Hg Methylation Rates Research Articles

Functional genes and microorganisms controlling in situ methylmercury production and degradation in marine sediments: A case study in the Eastern China Coastal Seas

Dominant microorganisms and functional genes, including hgcA, hgcB, merA, and merB, have been identified to be responsible for mercury (Hg) methylation or methylmercury (MeHg) demethylation. However, their in situ correlation with MeHg levels and the processes of Hg methylation and MeHg demethylation in coastal areas remains poorly understood. In this study, four functional genes related to Hg methylation and MeHg demethylation (hgcA, hgcB, merA, and merB) were all detected in the sediments of the Eastern China Coastal Seas (ECCSs) (representative coastal seas highly affected by human activities) using metagenomic approaches. HgcA was identified to be the key gene controlling the in situ net production of MeHg in the ECCSs. Based on metagenomic analysis and incubation experiments, sulfate-reducing bacteria were identified as the dominant microorganisms controlling Hg methylation in the ECCSs. In addition, hgcA gene was positively correlated with the MeHg content and Hg methylation rates, highlighting the potential roles of Hg methylation genes and microorganisms influenced by sediment physicochemical properties in MeHg cycling in the ECCSs. These findings highlighted the necessity of conducting similar studies in other natural systems for elucidating the molecular mechanisms underlying MeHg production in aquatic environments.

Properties influencing flux and diatom uptake of mercury and methylmercury from estuarine sediments

Mercury (Hg) is a conspicuous and persistent global pollutant. Ionic Hg can be methylated into noxious methylmercury (CH3Hg), which biomagnifies in marine tropic webs and poses a health risk to humans and organisms. Sediment Hg methylation rates are variable, and the output flux of created CH3Hg are dependent on sediment characteristics and environmental factors. Thus, uncertainties remain about the formation and flux of CH3Hg from sediment, and how this could contribute to the bioaccumulative burden for coastal organisms in shallow ecosystems. Cores were collected from 3 estuarine locations along the Eastern USA to examine how sediments characteristics influence the introduction of Hg and CH3Hg into the base of the food chain. Stable isotopes of inorganic 200Hg and CH3199Hg were injected into sediments of individual cores, with cultured diatoms constrained to overlying waters. Five different treatments were done on duplicate cores, spiked with: (1) no Hg isotopes (control); (2) inorganic 200Hg; (3) CH3199Hg; (4) both 200Hg and CH3199Hg isotopes, (5) both 200Hg and CH3199Hg into overlying waters (not sediment). Experimental cores were incubated for 3 days under temperature and light controlled conditions. These results demonstrate that upper sediments characteristics lead to high variability in Hg cycling. Notably, sediments which contained abundant and peaty organic material (∼28 %LOI), had the highest pore water DOC (3206 μM) and displayed bands of sulfur reducing bacteria yielded the greatest methylation rate (1.97 % day−1) and subsequent diatom uptake of CH3200Hg (cell quota 0.18 amol/cell) in the overlying water.

Cross-shelf processes of terrigenous organic matter drive mercury speciation on the east siberian shelf in the Arctic Ocean

The cross-shelf distributions of total mercury (THg), methylmercury (MeHg) and organic and inorganic matter, as well as the presence of the hgcA gene were investigated on the East Siberian Shelf (ESS) to understand the processes underlying the speciation of sedimentary Hg. Samples were collected from 12 stations grouped into four zones based on water depth: inner shelf (5 stations), mid-shelf (3 stations), outer shelf (2 stations), and slope (2 stations). The THg concentration in the surface sediment increased from the inner shelf (0.25 ± 0.023 nmol g−1) toward the slope (0.52 nmol g−1), and, when normalized to total organic carbon content, the THg showed a positive correlation with the clay-to-sand ratio (r2 = 0.48, p = 0.012) and degree of chemical weathering (r2 = 0.79, p = 0.0001). The highest MeHg concentrations (3.0 ± 1.8 pmol g−1), as well as peaks in the S/C ratio (0.012 ± 0.002) of sediment-leached organic matter, were found on the mid-shelf, suggesting that the activities of sulfate reducers control the net Hg(II) methylation rates in the sediment. This was supported by results from a principal component analysis (PCA) performed with Hg species concentrations and sediment-leached organic matter compositions. The site-specific variation in MeHg showed the highest similarity with that of CHONS compounds in the PCA, where Deltaproteobacteria were projected to be putative Hg(II) methylators in the gene analysis. In summary, the hydrodynamic sorting of lithogenic particles appears to govern the cross-shelf distribution of THg, and in situ methylation is considered a major source of MeHg in the ESS sediment.

