Hg Methylation Research Articles

S-adenosyl-L-methionine is the unexpected methyl donor for the methylation of mercury by the membrane-associated HgcAB complex

Mercury (Hg) is a heavy metal that exhibits high biological toxicity. Monomethylmercury and dimethylmercury are neurotoxins and a significant environmental concern as they bioaccumulate and biomagnify within the aquatic food web. Microbial Hg methylation involves two proteins, HgcA and HgcB. Here, we show that HgcA and HgcB can be heterologously coexpressed, and the HgcAB complex can be purified. We demonstrated that HgcA is a membrane-associated cobalamin-dependent methyltransferase and HgcB is a ferredoxin-like protein containing two [4Fe-4S] clusters. Further, spectroscopic and kinetic results demonstrate that S-adenosyl-L-methionine (SAM) donates the methyl group to Hg in a two-step reaction involving a methylcob(III)alamin intermediate including Co-thiolate ligation from a conserved Cys residue. Our findings uncover a biological role for SAM in microbial Hg methylation.

Influence of vegetative cover on snowpack mercury speciation and stocks in the greening Canadian Subarctic region.

A notable greening and warming of the Arctic and Subarctic due to climate change has uncertain implications for the global cycling of mercury (Hg). Snowpacks are dynamic reservoirs for Hg susceptible to solar radiation and wind pumping, with vegetative cover potentially altering Hg photochemistry. However, the impact of northern greening on the transformation of major Hg species and on Hg stocks remain poorly understood. Temporal surface snow and snowpit sampling was conducted under tree canopies and open tundra sites at the boreal-tundra ecotone in Nunavik, Canada. Maximum (mean) concentrations of 69.1 ng/L (8.8 ng/L) total mercury (HgT) and 46.9 ng/L (5.5 ng/L) reactive mercury (HgR) were measured in forest surface snow, with maximums attributed to rapid atmospheric oxidation events. Significant post-depositional reductions were recorded in the bay, tundra, and forest (67-99% HgR) and suggested greater Hg sequestration may occur under tree canopies. Increasing methylmercury (MeHg), HgT, and dissolved organic carbon (DOC) concentrations were detected across a vegetation gradient shifting towards humic-like organic matter. Notably, springtime depth profiles presented an approximate 12-fold greater accumulation of HgT under tree canopies compared to open tundra (p<0.01), with up to 16-times higher stocks (HgT, MeHg, DOC) at elevated vegetation density (p<0.05). In the North, increasing vegetation cover and surface warming may favor Hg accumulation and methylation in snowpacks, facilitated by interactions with organic matter, and further enriched by the reduced wind and solar exposure experienced under forest canopies.

How ambient temperature rise affects mercury dynamics and its pools in secondary forests

The forest ecosystem is a significant pool for capturing atmospheric mercury (Hg) deposition, with most Hg accumulating in forest soils. As secondary forests now dominate global forest cover, they are particularly sensitive to changes in ambient temperature. However, the impact of these changes on Hg dynamics in secondary forests remains poorly understood. Here, we quantified Hg inputs, outputs, and mass balances in two secondary forests in China, each with different ambient temperatures. We found that elevated ambient temperature (~1.0℃) advanced the germination of leaves by 2-3 days and extended the growing season by approximately one week, resulting in increased litterfall biomass by 1.18 Mg hm-2 yr-1 and a thicker litterfall layer by 0.22cm over 34 years. This temperature rise also facilitated Hg methylation within forest and enhanced methylmercury (MeHg) export, heightening the potential risk of MeHg exposure to surrounding ecosystems. Additionally, higher ambient temperature not only increased soil Hg emissions (2.75µgm-2 yr-1) but also led to significant Hg deposition via litterfall (9.26µgm-2 yr-1), resulting in a net annual Hg deposition of 6.88µgm-2 yr-1. This net Hg deposition accumulated in the topsoil, increasing the Hg pool by 0.51mgm-2 in organic and 0-10cm mineral soil horizons. Our findings suggest that even a ~1.0℃ temperature rise could enhance the role of secondary forests as atmospheric Hg sink by 45.10%. Therefore, the impact of ongoing climate warming on Hg cycling and pools in forests should receive increased attention and warrants further research.

