MeHg Production Research Articles

Experimental sulfate amendment alters peatland bacterial community structure

As part of a long-term, peatland-scale sulfate addition experiment, the impact of varying sulfate deposition on bacterial community responses was assessed using 16S tag encoded pyrosequencing. In three separate areas of the peatland, sulfate manipulations included an eight year quadrupling of atmospheric sulfate deposition (experimental), a 3-year recovery to background deposition following 5years of elevated deposition (recovery), and a control area. Peat concentrations of methylmercury (MeHg), a bioaccumulative neurotoxin, were measured, the production of which is attributable to a growing list of microorganisms, including many sulfate-reducing Deltaproteobacteria. The total bacterial and Deltaproteobacterial community structures in the experimental treatment differed significantly from those in the control and recovery treatments that were either indistinguishable or very similar to one another. Notably, the relatively rapid return (within three years) of bacterial community structure in the recovery treatment to a state similar to the control, demonstrates significant resilience of the peatland bacterial community to changes in atmospheric sulfate deposition. Changes in MeHg accumulation between sulfate treatments correlated with changes in the Deltaproteobacterial community, suggesting that sulfate may affect MeHg production through changes in the community structure of this group.

Mercury methylation in rice paddies and its possible controlling factors in the Hg mining area, Guizhou province, Southwest China

Understanding mercury (Hg) methylation/demethylation processes and the factors controlling methylmercury (MeHg) production within the rice paddy ecosystem of Hg mining areas is critical to assess the risk of MeHg contamination in rice grain. Two typical Hg-contaminated mining sites, a current-day artisanal site (Gouxi) and an abandoned site (Wukeng), were chosen in this study. We qualified the in situ specific methylation/demethylation rate constants in rice paddy soil during a complete rice-growing season. Our results demonstrate that MeHg levels in rice paddy soil were a function of both methylation and demethylation processes and the net methylation potential in the rice paddy soil reflected the measured MeHg production at any time point. Sulfate stimulating the activity of sulfate-reducing bacteria was a potentially important metabolic pathway for Hg methylation in rice paddies. We suggest that bioavailable Hg derived from new atmospheric deposition appears to be the primary factor regulating net MeHg production in rice paddies.

Warming increases methylmercury production in an Arctic soil

Rapid temperature rise in Arctic permafrost impacts not only the degradation of stored soil organic carbon (SOC) and climate feedback, but also the production and bioaccumulation of methylmercury (MeHg) toxin that can endanger humans, as well as wildlife in terrestrial and aquatic ecosystems. Currently little is known concerning the effects of rapid permafrost thaw on microbial methylation and how SOC degradation is coupled to MeHg biosynthesis. Here we describe the effects of warming on MeHg production in an Arctic soil during an 8-month anoxic incubation experiment. Net MeHg production increased >10 fold in both organic- and mineral-rich soil layers at warmer (8 °C) than colder (−2 °C) temperatures. The type and availability of labile SOC, such as reducing sugars and ethanol, were particularly important in fueling the rapid initial biosynthesis of MeHg. Freshly amended mercury was more readily methylated than preexisting mercury in the soil. Additionally, positive correlations between mercury methylation and methane and ferrous ion production indicate linkages between SOC degradation and MeHg production. These results show that climate warming and permafrost thaw could potentially enhance MeHg production by an order of magnitude, impacting Arctic terrestrial and aquatic ecosystems by increased exposure to mercury through bioaccumulation and biomagnification in the food web.