New insights into Hg[sbnd]Se antagonism: Minor impact on inorganic Hg mobility while potential impacts on microorganisms

Selenium (Se) is a crucial antagonistic factor of mercury (Hg) methylation in soil, with the transformation of inorganic Hg (IHg) to inert mercury selenide (HgSe) being the key mechanism. However, little evidence has been provided of the reduced Hg mobility at environmentally relevant doses of Hg and Se, and the potential impacts of Se on the activities of microbial methylators have been largely ignored. This knowledge gap hinders effective mitigation for methylmercury (MeHg) risks, considering that Hg supply and microbial methylators serve as materials and workers for MeHg production in soils. By monitoring the mobility of IHg and microbial activities after Se spike, we reported that 1) active methylation might be the premise of HgSe antagonism, as higher decreases in MeHg net production were found in soils with higher constants of Hg methylation rate; 2) IHg mobility did not significantly change upon Se addition in soils with high DOC concentrations, challenging the long-held view of Hg immobilization by Se; and 3) the activities of iron-reducing bacteria (FeRB), an important group of microbial methylators, might be potentially regulated by Se addition at a dose of 4 mg/kg. These findings provide empirical evidence that IHg mobility may not be the limiting factor under Se amendment and suggest the potential impacts of Se on microbial activities.

In Vivo Mercury (De)Methylation Metabolism in Cephalopods under Different pCO2 Scenarios.

This work quantified the accumulation efficiencies of Hg in cuttlefish, depending on both organic (MeHg) and inorganic (Hg(II)) forms, under increased pCO2 (1600 μatm). Cuttlefish were fed with live shrimps injected with two Hg stable isotopic tracers (Me202Hg and 199Hg(II)), which allowed for the simultaneous quantification of internal Hg accumulation, Hg(II) methylation, and MeHg demethylation rates in different organs. Results showed that pCO2 had no impact on Hg bioaccumulation and organotropism, and both Hg and pCO2 did not influence the microbiota diversity of gut and digestive gland. However, the results also demonstrated that the digestive gland is a key organ for in vivo MeHg demethylation. Consequently, cuttlefish exposed to environmental levels of MeHg could exhibit in vivo MeHg demethylation. We hypothesize that in vivo MeHg demethylation could be due to biologically induced reactions or to abiotic reactions. This has important implications as to how some marine organisms may respond to future ocean change and global mercury contamination.

Transcriptional Control of hgcAB by an ArsR-Like Regulator in Pseudodesulfovibrio mercurii ND132.

The hgcAB gene pair encodes mercury (Hg) methylation capability in a diverse group of microorganisms, but its evolution and transcriptional regulation remain unknown. Working from the possibility that the evolutionary function of HgcAB may not be Hg methylation, we test a possible link to arsenic resistance. Using model Hg methylator Pseudodesulfovibrio mercurii ND132, we evaluated transcriptional control of hgcAB by a putative ArsR encoded upstream and cotranscribed with hgcAB. This regulator shares homology with ArsR repressors of arsenic resistance and S-adenosylhomocysteine (SAH)-responsive regulators of methionine biosynthesis but is distinct from other ArsR/SahR proteins in P. mercurii. Using quantitative PCR (qPCR) and RNA sequencing (RNA-seq) transcriptome analyses, we confirmed this ArsR regulates hgcAB transcription and is responsive to arsenic and SAH. Additionally, RNA-seq indicated a possible link between hgcAB activity and arsenic transformations, with significant upregulation of other ArsR-regulated arsenic resistance operons alongside hgcAB. Interestingly, wild-type ND132 was less sensitive to As(V) (but not As(III)) than an hgcAB knockout strain, supporting the idea that hgcAB may be linked to arsenic resistance. Arsenic significantly impacted rates of Hg methylation by ND132; however, responses varied with culture conditions. Differences in growth and metabolic activity did not account for arsenic impacts on methylation. While arsenic significantly increased hgcAB expression, hgcAB gene and transcript abundance was not a good predictor of Hg methylation rates. Taken together, these results support the idea that Hg and As cycling are linked in P. mercurii ND132. Our results may hold clues to the evolution of hgcAB and the controls on Hg methylation in nature. IMPORTANCE This work reveals a link between microbial mercury methylation and arsenic resistance and may hold clues to the evolution of mercury methylation genes (hgcAB). Microbes with hgcAB produce methylmercury, a strong neurotoxin that readily accumulates in the food web. This study addresses a critical gap in our understanding about the environmental factors that control hgcAB expression. We show that hgcAB expression is controlled by an ArsR-like regulator responsive to both arsenic and S-adenosylhomocysteine in our model organism, Pseudodesulfovibrio mercurii ND132. Exposure to arsenic also significantly impacted Pseudodesulfovibrio mercurii ND132 mercury methylation rates. However, expression of hgcAB was not always a good predictor of Hg methylation rates, highlighting the roles of Hg bioavailability and other biochemical mechanisms in methylmercury production. This study improves our understanding of the controls on hgcAB expression, which is needed to better predict environmental methylmercury production.

