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The most critical step for methylmercury (MeHg) bioaccumulation in aquatic food webs is phytoplankton uptake of dissolved MeHg. Dissolved organic matter (DOM) has been known to influence MeHg uptake, but the mechanisms have remained unclear. Here we show that the concentration of DOM-associated thiol functional groups (DOM-RSH) varies substantially across contrasting aquatic systems and dictates MeHg speciation and bioavailability to phytoplankton. Across our 20 study sites, DOM-RSH concentrations decrease 40-fold from terrestrial to marine environments whereas dissolved organic carbon (DOC), the typical proxy for MeHg binding sites in DOM, only has a 5-fold decrease. MeHg accumulation into phytoplankton is shown to be directly linked to the concentration of specific MeHg binding sites (DOM-RSH), rather than DOC. Therefore, MeHg bioavailability increases systematically across the terrestrial-marine aquatic continuum as the DOM-RSH concentration decreases. Our results strongly suggest that measuring DOM-RSH concentrations will improve empirical models in phytoplankton uptake studies and will form a refined basis for modeling MeHg incorporation in aquatic food webs under various environmental conditions.

Sediments represent the main reservoir of mercury (Hg) in aquatic environments and may act as a source of Hg to aquatic food webs. Yet, accumulation routes of Hg from the sediment to benthic organisms are poorly constrained. We studied the bioaccumulation of inorganic and methylmercury (HgII and MeHg, respectively) from different geochemical pools of Hg into four groups of benthic invertebrates (amphipods, polychaetes, chironomids, and bivalves). The study was conducted using mesocosm experiments entailing the use of multiple isotopically enriched Hg tracers and simulation of estuarine systems with brackish water and sediment. We applied different loading regimes of nutrients and terrestrial organic matter and showed that the vertical localization and the chemical speciation of HgII and MeHg in the sediment, in combination with the diet composition of the invertebrates, consistently controlled the bioaccumulation of HgII and MeHg into the benthic organisms. Our results suggest a direct link between the concentration of MeHg in the pelagic planktonic food web and the concentration of MeHg in benthic amphipods and, to some extent, in bivalves. In contrast, the quantity of MeHg in benthic chironomids and polychaetes seems to be driven by MeHg accumulation via the benthic food web. Accounting for these geochemical and dietary drivers of Hg bioaccumulation in benthic invertebrates will be important to understand and predict Hg transfer between the benthic and the pelagic food web, under current and future environmental scenarios.

The potent neurotoxin methylmercury (MeHg) is a major concern due to its negative effects on wildlife and human health. Boreal wetlands play a crucial role in Hg cycling on a global scale, and therefore, it is crucial to understand the biogeochemical processes involved in MeHg formation in this landscape element. By combining high-throughput hgcA amplicon sequencing with molecular barcoding, we reveal diverse clades of potential HgII methylators in a wide range of wetland soils. Among Bacteria, Desulfuromonadota (14% of total reads), Desulfurobacterota_A, and Desulfurobacterota (up to 6% of total reads), previously classified as Deltaproteobacteria, were important members of the hgcA+ microbial community in the studied wetlands. We also identified Actinobacteriota (9.4% of total reads), Bacteroidota (2% of total reads), and Firmicutes (1.2% of total reads) as members of the hgcA+ microbial community. Within Archaea, Methanosarcinales represented up to 2.5% of the total reads. However, up to half of the hgcA+ community could not be resolved beyond domain Bacteria. Our survey also shows that local physicochemical conditions, such as pH, nutrient concentrations, water content, and prevailing redox states, are important for shaping the hgcA+ microbial community structure across the four studied wetlands. Furthermore, we observed a significant correlation between HgII methylation rate constants and the structure of the hgcA+ microbial community. Our findings expand the current knowledge on the hgcA+ microbial community composition in wetlands and the physicochemical factors underpinning spatial heterogeneity in such communities.

Methylmercury (MeHg) is a neurotoxin formed from inorganic divalent mercury (Hg-II) via microbial methylation, and boreal wetlands have been identified as major sources of MeHg. There is however a lack of studies investigating the relationship between the chemical speciation of Hg-II and MeHg formation in such environments, in particular regarding to role of thiol compounds. We determined Hg-II methylation potentials, k(meth), in boreal wetland soils using two Hg-II isotope tracers: Hg-198(OH)(2)(aq) and Hg-II bonded to thiol groups in natural organic matter, Hg-200(II)-NOM(ads), representing Hg-II sources with high and low availability for methylation. The Hg-198(OH)(2)(aq) tracer was consistently methylated to a 5-fold higher extent than Hg-200(II)-NOM(ads), independent of environmental conditions. This suggests that the concentration of Hg-II in porewater was a decisive factor for Hg-II methylation. A comprehensive thermodynamic speciation model (including Hg-II complexes with inorganic sulfide (H2S), polysulfides (H2Sn), thiols associated with natural organic matter (NOM-RSH) and specific low molecular mass thiols (LMM-RSH) provided new insights on the speciation of Hg-II in boreal wetland porewaters, but did not demonstrate any clear relationship between k(meth) and the calculated chemical speciation. In contrast, significant positive relationships were observed between k(meth) and the sum of LMM thiol compounds of biological origin. We suggest two possible mechanisms underlying these correlations: 1) LMM thiols kinetically control the size and composition of the HgII pool available for microbial uptake, and/or 2) LMM thiols are produced by microbes such that the correlation reflects a relation between microbial activity and MeHg formation. (C) 2020 The Author(s). Published by Elsevier B.V.

