MeHg Production Research Articles

Aerobic and Anaerobic Bacterial Mercury Uptake is Driven by Algal Organic Matter Composition and Molecular Weight.

The biological mobilization of mercury (Hg) into microbes capable of Hg methylation is one of the limiting steps in the formation of the neurotoxin methylmercury (MeHg). Although algal dissolved organic matter (DOM) has been associated with increased MeHg production, the relationship between bacterial Hg uptake and algal DOM remains unexplored. In this study, we aimed to address how the quantity and quality of DOM, freshly harvested from several algae, affected the bacterial uptake of Hg with the use of a biosensor capable of functioning both aerobically and anaerobically. We combined biosensor measurements with high-resolution mass spectrometry and field-flow fractionation to elucidate how DOM composition and molecular weight influenced microbial Hg uptake. We showed that freshly harvested DOM from Chlorophyte and Euglena mutabilis strongly inhibited aerobic and anaerobic Hg uptake, whereas DOM harvested from Euglena gracilis did not exhibit this same pronounced effect. Once fractionated, we found that amino acids and polyamines, most abundant in Euglena gracilis DOM, were positively correlated to increase Hg uptake, suggesting that these molecules are potentially underappreciated ligands affecting Hg bioavailability. As water quality is affected by eutrophication, algal community assemblages will change, leading to variations in the nature of autochthonous DOM released in aquatic systems. Our results highlight that variations in the emergent properties of DOM originating from varying algal species can have a profound effect on bacterial Hg uptake and thus methylation.

Total Hg and methylmercury dynamics in a river-floodplain system in the Western Amazon: Influence of seasonality, organic matter and physical and chemical parameters

Total mercury (Hg) and methylmercury (MeHg) circulation in a connected river-floodplain system composed of two black water (a small forest river, igarapé, and Cuniã Lake) and a white water body (Madeira River), located in the Madeira River Basin were evaluated during the rising-water, early and late falling-water periods. We assessed organic matter (C and N composition, (C:N)a; and δ13C isotopic signature), and physical and chemical influences (pH, dissolved O2, electric conductivity) in relationship to Hg and MeHg concentrations. Hg and MeHg concentrations in a sediment profile and three aquatic macrophytes (E. crassipes, E. azuera and Oryza sp.) were measured. Igarapé and Cuniã Lake showed higher Hg and MeHg concentrations (115–709; 10–25 ng g−1) in the suspended particulate matter compared (SPM) compared to the Madeira River (Hg: 5–16; MeHg: 0.2–0.3 ng g−1), partially independent of seasonality (p = 0.06). Total Hg had higher affinity for the SPM (1.75 times) than for dissolved organic matter. Organic matter characteristics correlated with MeHg concentrations (δ13C and (C:N)a; r2 = 0.79; p < 0.0001), as well as physical and chemical parameters of the water column (dissolved O2 and pH; r2 = 0.80; p < 0.0001), demonstrating that physical and chemical changes between the river-floodplain system affect MeHg circulation and production. The inverse correlation of MeHg and SO42− concentrations (r2 = 0.73; p < 0.0001) suggests the action of sulfate-reducing bacteria. Total Hg and MeHg concentrations as well as %MeHg were detected in the sediment profile (Hg: 24–51; MeHg: 0.6–3.2 ng g−1; %MeHg: 1.8–6.2) and aquatic macrophytes (Hg: 1–30; MeHg: 0.3–7.5 ng g−1; %MeHg: 1.6–33.7). We conclude that the highest Hg and MeHg concentrations in Cuniã Lake, compared to the Madeira River, are due to the physical and chemical differences between these environments.

Biochar amendment to further reduce methylmercury accumulation in rice grown in selenium-amended paddy soil.

Methylmercury (MeHg) accumulation in rice is an emerging food safety issue in China and other countries; however, mitigation methods are scarce. Here, the effects of selenium (Se) and multiple applications of Se and biochar on rice MeHg bioaccumulation were investigated using pot and microcosm experiments. We report that Se amendment was still effective in reducing MeHg levels in paddy soil and rice grain after three years of aging. Biochar amendment (0.5% w/w) further decreased grain (brown rice) MeHg levels by 82-87%. The grain MeHg level decrease following the combination of Se and biochar amendment could be partly attributed to inhibition of net MeHg production in soil by Se. In addition, biochar decreased not only net MeHg production but also MeHg bioavailability in the soil, which could be due to organosulfur compounds in the biochar. Our findings suggest that multiple applications of Se and biochar could be a novel remediation strategy to mitigate MeHg accumulation in rice.

