MeHg Bioavailability Research Articles

Dissolved organic matter thiol concentrations determine methylmercury bioavailability across the terrestrial-marine aquatic continuum

The most critical step for methylmercury (MeHg) bioaccumulation in aquatic food webs is phytoplankton uptake of dissolved MeHg. Dissolved organic matter (DOM) has been known to influence MeHg uptake, but the mechanisms have remained unclear. Here we show that the concentration of DOM-associated thiol functional groups (DOM-RSH) varies substantially across contrasting aquatic systems and dictates MeHg speciation and bioavailability to phytoplankton. Across our 20 study sites, DOM-RSH concentrations decrease 40-fold from terrestrial to marine environments whereas dissolved organic carbon (DOC), the typical proxy for MeHg binding sites in DOM, only has a 5-fold decrease. MeHg accumulation into phytoplankton is shown to be directly linked to the concentration of specific MeHg binding sites (DOM-RSH), rather than DOC. Therefore, MeHg bioavailability increases systematically across the terrestrial-marine aquatic continuum as the DOM-RSH concentration decreases. Our results strongly suggest that measuring DOM-RSH concentrations will improve empirical models in phytoplankton uptake studies and will form a refined basis for modeling MeHg incorporation in aquatic food webs under various environmental conditions.

Aging rice straw reduces the bioavailability of mercury and methylmercury in paddy soil

Straw amendment is a prevalent agricultural practice worldwide, which can reduce air pollution and improve soil fertility. However, the impact of aging straw amendment on the bioavailability of mercury (Hg) and methylmercury (MeHg) in paddy soil remains unclear. To investigate this, incubation experiments were conducted using the diffusive gradient in thin-film technique. Results showed that amendments of dry-wet aging (DRS), photochemical aging (LRS), and freeze-thaw aging rice straw (FRS) reduced the bioavailable MeHg in paddy soil by 2.2–27.6%, 13.5–69.8%, and 23.5–86.1%, respectively, compared to fresh rice straw (RS) amendment. This result could be due to changes in soil properties such as soil pH and overlying water Fe and Mn as well as microbial abundance (including Clostridiaceae, Firmicutes, and Actinobacteriota). Simultaneously, The LRS and FRS amendments reduced bioavailable Hg in paddy soil by 20.0–40.8% and 17.1–48.6%, respectively, while DRS increased the bioavailable Hg by 15.8–120.0%. This could be attributed to changes in soil oxidation-reduction potential and overlying water SO42− content. Additionally, the results of sand culture experiments showed that the concentrations of Hg uptake by rice seedlings were 97.1–118.2%, 28.1–35.6%, and 198.0–217.1% higher in dissolved organic matter (DOM) derived from DRS, LRS, and FRS than RS, indicating that aging straw leached DOM may promote the Hg bioavailable when straw amendment. This result could be due to lower molecular weight and higher CO functional group content. These results provide new insight into how aging straw amendment affects the bioavailability of Hg and MeHg in paddy soil under different climates.

Effects of varying amounts of different biochars on mercury methylation in paddy soils and methylmercury accumulation in rice (Oryza sativa L.)

There is growing evidence for the potential of biochars (BCs) in remediating mercury-contaminated paddy soils, but the high doses commonly used in laboratory studies discourage BC application in practice. To address these difficulties, we compared the effects of varying amounts of BCs from different sources on the formation of methylmercury (MeHg) in soil and its accumulation in rice through microcosm and pot experiments. The addition of a wide range of added doses (0.3, 0.6, 1, 2, 4 and 5 %, w/w) of BCs derived from different biomass feedstocks (i.e., corn stalk, wheat straw, bamboo, oak and poplar) significantly decreased the fraction of ammonium thiosulfate ((NH4)2S2O3)-extractable MeHg in the soil, although the MeHg contents varied with BC types and doses during soil incubation. However, the extractable MeHg in the soil did not continuously decrease with increasing BC doses, especially at doses of >1 %, resulting in limited further reductions. Moreover, a relatively low application rate (0.3–0.6 %, w/w) of BCs (i.e., corn stalk, wheat straw and bamboo-derived BC), especially of bamboo-derived BCs, significantly decreased the MeHg levels (42–76 %) in rice grains (brown rice). Meanwhile, the extractable soil MeHg decreased (57–85 %), although the MeHg in the soil varied under BC amendment during rice cultivation. These results provide further evidence that applying BC produced from different raw carbon materials (e.g., lignocellulosic biomass) could effectively reduce MeHg accumulation in rice grains, possibly due to MeHg bioavailability reduction in the soil. Our results suggest the possibility of mitigating MeHg accumulation in rice with a low dose of BCs, with great potential for use in remediating moderately contaminated paddy soils.