We present a sensitive, selective and robust method for the determination of 14 thiol compounds in aqueous samples. Thiols were derivatized with omega-bromoacetonylquinolinium bromide (BQB) and its deuterium labeled equivalent D7-ω-bromoacetonylquinolinium bromide (D7). Derivatized thiols were preconcentrated by online solid-phase extraction (SPE) followed by liquid chromatography separation and electrospray ionization tandem mass spectrometry determination (SPE/LC-ESI-MS/MS). The robustness of the method was validated for wide ranges in pH, salinity, and concentrations of sulfide and dissolved organic carbon (DOC) to cover contrasting natural water types. The limits of detection (LODs) for the thiols were 3.1-66 pM. Between 6 and 14 of the thiols were detected in different natural sample types at variable concentrations: boreal wetland porewater (0.7-51 nM), estuarine sediment porewater (50 pM-11 nM), coastal sea water (60 pM-16 nM), and sulfate reducing bacterium cultures (80 pM-4 nM). MS/MS fragmentation of the compounds produces two pairs of common product ions, m/z 130.2/137.1 and 218.1/225.1, which enables scanning for unknown thiols in precursor ion scan mode. Using this approach, we identified cysteine, mercaptoacetic acid, N-acetyl-L-cysteine and sulfurothioic S-acid in boreal wetland porewater. The performance of the developed method sets a new state of the art for the determination of thiol compounds in environmental and biological samples.

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)<INF><INF><INF>2</INF></INF> </INF>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)<INF>2</INF> complexes. The Hg(II) methylation rate across different Hg(LMM-RS)<INF>2</INF> 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.

Oxygen-depleted areas are spreading in coastal and offshore waters worldwide, but the implication for production and bioaccumulation of neurotoxic methylmercury (MeHg) is uncertain. We combined observations from six cruises in the Baltic Sea with speciation modeling and incubation experiments to gain insights into mercury (Hg) dynamics in oxygen depleted systems. We then developed a conceptual model describing the main drivers of Hg speciation, fluxes, and transformations in water columns with steep redox gradients. MeHg concentrations were 2-6 and 30-55 times higher in hypoxic and anoxic than in normoxic water, respectively, while only 1-3 and 1-2 times higher for total Hg (THg). We systematically detected divalent inorganic Hg (Hg-II) methylation in anoxic water but rarely in other waters. In anoxic water, high concentrations of dissolved sulfide cause formation of dissolved species of Hg-II: HgS2H(aq)- and Hg (SH)(2)(0)((aq)). This prolongs the lifetime and increases the reservoir of Hg-II readily available for methylation, driving the high MeHg concentrations in anoxic zones. In the hypoxic zone and at the hypoxic-anoxic interface, Hg concentrations, partitioning, and speciation are all highly dynamic due to processes linked to the iron and sulfur cycles. This causes a large variability in bioavailability of Hg, and thereby MeHg concentrations, in these zones. We find that zooplankton in the summertime are exposed to 2-6 times higher MeHg concentrations in hypoxic than in normoxic water. The current spread of hypoxic zones in coastal systems worldwide could thus cause an increase in the MeHg exposure of food webs.

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 HgII and MeHg, factors and conditions in control of the solubility and chemical speciation of HgII and MeHg need to be clarified. Here we explore the ability of thermodynamic models to simulate measured solubility of HgII and 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 HgII successfully 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 HgII solubility 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.

Boreal wetlands have been identified as environmentsin 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 HgII and MeHg, factors and conditions in control of the solubility and chemical speciation of HgII and MeHg need to be clarified. Here we explore the ability of thermodynamic models to simulate measuredsolubility of HgII and 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 naturalorganic matter (NOM), as determined by sulfur K-edge X-rayabsorption near-edge structure (XANES) spectroscopy and Hg LIII-edgeextended X-ray absorption fine structure spectroscopy (EXAFS),the model could accurately predict porewater concentrations of MeHg in the wetlands. A similar model for HgII successfully 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 HgII solubility 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 aqueousphases were dominated by NOM associated thiol complexes for MeHg and by an equal contribution from NOM associated thiolsand HgS(s) for HgII.

Inorganic divalent mercury (Hg-II) has a very high affinity for reduced sulfur functional groups. Reports from laboratory experiments suggest that Hg-II complexes with specific low-molecular-mass (LMM) thiol (RSH) ligands control rates of Hg-II transformation reactions. Because of methodological limitations for precise determination of the highly stable Hg-II complexes with LMM thiol ligands, constants reported in the literature remain inconsistent. This uncertainty impedes accurate modelling of the chemical speciation of Hg-II and the possibility to elucidate the role of Hg-II complexes with LMM thiols for Hg transformation reactions. Here, we report values of thermodynamic stability constants for 15 monodentate, two-coordinated Hg-II complexes, Hg(SR)(2), formed with biogeochemically relevant LMM thiol ligands. The constants were determined by a two-step ligand-exchange procedure where the specific Hg(SR)(2) complexes were quantified by liquid chromatography-inductively coupled plasma mass spectrometry. Thermodynamic stability constants (log (2)) determined for the Hg(SR)(2) complexes ranged from 34.6, N-cysteinylglycine, to 42.1, 3-mercaptopropionic acid, for the general reaction Hg2++2RS(-) Hg(SR)(2). Density functional theory (DFT) calculations showed that electron-donating carboxyl and carbonyl groups have a stabilising effect on the Hg-II-LMM thiol complexes, whereas electron-withdrawing protonated primary amino groups have a destabilising effect. Experimental results and DFT calculations demonstrated that the presence of such functional groups in the vicinity of the RSH group caused significant differences in the stability of Hg(SR)(2) complexes. These differences are expected to be important for the chemical speciation of Hg-II and its transformation reactions in environments where a multitude of LMM thiol compounds are present.