Inhibitory effects of Skeletonema costatum on mercury methylation by Geobacter sulfurreducens PCA

Algae and mercury (Hg) are ubiquitous in marine environments. In this study, we investigated the effects of a typical marine algae of diatom Skeletonema costatum on Hg methylation by an iron-reducing bacterium of Geobacter sulfurreducens (G. sulfurreducens) PCA. In the absence of Skeletonema costatum, the bacterial MeHg production rate maximized at 104.06 ± 11.7 ng L−1 h−1 with a high Hg level, while the highest methylation efficiency was achieved at a low Hg concentration. The existence of Skeletonema costatum greatly inhibited the capability of G. sulfurreducens PCA to methylate Hg. With the increase in algal biomass, there was a significant mitigation of MeHg formation and Hg0 release, leaving a considerable proportion of immobilized Hg2+ species (up to 47%) associated with algal cell materials. These results suggest that marine algae are crucial in determining the bioavailability of Hg contaminants and the methylating potential of G. sulfurreducens PCA.

Methylmercury in environmental compartments of a hydroelectric reservoir in the Western Amazon, Brazil

Damming rivers to generate electricity creates a lentic environment that favors methylmercury (MeHg) formation. Reservoirs in the Amazon are critical environments for MeHg formation, considering its old soils and the use of Hg in gold mining in the region. The objective of this study was to evaluate MeHg accumulation in three environmental compartments (aquatic macrophytes, suspended particulate matter (SPM) and sediment) of the Samuel reservoir (Western Amazon, Brazil), during the low water, ebb and high water hydrological periods, characterizing the dry season, the end of the rainy season and the rainy season, respectively. MeHg concentrations were determined through GC-AFS. The aquatic macrophytes presented higher %MeHg in their roots (up to 12%) compared to their other tissues. This ratio was 1.7 and 5.9 times higher than those observed for SPM and the sediment, but MeHg concentrations were the lowest (0.5–4.5 ng g−1) among the three environmental compartments. Contrary, the highest MeHg concentration was observed in SPM (104 ng g−1) during the low water period. The MeHg concentration in the sediment profile decreased with increasing depth (0.93–0.48 ng g−1) and with decreasing organic matter lability (increasing C:N ratio). In the SPM, on the other hand, MeHg concentration showed a positive association with increasing C:N ratio. We conclude that MeHg dynamics in the SPM are associated with the hydrological periods, with peaks during the low water period. The organic matter lability of the sediments is more limiting to the production of MeHg than the total Hg concentrations.

Quantitative Proteomic Analysis of Biological Processes and Responses of the Bacterium Desulfovibrio desulfuricans ND132 upon Deletion of Its Mercury Methylation Genes.

Recent studies of microbial mercury (Hg) methylation revealed a key gene pair, hgcAB, which is essential for methylmercury (MeHg) production in the environment. However, many aspects of the mechanism and biological processes underlying Hg methylation, as well as any additional physiological functions of the hgcAB genes, remain unknown. Here, quantitative proteomics are used to identify changes in potential functional processes related to hgcAB gene deletion in the Hg-methylating bacterium Desulfovibrio desulfuricans ND132. Global proteomics analyses indicate that the wild type and ΔhgcAB strains are similar with respect to the whole proteome and the identified number of proteins, but differ significantly in the abundance of specific proteins. The authors observe changes in the abundance of proteins related to the glycolysis pathway and one-carbon metabolism, suggesting that the hgcAB gene pair is linked to carbon metabolism. Unexpectedly, the authors find that the deletion of hgcAB significantly impacts a range of metal transport proteins, specifically membrane efflux pumps such as those associated with heavy metal copper (Cu) export, leading to decreased Cu uptake in the ΔhgcAB mutant. This observation indicates possible linkages between this set of proteins and metal homeostasis in the cell. However, hgcAB gene expression is not induced by Hg, as evidenced by similarly low abundance of HgcA and HgcB proteins in the absence or presence of Hg (500nm). Taken together, these results suggest an apparent link between HgcAB, one-carbon metabolism, and metal homeostasis, thereby providing insights for further exploration of biochemical mechanisms and biological functions of microbial Hg methylation.