Toward efficient bioremediation of methylmercury in sediment using merB overexpressed Escherichia coli

Sediment is the primary hotspot for microbial production of toxic and bio-accumulative methylmercury (MeHg). Common remediation strategies such as sediment dredging and capping can be too expensive and cannot degrade MeHg efficiently. Here, we constructed an Escherichia coli strain overexpressing merB gene (DH5α J23106) and assessed the effectiveness of this recombinant strain in degradation of MeHg in culture medium and sediment. DH5α J23106 can efficiently degrade MeHg (with initial concentration from 0.01 to 50 ng/mL) to more than 81.6% in a culture medium under anoxic and oxic conditions. Enriched isotope addition (199HgCl2) revealed that this recombinant strain can degrade 78.6% of newly produced Me199Hg in actual sediment, however the biodegradation decreased to 36.3% for intrinsic MeHg. Degradation of spiked MeHg after aging in anoxic and oxic sediments further demonstrated DH5α J23106 can efficiently degrade newly produced MeHg and the degradation decreased with aging significantly, especially for oxic sediment. Eight sediments were further assessed for the biodegradation of aged MeHg by DH5α J23106 under oxic conditions, with degradation ratios ranging from 9.0% to 66.9%. When combined with (NH4)2S2O3 leaching, the degradation of MeHg increased by 15.8–38.8% in on-site and off-site modes through enhanced MeHg bioavailability in some of these sediments. Thus, this recombinant strain DH5α J23106 can degrade MeHg efficiently and have the potential for remediating bioavailable MeHg in contaminated sediments.

Important Roles of Thiols in Methylmercury Uptake and Translocation by Rice Plants.

The bioaccumulation of the neurotoxin methylmercury (MeHg) in rice is a significant concern due to its potential risk to humans. Thiols have been known to affect MeHg bioavailability in microorganisms, but how thiols influence MeHg accumulation in rice plants remains unknown. Here, we investigated effects of common low-molecular-weight thiols, including cysteine (Cys), glutathione (GSH), and penicillamine (PEN), on MeHg uptake and translocation by rice plants. Results show that rice roots can rapidly take up MeHg, and this process is influenced by the types and concentrations of thiols in the system. The presence of Cys facilitated MeHg uptake by roots and translocation to shoots, while GSH could only promote MeHg uptake, but not translocation, by roots. Conversely, PEN significantly inhibited MeHg uptake and translocation to shoots. Using labeled 13Cys assays, we also found that MeHg uptake was coupled with Cys accumulation in rice roots. Moreover, analyses of comparative transcriptomics revealed that key genes associated with metallothionein and SULTR transporter families may be involved in MeHg uptake. These findings provide new insights into the uptake and translocation of MeHg in rice plants and suggest potential roles of thiol attributes in affecting MeHg bioavailability and bioaccumulation in rice.

Utility of Diffusive Gradient in Thin-Film Passive Samplers for Predicting Mercury Methylation Potential and Bioaccumulation in Freshwater Wetlands.

Mercury is a risk in aquatic ecosystems when the metal is converted to methylmercury (MeHg) and subsequently bioaccumulates in aquatic food webs. This risk can be difficult to manage because of the complexity of biogeochemical processes for mercury and the need for accessible techniques to navigate this complexity. Here, we explored the use of diffusive gradient in thin-film (DGT) passive samplers as a tool to simultaneously quantify the methylation potential of inorganic Hg (IHg) and the bioaccumulation potential of MeHg in freshwater wetlands. Outdoor freshwater wetland mesocosms were amended with four isotopically labeled and geochemically relevant IHg forms that represent a range of methylation potentials (202Hg2+, 201Hg-humic acid, 199Hg-sorbed to FeS, and 200HgS nanoparticles). Six weeks after the spikes, we deployed DGT samplers in the mesocosm water and sediments, evaluated DGT-uptake rates of total Hg, MeHg, and IHg (calculated by difference) for the Hg isotope spikes, and examined correlations with total Hg, MeHg, and IHg concentrations in sediment, water, and micro and macrofauna in the ecosystem. In the sediments, we observed greater relative MeHg concentrations from the initially dissolved IHg isotope spikes and lower MeHg levels from the initially particulate IHg spikes. These trends were consistent with uptake flux of IHg into DGTs deployed in surface sediments. Moreover, we observed correlations between total Hg-DGT uptake flux and MeHg levels in periphyton biofilms, submergent plant stems, snails, and mosquitofish in the ecosystem. These correlations were better for DGTs deployed in the water column compared to DGTs in the sediments, suggesting the importance of vertical distribution of bioavailable MeHg in relation to food sources for macrofauna. Overall, these results demonstrate that DGT passive samplers are a relatively simple and efficient tool for predicting IHg methylation and MeHg bioaccumulation potentials without the need to explicitly delineate IHg and MeHg speciation and partitioning in complex ecosystems.