Mercury methylation in paddy soil: source and distribution of mercury species at a Hg mining area, Guizhou Province, China

Abstract. Rice paddy plantation is the dominant agricultural land use throughout Asia. Rice paddy fields have been identified as important sites for methylmercury (MeHg) production in the terrestrial ecosystem and a primary pathway of MeHg exposure to humans in mercury (Hg) mining areas. We compared the source and distribution of Hg species in different compartments of the rice paddy during a complete rice-growing season at two different typical Hg-contaminated mining sites in Guizhou province, China: an abandoned site with a high Hg concentration in soil but a low concentration in the atmosphere and a current-day artisanal site with a low concentration in soil but a high concentration in the atmosphere. Our results showed that the flux of new Hg to the ecosystem from irrigation and atmospheric deposition was insignificant relative to the pool of old Hg in soil; the dominant source of MeHg to paddy soil is in situ methylation of inorganic Hg (IHg). Elevated MeHg concentrations and the high proportion of Hg as MeHg in paddy water and the surface soil layer at the artisanal site demonstrated active Hg methylation at this site only. We propose that the in situ production of MeHg in paddy water and surface soil is dependent on elevated Hg in the atmosphere and the consequential deposition of new Hg into a low-pH anoxic geochemical system. The absence of depth-dependent variability in the MeHg concentration in soil cores collected from the abandoned Hg mining site, consistent with the low concentration of Hg in the atmosphere and high pH of the paddy water and irrigation water, suggested that net production of MeHg at this site was limited. We propose that the concentration of Hg in ambient air is an indicator for the risk of MeHg accumulation in paddy rice.

Net methylmercury production in 2 contrasting stream sediments and associated accumulation and toxicity to periphyton.

Periphyton uptake of bioaccumulative methylmercury (MeHg) may be an important entryway into the food web of many stream ecosystems where periphyton can be dominant primary producers. The net production of MeHg in stream sediment, its bioaccumulation in periphyton, and the potential toxicity of divalent Hg (Hg[II]) and MeHg in sediment to periphyton were investigated with a 67-d in situ incubation experiment using chemical exposure substrates containing either a fine-grained, organic-rich or a sandy, low-organic sediment, each amended with varying concentrations of mercuric chloride. Methylmercury was produced in sediment, and concentrations increased with greater amounts of added Hg(II); however, the net production of MeHg was inhibited in the highest Hg(II) treatments of both sediments. The range of total Hg concentrations that inhibited MeHg production was between approximately 80 000 ng Hg and 350 000 ng Hg per gram of organic matter for both sediments. Periphyton colonizing substrates accumulated MeHg in proportion to the concentration in sediment, but periphyton exposed to the sandy sediment accumulated approximately 20-fold more than those exposed to the organic-rich sediment relative to sediment MeHg concentrations. Toxicity of either Hg(II) or MeHg to periphyton was not observed with either periphyton organic content, net primary production, or respiration as endpoints. These results suggest that in situ production and bioaccumulation of MeHg in stream ecosystems can vary as a function of sediment characteristics and Hg(II) loadings to the sediment. Environ Toxicol Chem 2016;35:1759-1765. © 2015 SETAC.

Spatial and temporal patterns of mercury concentrations in freshwater fish across the Western United States and Canada

Methylmercury contamination of fish is a global threat to environmental health. Mercury (Hg) monitoring programs are valuable for generating data that can be compiled for spatially broad syntheses to identify emergent ecosystem properties that influence fish Hg bioaccumulation. Fish total Hg (THg) concentrations were evaluated across the Western United States (US) and Canada, a region defined by extreme gradients in habitat structure and water management. A database was compiled with THg concentrations in 96,310 fish that comprised 206 species from 4262 locations, and used to evaluate the spatial distribution of fish THg across the region and effects of species, foraging guilds, habitats, and ecoregions. Areas of elevated THg exposure were identified by developing a relativized estimate of fish mercury concentrations at a watershed scale that accounted for the variability associated with fish species, fish size, and site effects. THg concentrations in fish muscle ranged between 0.001 and 28.4 (μg/g wet weight (ww)) with a geometric mean of 0.17. Overall, 30% of individual fish samples and 17% of means by location exceeded the 0.30μg/g ww US EPA fish tissue criterion. Fish THg concentrations differed among habitat types, with riverine habitats consistently higher than lacustrine habitats. Importantly, fish THg concentrations were not correlated with sediment THg concentrations at a watershed scale, but were weakly correlated with sediment MeHg concentrations, suggesting that factors influencing MeHg production may be more important than inorganic Hg loading for determining fish MeHg exposure. There was large heterogeneity in fish THg concentrations across the landscape; THg concentrations were generally higher in semi-arid and arid regions such as the Great Basin and Desert Southwest, than in temperate forests. Results suggest that fish mercury exposure is widespread throughout Western US and Canada, and that species, habitat type, and region play an important role in influencing ecological risk of mercury in aquatic ecosystems.