Nitrogen and sulfur isotopes predict variation in mercury levels in Arctic seabird prey

Mercury (Hg) biotransformation and biomagnification are processes that affect Hg burdens in wildlife. To interpret variation in Hg in seabird eggs, used as Hg bioindicators in the Arctic, it is important to understand how Hg biomagnifies through the food web. We evaluated the use of δ34S, along with other commonly used stable isotope signatures (δ15N and δ13C), for the determination of possible sources of Hg in an Arctic food web (56 individuals of 15 species of fish and invertebrates). Hg correlated with δ34S (R2 = 0.72). When the combined effects of δ34S and δ15N were considered in mixed-effects models, both δ34S and δ15N together described Hg patterns in Arctic food webs better than either isotope alone. Our results demonstrate the usefulness of δ34S to account for variation in Hg among marine animals and to study the possible underlying effects that MeHg production may have on Hg pathways in Arctic ecosystems.

Effect of oxygen, nitrate and aluminum addition on methylmercury efflux from mine-impacted reservoir sediment

Extensive contamination of aquatic ecosystems with mercury (Hg) has led to a growing interest in developing in situ management strategies to repress Hg bioaccumulation in aquatic biota in reservoirs. This study used experimental chamber incubations to assess the impact of three potential treatments, oxygen addition, nitrate addition and aluminum addition, to reduce the flux of toxic methylmercury (MeHg) from profundal reservoir sediment. The study sites, Almaden Lake and Guadalupe Reservoir, are located downstream of the historic New Almaden mining district in Santa Clara Valley, California, USA. In the first experiment (experiment 1), replicate chambers from both sites were incubated sequentially under aerobic and anaerobic conditions. At both sites, mean anaerobic fluxes of MeHg were higher than aerobic fluxes (Almaden: 11.0 vs. −2.3 ng/m2·d; Guadalupe: 22.3 vs 5.5 ng/m2·d), and anaerobic MeHg fluxes correlated with rates of sediment sulfate uptake, highlighting the linkage between MeHg production and microbial sulfate reduction. Under aerobic conditions, sediment from Guadalupe Reservoir released Hg(II), iron and sulfate, suggesting the oxidative dissolution of Hg-bearing sulfide minerals. A follow-up study at Almaden Lake (experiment 2) found that mean MeHg fluxes under aerobic conditions (5 ng/m2·d) and anoxic (nitrate-rich) conditions (1.7 ng/m2·d) were lower than anaerobic conditions (174 ng/m2·d), but aluminum addition had little effect (105 ng/m2·d) on MeHg flux. In both anaerobic and aluminum treated chambers, MeHg flux turned negative during the second half of the incubation, suggesting that highly reduced, sulfidic conditions lowered net methylation, possibly by enhancing demethylation or repressing Hg(II) bioavailability for methylation.

Rice root exudates affect microbial methylmercury production in paddy soils

Microbial methylmercury (MeHg) production in contaminated soil-rice systems and its accumulation in rice pose health risks to consumers, especially those in Asia. However, the mechanism responsible for microbial MeHg production in paddy soils is far from clear. While previous studies examined the effect of soil and microbial factors on soil MeHg levels, in this work we explored the impact of rice cultivation itself on microbial MeHg production, focusing on the root exudate organic matter as a potential source of electron donors for microbial methylators. Effects of the cultivation of two rice cultivars, Heigu246 (H-rice) and Neiwuyou8015 (N-rice), on MeHg production in soils were therefore investigated in pot and batch incubation experiments. Soil MeHg levels measured in H-rice treatment during the heading and harvest stages were 18–49% higher than in the control and 23–108% higher than in N-rice treatment. Consequently, MeHg levels in grain, straw, and root were 38%, 81%, and 40% higher in H-rice than those in N-rice, which was mainly attributed to cultivar-specific MeHg production in soils. Results of the batch experiments suggested that root exudate organic matter could be responsible for MeHg production in soils during rice cultivation, by increasing the abundances of potential microbial methylators. For instance, root exudate organic matter increased copy numbers of Hg methylation genes (hgcA) in soils 4.1-fold. Furthermore, the 211% higher concentration of acetate (a key electron donor for microbial methylators) in the root exudate of H-rice could account for the higher MeHg production under H-rice than N-rice cultivation. Our results suggest that root exudate organic matter, especially acetate, as its key component, contributes to the elevated soil MeHg concentrations during rice cultivation. The proposed mechanism provides new insights into the elevated risk of MeHg production in contaminated soil-rice systems, as well as cultivar-specific MeHg bioaccumulation.