Methylmercury formation in biofilms of Geobacter sulfurreducens.

Mercury (Hg) is a major environmental pollutant that accumulates in biota predominantly in the form of methylmercury (MeHg). Surface-associated microbial communities (biofilms) represent an important source of MeHg in natural aquatic systems. In this work, we report MeHg formation in biofilms of the iron-reducing bacterium Geobacter sulfurreducens. Biofilms were prepared in media with varied nutrient load for 3, 5, or 7 days, and their structural properties were characterized using confocal laser scanning microscopy, cryo-scanning electron microscopy and Fourier-transform infrared spectroscopy. Biofilms cultivated for 3 days with vitamins in the medium had the highest surface coverage, and they also contained abundant extracellular matrix. Using 3 and 7-days-old biofilms, we demonstrate that G. sulfurreducens biofilms prepared in media with various nutrient load produce MeHg, of which a significant portion is released to the surrounding medium. The Hg methylation rate constant determined in 6-h assays in a low-nutrient assay medium with 3-days-old biofilms was 3.9 ± 2.0 ∙ 10-14 L ∙ cell-1 ∙ h-1, which is three to five times lower than the rates found in assays with planktonic cultures of G. sulfurreducens in this and previous studies. The fraction of MeHg of total Hg within the biofilms was, however, remarkably high (close to 50%), and medium/biofilm partitioning of inorganic Hg (Hg(II)) indicated low accumulation of Hg(II) in biofilms. These findings suggest a high Hg(II) methylation capacity of G. sulfurreducens biofilms and that Hg(II) transfer to the biofilm is the rate-limiting step for MeHg formation in this systems.

Mercury methylation linked to nitrification in the tropical North Atlantic Ocean

Methylmercury (MeHg) is a toxin that poses health risks to humans and wildlife, primarily through consumption of seafood (Sunderland and Mason, 2007). Most MeHg bioaccumulation by marine fish likely occurs in the upper 200 m of the ocean, which is mostly oxygenated (Mason et al., 2012). However, mechanisms of Hg methylation in oxic seawater remain unknown, since the hgcAB gene cluster, which encodes proteins for MeHg production, had been found exclusively in anaerobic microbes (Gilmour et al., 2013; Parks et al., 2013). Recent work, however, has shown that hgc genes are widespread in oxic seawater, including in the microaerophilic nitrifier, Nitrospina (Tada et al., 2020; Tada et al., 2021; Gionfriddo et al., 2016; Bowman et al., 2020). Here, we show that potential MeHg production rates in Western Tropical North Atlantic Ocean surface waters, within and near the Amazon River plume, were correlated positively and strongly to nitrification rates and Nitrospina-specific 16S gene expression. Potential Hg methylation and nitrification rates were highest at the most saline and least turbid stations, indicating that sediment particles and nutrient-rich, riverine discharges were not the primary factors promoting either process. These novel results in oxic seawater provide further evidence that Hg methylation is linked to abundant, nitrifying microbes and may help explain marine MeHg distributions.

The Influence of the Degree of Forest Management on Methylmercury and the Composition of Microbial Communities in the Sediments of Boreal Drainage Ditches.

