MeHg Production Research Articles

Methylmercury in lake bed soils during re-flooding of an Appalachian reservoir in the northeastern USA

Mercury methylation, where inorganic mercury (Hg) is converted to methylmercury (MeHg), can increase in soils when flooded. While effects of the initial flooding of soils on MeHg production have been well studied, less is known about impacts of re-flooding on MeHg production. Lake Perez, an impounded recreational reservoir in the Appalachian Highlands, was completely drained then re-filled 7 years later. We use a combination of chemical, soil physical, and microbial data to quantify changes in MeHg before and after re-flooding of the lakebed. Portions that were transiently saturated due to pluvial flooding had the highest pre-flooded MeHg concentrations. When the lake was re-flooded, concentrations of MeHg in subaqueous soils increased by a factor of 2.74 (+174%) on average. Substantial variability was observed among the sampling sites, with smaller increases in MeHg at sites subjected to seasonal flooding during periods when the reservoir was drained. The increase of soil MeHg after re-flooding was lower in this study compared to studies that evaluated soil MeHg after initial flooding, indicating that re-flooding of a former lake bed caused a smaller response in MeHg production compared to initial flooding of terrestrial land. This study advances understanding of the environmental impact of impounded reservoirs.

Algal Organic Matter Drives Methanogen-Mediated Methylmercury Production in Water from Eutrophic Shallow Lakes.

Algal blooms bring massive amounts of algal organic matter (AOM) into eutrophic lakes, which influences microbial methylmercury (MeHg) production. However, because of the complexity of AOM and its dynamic changes during algal decomposition, the relationship between AOM and microbial Hg methylators remains poorly understood, which hinders predicting MeHg production and its bioaccumulation in eutrophic shallow lakes. To address that, we explored the impacts of AOM on microbial Hg methylators and MeHg production by characterizing dissolved organic matter with Fourier transform ion cyclotron resonance mass spectrometry (FTICR-MS) and three-dimensional excitation-emission matrix (3D-EEM) fluorescence spectroscopy and quantifying the microbial Hg methylation gene hgcA. We first reveal that the predominance of methanogens, facilitated by eutrophication-induced carbon input, could drive MeHg production in lake water. Specifically, bioavailable components of AOM (i.e., CHONs such as aromatic proteins and soluble microbial byproduct-like materials) increased the abundances (Archaea-hgcA gene: 438-2240% higher) and activities (net CH4 production: 16.0-44.4% higher) of Archaea (e.g., methanogens). These in turn led to enhanced dissolved MeHg levels (24.3-15,918% higher) for three major eutrophic shallow lakes in China. Nevertheless, our model results indicate that AOM-facilitated MeHg production could be offset by AOM-induced MeHg biodilution under eutrophication. Our study would help reduce uncertainties in predicting MeHg production, providing a basis for mitigating the MeHg risk in eutrophic lakes.

Mobilization, Methylation, and Demethylation of Mercury in a Paddy Soil Under Systematic Redox Changes.

Methylmercury (MeHg) contamination in paddy fields is a significant environmental issue globally since over half of the population of our planet consumes rice. MeHg is a neurotoxin produced by microorganisms in oxygen-limited environments. Microbial effect on MeHg production is a hotspot of research; however, it has been largely ignored how the oxidation-reduction potential (Eh) shapes MeHg formation. Here, we elucidated Hg (de)-methylation in a contaminated soil by increasing Eh stepwise from -300 to +300 mV using a sophisticated biogeochemical microcosm. At the Eh range from -300 to -100 mV, high MeHg concentration and dissolved total Hg (THg) concentration were found due to a high relative abundance of Hg-methylation bacteria (e.g., Desulfitobacterium spp.), acidification, and reductive dissolution of Fe(oxyhydr)oxides. At the Eh range from 0 to +200 mV, the formation of colloids leads to adsorption of Hg and as a result colloidal Hg increased. MeHg reduction with Eh (-300 to +200 mV) increase was mainly attributed to a reduced Hg methylation, as dissolved THg and relative abundance of Desulfitobacterium spp. decreased by 50 and 96%, respectively, at Eh of +200 mV as compared to Eh of -300 mV. Mercury demethylation might be less important since the relative abundance of demethylation bacteria (Clostridium spp.) also decreased over 93% at Eh of +200 mV. These new results are crucial for predicting Hg risks in paddy fields.