System efficiency of methylmercury production, an important indicator for evaluating the long-term risk of mercury: From a case study in the Jiaozhou Bay to global coastal seas

With the implementation of the Minamata Convention, total Hg (THg) in coastal seas are expected to be reduced. However, methylmercury (MeHg) levels in aquatic environments depend not only on THg, but also the system efficiency of MeHg production (represented by MeHg/THg ratio in seawater) whose variations with time remain unclear. By choosing the Jiaozhou Bay (JZB) as a typical coastal system, combined with the published data from the global coastal systems, system efficiency of MeHg production in coastal seas were investigated. The mass budget of MeHg showed that the in situ production and degradation are the major source and sink of MeHg in the JZB. The relationships of MeHg in the seawater and fish with MeHg/THg in seawater indicate that system efficiency of MeHg production may control the risk of MeHg in coastal systems. The sulfate and nitrate in seawater, organic matter in sediment, biotic methylation, and transport of inorganic Hg from the seawater to sediment were identified to be critical parameters and processes for the MeHg/THg in global coastal seas. The findings of this study highlight the importance of monitoring the system efficiency of MeHg production and its controlling processes and parameters for evaluating the long-term risk of Hg.

The origin of methyl group in methanogen-mediated mercury methylation: From the Wolfe cycle

Methylmercury (MeHg) is a bioaccumulating neurotoxin mainly produced by anaerobic microorganisms, with methanogen being one of the important methylators. A critical aspect for understanding the mechanism for microbial mercury (Hg) methylation is the origin of the methyl group. However, the origin of methyl group in methanogen-mediated Hg methylation remains unclear. This study aims to identify the source of methyl group for MeHg synthesis in methanogens. Our study revealed that Hg methylation in Methanospirillum hungatei JF-1 is closely related to methanogenesis process, according to the results of proteomic study and substrate limitation study. Next, we proved that nearly all methyl group in MeHg derives from the Wolfe cycle in this species, rather than the previously demonstrated acetyl-coenzyme A pathway, based on the results of 13C labeling study. We then proposed the Wolfe cycle-dependent Hg methylation mechanism in this species. Further genome analyses and 13C labeling experiments indicated that the involvement of the Wolfe cycle in Hg methylation is probably a universal feature among Hg-methylating methanogens. These findings reveal a unique Hg methylation mechanism in methanogens. Our study broadens the carbon substrates and controlling factors for MeHg synthesis in the environment, which can inform the prediction of MeHg production potential and remediation strategies for MeHg contamination.

Synergetic effect of pyrrhotite and zero-valent iron on Hg(Ⅱ) removal in constructed wetland: Mechanisms of electron transfer and microbial reaction

Effective removal of mercury (Hg) from wastewater is significant due to its high toxicity, especially methylmercury (MeHg). Reducing of Hg(II) to Hg(0) in constructed wetlands (CWs) using iron-based materials is an effective strategy for preventing the formation of MeHg. However, the surface passivation of zero-valent iron (ZVI) limits its application. Herein, synergetic ZVI and pyrrhotite were utilized to enhance Hg removal in CWs. Results indicated that the removal of total Hg, dissolved Hg, and particulate Hg in CWs with ZVI and pyrrhotite were improved by 21.68 ± 0.76 %, 13.02 ± 0.88 %, and 22.27 ± 0.76 % compared to that with single ZVI or pyrrhotite. Pyrrhotite increased the surface corrosion of ZVI, thereby facilitating the process of iron reduction. The redox of iron promoted the generation of EPS, which could provide electrons for Hg(II) reduction. The sulfur also participates in electron transfer by driving the methylation of Hg and provides sulfides to form FeS-Hg complexes and HgS precipitation. The abundance of key enzymes that involved in iron reduction and Hg transformation was enhanced with the addition of ZVI and pyrrhotite. The synergetic of pyrrhotite and ZVI enhances the removal of Hg in CW, offering a promising technology for high-efficiency treatment of Hg.