Inorganic mercury (Hg) can be methylated to the highly toxic and bioavailable methylmercury (MeHg) by microorganisms in anaerobic environments. The Hg methylation rate may be affected by forest management activities, which can influence the catchment soils, water, and sediments. Here, we investigate the influence of forest management in the form of ditch cleaning and beaver dam removal, as well as the seasonal variations, on sediment chemistry and microbiota. The relationships between MeHg concentrations in sediment samples and archaeal and bacterial communities assessed by 16S rRNA gene amplicon sequencing were investigated to determine the microbial conditions that facilitated the formation of MeHg. Concentrations of MeHg were highest in undisturbed catchments compared to disturbed or slightly disturbed sites. The undisturbed sites also had the highest microbial diversity, which may have facilitated the formation of MeHg. Low MeHg concentrations and microbial diversity were observed in disturbed sites, which may be due to the removal of organic sediment layers during ditch cleaning and beaver dam removal, resulting in more homogenous, mineral-rich environments with less microbial activity. MeHg concentrations were higher in summer and autumn compared to winter and spring, but the temporal variation in the composition and diversity of the microbial community was less than the spatial variation between sites. Beta diversity was more affected by the environment than alpha diversity. The MeHg concentrations in the sediment were positively correlated to several taxa, including Cyanobacteria, Proteobacteria, Desulfobacterota, Chloroflexi, and Bacteroidota, which could represent either Hg-methylating microbes or the growth substrates of Hg-methylating microbes.

Mercury Methylation Potentials in Sediments of an Ancient Cypress Wetland Using Species-Specific Isotope Dilution GC-ICP-MS.

Wetlands are of a considerable environmental value as they provide food and habitat for plants and animals. Several important chemical transformations take place in wetland media, including the conversion of inorganic mercury (Hg) to monomethylmercury (MeHg), a toxic compound with a strong tendency for bioconcentration. Considering the fact that wetlands are hotspots for Hg methylation, we investigated, for the first time, Hg methylation and demethylation rates in an old growth cypress wetland at Sky Lake in the Mississippi Delta. The Sky Lake ecosystem undergoes large-scale water level fluctuations causing alternating periods of oxic and anoxic conditions in the sediment. These oscillating redox conditions, in turn, can influence the transformation, speciation, and bioavailability of Hg. In the present study, sediment cores from the wetland and Sky Lake itself were spiked with enriched stable isotope tracers of inorganic Hg and MeHg and allowed to incubate (in-situ) before freezing, sectioning, and analysis. Methylation rates (day−1) ranged from 0.012 ± 0.003 to 0.054 ± 0.019, with the lowest rate in the winter and the highest in the summer. Demethylation rates were about two orders of magnitude higher, and also greater in the warmer seasons (e.g., 1.84 ± 0.78 and 4.63 ± 0.51 for wetland sediment in the winter and summer, respectively). Methylation rates were generally higher in the open water sediment compared to wetland sediment, with the latter shaded and cooler. Both methylation (r = 0.76, p = 0.034) and demethylation (0.97, p = 0.016) rates (day−1) were positively correlated with temperature, but not with most other water quality parameters. MeHg concentration in the water was correlated with pH (r = 0.80, p < 0.05), but methylation rates were only marginally correlated (r = 0.71). Environmental factors driving microbial production of MeHg in the system include warm temperatures, high levels of labile natural organic matter, and to a lesser extent the relatively low pH and the residence time of the water. This study also provides baseline data that can be used to quantify the impacts of modifying the natural flow of water to the system on Hg methylation and demethylation rates.

Occurrence of methylmercury in aerobic environments: Evidence of mercury bacterial methylation based on simulation experiments

