Net MeHg Production 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.

Moisture contents regulate peat water-leachable concentrations of methylmercury, inorganic mercury, and dissolved organic matter from boreal peat soils

Boreal peatlands are “hotspots” of net methylmercury (MeHg) production and may become drier in the future due to climate change. This study investigates a critical gap by analyzing the nuanced relationship between soil moisture content and the release of MeHg, inorganic mercury (IHg), sulfate (SO42-), and dissolved organic matter (DOM) in a laboratory incubation of boreal peat soils. Dried peat soils exhibited heightened releases of IHg, MeHg, and SO42- during re-wetting events. Both dried and saturated peat soils released more DOM than moist peat soils during re-wetting events, and DOM released from dried soils had higher bioaccessibility than that from the saturated soils (p<0.05). There was an equilibrium of IHg concentrations between peat soils and pore waters, but long-term severe drought may disrupt this equilibrium and then release more IHg to pore waters during re-wetting events. Contrary to expectations, positive relationships between IHg concentrations and SUVA254 did not exist in all treatments. MeHg and SO42- were depleted quickly because there was no external input of Hg and SO42- to this static system. More bioaccessible DOM than aromatic DOM was released from peat soils with different soil moisture contents after 32 weeks during the re-wetting event (p<0.05). These results imply that re-wetting of peat soils after droughts can increase the release of MeHg from peat soils and may also increase net MeHg production due to the release of SO42- and bioaccessible DOM from peat soils, reshaping our understanding of soil moisture's role in mercury dynamics. This novel insight into soil moisture and MeHg dynamics carries significant implications for mitigating mercury contamination in aquatic ecosystems.

Warming inhibits HgII methylation but stimulates methylmercury demethylation in paddy soils

Inorganic mercury (HgII) can be transformed into neurotoxic methylmercury (MeHg) by microorganisms in paddy soils, and the subsequent accumulation in rice grains poses an exposure risk for human health. Warming as an important manifestation of climate change, changes the composition and structure of microbial communities, and regulates the biogeochemical cycles of Hg in natural environments. However, the response of specific HgII methylation/demethylation to the changes in microbial communities caused by warming remain unclear. Here, nationwide sampling of rice paddy soils and a temperature-adjusted incubation experiment coupled with isotope labeling technique (202HgII and Me198Hg) were conducted to investigate the effects of temperature on HgII methylation, MeHg demethylation, and microbial mechanisms in paddy soils along Hg gradients. We showed that increasing temperature significantly inhibited HgII methylation but promoted MeHg demethylation. The reduction in the relative abundance of Hg-methylating microorganisms and increase in the relative abundance of MeHg-demethylating microorganisms are the likely reasons. Consequently, the net Hg methylation production potential in rice paddy soils was largely inhibited under the increasing temperature. Collectively, our findings offer insights into the decrease in net MeHg production potential associated with increasing temperature and highlight the need for further evaluation of climate change for its potential effect on Hg transformation in Hg-sensitive ecosystems.

Differential response of Hg-methylating and MeHg-demethylating microbiomes to dissolved organic matter components in eutrophic lake water

Methylmercury (MeHg) production in aquatic ecosystems is a global concern because of its neurotoxic effect. Dissolved organic matter (DOM) plays a crucial role in biogeochemical cycling of Hg. However, owing to its complex composition, the effects of DOM on net MeHg production have not been fully understood. Here, the Hg isotope tracer technique combined with different DOM treatments was employed to explore the influences of DOM with divergent compositions on Hg methylation/demethylation and its microbial mechanisms in eutrophic lake waters. Our results showed that algae-derived DOM treatments enhanced MeHg concentrations by 1.42−1.53 times compared with terrestrial-derived DOM. Algae-derived DOM had largely increased the methylation rate constants by approximately 1−2 orders of magnitude compared to terrestrial-derived DOM, but its effects on demethylation rate constants were less pronounced, resulting in the enhancement of net MeHg formation. The abundance of hgcA and merB genes suggested that Hg-methylating and MeHg-demethylating microbiomes responded differently to DOM treatments. Specific DOM components (e.g., aromatic proteins and soluble microbial byproducts) were positively correlated with both methylation rate constants and the abundance of Hg-methylating microbiomes. Our results highlight that the DOM composition influences the Hg methylation and MeHg demethylation differently and should be incorporated into future Hg risk assessments in aquatic ecosystems.