Seasonal patterns of methylmercury production, release, and degradation in profundal sediment of a hypereutrophic reservoir

Fuhrmann B, Beutel M, Ganguli P, Zhao L, Brower S, Funk A, Pasek J. 2021. Seasonal patterns of methylmercury production, release, and degradation in profundal sediment of a hypereutrophic reservoir. Lake Reserv Manage. 37:360–377. Profundal lake sediment is an important site of toxic methylmercury (MeHg) production by anaerobic bacteria. This study tracked sediment MeHg cycling in hypereutrophic Hodges Reservoir, in the United States. Sediment-associated MeHg was most elevated in the early spring during moderately reduced conditions. In the late spring, MeHg and iron were released into hypolimnetic water during the progression from iron-reducing to sulfate-reducing conditions at the sediment–water interface. A decrease in porewater sulfate in the early summer indicated enhanced sulfate-reducing bacteria (SRB) activity and was associated with sediment buildup of MeHg, likely due to enhanced sorption to iron sulfides. Depletion of sulfate in the sediment during the fall corresponded with a substantial decrease in both sediment and water-column MeHg, suggesting that methanogenic conditions led to enhanced MeHg degradation. Shortly afterward, MeHg increased in the hypolimnion, indicating an upward shift in the zone of SRB methylation. Our study suggests 2 “hot moments” of MeHg entry into the water column, where it is susceptible to uptake into the pelagic food web: a spring window of mildly reduced conditions that promote MeHg release from sediment, and a fall window where MeHg is produced in the upper hypolimnion. These hot moments may potentially be managed to lower mercury bioaccumulation via redox enhancement of the profundal zone with approaches such as bottom water oxygenation, which began operation in Hodges Reservoir in 2020. However, the complexity of biogeochemical responses to such management perturbations in regard to MeHg cycling makes it difficult to predict the ultimate effect of oxygenation on mercury bioaccumulation. Supplemental data for this article is available online at https://doi.org/10.1080/10402381.2021.1940397 .

Effect of different rice farming practices on the bioavailability of mercury: A mesocosm experiment with common goldfish (Carassius auratus)

Wetlands such as rice paddies are important ecosystems that provide habitat for a numerous range of species but are considered as a major source of mercury in the most toxic form of methylmercury. An in situ mesocosm experiment was conducted during the rice cultivation season of 2018 in rice paddies from the Ebro Delta (NE Spain) to investigate the bioaccumulation of mercury in fish. Common goldfish (Carassius auratus) were exposed to three types of rice-fields subject to different agricultural management (conventional or ecological agriculture) and different hydric practices (wet, dry) and were sampled monthly. Total mercury concentration in fish increased over time for almost all the fields under study, but the mercury increase was particularly higher for fish exposed to ecological fields. We conducted δ15N and δ13C measurements to follow up fish diet changes within or among fields. The results have shown there were no variations in the diet of the fish over time within fields, although differences among management practices were observed, which could explain to some extent the THg variation in fish exposed to each of the agricultural practices. Results indicate that wetting and drying rice fields might be a greater source of mercury for fish and a potential hotspot for MeHg production enhanced by physicochemical parameters. Thus, mercury bioaccumulation in fish inhabiting rice paddies depend on several factors what, in turn, could lead to biomagnification across the food webs.

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.

Methylmercury Production and Degradation under Light and Dark Conditions in the Water Column of the Hells Canyon Reservoirs, USA.

Methylmercury (MeHg) is a highly toxic form of mercury that can bioaccumulate in fish tissue. Methylmercury is produced by anaerobic bacteria, many of which are also capable of MeHg degradation. In addition, demethylation in surface waters can occur via abiotic sunlight-mediated processes. The goal of the present study was to understand the relative importance of microbial Hg methylation/demethylation and abiotic photodemethylation that govern the mass of MeHg within an aquatic system. The study location was the Hells Canyon complex of 3 reservoirs on the Idaho-Oregon border, USA, that has fish consumption advisories as a result of elevated MeHg concentrations. Our study utilized stable isotope addition experiments to trace MeHg formation and degradation within the water column of the reservoirs to understand the relative importance of these processes on the mass of MeHg using the Water Quality Analysis Simulation Program. The results showed that rates of MeHg production and degradation within the water column were relatively low (<0.07 d-1 ) but sufficient to account for most of the MeHg observed with the system. Most MeHg production within the water column appeared to occur in the spring when much of the water column was in the processes of becoming anoxic. In the surface waters, rates of photodemethylation were relatively large (up to -0.25 d-1 ) but quickly decreased at depths >0.5 m below the surface. These results can be used to identify the relative importance of MeHg processes that can help guide reservoir management decisions. Environ Toxicol Chem 2021;40:1829-1839. © 2021 SETAC. This article has been contributed to by US Government employees and their work is in the public domain in the USA.