Investigation of biogeochemical controls on the formation, uptake and accumulation of methylmercury in rice paddies in the vicinity of a coal-fired power plant and a municipal solid waste incinerator in Taiwan

Recent studies have shown that rice consumption is another critical route of human exposure to methylmercury (MeHg), the most toxic and accumulative form of mercury (Hg) in the food web. Yet, the mechanisms that underlie the production and accumulation of MeHg in the paddy ecosystem are still poorly understood. In 2013 and 2014, we conducted field campaigns and laboratory experiments over a rice growing season to examine Hg and MeHg cycling, as well as associated biogeochemistry in a suite of paddies close to a municipal solid waste incinerator and a coal-fired power plant station in Taiwan. Concentrations of total Hg and MeHg in paddy soil and rice grain at both sites were low and found not to exceed the control standards for farmland soil and edible rice in Taiwan. However, seasonal variations of MeHg concentrations observed in pore water samples indicate that the in situ bioavailability of inorganic Hg and activity of Hg-methylating microbes in the rhizosphere increased from the early-season and peaked at the mid-season, presumably due to the anoxia created under flooded conditions and root exudation of organic compounds. The presence of Hg-methylators was also confirmed by the hgcA gene detected in all root soil samples. Subsequent methylation tests performed by incubating the root soil with inorganic Hg and an inhibitor or stimulant specific for certain microbes further revealed that sulfate-reducers might have been the principal Hg-methylting guild at the study sites. Interestingly, results of hydroponic experiments conducted by cultivating rice in a defined nutrient solution amended with fixed MeHg and varying levels of MeHg-binding ligands suggested that chemical speciation in soil pore water may play a key role in controlling MeHg accumulation in rice, and both passive and active transport pathways seem to take place in the uptake of MeHg in rice roots.

Anaerobic Mercury Methylation and Demethylation by Geobacter bemidjiensis Bem.

Microbial methylation and demethylation are two competing processes controlling the net production and bioaccumulation of neurotoxic methylmercury (MeHg) in natural ecosystems. Although mercury (Hg) methylation by anaerobic microorganisms and demethylation by aerobic Hg-resistant bacteria have both been extensively studied, little attention has been given to MeHg degradation by anaerobic bacteria, particularly the iron-reducing bacterium Geobacter bemidjiensis Bem. Here we report, for the first time, that the strain G. bemidjiensis Bem can mediate a suite of Hg transformations, including Hg(II) reduction, Hg(0) oxidation, MeHg production and degradation under anoxic conditions. Results suggest that G. bemidjiensis utilizes a reductive demethylation pathway to degrade MeHg, with elemental Hg(0) as the major reaction product, possibly due to the presence of genes encoding homologues of an organomercurial lyase (MerB) and a mercuric reductase (MerA). In addition, the cells can strongly sorb Hg(II) and MeHg, reduce or oxidize Hg, resulting in both time and concentration-dependent Hg species transformations. Moderate concentrations (10-500 μM) of Hg-binding ligands such as cysteine enhance Hg(II) methylation but inhibit MeHg degradation. These findings indicate a cycle of Hg methylation and demethylation among anaerobic bacteria, thereby influencing net MeHg production in anoxic water and sediments.