Relative importance of aceticlastic methanogens and hydrogenotrophic methanogens on mercury methylation and methylmercury demethylation in paddy soils

The accumulation of methylmercury (MeHg) in paddy soil results from a subtle balance between inorganic mercury (e.g., HgII) methylation and MeHg demethylation. Methanogens not only act as Hg methylators but may also facilitate MeHg demethylation. However, the diverse methanogen flora (e.g., aceticlastic and hydrogenotrophic types) that exists under ambient conditions has not previously been considered. Accordingly, the roles of different types of methanogens in HgII methylation and MeHg degradation in paddy soils were studied using the Hg isotope tracing technique combined with the application of methanogen inhibitors/stimulants. It was found that the response of HgII methylation to methanogen inhibitors or stimulants was site-dependent. Specifically, aceticlastic methanogens were suggested as the potential HgII methylators at the low Hg level background site, whereas hydrogenotrophic methanogens were potentially involved in MeHg production as Hg levels increased. In contrast, both aceticlastic and hydrogenotrophic methanogens facilitated MeHg degradation across the sampling sites. Additionally, competition between hydrogenotrophic and aceticlastic methanogens was observed in Hg-polluted paddy soils, implying that net MeHg production could be alleviated by promoting aceticlastic methanogens or inhibiting hydrogenotrophic methanogens. The findings gained from this study improve the understanding of the role of methanogens in net MeHg formation and link carbon turnover to Hg biogeochemistry in rice paddy ecosystems.

Sulfate-reduction and methanogenesis are coupled to Hg(II) and MeHg reduction in rice paddies

Methylmercury (MeHg) produced in rice paddies is the main source of MeHg accumulation in rice, resulting in high risk of MeHg exposure to humans and wildlife. Net MeHg production is affected by Hg(II) reduction and MeHg demethylation, but it remains unclear to what extent these processes influence net MeHg production, as well as the role of the microbial guilds involved. We used isotopically labeled Hg species and specific microbial inhibitors in microcosm experiments to simultaneously investigate the rates of Hg(II) and MeHg transformations, as well as the key microbial guilds controlling these processes. Results showed that Hg(II) and MeHg reduction rate constants significantly decreased with addition of molybdate or BES, which inhibit sulfate-reduction and methanogenesis, respectively. This suggests that both sulfate-reduction and methanogenesis are important processes controlling Hg(II) and MeHg reduction in rice paddies. Meanwhile, up to 99% of MeHg demethylation was oxidative demethylation (OD) under the incubation conditions, suggesting that OD was the main MeHg degradative pathway in rice paddies. In addition, [202Hg(0)/Me202Hg] from the added 202Hg(NO3)2 was up to 13.9%, suggesting that Hg(II) reduction may constrain Hg(II) methylation in rice paddies at the abandoned Hg mining site. This study improves our understanding of Hg cycling pathways in rice paddies, and more specifically how reduction processes affect net MeHg production and related microbial metabolisms.

Riverine Discharge Fuels the Production of Methylmercury in a Large Temperate Estuary.

