 7.5 ± 0.4 μmol g NOM by Hg L-edge EXAFS spectroscopy. The Hg(Cys) molecule concentration in chemical equilibrium with the Hg(II)-NOM complexes was directly determined by HPLC-ICPMS and losses of free Cys due to secondary reactions with NOM was accounted for in experiments using H NMR spectroscopy andC isotope labeled Cys. The log K ± SD for the formation of the Hg(NOM-RS) molecular structure, Hg + 2NOM-RS = Hg(NOM-RS), and for the Hg(Cys)(NOM-RS) mixed complex, Hg + Cys + NOM-RS = Hg(Cys)(NOM-RS), were determined to be 40.0 ± 0.2 and 38.5 ± 0.2, respectively, at pH 3.0. The magnitude of these constants was further confirmed by H NMR spectroscopy and the Hg(NOM-RS) structure was verified by Hg L-edge EXAFS spectroscopy. An important finding is that the thermodynamic stabilities of the complexes Hg(NOM-RS), Hg(Cys)(NOM-RS) and Hg(Cys) are very similar in magnitude at pH values <7, when all thiol groups are protonated. Together with data on 15 low molecular mass (LMM) thiols, as determined by the same method ( Liem-Ngyuen et al. Thermodynamic stability of mercury(II) complexes formed with environmentally relevant low-molecular-mass thiols studied by competing ligand exchange and density functional theory . Environ. Chem. 2017 , 14 , ( 4 ), 243 - 253 .), the constants for Hg(NOM-RS) and Hg(Cys)(NOM-RS) represent an internally consistent thermodynamic data set that we recommend is used in studies where the chemical speciation of Hg(II) is determined in the presence of NOM and LMM thiols.

Cellular uptake of inorganic divalent mercury (Hg(II)) is a key step in microbial formation of neurotoxic methylmercury (MeHg), but the mechanisms remain largely unidentified. We show that the iron reducing bacterium Geobacter sulfurreducens produces and exports appreciable amounts of low molecular mass thiol (LMM-RSH) compounds reaching concentrations of about 100 nM in the assay medium. These compounds largely control the chemical speciation and bioavailability of Hg(II) by the formation of Hg(LMM-RS) 2 complexes (primarily with cysteine) in assays without added thiols. By characterizing these effects, we show that the thermodynamic stability of Hg(II)-complexes is a principal controlling factor for Hg(II) methylation by this bacterium such that less stable complexes with mixed ligation involving LMM-RSH, OH − , and Cl − are methylated at higher rates than the more stable Hg(LMM-RS) 2 complexes. The Hg(II) methylation rate across different Hg(LMM-RS) 2 compounds is also influenced by the chemical structure of the complexes. In contrast to the current perception of microbial uptake of Hg, our results adhere to generalized theories for metal biouptake based on metal complexation with cell surface ligands and refine the mechanistic understanding of Hg(II) availability for microbial methylation.

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