Methylmercury (MeHg) is mainly produced by anaerobic δ-proteobacteria such as sulfate-reducing bacteria (SRB). However, mercury bio-methylation has also been found to occur in the aerobic soil of the Three Gorges Reservoir (TGR). Using γ-proteobacterial TGR bacteria (TGRB) and δ-proteobacterial Desulfomicrobium escambiense strains, the efficiency of mercury methylation and demethylation was evaluated using an isotope tracer technique. Kinetics simulation showed that the bacterial Hg methylation rate (km) of TGRB3 was 4.36 × 10−9 pg·cell−1·h−1, which was significantly lower than that of D. escambiense (170.74 ×10−9 pg·cell−1·h−1) under anaerobic conditions. Under facultative and/or aerobic conditions, D. escambiense could not survive, while the km of TGRB3 were 0.35 × 10−9 and 0.29 × 10−9 pg·cell−1·h−1, respectively. Furthermore, the bacterial MeHg tolerance threshold of TGRB3 was 3.47 × 10−9 pg·cell−1, which was 98.6-fold lower than that of D. escambiense under anaerobic conditions. However, the MeHg tolerance threshold of TGRB3 remained at 0.50–0.52 × 10−9 pg·cell−1 under facultative and/or aerobic conditions. Notably, bacterial Hg methylation rates (km) were higher than the corresponding bacterial MeHg demethylation rates (kd1). These results establish the contribution of some aerobic and/or facultative anaerobic bacteria to net environmental MeHg production in terrestrial ecosystems and provide a novel understanding of the biogeochemical cycle of MeHg. SynopsisHg methylation of facultative and/or aerobic bacteria may contribute to the net production of environmental methylmercury in terrestrial ecosystems.

Experiments revealing the formation of refractory methylmercury pools in natural sediments and soils

Methylation and demethylation of mercury (Hg) are well recognized as processes controlling the concentrations of monomethylmercury (MeHg) in natural environments, and thus the pool of Hg available for biological uptake. In addition, studies have indicated the potential role of refractory MeHg pools (not readily available for demethylation) on the pool of MeHg in, for example, sediments and soils. These studies, however, remain scarce and often the role of refractory MeHg pools is overlooked. Here, we have conducted incubation experiments aiming to quantify refractory MeHg pools in contrasting environments. In our study, sediments (from lakes and brackish seawater sites) and soils (from forests and marshes) were incubated with isotopically enriched Hg tracers (Me201Hg and 198Hg) for up to 6 weeks. To follow the potential formation of refractory MeHg pools, %MeHg (fraction of Hg occurring as MeHg) after the first week of incubation for the added 198Hg and Me201Hg tracers, and ambient Hg was compared. The high %MeHg for the 198Hg tracer compared to the %MeHg of ambient Hg suggests a higher initial availability of added 198Hg in comparison to the ambient Hg in the sediments. For the soils, low %MeHg for the 198Hg tracer suggests low Hg methylation rates. The discrepancy observed between the sediments and soils can be explained by a higher availability of inorganic Hg in the sediments, as suggested by the Hg thermal fractional analysis conducted. The %MeHg steady state for the added Me201Hg tracer remained high (>17%) throughout the experiment, suggesting refractory pools of MeHg to be built-up in all tested sediments and soils. Together, the %MeHg for the added Hg tracers demonstrate that a significant fraction of the MeHg produced in sediments and soils is sequestered into refractory pools not readily available for demethylation. Furthermore, these results show that conditions favoring net methylation in sediments and soil could result in elevated concentrations of MeHg for a significant amount of time (months) even if the conditions favoring Hg net methylation are only temporary.

Effect of trophic position on mercury concentrations in bottlenose dolphins (Tursiops truncatus) from the northern Gulf of Mexico

Marine species from the Gulf of Mexico often have higher mercury (Hg) concentrations than conspecifics in the Atlantic Ocean. Spatial differences in Hg sources, environmental conditions, and microbial communities influence both Hg methylation rates and the bioavailability of Hg to organisms at the base of the food web. Mercury bioaccumulates within organisms and biomagnifies in marine food webs, and therefore reaches the greatest concentrations in long-lived marine carnivores, such as dolphins. In this study, we explored whether differences in trophic position and foraging habitat among bottlenose dolphins (Tursiops truncatus) from the northern Gulf of Mexico (nGoM) contributed to the observed variation in skin total Hg (THg) concentrations. Using the δ13C and δ34S values in dolphin skin, we assigned deceased stranded dolphins from Florida (FL; n=29) and Louisiana (LA; n=72) to habitats (estuarine, barrier island, and coastal) east and west of the Mississippi River Delta (MRD). We estimated the mean trophic position of dolphins from each habitat using δ15N values from stranded dolphin skin and tissues of primary consumers taken from the literature following a Bayesian framework. Finally, we compared trophic positions and THg concentrations among dolphins from each habitat, accounting for sex and body length. Estimated marginal mean THg concentrations (μg/g dry weight) were greatest in dolphins assigned to the coastal habitat and estuarine habitats east of the MRD (range: 2.59-4.81), and lowest in dolphins assigned to estuarine and barrier island habitats west of the MRD (range: 0.675-0.993). On average, dolphins from habitats with greater THg concentrations also had higher estimated trophic positions, except for coastal dolphins. Our results suggest that differences in trophic positions and foraging habitats contribute to spatial variability in skin THg concentrations among nGoM bottlenose dolphins, however, the relative influence of these factors on THg concentrations are not easily partitioned.