Precipitation patterns strongly affect vertical migration and methylation of mercury in legacy contaminated sites

Legacy-contaminated sites act as significant sources of mercury (Hg) to their surrounding surface and underground environments. Intensified extreme precipitation is posing great threats to the environment and human health by changing the fate of pollutants, yet little is known about its effect on the vertical migration and methylation of Hg in contaminated sites. Here, we applied a range of simulated extreme precipitation patterns (frequency and intensity) to column leaching assays with soils collected near a contaminated site. We observed that precipitation with high frequency but low intensity resulted in more vertical migration of Hg through the soil profile than that with low frequency but high intensity. The majority (> 90%) of leached Hg was prone to migrate vertically within the top 10 cm of the soil profile. Furthermore, rainfall stimulated microbial Hg methylation, as demonstrated by enhanced production of methylmercury (MeHg) in both simulated and field-contaminated soils. We identified specific microbial taxa including Geobacteraceae, Desulfuromonadaceae, Syntrophaceae, Oscillospiraceae, and Methanomicrobiaceae as key predictors of MeHg production, which differed from those typically observed in overlying water of croplands. Particularly, the relative abundance of these dominant Hg methylators significantly increased during rainfall-induced leaching compared to that of the control, suggesting the crucial yet previously overlooked impacts of increased precipitation events on the process of microbial Hg methylation in industry-contaminated sites. Given the rising incidences of extreme precipitation events worldwide due to climate change, this study highlights the significance of assessing Hg mobility and microbial transformation in legacy contaminated sites.

Structural analyses of apricot pectin polysaccharides

Apricot pectin polysaccharides' fine structure was performed using HPSEC, HPAEC-PAD, GC–MS, NMR and FTIR spectroscopies. Purified pectin fraction (F1AP) was composed of D-galacturonic acid, L-rhamnose, D-arabinose and D-galactose, Mw ∼ 1588 kDa. F1AP was eluted by water and with 0.2 M NaCl from DEAE Sepharose fraction resulting in two distinct fractions, F1AP1 and F1AP6, with different structures, molecular weights, and conformations, providing insights into their structural diversity. F1AP1 neutral properties were related to its association with protein. F1AP1 had a backbone of (1 → 4)-linked-D-galacturonic acid and (1 → 2)-linked-L-rhamnopyranosyl residues branched with arabinogalactan including multiple glycosidic linkages of T-α-Araf, 3-α-Araf, 5-α-Araf, T-α-Arap, 2-α-Arap, t-Galp, 2-Galp, 3-Galp, 4-Galp, 6-Galp, 2,4-Galp, 3,4-Galp, 3,6-Galp and 4,6-Galp side chains, having methyl and acetylated groups, and a high molecular weight (1945 kDa). The Mark-Houwink exponent was 0.276, indicating a compact spherical conformation. While the other F1AP6 fraction consists predominately of less methylated HG regions of pectin polysaccharides. The molar mass of this fraction was 117.5 kDa, which adopted a stiffer and random coil conformation. This knowledge allows us to evaluate how the balance of chemical structure and physical properties of the two pectin domains may manifest itself in the isolated structure of apricot pectin and its applications.

Quinolone antibiotics stimulate bacterial mercury methylation by Geobacter metallireducens GS-15

Bacterial mercury (Hg) methylation is critical for bioremediating Hg pollution, but the impact of emerging antibiotics on this process has rarely been reported. This study innovatively investigated the interactions between Hg-methylating bacteria of Geobacter metallireducens GS-15 and two quinolone antibiotics: lomefloxacin (LOM) and ciprofloxacin (CIP) at 5 μg/L. Short-term LOM exposure increased methylmercury (MeHg) yield by 36 % compared to antibiotic-free conditions, caused by hormesis to alter bioactivities of single GS-15 cells. Long-term CIP exposure led to more antibiotic resistance and mercury tolerance in GS-15 cells, doubling MeHg productivity and significantly increasing expression of Hg methylation (hgcA by 95 folds) and antibiotic resistance (gyrA by 54 folds) genes, while mercury resistance gene merA only increased by 2.5 folds than without selective pressure. These results suggest quinolone antibiotics at environmentally contaminated concentrations stimulate bacterial Hg methylation to form highly toxic MeHg, raising considerable concern for the Hg-antibiotic complex in contaminated environments.