A mass budget for mercury and methylmercury in the Arctic Ocean

AbstractElevated biological concentrations of methylmercury (MeHg), a bioaccumulative neurotoxin, are observed throughout the Arctic Ocean, but major sources and degradation pathways in seawater are not well understood. We develop a mass budget for mercury species in the Arctic Ocean based on available data since 2004 and discuss implications and uncertainties. Our calculations show that high total mercury (Hg) in Arctic seawater relative to other basins reflect large freshwater inputs and sea ice cover that inhibits losses through evasion. We find that most net MeHg production (20 Mg a−1) occurs in the subsurface ocean (20–200 m). There it is converted to dimethylmercury (Me2Hg: 17 Mg a−1), which diffuses to the polar mixed layer and evades to the atmosphere (14 Mg a−1). Me2Hg has a short atmospheric lifetime and rapidly degrades back to MeHg. We postulate that most evaded Me2Hg is redeposited as MeHg and that atmospheric deposition is the largest net MeHg source (8 Mg a−1) to the biologically productive surface ocean. MeHg concentrations in Arctic Ocean seawater are elevated compared to lower latitudes. Riverine MeHg inputs account for approximately 15% of inputs to the surface ocean (2.5 Mg a−1) but greater importance in the future is likely given increasing freshwater discharges and permafrost melt. This may offset potential declines driven by increasing evasion from ice‐free surface waters. Geochemical model simulations illustrate that for the most biologically relevant regions of the ocean, regulatory actions that decrease Hg inputs have the capacity to rapidly affect aquatic Hg concentrations.

Biochar amendment reduced methylmercury accumulation in rice plants

There is growing concern about methylmercury (MeHg) accumulation in rice grains and thus enhanced dietary exposure to MeHg in Asian countries. Here, we explored the possibility of reducing grain MeHg levels by biochar amendment, and the underlying mechanisms. Pot (i.e., rice cultivation in biochar amended soils) and batch experiments (i.e., incubation of amended soils under laboratory conditions) were carried out, to investigate MeHg dynamics (i.e., MeHg production, partitioning and phytoavailability in paddy soils, and MeHg uptake by rice) under biochar amendment (1–4% of soil mass). We demonstrate for the first time that biochar amendment could evidently reduce grain MeHg levels (49–92%). The declines could be attributed to the combined effects of: (1) increased soil MeHg concentrations, probably explained by the release of sulfate from biochar and thus enhanced microbial production of MeHg (e.g., by sulfate-reducing bacteria), (2) MeHg immobilization in soils, facilitated by the large surface areas and high organosulfur content of biochar, and (3) biodilution of MeHg in rice grains, due to the increased grain biomass under biochar amendment (35–79%). These observations together with mechanistic explanations improve understanding of MeHg dynamics in soil-rice systems, and support the possibility of reducing MeHg phytoaccumulation under biochar amendment.

Total and methyl mercury concentrations in sediment and water of a constructed wetland in the Athabasca Oil Sands Region

In the Athabasca Oil Sands Region in northeastern Alberta, Canada, oil sands operators are testing the feasibility of peatland construction on the post-mining landscape. In 2009, Syncrude Canada Ltd. began construction of the 52 ha Sandhill Fen pilot watershed, including a 15 ha, hydrologically managed fen peatland built on sand-capped soft oil sands tailings. An integral component of fen reclamation is post-construction monitoring of water quality, including salinity, fluvial carbon, and priority pollutant elements. In this study, the effects of fen reclamation and elevated sulfate levels on mercury (Hg) fate and transport in the constructed system were assessed. Total mercury (THg) and methylmercury (MeHg) concentrations in the fen sediment were lower than in two nearby natural fens, which may be due to the higher mineral content of the Sandhill Fen peat mix and/or a loss of Hg through evasion during the peat harvesting, stockpiling and placement processes. Porewater MeHg concentrations in the Sandhill Fen typically did not exceed 1.0 ng L−1. The low MeHg concentrations may be a result of elevated porewater sulfate concentrations (mean 346 mg L−1) and an increase in sulphide concentrations with depth in the peat, which are known to suppress MeHg production. Total Hg and MeHg concentrations increased during a controlled mid-summer flooding event where the water table rose above the ground surface in most of the fen. The Hg dynamics during this event showed that hydrologic fluctuations in this system exacerbate the release of THg and MeHg downstream. In addition, the elevated SO42− concentrations in the peat porewaters may become a problem with respect to downstream MeHg production once the fen is hydrologically connected to a larger wetland network that is currently being constructed.