Estuaries are an important food source for the world's growing population, yet human health is at risk from elevated exposure to methylmercury (MeHg) via the consumption of estuarine fish. Moreover, the sources and cycling of MeHg in temperate estuarine ecosystems are poorly understood. Here, we investigated the seasonal and tidal patterns of mercury (Hg) forms in Long Island Sound (LIS), in a location where North Atlantic Ocean waters mix with the Connecticut River. We found that seasonal variations in Hg and MeHg in LIS followed the extent of riverine Hg delivery, while tides further exacerbated the remobilization of earlier deposited riverine Hg. The net production of MeHg near the river plume was significant compared to that in other locations and enhanced during high tide, possibly resulting from the enhanced microbial activity and organic carbon remineralization in the river plume. Statistical models, driven by our novel data, further support the hypothesis that the river-delivered organic matter and inorganic Hg drive net MeHg production in the estuarine water column. Our study sheds light on the significance of water column biogeochemical processes in temperate tidal estuaries in regulating MeHg levels and inspires new questions in our quest to understand MeHg sources and dynamics in coastal oceans.

Resupply, diffusion, and bioavailability of Hg in paddy soil-water environment with flood-drain-reflood and straw amendment

Mercury (Hg) poses a significant risk in paddy fields, particularly when it is converted to methylmercury (MeHg) and accumulates in rice. However, the bioavailability and resupply kinetics of Hg in the paddy soil-water environment are not well understood. In this study, the diffusive gradients in thin films (DGT) and the ‘DGT-induced fluxes in sediments’ model (DIFS) were first adopted to investigate the Hg resupply kinetics, diffusion fluxes and bioavailability in a paddy environment subjected to flood-drain-reflood treatment and straw amendment. Our results show that although the straw amendment limited the bioavailability of Hg (38.2%–47.9% lower than control) in porewater by decreasing its resupply capacity, especially with smaller straw particles, the net production of MeHg in paddy fields was significantly increased after straw amendment (73.5%–77.9% higher than control). The results of microbial sequencing indicate that enhanced methylators (e.g., family Geobacter) and non-Hg methylators (e.g., Methanosarcinaceae) played a crucial role in MeHg production following straw amendment. Moreover, Hg-containing paddy soils generally tend to release Hg into the overlying water, while drain-reflood treatment changes the direction of Hg diffusion fluxes in the paddy soil-water interface. The drainage-reflooded treatment decreases the Hg reactive and resupply capacity of the paddy soil, thereby hindering the release of Hg from soil into overlying water during the early stages of reflooding. Overall, this study provides novel insights into the behavior of Hg in paddy soil-water surface microlayers.

Seasonal variation in mercury and methylmercury production in vegetated sediment in the Dongtan wetlands of the Yangtze River Estuary, China

The seasonal cycling of mercury (Hg) in vegetated sediments in the Dongtan wetlands of the Yangtze River Estuary were determined, and microcosm incubation experiments were conducted to evaluate methylmercury (MeHg) production after Hg input. The results showed that the seasonal variations of total Hg and MeHg were very different. The enhanced activity of methylating bacteria could have been the main contributor to the elevated MeHg in the upper surface layer (0–12 cm), which was supported by the higher copy numbers of the hgcA gene in the surface sediment and the MeHg increase during sediment incubation following litterfall addition. Moreover, the incubation results showed that Hg addition greatly increased net MeHg production and that this increase remained under suboxic conditions, suggesting that the potential health risk of Hg in estuarine wetlands could exist for a long time under changing redox conditions.

Response of methylmercury in paddy soil and paddy rice to pristine biochar: A meta-analysis and environmental implications

Biochar has received increased research attention due to its effectiveness in mitigating the potential risks of mercury (Hg) in agricultural soils. However, there is a lack of consensus on the effect of pristine biochar on the net production, availability, and accumulation of methylmercury (MeHg) in the paddy rice-soil system. As such, a meta-analysis with 189 observations was performed to quantitatively assess the effects of biochar on Hg methylation, MeHg availability in paddy soil, and the accumulation of MeHg in paddy rice. Results suggested that biochar application could significantly increase the production of MeHg in paddy soil by 19.01%; biochar could also decrease the dissolved and available MeHg in paddy soil by 88.64% and 75.69%, respectively. More importantly, biochar application significantly inhibited the MeHg accumulation in paddy rice by 61.10%. These results highlight that biochar could decrease the availability of MeHg in paddy soil and thus inhibit MeHg accumulation in paddy rice, although it might facilitate the net production of MeHg in paddy soil. Additionally, results also indicated that the biochar feedstock and its elementary composition significantly impacted the net MeHg production in paddy soil. Generally, biochar with a low carbon content, high sulfur content, and low application rate might be beneficial for inhibiting Hg methylation in paddy soil, meaning that Hg methylation depends on biochar feedstock. These findings suggested that biochar has great potential to inhibit MeHg accumulation in paddy rice, and further research should focus on selecting biochar feedstock to control Hg methylation potential and determine its long-term effects.