Impacts of oyster farms on sediment-associated mercury and methylmercury concentrations and health risks in an estuarine, mangrove forest, Zhanjiang Bay, China

Estuarine sediments serve as significant reservoirs for mercury (Hg) and methylmercury(MeHg), which can also interconvert in the external environment. The release of Hg in response to human activities raises concerns about its potential ecological and human health effects. Sediment samples were collected in December 2021 from four locations (sites), and Hg cycling by measuring the concentrations of, and controls on, the spatial distribution of total Hg (THg) and methylmercury (MeHg) in high-tidal zone (HTZ) and mid-tidal zone (MTZ) sediments of a mangrove forest (MF) and oyster farm (OF) was examined in northwestern Zhanjiang Bay, including simultaneous determination of sediment particle size, oxidation-reduction potential (Eh), pH, total organic carbon (TOC), sulfide concentration (S2-), and sulfate reducing bacteria (SRB). The research results indicated that concentrations of both THg and MeHg ranged between 20.0–104.0 ng/g and 0.011–0.277 ng/g in the sediments, respectively. The highest methylation potentials within the MF and OF were in sediments located approximately 10–15 cm below the surface. MeHg in the HTZ of the OF was likely derived from exogenous inputs as Hg methylation appears limited, and the formation of MeHg depended not only on the amount of inorganic mercury available for methylation in SRB, but also on the TOC, pH, Eh and S2- content in the sediment. A risk assessment of MeHg during the anthropogenic disturbance of this estuaries conducted on individuals eating oysters demonstrated that health risks are low.

Impact of geochemistry and microbes on the methylmercury production in mangrove sediments

Unraveling the geochemical and microbial controls on methylmercury (MeHg) dynamics in mangrove sediments is important, as MeHg can potentially pose risks to marine biota and people that rely on these ecosystems. While the important role of sulfate-reducing bacteria in MeHg formation has been examined in this ecologically important habitat, the contribution of non-Hg methylating communities on MeHg production remains particularly unclear. Here, we collected sediment samples from 13 mangrove forests in south China and examined the geochemical parameters and microbial communities related to the Hg methylation. MeHg concentrations were significantly correlated to the OM-related parameters such as organic carbon content, total nitrogen, and dissolved organic carbon concentrations, suggesting the importance of OM in the MeHg production. Sulfate-reducing bacteria were the major Hg-methylators in mangrove sediments. Desulfobacteraceae and Desulfobulbaceae dominated the Hg-methylating microbes. Classification random forest analysis detected strong co-occurrence between Hg methylators and putative non-Hg methylators, thus suggesting that both types of microorganisms contribute to the MeHg dynamics in the sediments. Our study provides an overview of MeHg contamination in south China and advances our understanding of Hg methylation in mangrove ecosystems.

Bacterial mercury methylation modulated by vitamin B9: An overlooked pathway leads to increased environmental risks

There has been a serious health and environmental concern in conversion of inorganic mercury (Hg) to the neurotoxin, methylmercury (MeHg) by anaerobic microbes, while very little is known about the potential role of vitamin B9 (VB9) regulator in the biochemical generation of MeHg. This study innovatively investigated bacterial Hg methylation by Geobacter sulfurreducens PCA in the presence of VB9 under two existing scenarios. In the low-complexing scenario, the bacterial MeHg yield reached 68 % higher than that without VB9 within 72 h, which was attributed to free VB9-protected PCA cells relieving oxidative stress, as manifested by the increased expression of Hg methylation gene (hgcAB cluster by 19–48 %). The high-complexing scenario emphasized the intracellular Hg accumulation (38–45 %) after 12 h, as indicated by the increased expression of outer membrane protein-related and mercuric reductase-encoding genes, indicating the inefficient bioavailability of Hg due to a gradual shift from Hg reduction toward Hg0 re-oxidation controlled by competitive ligand exchange. These results suggested that VB9 application significantly raised the potential for bacterial Hg methylation and cellular accumulation, thus proposing insights into the biochemical behaviors of hazardous Hg in farming environments where vulnerable organisms are more possibly co-exposed to higher levels of Hg and VB9.