Selenium inhibits sulfate-mediated methylmercury production in rice paddy soil

There is increasing interest in understanding factors controlling methylmercury (MeHg) production in mercury-contaminated rice paddy soil. Sulfate has been reported to affect MeHg biogeochemistry under anoxic conditions, and recent studies revealed that selenium (Se) could evidently reduce MeHg production in paddy soil. However, the controls of sulfate and Se on net MeHg production in paddy soil under fluctuating redox conditions remain largely unknown. Microcosm experiments were conducted to explore the effects of sulfate and Se on net MeHg production in rice paddy soil. Soil was added with 0–960 mg/kg sulfate, in the presence or absence of 3.0 mg/kg selenium (selenite or selenate), and incubated under anoxic (40 days) or suboxic conditions (5 days), simulating fluctuating redox conditions in rice paddy field. Sulfate addition moderately affected soil MeHg concentrations under anoxic conditions, while reoxidation resulted in evidently higher (18–40%) MeHg levels in sulfate amended soils than the control. The observed changes in net MeHg production were related to dynamics of sulfate and iron. However, Se could inhibit sulfate-mediated MeHg production in the soils: Se addition largely reduced net MeHg production in the soils (23–86%, compared to the control), despite of sulfate addition. Similarly, results of the pot experiments (i.e., rice cultivation in amended soils) indicated that soil MeHg levels were rather comparable in Se-amended soils during rice growth period, irrespective of added sulfate doses. The more important role of Se than sulfate in controlling MeHg production was explained by the formation of HgSe nanoparticles irrespective of the presence of sulfate, confirmed by TEM-EDX and XANES analysis. Our findings regarding the effects of sulfate and Se on net MeHg production in rice paddy soil together with the mechanistic explanation of the processes advance our understanding of MeHg dynamics and risk in soil-rice systems.

Mercury remediation in wetland sediment using zero-valent iron and granular activated carbon

Wetlands are hotspots for production of toxic methylmercury (MeHg) that can bioaccumulate in the food web. The objective of this study was to determine whether the application of zero-valent iron (ZVI) or granular activated carbon (GAC) to wetland sediment could reduce MeHg production and bioavailability to benthic organisms. Field mesocosms were installed in a wetland fringing Hodgdon Pond (Maine, USA), and ZVI and GAC were applied. Pore-water MeHg concentrations were lower in treated compared with untreated mesocosms; however, sediment MeHg, as well as total Hg (THg), concentrations were not significantly different between treated and untreated mesocosms, suggesting that smaller pore-water MeHg concentrations in treated sediment were likely due to adsorption to ZVI and GAC, rather than inhibition of MeHg production. In laboratory experiments with intact vegetated sediment clumps, amendments did not significantly change sediment THg and MeHg concentrations; however, the mean pore-water MeHg and MeHg:THg ratios were lower in the amended sediment than the control. In the laboratory microcosms, snails (Lymnaea stagnalis) accumulated less MeHg in sediment treated with ZVI or GAC. The study results suggest that both GAC and ZVI have potential for reducing MeHg bioaccumulation in wetland sediment.

Seasonal variation of methylmercury in sediment cores from the Tagus Estuary (Portugal)

Seasonal and spatial variations of dissolved and particulate methylmercury were evaluated for the first time in sediment cores from the Tagus Estuary.Results showed the highest MeHg concentrations in summer months indicating that the “seasonally” methylation process occurs not only at the topmost layers of the sediments but also in the deeper layers of the sediment column.The proportion of MeHg (up to 92%) in some of our pore water samples was higher than values reported in the literature for other estuaries suggesting that the sedimentary environment in the Tagus tends to favour Hg methylation.This work points to the importance of seasonal variation of the MeHg production in sediment cores. In physically dominated estuaries this enhances seasonal MeHg production in deeper sediments that can have serious ecological impacts due to resuspension or advection processes under extreme events by the increase of MeHg transported to the water column.

