Methylation In Soils Research Articles

Key active mercury methylating microorganisms and their synergistic effects on methylmercury production in paddy soils

Rice contamination with neurotoxic methylmercury (MeHg) from paddy soils is an escalating global concern. Identifying the microorganisms responsible for mercury (Hg) methylation in these soils is essential for controlling Hg contamination in the food chain and mitigating health impacts. Current research often focuses on total Hg-methylating microorganisms, overlooking the contributions of active ones, which can lead to either overestimating or neglecting the specific roles of microorganisms in Hg methylation within paddy soils. In this study, active Hg-methylating microorganisms in paddy soils were identified using a combination of DNA-SIP, Hg isotope labelling, and Hg methylation gene sequencing techniques. Our findings revealed that Geobacter and Anaerolinea are pivotal active Hg-methylating microorganisms across a contamination gradient in paddy soils. Transcriptomic analysis of soils from major rice-producing provinces in China confirmed the widespread and synergistic involvement of these microorganisms. Microbial incubation further validated their interaction significantly enhances Hg methylation, with Me198Hg concentrations increasing 2.8-fold compared to Geobacter alone and 5.2-fold compared to Anaerolinea alone. These findings enhance our understanding of microbial Hg methylation in paddy soils, providing critical insights for accurately predicting soil MeHg load, rice grain MeHg contamination, and human MeHg exposure risks.

Regulation of straw-derived DOM and clay mineral complexation on mercury accumulation in vegetables

Straw return-to-field releases substantial dissolved organic matter (DOM), which can interact with clay minerals and influence mercury (Hg) dynamics in soil-plant systems. However, its detailed mechanisms remain poorly understood. In this study, DOM-montmorillonite (DOM-M) complexes were synthesized using DOM extracted from composted rice straw (DOMrice) and rape straw (DOMrape). The objective of this study was to investigate their impacts on Hg methylation in soil and the accumulation of total Hg (THg) and methylmercury (MeHg) in vegetables. The results demonstrated that straw-derived DOM significantly increased MeHg levels in the soil and water spinach. However, humified straw-derived DOM effectively suppressed this elevation by 29.0–64.5%. Specifically, humified DOMrice resulted in lower MeHg concentrations in the soil and reduced THg and MeHg levels in water spinach compared to humified DOMrape. Natural montmorillonite reduced Hg methylation in the soil but increased the accumulation of THg and MeHg in water spinach. In contrast, the humified DOMrape-M complex significantly mitigated the MeHg accumulation in water spinach that was enhanced by montmorillonite, with a reduction percentage of 25.8–52.0%, while the humified DOMrice-M complex did not demonstrate a similar advantage. This discrepancy could be attributed to certain molecular components in DOMrape, such as higher thiol-rich protein-like fractions and oxidized S species, which could promote Hg retention within mineral layers. The reduced adsorption capacity of humified DOMrice-M for Hg2+ also emphasized the unique role of humified DOMrape-M. Overall, this study highlights the importance of humified straw-derived DOM and its interaction with soil minerals in shaping Hg dynamics within the plant-soil system.

Midseason draining of paddy water suppresses microbial arsenic methylation in soil and alleviates rice straighthead disease

Arsenic (As) methylation is an important component of As biogeochemical cycle. Microbial As methylation is enhanced under anoxic conditions in paddy soil, producing dimethylarsenate (DMA) which can cause physiological straighthead disease in rice. We conducted field experiments at two sites to test the effect of midseason draining of paddy water on microbial As methylation and the incidence of straighthead disease. Compared to continuous flooding, midseason draining increased soil Eh, decreased the abundances of microbial genes for arsenate reduction (arsC and arrA) and arsenite methylation (arsM), and lowered the concentrations of both inorganic As and DMA in soil porewater. Draining shifted microbial composition, resulting in decreases in the relative abundance of 17‐132 amplicon sequence variants. Draining decreased the accumulation of DMA in rice husk and of inorganic As and DMA in rice grain, decreased the incidence of straighthead disease, and increased grain yield by 20–45 %. Further experiments were conducted at eight field sites to assess the effect of midseason draining in a split field design. Draining decreased husk DMA concentration by 40–65 % and increased grain yield by 25–209 %. This study demonstrates that midseason draining can effectively suppress microbial As methylation and alleviate rice straighthead disease, benefiting both grain yield and safety.