Influence of Spartina alterniflora invasion on mercury storage and methylation in the sediments of Yangtze River estuarine wetlands

The influence of Spartina alterniflora invasion on mercury (Hg) cycling in the coastal wetlands of China and in other parts of the world is not well understood. By combining field sampling with laboratory-scale microcosm incubation experiments, we examined the effect of S. alterniflora invasion on mercury (Hg) storage and net methylmercury (MeHg) production in the sediments of the wetlands in the Yangtze River estuary. The results showed that (1) the estimated mean annual total Hg (THg) input to the wetlands from litterfall was 8.0–26.5 μg/m2 from S. alterniflora, Phragmites australis and Scirpus mariqueter, with the highest levels (26.5 ± 9.0 μg/m2) coming from S. alterniflora due to its high primary productivity. (2) The depth-integrated (<40 cm) mean concentrations of THg in vegetated sediments ranged from 47.5 to 109.1 ng/g, which showed significant positive correlations with the fraction of <16 μm particles and the loss-on-ignition content (P < 0.01). (3) The MeHg concentrations and MeHg/THg (%MeHg) spanned 0.14–1.30 ng/g and 0.2–1.7%, respectively, and showed similar decreasing patterns with depth across all the sites, thereby reflecting the higher rates of Hg methylation in the upper surface sediments. In addition, no significant differences in MeHg concentrations were observed among the sites vegetated by the three plants (P > 0.05). (4) During plant decomposition, net MeHg production was enhanced significantly, but it was inhibited in the presence of the sulfate reduction inhibitor molybdate; these results suggest that sulfate-reducing bacteria could be important methylation mediators in sediments. Moreover, a large fraction of reduced inorganic sulfur (S) species such as iron monosulfide formed during plant decomposition, as revealed by S K-edge XANES spectroscopy. All of these results suggest that S. alterniflora invasion facilitates Hg storage in wetland sediments and affects sulfur cycling but that its effects on MeHg production are similar to those of native plants in the Yangtze River estuarine wetlands.

Nutrient Inputs Stimulate Mercury Methylation by Syntrophs in a Subarctic Peatland

Climate change dramatically impacts Arctic and subarctic regions, inducing shifts in wetland nutrient regimes as a consequence of thawing permafrost. Altered hydrological regimes may drive changes in the dynamics of microbial mercury (Hg) methylation and bioavailability. Important knowledge gaps remain on the contribution of specific microbial groups to methylmercury (MeHg) production in wetlands of various trophic status. Here, we measured aqueous chemistry, potential methylation rates (kmeth), volatile fatty acid (VFA) dynamics in peat-soil incubations, and genetic potential for Hg methylation across a groundwater-driven nutrient gradient in an interior Alaskan fen. We tested the hypotheses that (1) nutrient inputs will result in increased methylation potentials, and (2) syntrophic interactions contribute to methylation in subarctic wetlands. We observed that concentrations of nutrients, total Hg, and MeHg, abundance of hgcA genes, and rates of methylation in peat incubations (kmeth) were highest near the groundwater input and declined downgradient. hgcA sequences near the input were closely related to those from sulfate-reducing bacteria (SRB), methanogens, and syntrophs. Hg methylation in peat incubations collected near the input source (FPF2) were impacted by the addition of sulfate and some metabolic inhibitors while those down-gradient (FPF5) were not. Sulfate amendment to FPF2 incubations had higher kmeth relative to unamended controls despite no effect on kmeth from addition of the sulfate reduction inhibitor molybdate. The addition of the methanogenic inhibitor BES (25 mM) led to the accumulation of VFAs, but unlike molybdate, it did not affect Hg methylation rates. Rather, the concurrent additions of BES and molybdate significantly decreased kmeth, suggesting a role for interactions between SRB and methanogens in Hg methylation. The reduction in kmeth with combined addition of BES and molybdate, and accumulation of VFA in peat incubations containing BES, and a high abundance of syntroph-related hgcA sequences in peat metagenomes provide evidence for MeHg production by microorganisms growing in syntrophy. Collectively the results suggest that wetland nutrient regimes influence the activity of Hg methylating microorganisms and, consequently, Hg methylation rates. Our results provide key information about microbial Hg methylation and methylating communities under nutrient conditions that are expected to become more common as permafrost soils thaw.