Mechanistic understanding of MeHg-Se antagonism in soil-rice systems: the key role of antagonism in soil.

Methylmercury (MeHg) accumulation in rice has great implications for human health. Here, effects of selenium (Se) on MeHg availability to rice are explored by growing rice under soil or foliar fertilization with Se. Results indicate that soil amendment with Se could reduce MeHg levels in soil and grain (maximally 73%). In contrast, foliar fertilization with Se enhanced plant Se levels (3–12 folds) without affecting grain MeHg concentrations. This evidence, along with the distinct distribution of MeHg and Se within the plant, demonstrate for the first time that Se-induced reduction in soil MeHg levels (i.e., MeHg-Se antagonism in soil) rather than MeHg-Se interactions within the plant might be the key process triggering the decreased grain MeHg levels under Se amendment. The reduction in soil MeHg concentrations could be mainly attributed to the formation of Hg-Se complexes (detected by TEM-EDX and XANES) and thus reduced microbial MeHg production. Moreover, selenite and selenate were equally effective in reducing soil MeHg concentrations, possibly because of rapid changes in Se speciation. The dominant role of Se-induced reduction in soil MeHg levels, which has been largely underestimated previously, together with the possible mechanisms advance our mechanistic understanding about MeHg dynamics in soil-rice systems.

The Effect of Natural Organic Matter on Mercury Methylation by Desulfobulbus propionicus 1pr3.

Methylation of tracer and ambient mercury (200Hg and 202Hg, respectively) equilibrated with four different natural organic matter (NOM) isolates was investigated in vivo using the Hg-methylating sulfate-reducing bacterium Desulfobulbus propionicus 1pr3. Desulfobulbus cultures grown fermentatively with environmentally representative concentrations of dissolved NOM isolates, Hg[II], and HS− were assayed for absolute methylmercury (MeHg) concentration and conversion of Hg(II) to MeHg relative to total unfiltered Hg(II). Results showed the 200Hg tracer was methylated more efficiently in the presence of hydrophobic NOM isolates than in the presence of transphilic NOM, or in the absence of NOM. Different NOM isolates were associated with variable methylation efficiencies for either the 202Hg tracer or ambient 200Hg. One hydrophobic NOM, F1 HpoA derived from dissolved organic matter from the Florida Everglades, was equilibrated for different times with Hg tracer, which resulted in different methylation rates. A 5 day equilibration with F1 HpoA resulted in more MeHg production than either the 4 h or 30 day equilibration periods, suggesting a time dependence for NOM-enhanced Hg bioavailability for methylation.

Influence of rice straw amendment on mercury methylation and nitrification in paddy soils

Currently, rice straw return in place of burning is becoming more intensive in China than observed previously. However, little is known on the effect of returned rice straw on mercury (Hg) methylation and microbial activity in contaminated paddy fields. Here, we conduct a microcosm experiment to evaluate the effect of rice straw amendment on the Hg methylation and potential nitrification in two paddy soils with distinct Hg levels. Our results show that amended rice straw enhanced Hg methylation for relatively high Hg content soil, but not for low Hg soil, spiking the same additional fresh Hg. methylmercury (MeHg) concentration was significantly correlated to the dissolved organic carbon (DOC) content and relative abundance of dominant microbes associated with Hg methylation. Similarly, amended rice straw was found to only enhance the potential nitrification rate in soil with relatively high Hg content. These findings provide evidence that amended rice straw differentially modulates Hg methylation and nitrification in Hg contaminated soils possibly resulting from different characteristics in the soil microbial community. This highlights that caution should be taken when returning rice straw to contaminated paddy fields, as this practice may increase the risk of more MeHg production. Main findingRice straw amendment enhanced both Hg methylation and nitrification potential in the relatively high, but not low, Hg soil.