Ground warming releases inorganic mercury and increases net methylmercury production in two boreal peatland types

Boreal peatlands are considered sinks for atmospheric mercury (Hg) and are important sources of methylmercury (MeHg) to downstream ecosystems. Climate change-driven increases in average annual temperature in coming decades will be amplified at higher latitudes and will modify many biogeochemical processes in high boreal and subarctic peatlands that are important landscape features in these regions. Changes in water quality are an important issue for Northern ecosystems and fish consumers, and the directionality of changes in mercury levels due to climate warming presents considerable uncertainty. Peatlands are key landscape hotspots for MeHg production, however, the impact of climate warming on Hg cycling in boreal peatlands is not well studied. We use a multi-year field-based warming experiment (2 years passive, 1 year active ground warming) across two boreal peatland types (moss and sedge dominated) to explore the effects of ground warming on inorganic Hg (IHg) release, net MeHg production, and biogeochemical controls on both of these processes including the availability of sulfate (SO42−) and dissolved organic matter (DOM) quality and concentration. There were higher porewater IHg and MeHg concentrations under active ground warming conditions in both peatlands, likely related to both increased microbial metabolism, and changes in biogeochemical conditions that favor Hg methylation. Both SO42− (electron acceptor) and bioaccessible DOM (electron donor) are nutrients for sulfate-reducing bacteria which are dominant Hg methylators in freshwater environments, and increases in SO42− and/or bioaccessible DOM concentrations under warming played an important role in the observed changes in net MeHg production. Warming increased SO42− concentrations in the sedge-dominated but not in the moss-dominated fen likely because of a larger pool of groundwater derived SO42− in the sedge-dominated site. Warming increased DOM concentration in both peatland sites through enhanced decomposition of peat and increased release of root exudates from vascular plants, and the balance of these processes varied by peatland type and degree of warming. Experimentally increased ground temperatures increased microbial metabolism, organic matter turnover, and the availability of IHg all of which resulted in increases in porewater MeHg, indicating that climate-driven ground warming will increase MeHg production in northern peatlands in the future.

Ferrous sulfide nanoparticles control mercury speciation and bioavailability to methylating bacteria in contaminated groundwater: Impacts of mercury species

Mercury speciation in groundwater affects its removal effectiveness and methylation potential. Yet, most studies focus on the removal of inorganic dissolved Hg(II) and few studies explored the mercury methylation before and after the treatment. This study comprehensively explored the removal performance of three model mercury species, namely, dissolved inorganic divalent Hg (Hg(II), including free Hg2+ and Hg2+ complexes with Cl− and OH−), Hg2+ bound to dissolved organic matter (Hg-DOM), and HgS nanoparticles by FeS nanoparticles and further investigated the resultant impacts on the microbial methylation of Hg. Among three different stabilizers (starch, carboxymethyl cellulose (CMC), carboxymethyl starch (CMS)), CMC stabilized FeS nanoparticles (CMC-FeS) demonstrated best physical stability and highest mercury uptake. The CMC-FeS nanoparticles efficiently immobilized the three mercury species within 20 h. The sorption isotherm data of Hg(II) and Hg-DOM were well fitted by the dual-mode isotherm model and the maximum sorption capacities were 3358.28 and 2396.38 mg/g, respectively. Hg(II) and Hg-DOM were predominantly removed via ion exchange, chemical precipitation, and surface complexation whereas HgS was mainly immobilized through heteroaggregation. The simple treatment greatly reduced the bioavailable Hg species, thereby diminishing the net MeHg production by 70.2 %, 32.7 %, and 11.3 %, respectively. This study provides compelling evidence that FeS nanoparticles efficiently removed various mercury species in groundwater and remarkably inhibited the microbial methylation of mercury.