Speciation and bioavailability of mercury in sediments from Mokolo River, Limpopo Province, South Africa

The presence of coal-based power plants and coal mine in the Waterberg area subjects the Mokolo River to potentially toxic elements (PTEs) such as mercury (Hg). Mercury is an extremely toxic element. Thus, monitoring and chemical speciation of Hg in water bodies; particularly in sediments is a vital tool for assessing water quality. The objective of this study was to investigate the levels of Hg(II) and methyl Hg (MeHg(I)) in sediment samples collected from Mokolo River in different seasons, as well as examining factors such as pH, temperature and organic matter content, which could affect Hg methylation rates. An ultrasonic based method was used for the extraction of Hg species in sediments. This was followed by the chromatographic separation and detection of Hg(II) and MeHg(I) by the on-line coupling of high-performance liquid chromatography (HPLC) to inductively coupled plasma-mass spectrometry (ICP-MS). A solution containing HCl and 2-mercaptoethanol was employed for the extraction of Hg species in sediments. Separation of the two species of Hg was achieved using isocratic elution mode with a mobile phase containing L-cysteine, 2-mercaptoethanol, ammonium acetate and methanol. The accuracy of the method was checked and yielded a percentage recovery of 86%. The Hg(II) concentrations ranged from 38.4 to 89.05 ng g−1 and 34.8 to 57.3 ng g−1 in low and high flow seasons, respectively. The concentrations of MeHg(I) ranged from 0.702 to 4.5 ng g−1 and 0.5 to 2.5 ng g−1 in the low and high flow seasons, respectively. Factors such as pH and temperature were found to influence the methylation rates, however correlation couldn’t be established to organic matter content due to similar amount of organic matter in all the samples.

Mercury methylation in cyanide influenced river sediments: A comparative study in Southwestern Ghana.

Studies on the influence of CN on Hg methylation rates in aquatic systems draining gold mining (artisanal and small-scale) communities in Africa are rare. The study assessed the influence of CN on Hg methylation in aquatic sediments of two major river systems draining artisanal and small-scale gold mining (ASGM) communities of the Prestea-Huni Valley district, Southwestern Ghana. The miners extract gold (Au) through exclusive amalgam [Hg-Au] formation or cyanidation of Au-rich Hg-contaminated tailings, or a combination of both techniques. Hg water solubility and probable mercuric compounds in sediments of Hg-contaminated CN-loaded (River Aprepre) and Hg-contaminated non-CN (River Ankobra) aquatic systems within the district were investigated. THg was determined by CV-AAS after HF/HNO3/HCl digestion. MeHg in sediments were extracted with H2SO4/KBr/CuSO4-CH2Cl2; followed by aqueous-phase propylation, preconcentration-on-Tenax, and GC-CV-AFS. River Aprepre showed 4.58-14.83 ngMeHg/g as Hg (1.4-3.7% THg as MeHg), with 241-415 ngTHg/g, and 0.05-0.21 mgCN/kg. For River Ankobra, MeHg ranged 0.24-1.21 ngMeHg/g (0.08-0.35% THg as MeHg) with 162-490 ngTHg/g dw and CN <0.001mg/kg. There was positive correlation (r2=0.5974; p<0.01) between MeHg and CN in River Aprepre. The water-soluble fraction of Hg in sediment from both rivers was <1% of THg. Hg in sediments from River Aprepre were generally more soluble than that from River Ankobra, indicating that Hg in sediments from River Aprepre were potentially more bioavailable for methylation. Accordingly, the presence of CN in Hg-dominated river sediments potentially influences and enhances the solubility and mobility of Hg, resulting in increased Hg methylation rates.