Soil Geobacteraceae are the key predictors of neurotoxic methylmercury bioaccumulation in rice.

Contamination of rice by the potent neurotoxin methylmercury (MeHg) originates from microbe-mediated Hg methylation in soils. However, the high diversity of Hg methylating microorganisms in soils hinders the prediction of MeHg formation and challenges the mitigation of MeHg bioaccumulation via regulating soil microbiomes. Here we explored the roles of various cropland microbial communities in MeHg formation in the potentials leading to MeHg accumulation in rice and reveal that Geobacteraceae are the key predictors of MeHg bioaccumulation in paddy soil systems. We characterized Hg methylating microorganisms from 67 cropland ecosystems across 3,600 latitudinal kilometres. The simulations of a rice-paddy biogeochemical model show that MeHg accumulation in rice is 1.3-1.7-fold more sensitive to changes in the relative abundance of Geobacteraceae compared to Hg input, which is recognized as the primary parameter in controlling MeHg exposure. These findings open up a window to predict MeHg formation and accumulation in human food webs, enabling more efficient mitigation of risks to human health through regulations of key soil microbiomes.

Effects of elevated CO2 on MeHg and IHg in rice

Methylmercury (MeHg) and, to a lesser extent, inorganic mercury (IHg) contamination of rice is a global public health concern, but little is known about how soil and grain Hg concentrations respond to elevated CO2 (ECO2), or how ECO2 alters movement of Hg through the soil-plant-grain system. To advance knowledge of how Hg contamination of rice will change in the future, this study explored the effect of elevated CO2 (ECO2, c. 800 ppm) on soil, iron plaque, root, stem/leaf, and grain concentrations of MeHg and IHg. We observed evidence that ECO2 increased accumulation of MeHg, but not IHg, in rice grain. For IHg, ECO2 did not alter its uptake from the soil, translocation through the plant, or concentration in rice grain. However, ECO2 did reduce uptake of IHg from the air into leaf tissues, likely as a result of the reduced stomatal conductivity and thus more limited direct uptake from the air.Methylmercury concentrations in the grain of plants grown at ECO2 were significantly higher than those of plants grown at ambient CO2. Moreover, MeHg concentrations were also elevated in stem/leaf (82 %) and root tissue (37 %) for ECO2 plants, although the root-tissue results were not statistically significant. In contrast, soil MeHg concentrations were virtually indistinguishable between treatments, indicating that higher rice grain MeHg concentrations were not likely due to higher microbial IHg methylation in soil. Plant uptake of MeHg into stem/leaves and grain from the soil was significantly greater in the ECO2 treatment; however, translocation patterns of MeHg within the plant itself did not differ between treatments. Notably, these patterns existed despite consistently lower transpiration in the ECO2 treatment, and thus less mass flow of solute towards and through the plant. Our results indicate that as CO2 concentrations rise, the human health risks related to MeHg in grain will likely increase.

Suppression of mercury methylation in soil and methylmercury accumulation in rice by dissolved organic matter derived from sulfur-rich rape straw