Assessment of mercury methylation and methylmercury demethylation potentials in water and sediments along the Wabigoon River system

Monomethylmercury (MMHg) plays a crucial role in the accumulation of mercury (Hg) within aquatic food chains. Since ambient levels of methylmercury are governed by the balance of simultaneous methylation and demethylation processes, determining in situ methylation and demethylation rates is critically important to understand the dynamics of methylmercury in the environment. This is especially important in the Wabigoon River system in Ontario, Canada, which is severely contaminated with Hg by a chlor-alkali facility operating in the 1960s, and still exhibits some of the highest recorded fish mercury concentrations in Canada. This work used a simultaneous addition of isotope enriched Hg and MMHg tracers to ascertain Hg methylation and MMHg demethylation potentials. At the locations investigated for this study, the most favourable conditions for Hg methylation were found at the Hydroelectric dam, being able to transform 4.2 % and 4.4 % of added Hg in water and sediments per day, respectively, to MMHg. This could correspond to 1.9 ng/L and 29 ng/g of new MMHg being produced from current ambient Hg. Clay Lake, which is considered a sink for mercury and exhibiting a seasonal anoxic environment at its bottom waters, also demonstrated significant MMHg generation, being able to produce 2.7 ng/L and 13 ng/g of MMHg per day, respectively. Demethylation rates in sediments of riverbed and wetland locations showed an average half-life for methylmercury of 2.1 days, indicating a rapid turnover of MMHg in the Wabigoon River. However, significantly lower demethylation rates were also measured near the inflow of Clay Lake, where it took up to 144 days for MMHg to decrease by 50 %. Generally, most of the investigated locations downstream of the pollution source displayed the potential to generate methylmercury, which could be distributed throughout the Wabigoon River system and therefore require attention with respect to future remediation activities.

Utilizing biochars to stabilize mercury in contaminated floodplain sediment: Implications on mercury remediation.

Major weather events contribute to the mobility and remobilization of legacy mercury (Hg) contamination and sequestration within sediments. Remediation using biochar as a soil amendment is a useful technique to immobilize and decrease Hg toxicity. This study explored whether biochar application is effective at stabilizing labile mercury (LaHg) from floodplain sediment. Controlled mesocosms simulating contamination events and flooding conditions were conducted. Floodplain sediment, which experiences annual periodic flooding, was collected. Sediment was spiked with inorganic Hg, applied with different types of biochar, and experienced simulated flooding events. Four types of biochar, pure rice husk (RH), pure peanut hull (PH), sulfur-modified rice husk (SMRH), and sulfur-modified peanut hull (SMPH), were applied at 10 and 40g/kg rates (i.e., RH 10, RH 40; PH 10, PH 40, SMRH 10, SMRH 40, SMPH 10, SMPH 40). Total Hg, methylmercury, and LaHg concentrations were analyzed by coupling with redox potential measurements. Results indicate that SMRH 10, PH 10, PH 40, SMPH 10, and SMPH 40 successfully remediate Hg by stabilizing and reducing LaHg species from floodplain sediment. However, a high Hg methylation potential was observed with unsulfated and sulfated peanut hulls (PH 10, PH 40, SMPH 10, and SMPH 40), as they tend to create a reducing microenvironment that favors sulfate reduction reactions. Additionally, sulfur-modified biochar tends to promote Hg methylation potential at high application rates (i.e., 40g/kg). We thus recommend using SMRH at a relatively low application rate (SMRH 10) for the remediation of Hg from floodplain sediment.

Functional Genes and Transcripts Indicate the Existent and Active Microbial Mercury-Methylating Community in Mangrove Intertidal Sediments of an Urbanized Bay.