Anaerobic guilds responsible for mercury methylation in boreal wetlands of varied trophic status serving as either a methylmercury source or sink.

Wetlands are common sites of active Hg methylation by anaerobic microbes; however, the amount of methylmercury produced varies greatly, as Hg methylation is dependent upon both the availability of Hg and the composition and activity of the microbial community involved. In this study, we identified the major microbial guilds responsible for Hg methylation along a trophic gradient composed of two sites and three different types of wetlands: a bog-fen peatland gradient and a black alder swamp, serving as net sources and a sink for methylmercury respectively. Iron-reducing bacteria in the Geobacteraceae were important Hg methylators across all wetlands and seasons examined, as evidenced by abundant 16S rRNA and hgcA transcripts clustering with this family. Molybdate inhibited Hg methylation more efficiently in the peatlands than in the swamp, suggesting an increasing role of sulfate-reducing bacteria and/or related syntrophs in the methylation of Hg with decreasing trophic status. Sulfate addition failed to increase Hg methylation rates in the peatlands, suggesting that SRBs/syntrophs were instead likely metabolizing alternative substrates such as syntrophic fermentation of organic compounds with methanogens. These results highlight the interconnectivity of anaerobic metabolism and importance of community dynamics on the methylation of Hg in wetlands with different trophic status.

Mercury methylation and demethylation potentials in Arctic lake sediments

Mercury (Hg) transformations in sediments are key factors in the Hg exposure pathway for wildlife and humans yet are poorly characterized in Arctic lakes. As the Arctic is rapidly warming, it is important to understand how the rates of Hg methylation and demethylation (wich determine Hg bioavailability) change with temperature in lake sediments. Methylation and demethylation potentials were determined for littoral sediments (2.5 m water depth) in two deep and two shallow lakes in the Canadian Arctic using Hg stable isotope tracers at incubation temperatures of 4, 8, or 16 °C for 24 h. Compared to sediments from other regions, Hg methylation and demethylation potentials in these sediments are low. The maximum depth of the lake from which sediment was collected exerted a stronger influence over methylation potential than sediment Hg concentration or organic matter content; the shallowest lake had the highest Hg methylation potential. Sediments from the shallowest lake also demonstrated the greatest response to the temperature treatments, with significantly higher methylation potentials in the 8 and 16 °C treatments. Sediments from the deep lakes demonstrated greater demethylation potentials than shallow lakes. The methylmercury to total Hg ratio in sediments supported the measured transformation potentials as the lake with the greatest methylation potential had the highest ratio. This study supports previous works indicating that Hg methylation potential may increase as the Arctic warms, but demethylation potential does not respond to warming to the same degree, indicating that Hg methylation may predominate in warming Arctic sediments.

The effects of climate, habitat, and trophic position on methylmercury bioavailability for breeding New York songbirds.

Mercury (Hg) is a global pollutant that affects songbird populations across a variety of ecosystems following conversion to methylmercury (MeHg)-a form of Hg with high potential for bioaccumulation and bioavailability. The amount of bioavailable MeHg in an ecosystem is a function of the amount of total Hg present as well as Hg methylation rates, which vary across the landscape in space and time, and trophic transfer. Using songbirds as an indicator of MeHg bioavailability in terrestrial ecosystems, we evaluated the role of habitat, climate, and trophic level in dictating MeHg exposure risk across a variety of ecosystems. To achieve this objective, 2243 blood Hg samples were collected from 81 passerine and near-passerine species in New York State, USA, spanning 10 different sampling regions from Long Island to western New York. Using a general linear mixed modeling framework that accounted for regional variation in sampling species composition, we found that wetland habitat area within 100 m of capture location, 50-year average of summer maximum temperatures, and trophic position inferred using stable isotope analysis were all correlated with songbird blood Hg concentrations statewide. Moreover, these patterns had a large degree of spatial variability suggesting that the drivers of MeHg bioavailability differed significantly across the state. Mercury deposition, land cover, and climate are all expected to change throughout the northeastern United States in the coming decades. Terrestrial MeHg bioavailability will likely respond to these changes. Focused research and monitoring efforts will be critical to understand how exposure risk responds to global environmental change across the landscape.