Methylmercury levels in cover soils from two landfills in Xi’an and Shanghai, China: Implications for mercury methylation potentials

Landfills are considered important sources of mercury for surrounding ecosystems. Methylmercury (MeHg) levels in waste layers have been studied extensively; however, the levels of MeHg in cover soils remain undefined. Here, total mercury (THg) and MeHg concentrations in surface cover soils and soil cores from two landfills in China and possible factors affecting Hg methylation were studied. The mean MeHg concentration in surface cover soils from both landfills was 0.048 ng g−1, suggesting that cover soil layers are not active sites of MeHg production. Soil MeHg concentrations in both landfills were affected little by closure time. In the Jiangcungou landfill, no correlations between MeHg concentration and the measured environmental factors (e.g., THg, soil pH, organic matter (OM), and S) were observed that indicated that these parameters might have indirect effects on MeHg concentration. However, in the Laogang landfill, significant correlations were found between MeHg concentration and the measured environmental factors. The results showed that MeHg concentration in the surface cover soil from area D of the Laogang landfill is regulated mainly by soil pH, OM, and S, and that its vertical distribution in areas C and D is regulated mainly by soil pH and soil OM, respectively. These findings fill a knowledge gap regarding MeHg levels in cover soils and they advance our understanding of Hg cycling in landfills, presenting positive implications for landfill management and risk assessment of MeHg.

Fifty years after its discharge, methylation of legacy mercury trapped in the Penobscot Estuary sustains high mercury in biota

Fifty years ago, the Penobscot Estuary was contaminated by mercury discharged from the chlor-alkali plant located in Orrington, Maine, USA. Almost all of the mercury was discharged from the plant during the late 1960s and early 1970s. Despite the much lower mercury discharges in recent decades, present-day concentrations in surface sediment remain high (averaging 350–1100 ng/g dw) and are still high in blood of marsh birds (up to 10.5 μg/g), black duck muscle (0.8 μg/g), and lobster muscle (0.4 μg/g). Methyl mercury (MeHg) concentrations in marsh birds exceed levels that impair reproduction. There are health advisories for duck hunters and closures of shellfish fisheries. These continuing high mercury concentrations are caused by the trapping of legacy mercury in a mobile pool of sediment that is retained in the upper estuary above a tidally forced salinity front, which travels up and down the estuary each tidal cycle - slowing the transport of particulate mercury to Penobscot Bay. The trapped legacy mercury continues to be available for methylation 50 years after it first entered the estuary. This is demonstrated by the fact that rates of MeHg production are positively related to the inorganic mercury concentration in parts of the estuary with elevated concentrations of legacy mercury. Thus, remediation measures that would lower the THg concentration in surface sediment would lower the MeHg in birds, fish and shellfish. All of this new information leads us to recommend two remediation options. Addition of mercury binding agents may lower mercury concentrations in birds in some wetland areas. System-wide, we also recommend Enhanced Natural Recovery (ENR), a novel approach that involves the partial removal of the contaminated mobile sediment pool followed by replacement with clean-clay particulates to dilute inorganic mercury concentrations, which would lower methylation rates and mercury concentrations in biota.

Quantification of Mercury Bioavailability for Methylation Using Diffusive Gradient in Thin-Film Samplers.