Straw amendment significantly enhances mercury (Hg) methylation and subsequent methylmercury (MeHg) bioaccumulation in Hg-contaminated paddy fields by releasing dissolved organic matter (DOM). This study comprehensively investigates the regulatory mechanisms of DOM and its different molecular weights derived from sulfur-rich rape straw (RaDOM) and composted rape straw (CRaDOM) applied in the rice-filling stage on soil MeHg production and subsequent bioaccumulation in rice grains. The results indicated that the amendment of RaDOM and CRaDOM significantly reduced soil MeHg content by 42.40–62.42%. This reduction can be attributed to several factors, including the suppression of Hg-methylating bacteria in soil, the supply of sulfate from RaDOM and CRaDOM, and the increase in the humification, molecular weight, and humic-like fractions of soil DOM. Additionally, adding RaDOM increased the MeHg bioaccumulation factor in roots by 27.55% while inhibiting MeHg transportation by 12.24% and ultimately reducing MeHg content in grains by 21.24% compared to the control group. Similarly, CRaDOM enhanced MeHg accumulation by 25.19%, suppressed MeHg transportation by 39.65%, and reduced MeHg levels in the grains by 27.94%. The assimilation of sulfate derived from RaDOM and CRaDOM into glutathione may be responsible for the increased retention of MeHg in the roots. Over the three days, there was a significant decrease in soil MeHg content as the molecular weight of RaDOM increased; conversely, altering the molecular weight of CRaDOM demonstrated an inverse trend. However, this pattern was not observed after 12 days. Applying sulfur-rich rape DOM can help mitigate MeHg accumulation in paddy fields by regulating the quality of soil DOM, sulfur cycling, and Hg-methylating bacteria.

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

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

Arsenic methylation and microbial communities in paddy soils under alternating anoxic and oxic conditions

Arsenic (As) methylation in soils affects the environmental behavior of As, excessive accumulation of dimethylarsenate (DMA) in rice plants leads to straighthead disease and a serious drop in crop yield. Understanding the mobility and transformation of methylated arsenic in redox-changing paddy fields is crucial for food security. Here, soils including un-arsenic contaminated (N-As), low-arsenic (L-As), medium-arsenic (M-As), and high-arsenic (H-As) soils were incubated under continuous anoxic, continuous oxic, and consecutive anoxic/oxic treatments respectively, to profile arsenic methylating process and microbial species involved in the As cycle. Under anoxic-oxic (A-O) treatment, methylated arsenic was significantly increased once oxygen was introduced into the incubation system. The methylated arsenic concentrations were up to 2–24 times higher than those in anoxic (A), oxic (O), and oxic-anoxic (O-A) treatments, under which arsenic was methylated slightly and then decreased in all four As concentration soils. In fact, the most plentiful arsenite S-adenosylmethionine methyltransferase genes (arsM) contributed to the increase in As methylation. Proteobacteria (40.8%–62.4%), Firmicutes (3.5%–15.7%), and Desulfobacterota (5.3%–13.3%) were the major microorganisms related to this process. These microbial increased markedly and played more important roles after oxygen was introduced, indicating that they were potential keystone microbial groups for As methylation in the alternating anoxic (flooding) and oxic (drainage) environment. The novel findings provided new insights into the reoxidation-driven arsenic methylation processes and the model could be used for further risk estimation in periodically flooded paddy fields.

Straw incorporation induces rice straighthead disease in As-contaminated paddy soil

Rice straw incorporation is globally recognized as a viable alternative to incineration. However, it might lead to arsenic (As) methylation in soils, resulting in increased accumulation of methylated As in rice plants, potentially contributing to the emergence of rice straighthead disease. To evaluate the effect of straw incorporation on the As transformation in the paddy field system, we conducted a pot experiment for rice cultivation in two paddy soils with different As background levels and also characterized the response of the soil microbial community to straw incorporation. The results showed that straw incorporation elevated the total and methylated As concentration within the soil solution and rice plants, which in turn reduced rice seed setting rate and yield, and caused straighthead disorder in rice cultivated in soils with high As levels. 16S rRNA-based sequencing demonstrated reduced abundance and diversity of microorganisms upon adding straw. Notably, the dominant phylum, Bacteroidetes, exhibited a significant increase in abundance due to straw integration, while the abundance of Proteobacteria and Acidobacteria decreased. At the family level, the prevalence of Rikenellaceae increased only in soils contaminated with As following straw incorporation. Redundancy analysis showed positive associations between Rikenellaceae and levels of methylated As present in both soil porewater and rice husks, suggesting a potentially pivotal role of Rikenellaceae in the As methylation process after straw integration. These findings collectively emphasize that including straw can reshape the soil's microbial community and amplify As methylation in the soil, thereby promoting the uptake and accumulation of methylated As in rice and inducing straighthead disease in As-contaminated soil.