Mercury (Hg) methylation in mangrove sediments can result in the accumulation of neurotoxic methylmercury (MeHg). Identification of Hg methyltransferase gene hgcA provides the means to directly characterize the microbial Hg-methylating consortia in environments. Hitherto, the microbial Hg-methylating community in mangrove sediments was scarcely investigated. An effort to assess the diversity and abundance of hgcA genes and transcripts and link them to Hg and MeHg contents was made in the mangrove intertidal sediments along the urbanized Shenzhen Bay, China. The hgcA genes and transcripts associated with Thermodesulfobacteria [mainly Geobacteraceae, Syntrophorhabdaceae, Desulfobacterales, and Desulfarculales (these four lineages were previously classified into the Deltaproteobacteria taxon)], as well as Euryarchaeota (mainly Methanomicrobia and Theionarchaea) dominated the hgcA-harboring communities, while Chloroflexota, Nitrospirota, Planctomycetota, and Lentisphaerota-like hgcA sequences accounted for a small proportion. The hgcA genes appeared in greater abundance and diversity than their transcript counterparts in each sampling site. Correlation analysis demonstrated that the MeHg content rather than Hg content significantly correlated with the structure of the existent/active hgcA-harboring community and the abundance of hgcA genes/transcripts. These findings provide better insights into the microbial Hg methylation drivers in mangrove sediments, which could be helpful for understanding the MeHg biotransformation therein.

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.

Molybdate inhibits mercury methylation capacity of Pseudodesulfovibrio hydrargyri BerOc1 regardless of the growth metabolism.

Molybdate inhibits sulfate respiration in sulfate-reducing bacteria (SRB). It is used as an inhibitor to indirectly evaluate the role of SRB in mercury methylation in the environment. Here, the SRB Pseudodesulfovibrio hydrargyri BerOc1 was used to assess the effect of molybdate on cell growth and mercury methylation under various metabolic conditions. Geobacter sulfurreducens PCA was used as the non-SRB counterpart strain with the ability to methylate mercury. While PCA growth and methylation are not affected by molybdate, 1 mM of molybdate inhibits BerOc1 growth under sulfate respiration (50% inhibition) but also under fumarate respiration (complete inhibition). Even more surprising, mercury methylation of BerOc1 is totally inhibited at 0.1 mM of molybdate when grown under sulfate or fumarate respiration with pyruvate as the electron donor. As molybdate is expected to reduce cellular ATP level, the lower Hg methylation observed with pyruvate could be the consequence of lower energy production. Although molybdate alters the expression of hgcA (mercury methylation marker) and sat (involved in sulfate reduction and molybdate sensitivity) in a metabolism-dependent manner, no relationship with mercury methylation rates could be found. Our results show, for the first time, a specific mercury methylation inhibition by molybdate in SRB.

Cumulative Effects of Watershed Disturbances and Run-of-river Dams on Mercury Cycling: Case Study and Recommendations for Environmental Managers.

Run-of-river power plants (ROR) represent the majority of hydroelectric plants worldwide. Their environmental impacts are not well documented and are believed to be limited, particularly regarding the contamination of food webs by methylmercury (MeHg), a neurotoxin. RORs are typically installed in small rivers where combined effects of watershed disturbances with dam construction can complicate environmental management. We report a multi-year case study on the Saint-Maurice River (Canada) where an unpredicted temporary increase in MeHg accumulation in predator fish was observed after the construction of two ROR plants. The associated pondages acted as sedimentation basins for mercury (Hg) and organic matter from a watershed disturbed by a forest fire and by logging. This fresh organic carbon likely fueled microbial MeHg production. Hg methylation was more associated with environmental conditions than to the presence of Hg, and main methylating microbial groups were identified. A constructed wetland was a site of significant Hg methylation but was not the main source of the fish Hg increase. Organic carbon degradation was the main driver of MeHg accumulation at the base of the food chain whereas trophic levels explained the variations at the top of the food chain. Overall, carbon cycling was a key driver of Hg dynamics in this system, and ROR plants can cause temporary (ca. 12 years) Hg increase in food webs when developed in disturbed watersheds, although this increase is smaller than for large reservoirs. Recommendations for future ROR construction are to establish a good environmental monitoring plan with initial high temporal resolution and to consider recent and potential watershed disturbances in the plan.