Declines of methylmercury along a salinity gradient in a low-lying coastal wetland ecosystem at South Carolina, USA

Wetlands are widely regarded as biogeochemical hotspots of highly toxic methylmercury (MeHg), mainly mediated by sulfate-reducing bacteria. In low-lying coastal wetlands, sea level rise, a phenomenon caused by global climate change, is slowly degrading numerous healthy freshwater forested wetlands into salt-degraded counterparts with a nickname “ghost forests”, and eventually converting them to saltmarshes. However, little is known about the changes of mercury (Hg) methylation, bioaccumulation, and biomagnification along the forest-to-saltmarsh gradient. Here, we conducted extensive field sampling in three wetland states (healthy forested wetlands, salt-degraded forested wetlands, and saltmarsh) along a salinity gradient (from 0 to 9.4 ppt) in Winyah Bay, South Carolina, USA. We found that in our study wetland systems the saltmarshes had the lowest levels of both total Hg and MeHg in sediments and biota, as compared to healthy forested wetlands and saltwater-degraded ghost forests. Our results suggest that the slow conversion of forested wetland to saltmarsh could reduce net MeHg production in our study wetland systems, which we hypothesized that could be attributed to increased sulfate reduction and excessive buildup of sulfide in sediment that inhibits microbial Hg methylation, and/or reduced canopy density and increased photodegradation of MeHg. However, it should be noted that biogeochemical MeHg responses to salinity changes may be site-specific and we urge more similar studies in other wetland systems along a salinity gradient. Therefore, long-term salinization of coastal wetlands and the slow conversion of forests to marshes could decrease long-term exposure of toxic MeHg levels in coastal food webs that are similar to our system, and ultimately reduce human exposure to this neurotoxin.

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.

Demethylation-The Other Side of the Mercury Methylation Coin: A Critical Review.

The public and environmental health consequences of mercury (Hg) methylation have drawn much attention and considerable research to Hg methylation processes and their dynamics in diverse environments and under a multitude of conditions. However, the net methylmercury (MeHg) concentration that accumulates in the environment is equally determined by the rate of MeHg degradation, a complex process mediated by a variety of biotic and abiotic mechanisms, about which our knowledge is limited. Here we review the current knowledge on MeHg degradation and its potential pathways and mechanisms. We describe detoxification by resistant microorganisms that employ the Hg resistance (mer) system to reductively break the carbon-mercury (C-Hg) bond producing methane (CH4) and inorganic mercuric Hg(II), which is then reduced by the mercuric reductase to elemental Hg(0). Very recent research has begun to elucidate a mechanism for the long-recognized mer-independent oxidative demethylation, likely involving some strains of anaerobic bacteria as well as aerobic methane-oxidizing bacteria, i.e., methanotrophs. In addition, photochemical and chemical demethylation processes are described, including the roles of dissolved organic matter (DOM) and free radicals as well as dark abiotic demethylation in the natural environment about which little is currently known. We focus on mechanisms and processes of demethylation and highlight the uncertainties and known effects of environmental factors leading to MeHg degradation. Finally, we suggest future research directions to further elucidate the chemical and biochemical mechanisms of biotic and abiotic demethylation and their significance in controlling net MeHg production in natural ecosystems.