Effects of sulfur-rich biochar amendment on microbial methylation of mercury in rhizosphere paddy soil and methylmercury accumulation in rice

Biochar amendment has the potential to reduce methylmercury (MeHg) uptake by rice grains in soil-rice ecosystem. Considering that sulfur can strongly bind Hg and thus reduce its bioavailability, S-modified biochar has been used to immobilize Hg in soils. However, whether natural S-enriched biochar can further reduce Hg and MeHg phytoavailability remains unknown. Moreover, the rhizosphere is one of the most important microbial hotspots regulating the pollutant dynamics in terrestrial ecosystems. Therefore, it is of greater practical significance to examine the impact of biochar amendment on MeHg production and phytoavailability in the rhizosphere versus nonrhizosphere. Here, by conducting a pot experiment, we evaluated the efficacy of biochar derived from sulfur-enriched oilseed rape straw to reduce MeHg accumulation in rice. The results demonstrated that: (1) biochar-induced enhancement of chloride ion and sulfate levels in the overlying water and pore water facilitate microbial methylation of Hg and thus MeHg production in rhizosphere soil. (2) biochar amendment increased rhizosphere soil sulfur content and humic acid-like substances, strengthening MeHg binding to soil, and thus reducing grain MeHg levels by 47%–75%. Our results highlight the necessity to applying natural sulfur-rich biochar accompanied with exogenous sulfur to further reduce MeHg phytoavailability.

Biomagnification and trophic transfer of total mercury and methylmercury in a sub-tropical montane forest food web, southwest China

Little is known about the bioaccumulation and trophic transfer of total mercury (THg) and methylmercury (MeHg) via food webs in terrestrial ecosystems, especially in subtropical forest ecosystems. In the present study, THg and MeHg were determined as well as the carbon (δ13C) and nitrogen (δ15N) isotope composition in samples of soils, plants, invertebrates, and songbird feathers to construct food webs in a remote subtropical montane forest in Mt. Ailao, southwest China and assess the bioaccumulation, biomagnification, and trophic transfer of Hg. Results showed that the trophic levels (TLs) of all consumers ranged from 0.8 to 3.3 and followed the order of songbirds > spiders > omnivorous insects > herbivorous insects > plants, and THg and MeHg exhibited a clear biomagnification up the food chain from plants-herbivorous/omnivorous insects-spiders-songbirds. The lowest MeHg concentration was observed in pine needles ranged from 0.104 to 0.949 ng g−1 with only a 1.6% ratio of MeHg to THg (MeHg%), while the highest MeHg concentrations ranged from 425 to 5272 ng g−1 in songbirds with MeHg% values of up to 96%. High values of trophic magnification slope (TMS) for THg (0.22) and MeHg (0.38) were observed in plant-invertebrate-songbird food chain, verifying the significant bioaccumulation of Hg, particularly MeHg, in the remote subtropical forest ecosystem. This study confirmed the production and efficient biomagnification of MeHg in remote subtropical montane forest and the significant bioaccumulation of MeHg in terrestrial top predators.

The exacerbation of mercury methylation by Geobacter sulfurreducens PCA in a freshwater algae-bacteria symbiotic system throughout the lifetime of algae

Mine-polluted wastewater with mercury (Hg) poses severe environmental pollution since Hg(II) can be converted to highly neurotoxic methylmercury (MeHg) under anaerobic conditions. Previous studies on Hg methylation have focused on aquatic sediments, but few have investigated the MeHg formation in water layers containing algae. In this study, we investigated the dynamic effect of algae on Hg methylation throughout the lifetime of algae. We found that Chlorella pyrenoidosa was a non-methylating alga and exhibited good tolerance to Hg stress (1–20 μg/L); thus Hg(II) could not inhibit the process of eutrophication. However, the presence of C. pyrenoidosa significantly enhanced the Hg methylation by Geobacter sulfurreducens PCA. Compared to the control sample without algae, the MeHg production rate of algae-bacteria samples remarkably exacerbated by 62.3–188.3% with the algal growth period at cell densities of 1.5 × 106–25 × 106 cells/mL. The increase of algal organic matter and thiols with the algal growth period resulted in the exacerbation of MeHg production. The Hg methylation was also enhanced with the presence of dead algae, of which the enhancement was ~62.4% lower than that with the presence of live algae. Accordingly, the potential mechanism of Hg methylation in a freshwater algae-bacteria symbiotic system throughout the algal lifetime was proposed.