Methylmercury cycling in the Bohai Sea and Yellow Sea: Reasons for the low system efficiency of methylmercury production

Coastal seas contribute the majority of human methylmercury (MeHg) exposure via marine fisheries. The terrestrial area surrounding the Bohai Sea and Yellow Sea (BS and YS) is one of the mercury (Hg) emission “hot spots” in the world, resulting in high concentrations of Hg in BS and YS seawater in comparison to other marine systems. However, comparable or even lower Hg levels were detected in seafood from the BS and YS than other coastal regions around the word, suggesting a low system bioaccumulation of Hg. Reasoning a low system efficiency of MeHg production (represented by MeHg/THg (total Hg) in seawater) may be present in these two systems, seven cruises were conducted in the BS and YS to test this hypothesis. MeHg/THg ratios in BS and YS seawater were found to be lower than that in most coastal systems, indicating that the system efficiency of MeHg production is relatively lower in the BS and YS. The low system efficiency of MeHg production reduces the risk of Hg in the BS and YS with high Hg discharge intensity. By measuring in situ production and degradation of MeHg using double stable isotope addition method, and MeHg discharge flux from various sources and its exchange at various interfaces, the budgets of MeHg in the BS and YS were estimated. The results indicate that in situ methylation and demethylation are the major source and sink of MeHg in the BS and YS. By comparing the potential controlling processes and environmental parameters for MeHg/THg in the BS and YS with the other coastal seas, estuaries and bays, lower transport efficiency of inorganic Hg from water column to the sediment, slower methylation of Hg, and rapid demethylation of MeHg were identified to be major reasons for the low system efficiency of MeHg production in the BS and YS. This study highlights the necessity of monitoring the system efficiency of MeHg production, associated processes, and controlling parameters to evaluate the efficiency of reducing Hg emissions in China as well as the other countries.

Diet choices determine mercury exposure risks for people living in gold mining regions of Peru

Artisanal and small-scale gold mining (ASGM) is the largest global anthropogenic mercury (Hg) source and is widespread in the Peruvian Amazon. Consuming Hg-laden foods exposes people to this potent neurotoxin. While numerous studies have examined fish Hg content near ASGM, Hg accumulation in other commonly consumed animal-and plant-based foods from terrestrial environments is often overlooked. In this study, we aim to address understudied dietary Hg exposures.To understand Hg exposure from food staples in the Peruvian Amazon, we measured total and methyl Hg in local crops, fish, chicken meat, chicken feathers, and eggs from ASGM-impacted and upstream (reference) communities. Diet surveys were used to estimate probable weekly Hg intake from each food. Fish and chicken stable carbon and nitrogen isotope signatures were analyzed to evaluate trophic magnification.Though few crops exceeded food safety recommendations, rice methyl Hg proportions were high (84%). Trophic level was an expected key predictor of fish Hg content. 81% (17 of 21) of local carnivorous fish exceeded WHO and EPA recommendations. Compared to upstream communities, mining-impacted communities demonstrated elevated total Hg in crops (1.55 (interquartile ranges (IQR): 0.60–3.03) μg kg−1 upstream versus 3.38 (IQR: 1.62–11.58) in mining areas), chicken meats (2.69 (IQR: BDL–9.96) μg kg−1 versus 19.68 (IQR: 6.33–48.1)), and feathers (91.20 (IQR: 39.19–216.13) μg kg−1 versus 329.99 (IQR: 173.22–464.99)). Chicken meats from mining areas exhibited over double the methyl Hg concentrations of those upstream. Methyl Hg fractions in chicken muscle tissue averaged 93%. Egg whites and livers exceeded Hg recommendations most frequently. Proximity to mining, but not trophic position, was a predictor of chicken Hg content.Our results demonstrate that terrestrial and aquatic foods can accumulate Hg from mining activity, introducing additional human Hg exposure routes. However, locally sourced carnivorous fish was the largest contributor to an estimated three-fold exceedance of the provisional tolerable weekly Hg intake.