DOM influences Hg methylation in paddy soils across a Hg contamination gradient

Rice paddies provide optimum conditions for Hg methylation, and paddy soil is a hot spot for Hg methylation and the predominant source of methylmercury (MeHg) accumulated in rice grains. The role of dissolved organic matter (DOM) in controlling Hg bioavailability and methylation in rice paddy systems remains unclear. Paddy soils from eight various cultivation sites in China were chosen to investigate the variations in soil DOM and the influence of DOM concentration and optical characteristics on Hg methylation in rice paddy systems. In the present study, 151 rhizosphere soil samples were collected, and UV–Vis absorption and fluorescent spectroscopy were used to identify the optical properties of DOM. The relationship between MeHg and DOM's optical property indices revealed the production of MeHg consumes lower molecular weight DOM. Moreover, the correlation between DOM concentration and its optical characteristics highlighted the significant role of humic components on MeHg variability in paddy soil. Variation and correlation results demonstrated the allochthonous origin of DOM in the Hg-contaminated soil, with a higher molecular weight and humic character of DOM, as well as the dominant role of autochthonous DOM in promoting Hg methylation in uncontaminated soil. The current study indicated that soil organic matter and its dissolved fractions tend to limit Hg bioavailability and subsequently diminish MeHg production in contaminated paddy soils. Furthermore, the leading roles of allochthonous DOM in protecting MeHg from degradation and autochthonous DOM signatures in enhancing MeHg production in paddy soils. Overall, these findings provide insight into the correlative distributions of DOM and Hg along a Hg concentration gradient in paddy soil, thereby highlighting their potential role in controlling Hg bioavailability and regulating Hg methylation in the soil ecosystems.

Distinct arsenic uptake feature in rice reveals the importance of N fertilization strategies

The environmental behavior of arsenic (As) is commonly affected by the biogeochemical processes of iron (Fe) and nitrogen (N). In this study, field experiments were conducted to explore As uptake in rice and As translation and distribution in As-contaminated iron-rich paddy soils after applying different forms of N fertilizers, including urea (CO(NH2)2), ammonium bicarbonate (NH4HCO3), nitrate of potash (KNO3), and ammonium bicarbonate + nitrate of potash (NH4HCO3 + KNO3). The results indicated that applying nitrate N fertilizer inhibited the reduction and dissolution of As-bearing iron minerals and promoted microbial-mediated As(III) oxidation in flooded soil, thus reducing the soil As bioavailability. The concentrations of total As and inorganic As ratio (iAs/TAs) in rice grain decreased by 32.4 % and 15.4 %, respectively. However, the application of ammonium nitrogen promoted the reductive dissolution of As-bearing iron minerals and stimulated microbial As(V) reduction in flooded soil, leading to the release of As from soil to porewater. The total As concentration and inorganic As uptake ratio in rice grain increased by 20.1 % and 6.2 %, respectively, when urea was applied, and by 29.6 % and 10.5 %, respectively, when ammonium bicarbonate was applied. However, the simultaneous application of NH4+ and NO3− had no significant effect on As concentration in rice grain and its transformation in paddy soils. Ammonium nitrogen enhanced the organic As concentration in rice grain because the increased As(III) promoted As methylation in soil. In contrast, nitrate decreased the organic As uptake by rice grain because the decreased As(III) diminished As methylation in soil. The results provide reasonable N fertilization strategies for regulating the As biogeochemical process and reducing the risk of As contamination in rice.

Effects of fulvic acid and humic acid from different sources on Hg methylation in soil and accumulation in rice