Understanding the effects of sulfur input on mercury methylation in rice paddy soils.

Sulfur could be introduced into paddy soils via dry or wet deposition, irrigation, and fertilization, which subsequently impacts the production of methylmercury (MeHg), a bioaccumulative neurotoxicant. However, effects of sulfur input on MeHg production are variable, possibly due to the multiple effects of sulfur on Hg mobility and/or microbial Hg methylators, leading to uncertainties in predicting MeHg risk. To address that, we explored the effects of different types and amounts of sulfur as well as concentrations of ambient sulfate on Hg methylation in paddy soils, and elucidated the mechanisms by quantifying changes in (1) Hg mobility and (2) microbial Hg methylators (e.g., sulfate-reducing bacteria, SRB). Our results indicated that MeHg levels increased by 40-86% and 30-96% in soils under various types (i.e., 200mgkg-1 elemental sulfur, ammonium sulfate, sulfur-coated urea and potassium sulfate (K2SO4)) and different amounts (i.e., 100, 200 and 400mgkg-1 K2SO4) of sulfur input. The enhanced MeHg production could be explained by increased Hg mobility but not changes in microbial Hg methylators. Besides, sulfate input increased MeHg levels (89-240%) in soils with low ambient sulfate levels (<100mgkg-1) but had no effect on high-sulfate soils (>380mgkg-1). These could be explained by the diverse responses of Hg mobility and microbial Hg methylators to sulfate input at different ambient sulfate levels. Our study opens the "black box" of Hg methylation under sulfur input, which would help reduce uncertainties in predicting MeHg risk in soils.

Effects of Chitosan-modified Biochar on Formation of Methylmercury in Paddy Soils and Its Accumulation in Rice

Rice is well known to accumulate methylmercury (MeHg) and the consumption of rice in mercury (Hg) polluted areas has been confirmed to be a primary source of MeHg exposure. Therefore, how to inhibit the formation and accumulation of MeHg in the paddy field system needs to be solved urgently. Chitosan modified biochar, a potential inhibitor, was selected in this study to explore its effect on MeHg production and accumulation in the paddy field system by analyzing the mercury content of interstitial water, soil, and rice plant tissues. The results showed that the addition of chitosan modified biochar could significantly reduce MeHg concentration in the soil with the decreased methylation rate of 51.1%-79.1%, and could also decrease the total mercury (THg) and MeHg content of interstitial water. At the maturation stage of rice, the MeHg content of rice roots treated with chitosan modified biochar (CMBC) was 73.1% lower than without biochar (CK1) and 62.0% lower than with unmodified biochar (CK2), and the rice MeHg was 75.8% lower than that of CK1 and 72.9% lower than that of CK2. In addition, the application of biochar could promote the growth of rice with the plant biomass of CMBC and CK2 of 1.6 and 1.7 times higher than that of CK1. Generally, the application of chitosan modified biochar into paddy soil could not only promote the growth of rice, but also inhibit the accumulation of MeHg in rice, suggesting that the chitosan modified biochar has a certain application value in the inhibition of the MeHg formation and accumulation in paddy field system.

Understanding the effects of long-term different fertilizer applications on methylmercury accumulation in rice (Oryza sativa L.) plants

The effects of long-term applications of fertilizer form and rate on methylmercury concentration in rice grain have been previously reported. However, there remains a large gap in understanding fertilizer treatments affect the transformation of mercury (Hg) in paddy soils and the translocation of Methylmercury (MeHg) in rice plants. Thus, we investigated the effects of four fertilizer treatments (NK, nitrogen and potassium; NPK, nitrogen, phosphorus and potassium; NPKM, nitrogen, phosphorus, potassium and swine manure; and NPKS, nitrogen, phosphorus, potassium and rice straw) on mercury (Hg) methylation in paddy soils and on MeHg translocation in rice plants after a 24-year period; specifically, we investigated differences in MeHg production in paddy soils and MeHg mass flow in rice plants. The results showed that Geobacteracea and Methanosarcinacea were the major Hg-methylating microorganisms and their relative abundances were significantly promoted by rice straw return, which led to the significantly higher MeHg concentration both in paddy soils and in the rice grain of NPKS treatment compared with control. In addition, the phosphate and organic fertilizers increased MeHg translocation from the roots to the leaves and grain more than the nitrogen and potassium fertilizers did. In detail, compared with the control, NK increased MeHg concentrations in the rice grain by approximately 1-fold; NPK and NPKM, by approximately 3-fold; and NPKS, by approximately 8-fold. Last, we suggest that policy-makers worldwide should comprehensively assess the high potential risk of MeHg in rice grain in large production areas where rice straw is returned.