The impacts of organic matter on the distribution and methylation of mercury in a hydroelectric reservoir in Wujiang River, Southwest China.

To understand the impacts of organic matter on the geochemical processing of Hg in a hydroelectric reservoir, spatial and seasonal distributions of total mercury (THg) and methylmercury (MeHg) in both solid and liquid phases of sediment cores were investigated in the Wujiangdu Reservoir in Guizhou Province, China. Four sampling sites with different intensities of cage aquaculture activities were chosen and were evenly distributed from upstream to downstream of the Wujiangdu Reservoir. Elevated MeHg concentrations and the high percentage of MeHg in solid and liquid phases of the surface sediment demonstrated that the active Hg methylation process occurred downstream of the Wujiangdu Reservoir. In contrast, the absence of obvious peaks for MeHg in sediment from the upper reaches of the Wujiangdu Reservoir, consistent with low levels of organic matter, suggested that production of MeHg was limited. In sediment with high organic matter content, reduction occurred closer to the sediment surface, resulting in maximum MeHg concentration in these layers. The correlation between MeHg and organic carbon implied that organic matter content in the sediment originating from cage aquaculture activities can help to predict MeHg production rates in reservoirs, which could be used to assess possible MeHg contamination in a reservoir ecosystem.

Effects of sulfate and selenite on mercury methylation in a mercury-contaminated rice paddy soil under anoxic conditions.

Biogeochemical cycling of sulfur and selenium (Se) could play an important role in methylmercury (MeHg) dynamics in soil, while their potential effects on MeHg production in rice paddy soil are less understood. The main objective of this study was to explore the effects of sulfate and selenite on net MeHg production in contaminated rice paddy soil, characterized with massive MeHg production and thus MeHg accumulation in rice. A series of microcosm incubation experiments were conducted using a contaminated paddy soil amended with sulfate and/or selenite, in which sulfate-reducing bacteria were mainly responsible for MeHg production. Our results demonstrated that sulfate addition reduced solid and dissolved MeHg levels in soils by ≤18 and ≤25 %, respectively. Compared to sulfate, selenite was more effective in inhibiting net MeHg production, and the inhibitory effect depended largely on amended selenite doses. Moreover, sulfate input played a dual role in affecting Hg-Se interactions in soil, which could be explained by the dynamics of sulfate under anoxic conditions. Therefore, the effects of sulfate and selenium input should be carefully considered when assessing risk of Hg in anoxic environments (e.g., rice paddy field and wetland).

A comprehensive assessment of the mercury budget in the Marano–Grado Lagoon (Adriatic Sea) using a combined observational modeling approach

In this study, a biogeochemical model of the mercury cycle is applied to the Marano–Grado Lagoon (North Adriatic Sea, Italy) to 1) integrate the ensemble of disconnected and snap shot measurements collected over the last decade into a common and coherent framework, 2) assess the concentration of mercury species (HgII, MeHg, Hg0) in water, sediment and particulates, and 3) quantify the mercury fluxes and budgets within the lagoon and among the lagoon, the atmosphere and the Adriatic Sea. As a result of long-term industrial and natural contamination, the Marano–Grado Lagoon is a hot spot of mercury contamination in the Mediterranean Region. Several monitoring activities have been undertaken to evaluate the environmental impacts and to better understand mercury cycling in this region. We used the results from these studies to build a mercury biogeochemical model and assess its ability to accurately predict mercury concentrations and fluxes. The results indicate that 1) the lagoon is a contaminated site, with water and sediment concentrations of Hg and MeHg higher than those of comparable environments; 2) there is substantial production of MeHg favored high productivity, occurrence of seasonal anoxia, and shallow conditions; and 3) the lagoon is a source of mercury contamination for the Mediterranean Sea, contributing to about 5% of the total HgT load. Research also indicates that the most critical shortcoming of the currently available data sets is the lack of complete synoptic measurements, even for short time periods. Future research programs must also include information on the photo-transformation rates, such as of photo-reduction, photo-oxidation and photo-demethylation.