Humus is often used as an organic modifier to reduce the bioaccumulation of heavy metals in plants, but the effects of different humus components from different sources on the fate of mercury (Hg) in paddy fields are still unclear. Here, fulvic acid (FA) and humic acid (HA) extracted from composted straw (CS), composted cow dung (CCD), peat soil (PM) and lignite coal (LC) were used to understand their effects on the methylation and bioaccumulation of Hg in paddy soil by pot experiments. Amendments of both FA and HA largely increased the abundance of Hg-methylating microbes and low-molecular-weight organic matters (e.g, cysteine) in paddy soil. They were also found to change the aromaticity, molecular size and Chromophoric DOM concentration of DOM, and resulted in heterogeneous effects on migration and transformation of Hg. All the FA-amended treatments increased the mobility and methylation of Hg in soil and its absorption in roots. Nevertheless, FA from different sources have heterogeneous effects on transport of Hg between rice tissues. FA-CCD and FA-PM promoted the translocation of MeHg from roots to rice grains by 32.95% and 41.12%, while FA-CS and FA-LC significantly inhibited the translocation of inorganic Hg (IHg) by 52.65% and 66.06% and of MeHg by 46.65% and 36.23%, respectively. In contrast, all HA-amended treatments reduced the mobility of soil Hg, but promoted Hg methylation in soil. Among which, HA-CCD and HA-PM promoted the translocation of MeHg in rice tissues by 88.95% and 64.10%, while its accumulation in rice grains by 28.43% and 28.69%, respectively. In general, the application of some FA and HA as organic modifiers to reduce Hg bioaccumulation in rice is not feasible.

Unravelling biogeochemical drivers of methylmercury production in an Arctic fen soil and a bog soil

Arctic tundra soils store a globally significant amount of mercury (Hg), which could be transformed to the neurotoxic methylmercury (MeHg) upon warming and thus poses serious threats to the Arctic ecosystem. However, our knowledge of the biogeochemical drivers of MeHg production is limited in these soils. Using substrate addition (acetate and sulfate) and selective microbial inhibition approaches, we investigated the geochemical drivers and dominant microbial methylators in 60-day microcosm incubations with two tundra soils: a circumneutral fen soil and an acidic bog soil, collected near Nome, Alaska, United States. Results showed that increasing acetate concentration had negligible influences on MeHg production in both soils. However, inhibition of sulfate-reducing bacteria (SRB) completely stalled MeHg production in the fen soil in the first 15 days, whereas addition of sulfate in the low-sulfate bog soil increased MeHg production by 5-fold, suggesting prominent roles of SRB in Hg(II) methylation. Without the addition of sulfate in the bog soil or when sulfate was depleted in the fen soil (after 15 days), both SRB and methanogens contributed to MeHg production. Analysis of microbial community composition confirmed the presence of several phyla known to harbor microorganisms associated with Hg(II) methylation in the soils. The observations suggest that SRB and methanogens were mainly responsible for Hg(II) methylation in these tundra soils, although their relative contributions depended on the availability of sulfate and possibly syntrophic metabolisms between SRB and methanogens.

Arsenic speciation, mechanisms, and factors affecting rice uptake and potential human health risk: A systematic review

Arsenic (As), being the first class of carcinogen, reflects disastrous threats to living beings owing to its high persistence, toxicity, bioaccumulation, and bioavailability in the environment. The toxicity of As notably linked with its inorganic forms such as arsenite (AsIII) and arsenate (AsV). The As-contaminated water irrigation of rice field led to its accumulation in topsoil and bioavailability to rice crops. Among As species, the AsIII is predominant species in the topsoil of paddy fields and growing rice grain. Rice grain ranked as the second extensive global cultivated cereal crop and used as a staple food by billions of people around the world. This study presents an overview regarding the conditions, factors, and mechanisms in the soils that affect the As oxidation, reduction and methylation in soils and uptake in rice plants. This paper not only considers the As uptake in the grains of rice varieties but also focused on its biotransformation to the diet of human and cancer risk. The uptake of As by rice crops showed a major exposure pathway in the people having high rice consumption. The relevant updated findings of As and its speciation in rice, mechanisms, and controlling factors are critically discussed, while the gaps in the existing literature and directions for future research work are identified in this study which may be helpful for global scientific communities.

Microbial Arsenic Methylation in Soil and Uptake and Metabolism of Methylated Arsenic in Plants: A Review.

Arsenic (As) poses a risk to the human health in excess exposure and microbes play an important role in the toxicity of As. Arsenic methylation mediated by microbes is a key driver of As toxicity in the environment and this paper reviews the role of microbial arsenic methylation and volatilization in the biogeochemical cycle of arsenic. In specific, little is presently known about the molecular mechanism and gene characterization of arsenic methylation. The uptake of methylated arsenic in plants is influenced by microbial arsenic methylation in soil, thus enhancing the volatilization of methylated arsenic is a potential mitigation point for arsenic mobility and toxicity in the environment. On the other hand, the potential risk of methylated arsenic on organisms is also discussed. And the directions for future research, theoretical reference for the control and remediation of arsenic methylation, are presented.