Release of legacy mercury and effect of aquaculture on mercury biogeochemical cycling in highly polluted Ya-Er Lake, China

Although global mercury (Hg) emission from chlor-alkali industry is decreasing, the legacy Hg may still have potential risks due to its environmental persistence. The objective of this work is to study the biogeochemical cycling and potential risk of Hg in the Ya-Er Lake, which was heavily contaminated by historical chlor-alkali production. Higher concentrations of total Hg (THg) in Ya-Er Lake water (16.8 ± 8.4 ng L−1) and sediment (547 ± 489 ng g−1) than other lake systems were observed, reflecting serious Hg pollution in this system. Diffusion rates of Hg at sediment-water interface and budget of Hg showed that release of legacy Hg in sediment (accounting for ∼80%) dominated THg in water, and about 80% methylmercury (MeHg) of total was diffused from sediment. Significant correlations between total organic carbon (TOC) derived from aquaculture and THg diffusion and MeHg concentrations in sediment suggest that TOC plays important roles in controlling legacy Hg release and MeHg production. The actual weekly intakes of Hg via consumption of cultured catfish and wild topmouth culter were higher than the established provisional tolerable weekly intake (PTWI) of MeHg. These results indicated that although the nearby chlor-alkali plant has been shut down for three decades, the release of legacy Hg stored in the sediment still adversely affects this ecosystem. Moreover, aquaculture could enhance MeHg production and control MeHg distribution in the polluted aquatic ecosystem, potentially posing a health risk to surrounding inhabitants through consumption of fish.

Impacts of climate change on methylmercury formation and bioaccumulation in the 21st century ocean

Impacts of climate change on methylmercury formation and bioaccumulation in the 21st century ocean

Assessing Microbial Communities Related to Mercury Transformations in Contaminated Streambank Soils

In nature, the bioaccumulative potent neurotoxin methylmercury (MeHg) is produced from inorganic mercury (Hg) predominantly by anaerobic microorganisms. Hg-contaminated soils are a potential source of MeHg due to microbial activity. We examine streambank soils collected from the contaminated East Fork Poplar Creek (EFPC) in Tennessee, USA, where seasonal variations in MeHg levels have been observed throughout the year, suggesting active microbial Hg methylation. In this study, we characterized the microbial community in contaminated bank soil samples collected from two locations over a period of one year and compared the results to soil samples from an uncontaminated reference site with similar geochemistry (n = 12). Microbial community composition and diversity were assessed by 16S rRNA gene amplicon sequencing. Furthermore, to isolate potential methylators from soils, enrichment cultures were prepared using selective media. A set of three clade-specific primers targeting the gene hgcA were used to detect Hg methylators among the δ-Proteobacteria in EFPC bank soils across all seasons. Two families among the δ-Proteobacteria that have been previously associated with Hg methylation, Geobacteraceae and Syntrophobacteraceae, were found to be predominant with relative abundances of 0.13% and 4.0%, respectively. However, in soil enrichment cultures, Firmicutes were predominant among families associated with Hg methylation. Specifically, Clostridiaceae and Peptococcaceae and their genera Clostridium and Desulfosporosinus were among the ten most abundant genera with relative abundances of 2.6% and 1.7%, respectively. These results offer insights into the role of microbial communities on Hg transformation processes in contaminated bank soils in EFPC. Identifying the biogeochemical drivers of MeHg production is critical for future remediation efforts.

Methylmercury Transport and Fate Shows Strong Seasonal and Spatial Variability along a High Arctic Freshwater Hydrologic Continuum.