Mercury-contaminated sediment and water contain various Hg species, with a small fraction available for microbial conversion to the bioaccumulative neurotoxin monomethylmercury (MeHg). Quantification of this available Hg pool is needed to prioritize sites for risk management. This study compared the efficacy of diffusive gradient in thin-film (DGT) passive samplers to a thiol-based selective extraction method with glutathione (GSH) and conventional filtration (<0.2 μm) as indicators of Hg bioavailability. Anaerobic sediment slurry microcosms were amended with isotopically labeled inorganic Hg “endmembers” (dissolved Hg2+, Hg-humic acid, Hg-sorbed to FeS, HgS nanoparticles) with a known range of bioavailability and methylation potentials. Net MeHg production (expressed as percent of total Hg as MeHg) over 1 week correlated with mass accumulation of Hg endmembers on the DGTs and only sometimes correlated with the 0.2 μm filter passing Hg fraction and the GSH-extractable Hg fraction. These results suggest for the first time that inorganic Hg uptake in DGTs may indicate bioavailability for methylating microbes. Moreover, the methylating microbial community assessed by hgcA gene abundance was not always consistent with methylation rates between the experiments, indicating that knowledge of the methylating community should target the transcript or protein level. Altogether, these results suggest that DGTs could be used to quantify the bioavailable Hg fraction as part of a method to assess net MeHg production potential in the environment.

Geochemical modeling of mercury speciation in surface water and implications on mercury cycling in the everglades wetland

The geochemical model PHREEQC, abbreviated from PH (pH), RE (redox), EQ (equilibrium), and C (program written in C), was employed on the datasets generated by the USEPA Everglades Regional Environmental Monitoring and Assessment Program (R-EMAP) to determine the speciation distribution of inorganic mercury (iHg) in Everglades water and to explore the implications of iHg speciation on mercury cycling. The results suggest that sulfide and DOM were the key factors that regulate inorganic Hg speciation in the Everglades. When sulfide was present at measurable concentrations (>0.02 mg/L), Hg-S complexes dominated iHg species, occurring in the forms of HgS22−, HgHS2−, and Hg(HS)2 that were affected by a variety of environmental factors. When sulfide was assumed nonexistent, Hg-DOM complexes occurred as the predominant Hg species, accounting for almost 100% of iHg species. However, when sulfide was presumably present at a very low, environmentally relevant concentration (3.2 × 10−7 mg/L), both Hg-DOM and Hg-S complexes were present as the major iHg species. These Hg-S species and Hg-DOM complex could be related to methylmercury (MeHg) in environmental matrices such floc, periphyton, and soil, and the correlations are dependent upon different circumstances (e.g., sulfide concentrations). The implications of the distribution of iHg species on MeHg production and fate in the Everglades were discussed.

Distribution and biogeochemical controls on net methylmercury production in Penobscot River marshes and sediment

The distribution of mercury and methylmercury (MeHg) in sediment, mudflats, and marsh soils of the Hg-contaminated tidal Penobscot River was investigated, along with biogeochemical controls on production. Average total Hg in surface samples (0–3 cm) ranged from 100 to 1200 ng/g; average MeHg ranged from 5 to 50 ng/g. MeHg was usually highest at or near the surface except in highly mobile mudflats. Although total Hg concentrations in the Penobscot are elevated, it is the accumulation of MeHg that stands out in comparison to other ecosystems. Surface soils in the large Mendall Marsh, about 17 km downstream from the contamination source, contained particularly high %MeHg (averaging 8%). In Mendall marsh soil porewaters, MeHg often accounted for more than half of total Hg.Salt marshes are areas of particular concern in the Penobscot River, for they are depositional environments for a Hg-contaminated mobile pool of river sediment, hot spots for net MeHg production, and sources of risk to marsh animals. We hypothesized that exceptionally low mercury partitioning between the solid and aqueous phases (with log Kd averaging ~4.5) drives high MeHg in Penobscot marshes. The co-occurrence of iron and sulfide in filtered soil porewaters, sometimes both above 100 μM, suggests the presence of nanoparticulate and/or colloidal metal sulfides. These colloids may be stabilized by high concentrations of aromatic and potentially sulfurized dissolved organic matter (DOM) in marsh soils. Thus, Hg in Penobscot marsh soils appears to be in a highly available for microbial methylation through the formation of DOM-associated HgS complexes. Additionally, low partitioning of MeHg to marsh soils suggests high MeHg bioavailability to animals. Overall, drivers of high MeHg in Penobscot marshes include elevated Hg in soils, low partitioning of Hg to solids, high Hg bioavailability for methylation, rapidly shifting redox conditions in surface marsh soils, and high rates of microbial activity.