Mercury and methylmercury levels in soils associated with coal-fired power plants in central-northern Chile

Mercury pollution is a worldwide problem, and is associated with a number of natural and anthropogenic processes. The present work, conducted in Chile, a country that has traditionally depended heavily on fossil fuels for power generation, examines total mercury (THg) and monomethylmercury (MMHg) concentrations in soils across different sites exposed to coal fired power plant emissions. Samples from four selected (Renca, Laguna Verde, Las Ventanas, Huasco) and 1 control (Quintay) sites were analyzed using cold vapour and fluorescence spectroscopy (CV-AFS) for THg determination and chromatographic separation with atomic fluorescence detection (DI-GC-AFS) was followed for speciation analysis.From the sites analyzed, Renca and Las Ventanas showed high concentrations of total mercury, exhibiting ranges between 135 – 568 and 94–464 ng g−1 respectively, while Laguna Verde and Huasco exhibited lower values ranged 5–27 and 9–44 ng g−1 respectively. Conversely, analysis of MMHg concentrations showed that only Renca site possessed high values, ranging between 0.1 and 3.0 ng g−1, resulting in this site being considered contaminated. Conversely, other sites showed minimal values comparable to the control site (0.024 ± 0.003 ng g−1) in terms of MMHg concentrations. An analysis of the differences between MMHg and THg concentrations in contaminated sites, suggests an overall absence of methylation in soils of Las Ventanas, probably related to the very high levels of soil heavy metals, especially copper. Moreover, the influence of the composition and physicochemical properties of the different soils on the mobility of the species was assessed. Results obtained (as Log Kd) were 3.5 and 4.1 for Renca and Las Ventanas respectively, suggesting low mobility of mercury species in the environment for both sites.Finally, the data obtained allowed us to establish a first approximation of the differences in concentration and mobility of total and MMHg associated with coal fired power plants emission in central-northern Chile, an area previously understudied in a country heavily dependent on fossil-fuels.

Increased Methylmercury Accumulation in Rice after Straw Amendment.

Consumption of rice has been shown to be an important route of dietary exposure to methylmercury (MeHg, a neurotoxin) for Asians having a low fish but high rice diet. Therefore, factors that increase MeHg production and bioaccumulation in soil-rice systems, could enhance the risk of MeHg exposure. On the basis of a national-scale survey in China (64 sites in 12 provinces) and rice cultivation experiments, we report that straw amendment, a globally prevalent farming practice, could increase MeHg concentrations in paddy soils (11-1043%) and rice grains (95%). By carrying out a series of batch incubation, seedling uptake and sand culture experiments, we demonstrate that these increases could be attributed to (1) enhanced abundances/activities of microbial methylators and the transformation of refractory HgS to organic matter-complexed Hg, facilitating microbial Hg methylation in soils; (2) enhanced MeHg mobility, and increased root lengths (35-41%) and tip numbers (60-105%), increasing MeHg uptake by rice roots; and (3) enhanced MeHg translocation to rice grains from other tissues. Results of this study emphasize fresh organic matter-enhanced MeHg production and bioaccumulation, and highlight the increased risk of MeHg after straw amendment and thus the need for new policies concerning straw management.

Understanding Enhanced Microbial MeHg Production in Mining-Contaminated Paddy Soils under Sulfate Amendment: Changes in Hg Mobility or Microbial Methylators?