The presence of toxic methylmercury (MeHg) in Arctic freshwater ecosystems and foodwebs is a potential health concern for northern Indigenous people. Addressing this issue requires a better understanding of MeHg production, fate during transport, and uptake into foodwebs. We used methylation assays and spatiotemporal surveys of MeHg concentrations, during the ice-covered and open water seasons, across a hydrologic continuum (composed of thaw seeps, lake/ponds, and a wetland) to identify Hg methylation hotspots and seasonal differences in MeHg cycling unique to Arctic ecosystems. Ponds and saturated wetland soils support methylation hotspots during the open water season, but subsequent export of MeHg to downstream ecosystems is limited by particle settling, binding of MeHg on soil organic matter, and/or demethylation in drier wetland soils. During the ice-covered season, MeHg concentrations in lake waters were approximately ten-fold greater than in summer; however, zooplankton MeHg concentrations were paradoxically five times lower at this time. Despite limited evidence of snow-phase methylation, the snowpack is an important MeHg reservoir. Changes in ice-cover duration will alter MeHg production and bioaccumulation in lakes, while increased thaw and surface water flow will likely result in higher methylation rates at the aquatic-terrestrial interface and more efficient downstream transport of MeHg.

Effect of organic matter concentration and characteristics on mercury mobilization and methylmercury production at an abandoned mine site.

Thousands of abandoned mines throughout the western region of North America contain elevated total-mercury (THg) concentrations. Mercury is mobilized from these sites primarily due to erosion of particulate-bound Hg (THg-P). Organic matter-based soil amendments can promote vegetation growth on mine tailings, reducing erosion and subsequent loading of THg-P into downstream waterbodies. However, the introduction of a labile carbon source may stimulate microbial activity that can produce methylmercury (MeHg)-the more toxic and bioaccumulative form of Hg. Our objectives were to investigate how additions of different organic matter substrates impact Hg mobilization and methylation using a combination of field observations and controlled experiments. Field measurements of water, sediment, and porewater were collected downstream of the site and multi-year monitoring (and load calculations) were conducted at a downstream gaging station. MeHg production was assessed using stable isotope methylation assays and mesocosm experiments that were conducted using different types of organic carbon soil amendments mixed with materials from the mine site. The results showed that >80% of the THg mobilized from the mine was bound to particles and that >90% of the annual Hg loading occurred during the period of elevated discharge during spring snowmelt. Methylation rates varied between different types of soil amendments and were correlated with the components of excitation emission matrices (EEMs) associated with humic acid fractions of organic matter. The mesocosm experiments showed that under anoxic conditions carbon amendments to tailings could significantly increase porewater MeHg concentrations (up to 13±3ng/L). In addition, the carbon amendments significantly increased THg partitioning into porewater. Overall, these results indicate that soil amendment applications to reduce surface erosion at abandoned mine sites could be effective at reducing particulate Hg mobilization to downstream waterbodies; however, some types of carbon amendments can significantly increase Hg methylation as well as increase the mobilization of dissolved THg from the site.

Global distribution and environmental drivers of methylmercury production in sediments

Neurotoxic methylmercury (MeHg) in environments poses substantial risks to human health. Saturated sediments are basic sources of MeHg in food chains; however, distribution patterns and environmental drivers of MeHg at a global scale remain largely unexplored. Here, we characterized global patterns of MeHg distribution and environmental drivers of MeHg production based on 495 sediment samples across five typical ecosystems from the literature (1995–2018) and our own field survey. Our results showed the MeHg concentration ranged from 0.009 to 55.7 μg kg−1 across the different ecosystems, and the highest MeHg concentration and Hg methylation potential were from the sediments of paddy and marine environments, respectively. Further, using combined analysis of random forest and structural equation modeling, we identified temperature and precipitation as important regulators of MeHg production after accounting for the well-known drivers including Hg availability and sediment geochemistry. More importantly, we found increased MeHg production in sediments with elevated mean annual Hg precipitation, and warmer temperature could also accelerate MeHg production by facilitating activities of microbial methylators. Together, this work advances our understanding of global MeHg distribution in sediments and environmental drivers, which are fundamental to the prediction and management of MeHg production and its potential health risk globally.

Production of methylmercury by methanogens in mercury contaminated estuarine sediments.

Anaerobic bacteria are known to produce neurotoxic methylmercury [MeHg] when elemental mercury [Hg(0)] is provided as the sole mercury source. In this study, we examined the formation of MeHg in anaerobic incubations of sediment collected from the San Jacinto River estuary (Texas, USA) amended with aqueous Hg(0) to investigate the microbial communities involved in the conversion of Hg(0) to MeHg. The results show that the addition of the methanogen inhibitor 2-bromoethanesulfonate (BES) significantly decreased MeHg production. The mercury methylation gene, hgcA, was detected in these sediments using archaeal specific primers, and 16S rRNA sequencing showed that a member of the Methanosarcinaceae family of methanogens was active. These results suggest that methanogenic archaea play an underappreciated role in the production of MeHg in estuarine sediments contaminated with Hg(0).