The underappreciated role of natural organic matter bond Hg(II) and nanoparticulate HgS as substrates for methylation in paddy soils across a Hg concentration gradient

Rice consumption is the major pathway for human methylmercury (MeHg) exposure in inland China, especially in mercury (Hg) contaminated regions. MeHg production, a microbially driven process, depends on both the chemical speciation of inorganic divalent mercury, Hg(II), that determines Hg bioavailability for methylation. Studies have shown that Hg(II) speciation in contaminated paddy soils is mostly controlled by natural organic matter and sulfide levels, which are typically thought to limit Hg mobility and bioavailability. Yet, high levels of MeHg are found in rice, calling for reconsideration of the nature of Hg species bioavailable to methylators in paddy soils. Here, we conducted incubation experiments using a multi-isotope tracer technique including 198Hg(NO3)2, natural organic matter bond Hg(II) (NOM-199Hg(II)), ferrous sulfide sorbed Hg(II) (≡FeS-200Hg(II)), and nanoparticulate mercuric sulfide (nano-202HgS), to investigate the relative importance of geochemically diverse yet relevant Hg(II) species on Hg methylation in paddy soils across a Hg concentration gradient. We show that methylation rates for all Hg(II) species tested decreased with increasing Hg concentrations, and that methylation rates using NOM-199Hg(II) and nano-202HgS as substrates were similar or greater than rates obtained using the labile 198Hg(NO3)2 substrate. ≡FeS-200Hg(II) yielded the lowest methylation rate in all sites, and thus the formation of FeS is likely a sink for labile 198Hg(NO3)2 in sulfide-rich paddy soils. Moreover, the variability in the methylation data for a given site (1 to 5-fold variation depending on the Hg species) was smaller than what was observed across the Hg concentration gradient (103–104 fold variation between sites). These findings emphasize that at broad spatial scales, site-specific characteristics, such as microbial community structure, need to be taken into consideration, alongside the nature of the Hg substrate available for methylation, to determine net MeHg production. This study highlights the importance of developing site-specific strategies for remediating Hg pollution.

Mercury mobility, colloid formation and methylation in a polluted Fluvisol as affected by manure application and flooding–draining cycle

Abstract. Floodplain soils polluted with high levels of mercury (Hg) are potential point sources to downstream ecosystems. Repeated flooding (e.g., redox cycling) and agricultural activities (e.g., organic matter addition) may influence the fate and speciation of Hg in these soil systems. The formation and aggregation of colloids and particles influence both Hg mobility and its bioavailability to microbes that form methylmercury (MeHg). In this study, we conducted a microcosm flooding–draining experiment on Hg-polluted floodplain soils originating from an agriculturally used area situated in the Rhone Valley (Valais, Switzerland). The experiment comprised two 14 d flooding periods separated by one 14 d draining period. The effect of freshly added natural organic matter on Hg dynamics was assessed by adding liquid cow manure (+MNR) to two soils characterized by different Hg (47.3±0.5 or 2.38±0.01 mg kg−1) and organic carbon (OC: 1.92 wt % or 3.45 wt %) contents. During the experiment, the release, colloid formation of Hg in soil solution and net MeHg production in the soil were monitored. Upon manure addition in the highly polluted soil (lower OC), an accelerated release of Hg to the soil solution could be linked to a fast reductive dissolution of Mn oxides. The manure treatments showed a fast sequestration of Hg and a higher percentage of Hg bound by particulate (0.02–10 µm). Also, analyses of soil solutions by asymmetrical flow field-flow fractionation coupled with inductively coupled plasma mass spectrometry (AF4–ICP–MS) revealed a relative increase in colloidal Hg bound to dissolved organic matter (Hg–DOM) and inorganic colloidal Hg (70 %–100 %) upon manure addition. Our experiment shows a net MeHg production the first flooding and draining period and a subsequent decrease in absolute MeHg concentrations after the second flooding period. Manure addition did not change net MeHg production significantly in the incubated soils. The results of this study suggest that manure addition may promote Hg sequestration by Hg complexation on large organic matter components and the formation and aggregation of inorganic HgS(s) colloids in Hg-polluted Fluvisols with low levels of natural organic matter.