Nanomolar Copper Enhances Mercury Methylation by Desulfovibrio desulfuricans ND132

Methylmercury (MeHg) is produced by certain anaerobic microorganisms, such as the sulfate-reducing bacterium Desulfovibrio desulfuricans ND132, but environmental factors affecting inorganic mercury [Hg(II)] uptake and methylation remain unclear. We report that the presence of a small amount of copper ions [Cu(II), <100 nM] enhances Hg(II) uptake and methylation by washed cells of ND132, while Hg(II) methylation is inhibited at higher Cu(II) concentrations because of the toxicity of copper to the microorganism. The enhancement or inhibitory effect of Cu(II) is dependent on both time and concentration. The presence of nanomolar concentrations of Cu(II) facilitates rapid uptake of Hg(II) (within minutes) and doubles MeHg production within a 24 h period, but micromolar concentrations of Cu(II) completely inhibit Hg(II) methylation. Metal ions such as zinc [Zn(II)] and nickel [Ni(II)] also inhibit but do not enhance Hg(II) methylation under the same experimental conditions. These observations suggest a synergi...

Effects of soil properties on production and bioaccumulation of methylmercury in rice paddies at a mercury mining area, China

Rice paddy soil is recognized as the hotspot of mercury (Hg) methylation, which is mainly a biotic process mediated by many abiotic factors. In this study, effects of key soil properties on the production and bioaccumulation of Hg and methylmercury (MeHg) in Hg-contaminated rice paddies were investigated. Rice and soil samples were collected from the active Hg smelting site and abandoned Hg mining sites (a total of 124 paddy fields) in the Wanshan Mercury Mine, China. Total Hg (THg) and MeHg in soils and rice grains, together with sulfur (S), selenium (Se), organic matter (OM), nitrogen (N), phosphorus (P), mineral compositions (e.g., SiO2, Al2O3 and Fe2O3) and pH in soils were quantified. The results showed that long-term Hg mining activities had resulted in THg and MeHg contaminations in soil-rice system. The newly-deposited atmospheric Hg was more readily methylated relative to the native Hg already in soils, which could be responsible for the elevated MeHg levels in soils and rice grains around the active artificial Hg smelting site. The MeHg concentrations in soils and rice grains showed a significantly negative relationship with soil N/Hg, S/Hg and OM/Hg ratio possibly due to the formation of low-bioavailability Hg–S(N)–OM complexes in rhizosphere. The Hg–Se antagonism undoubtedly occurred in soil-rice system, while its role in bioaccumulation of MeHg in the MeHg-contaminated rice paddies was minor. However, other soil properties showed less influence on the production and bioaccumulation of MeHg in rice paddies located at the Wanshan Mercury Mine zone.

Robust Mercury Methylation across Diverse Methanogenic Archaea.

ABSTRACTMethylmercury (MeHg) production was compared among nine cultured methanogenic archaea that contain hgcAB, a gene pair that codes for mercury (Hg) methylation. The methanogens tested produced MeHg at inherently different rates, even when normalized to growth rate and Hg availability. Eight of the nine tested were capable of MeHg production greater than that of spent- and uninoculated-medium controls during batch culture growth. Methanococcoides methylutens, an hgcAB+ strain with a fused gene pair, was unable to produce more MeHg than controls. Maximal conversion of Hg to MeHg through a full batch culture growth cycle for each species (except M. methylutens) ranged from 2 to >50% of the added Hg(II) or between 0.2 and 17 pmol of MeHg/mg of protein. Three of the species produced >10% MeHg. The ability to produce MeHg was confirmed in several hgcAB+ methanogens that had not previously been tested (Methanocella paludicola SANAE, Methanocorpusculum bavaricum, Methanofollis liminatans GKZPZ, and Methanosphaerula palustris E1-9c). Maximal methylation was observed at low sulfide concentrations (<100 μM) and in the presence of 0.5 to 5 mM cysteine. For M. hollandica, the addition of up to 5 mM cysteine enhanced MeHg production and cell growth in a concentration-dependent manner. As observed for bacterial Hg methylators, sulfide inhibited MeHg production. An initial evaluation of sulfide and thiol impacts on bioavailability showed methanogens responding to Hg complexation in the same way as do Deltaproteobacteria. The mercury methylation rates of several methanogens rival those of the better-studied Hg-methylating sulfate- and iron-reducing Deltaproteobacteria.