Elevated methylmercury (MeHg) production in mining-contaminated paddy soils, despite the high fraction of refractory HgS(s), has been frequently reported, while the underlying mechanisms are not fully understood. Here, we hypothesized that sulfate input, via fertilization, rainfall, and irrigation, is critical in mobilizing refractory HgS(s) and thus enhancing Hg methylation in mining-contaminated paddy soils. To test this hypothesis, the effects of sulfate amendment on Hg methylation and MeHg bioaccumulation in mining-contaminated soil-rice systems were examined. The results indicated 28-61% higher net MeHg production in soils under sulfate amendment (50-1000 mg kg-1), which in turn increased grain MeHg levels by 22-55%. The enhancement of Hg methylation by Hg mobilization in sulfate-amended soils was supported by two observations: (1) the increased Hg(aq) release from HgS(s), the dominant Hg species in the paddy soils, in the presence of sulfide produced following sulfate reduction and (2) the decreases of refractory HgS(s) in soils under sulfate amendment. By contrast, changes in the abundances/activities of potential microbial Hg methylators in different Hg-contaminated soils were not significant following sulfate amendment. Our results highlight the importance to consider enhanced Hg mobility and thus methylation in soils under sulfate amendment.

Mercury speciation, bioavailability and risk assessment on soil–rice systems from a watershed impacted by abandoned Hg mine-waste tailings

Mercury (Hg) is a global pollutant and can be accumulated in the food chain, posing exposure risks to humans. In this study, rice plants and corresponding rhizosphere soil samples were collected from a watershed of the Wawu River Basin that is heavily impacted by historic Hg mining and retorting activities. Total mercury (THg) and methylmercury (MeHg) in rice grains, as well as other tissues and soil samples, were measured. Five soil Hg fractions, as well as soil parameters, were also determined. The results show that the average concentrations of THg and MeHg in rice grains were 14 ± 7.0 μg kg−1 and 7.2 ± 4.0 μg kg−1. Soil organic-bound (Hg-o) and strong complex-bound (Hg-s) were the main Hg fractions, accounting for 44% of the total. To estimate the Hg–ligand interaction in the soils, soil -N/Hg (R = 0.451, p < 0.05), -S/Hg (R = 0.372, p < 0.1), and -OM/Hg ratio (R = 0.320, p < 0.5) with MeHgsoil were observed with significant positive correlations, indicating that the formation of Hg–OM, Hg–N–OM or Hg–S–OM complexes could prevent Hg(II) from methylation in soils. The significant positive correlations of the -N/Hg ratio, -S/Hg ratio and -OM/Hg ratio with MeHg in rice tissues suggested that Hg methylation and MeHg demethylation occurred throughout the rice paddy ecosystem. The estimated MeHg daily intake (EDI) was 0.075 ± 0.041 μg kg−1 bw d−1 and was lower than the RfD level of 0.1 μg kg−1 bw d−1 recommended by the US EPA. However, approximately 29% of the hazardous index (HI) of MeHg in grain exceeded 1, posing a potential threat to local populations, particularly pregnant women and children.

Water level fluctuations influence microbial communities and mercury methylation in soils in the Three Gorges Reservoir, China

Reservoirs tend to have enhanced methylmercury (MeHg) concentrations compared to natural lakes and rivers, and water level fluctuations can promote MeHg production. Until now, little research has been conducted on the effects of microorganisms in soils for the formation of MeHg during different drying and flooding alternating conditions in the Three Gorges Reservoir (TGR). This study aimed to understand how water level fluctuations affect soil microbial composition and mercury concentrations, and if such microbial variations are related to Hg methylation. The results showed that MeHg concentrations and the ratios of MeHg to THg (MeHg%) in soils were higher in the seasonally drying and flooding alternating areas (DFAs, 175–155m) than those in the non-inundated (NIAs, >175m) and inundated areas (IAs, <145m). However, MeHg% in all samples was less than 1%, indicating that the Hg methylation activity in the soils of the TGR was under a low level. 454 high-throughput sequencing of 16S rRNA gene amplicons showed that soil bacterial abundance and diversity were relatively higher in DFA compared to those in NIA and IA, and microbial community composition varied in these three areas. At the family level, those groups in Deltaproteobacteria and Methanomicrobia that might have many Hg methylators were also showed a higher relative abundance in DFA, which might be the reason for the higher MeHg production in these areas. Overall, our results suggested that seasonally water level fluctuations can enhance the microbial abundance and diversity, as well as MeHg production in the TGR.