Mercury methylation from mercury selenide particles in soils

Selenium-inhibited monomethylmercury (MeHg) production is an attractive strategy for mitigating the risks of MeHg exposure. However, it is poorly understood the methylation potential of mercury selenide (HgSe) particles during their aging in soils and sediments. Net MeHg production in three floodplain soils amended with different geochemical species of mercury selenides, i.e., dissolved inorganic mercury freshly mixed with selenite (Hg(II)+Se(IV)), HgSe nanoparticles (45.2 ± 0.5 nm) and microparticles (> 1 μm) is examined. Among mercury types, the methylation from nanoparticulate HgSe was similar to (0.05 – 0.5 % vs. 0.1 – 0.4 %, yellow brown soil) or 12.9 – 21.0 times lower (0.02 – 0.1 vs. 0.6 – 1.5 %, black soil) than that from Hg(II)+Se(IV); however, net MeHg production from HgSe nanoparticles (0.02 – 0.5 %) was 1.9 – 15.5 times greater than HgSe microparticles (< 0.05 %) in all soils. Furthermore, net MeHg production from nanoparticulate HgSe varied significantly among soil types, attributable to differences in soil organic matter contents (2.4–5.8%) and microbial methylator community among soils. These results address the importance of geochemical intermediates of mercury selenide precipitation reactions and soil properties in MeHg production, and develop Se-based remediation strategy to minimize negative effects of MeHg on environmental and human health.

Marine mercury-methylating microbial communities from coastal to Capbreton Canyon sediments (North Atlantic Ocean)

Microbial mercury (Hg) methylation transforms inorganic mercury to neurotoxic methylmercury (MeHg) mainly in aquatic anoxic environments. Sampling challenges in marine ecosystems, particularly in submarine canyons, leads to a lack of knowledge about the Hg methylating microbia in marine sediments. A previous study showed an enrichment of mercury species in sediments from the Capbreton Canyon where both geochemical parameters and microbial activities constrained the net MeHg production. In order to characterize Hg-methylating microbial communities from coastal to deeper sediments, we analysed the diversity of microorganisms’ (16S rDNA-based sequencing) and Hg methylators (hgcA based cloning and sequencing). Both, 16S rDNA and hgcA gene analysis demonstrated that the putative Hg-methylating prokaryotes were likely within the Deltaproteobacteria, dominated by sulfur-compounds based reducing bacteria (mainly sulfate reducers). Additionally, others clades were also identified as carrying HgcA gene, such as, Chloroflexi, Spirochaetes, Elusimicrobia, PVC superphylum (Plantomycetes, Verrucomicrobia and Chlamydiae) and Euryarchaea. Nevertheless, 61% of the hgcA sequences were not assigned to specific clade, indicating that further studies are needed to understand the implication of new microorganisms carrying hgcA in the Hg methylation in marine environments. These first results suggest that sulfur cycle drives the Hg-methylation in marine ecosystem.

Opposing spatial trends in methylmercury and total mercury along a peatland chronosequence trophic gradient

Peatlands are abundant elements of boreal landscapes where inorganic mercury (IHg) can be transformed into bioaccumulating and highly toxic methylmercury (MeHg). We studied fifteen peatlands divided into three age classes (young, intermediate and old) along a geographically constrained chronosequence to determine the role of biogeochemical factors and nutrient availability in controlling the formation of MeHg. In the 10 cm soil layer just below the average annual growing season water table, concentrations of MeHg and %MeHg (of total Hg) were higher in younger, more mesotrophic peatlands than in older, more oligotrophic peatlands. In contrast, total mercury (THg) concentrations were higher in the older peatlands. Partial least squares (PLS) analysis indicates that the net MeHg production was positively correlated to trophic demands of vegetation and an increased availability of potential electron acceptors and donors for Hg methylating microorganisms. An important question for further studies will be to elucidate why there is less THg in the younger peatlands compared to the older peatlands, even though the age of the superficial peat itself is similar for all sites. We hypothesize that ecosystem features which enhance microbial processes involved in Hg methylation also promote Hg reduction that makes previously deposited Hg more available for evasion back to the atmosphere.