Long-Term Feeding of Elemental Sulfur Alters Microbial Community Structure and Eliminates Mercury Methylation Potential in Sulfate-Reducing Bacteria Abundant Activated Sludge.

This study reported a novel observation that the long-term cultivation of sulfur-reducing bacteria (S0RB) from a sulfate-reducing bacteria (SRB)-abundant seeding sludge with elemental sulfur feeding significantly shaped the microbial community structure and eliminated the mercury methylation potential in the S0RB-enriched sludge. In this study, the enrichments of SRB and S0RB from activated sludge were obtained through long-term cultivations. Subsequently, the batch tests showed that approximately 5000 μg/L Hg (II) was completely removed from the solution by both the SRB-enriched and S0RB-enriched sludge. Extremely low or no MeHg production was observed in the S0RB-enriched sludge (less than the limit of detection, 0.01 μg/L), while 1.49 μg/L MeHg accumulated in the SRB-enriched sludge. Other batch tests using the sludge samples from a replication of the cultivation showed that the methylation capability of the S0RB-enriching sludge gradually diminished to a negligible level over a 6 month cultivation time. However, some mercury-methylation-related bacteria were present in the enrichment of S0RB such as Geobacter. The absence of MeHg in the S0RB-enriched sludge may be attributed to the dissolved organic matter (DOM) instead of the sulfur- and sulfate-reduction pathway or MeHg demethylation when exposed to Hg (II). The cultivated S0RB could be used for mercury-contaminated wastewater treatment without MeHg concern.

Oligotrophic wetland sediments susceptible to shifts in microbiomes and mercury cycling with dissolved organic matter addition

Recent advances have allowed for greater investigation into microbial regulation of mercury toxicity in the environment. In wetlands in particular, dissolved organic matter (DOM) may influence methylmercury (MeHg) production both through chemical interactions and through substrate effects on microbiomes. We conducted microcosm experiments in two disparate wetland environments (oligotrophic unvegetated and high-C vegetated sediments) to examine the impacts of plant leachate and inorganic mercury loadings (20 mg/L HgCl2) on microbiomes and MeHg production in the St. Louis River Estuary. Our research reveals the greater relative capacity for mercury methylation in vegetated over unvegetated sediments. Further, our work shows how mercury cycling in oligotrophic unvegetated sediments may be susceptible to DOM inputs in the St. Louis River Estuary: unvegetated microcosms receiving leachate produced substantially more MeHg than unamended microcosms. We also demonstrate (1) changes in microbiome structure towards Clostridia, (2) metagenomic shifts toward fermentation, and (3) degradation of complex DOM; all of which coincide with elevated net MeHg production in unvegetated microcosms receiving leachate. Together, our work shows the influence of wetland vegetation in controlling MeHg production in the Great Lakes region and provides evidence that this may be due to both enhanced microbial activity as well as differences in microbiome composition.

Mercury in the Black Sea: New Insights From Measurements and Numerical Modeling.

Redox conditions and organic matter control marine methylmercury (MeHg) production. The Black Sea is the world's largest and deepest anoxic basin and is thus ideal to study Hg species along the extended redox gradient. Here we present new dissolved Hg and MeHg data from the 2013 GEOTRACES MEDBlack cruise (GN04_leg2) that we integrated into a numerical 1‐D model, to track the fate and dynamics of Hg and MeHg. Contrary to a previous study, our new data show highest MeHg concentrations in the permanently anoxic waters. Observed MeHg/Hg percentage (range 9–57%) in the anoxic waters is comparable to other subsurface maxima in oxic open‐ocean waters. With the modeling we tested for various Hg methylation and demethylation scenarios along the redox gradient. The results show that Hg methylation must occur in the anoxic waters. The model was then used to simulate the time evolution (1850–2050) of Hg species in the Black Sea. Our findings quantify (1) inputs and outputs of HgT (~31 and ~28 kmol yr−1) and MeHgT (~5 and ~4 kmol yr−1) to the basin, (2) the extent of net demethylation occurring in oxic (~1 kmol yr−1) and suboxic water (~6 kmol yr−1), (3) and the net Hg methylation in the anoxic waters of the Black Sea (~11 kmol yr−1). The model was also used to estimate the amount of anthropogenic Hg (85–93%) in the Black Sea.