Decreased bioavailability of both inorganic mercury and methylmercury in anaerobic sediments by sorption on iron sulfide nanoparticles

Methylmercury (MeHg), derived via inorganic mercury (Hg(II)) methylation by anaerobic microorganisms, is a neurotoxic contaminant causing concern worldwide. Establishing how to reduce Hg(II) methylation and MeHg bioavailability is essential for effective control of Hg pollution. Iron sulfide nanoparticles (FeSNP) is a promising passivator for Hg(II) methylation. However, its effect on the fate of MeHg in aquatic systems remains poorly understood. This study investigated the effect of FeSNP on Hg(II) bioavailability, MeHg production and bioavailability in aquatic environments. Results demonstrated that FeSNP rapidly sorbed Hg(II) and MeHg, with sorption affected by pH, chloride ion and dissolved organic matter. Hg-specific biosensor analysis showed that Hg(II) sorbed onto FeSNP significantly reduced its bioavailability to microorganisms. Double stable isotope (199Hg(II) and Me201Hg) addition revealed that FeSNP significantly inhibited MeHg production in anaerobic sediments. Furthermore, synthetic gut juice extraction suggested that FeSNP decrease concentrations of bioavailable MeHg and Hg(II), reducing their integration into food webs. However, the sorbed MeHg and Hg(II) in sediments can be released after FeSNP oxidation, potentially enhancing the risk of exposure to aquatic organisms. Overall, these findings increase our understanding of Hg transformation and exposure risks in aquatic systems, providing valuable information for the development of in situ Hg remediation systems.

Bluefin tuna reveal global patterns of mercury pollution and bioavailability in the world's oceans

Bluefin tuna (BFT), highly prized among consumers, accumulate high levels of mercury (Hg) as neurotoxic methylmercury (MeHg). However, how Hg bioaccumulation varies among globally distributed BFT populations is not understood. Here, we show mercury accumulation rates (MARs) in BFT are highest in the Mediterranean Sea and decrease as North Pacific Ocean > Indian Ocean > North Atlantic Ocean. Moreover, MARs increase in proportion to the concentrations of MeHg in regional seawater and zooplankton, linking MeHg accumulation in BFT to MeHg bioavailability at the base of each subbasin's food web. Observed global patterns correspond to levels of Hg in each ocean subbasin; the Mediterranean, North Pacific, and Indian Oceans are subject to geogenic enrichment and anthropogenic contamination, while the North Atlantic Ocean is less so. MAR in BFT as a global pollution index reflects natural and human sources and global thermohaline circulation.

Microplastics influence on Hg methylation in diverse paddy soils

Microplastics are widespread in estuarine, coastal, and deep sea sediments. The influence of microplastics on mercury (Hg) methylation in paddy soils with different characteristics, however, has not been well reported. In this research, we conducted a microcosmic experiment using red soil and alkaline soil with 2%, 7% and 10% polyvinyl chloride microplastics (PVC-MPs). Diffusive gradients in thin film (DGT) were used to test bioavailable Hg2+ and bioavailable methylmercury (MeHg) in soils. Results showed that PVC-MPs could decrease bioavailable MeHg concentrations both in red soil and alkaline soil. We demonstrated that these decreases could be due to three possible mechanisms: (1) PVC-MPs affected DOM composition, which resulted in a difference in combining capacity for bioavailable Hg2+; (2) PVC-MPs decreased MeHg via changing soil properties (including sulfate and dissolved Fe); (3) PVC-MPs affected the abundance of Proteobacteria, Firmicutes, and hgcA gene in soils. Our results emphasized the significance of investigating effects of microplastics on specific contaminants to implement effective environmental remediation strategies in polluted paddy soils.

Assessment of In Vitro Bioaccessibility and In Vivo Oral Bioavailability as Complementary Tools to Better Understand the Effect of Cooking on Methylmercury, Arsenic, and Selenium in Tuna.

Fish consumption is the main exposure pathway of the neurotoxicant methylmercury (MeHg) in humans. The risk associated with exposure to MeHg may be modified by its interactions with selenium (Se) and arsenic (As). In vitro bioaccessibility studies have demonstrated that cooking the fish muscle decreases MeHg solubility markedly and, as a consequence, its potential absorption by the consumer. However, this phenomenon has yet to be validated by in vivo models. Our study aimed to test whether MeHg bioaccessibility can be used as a surrogate to assess the effect of cooking on MeHg in vivo availability. We fed pigs raw and cooked tuna meals and collected blood samples from catheters in the portal vein and carotid artery at: 0, 30, 60, 90, 120, 180, 240, 300, 360, 420, 480 and 540 min post-meal. In contrast to in vitro models, pig oral bioavailability of MeHg was not affected by cooking, although the MeHg kinetics of absorption was faster for the cooked meal than for the raw meal. We conclude that bioaccessibility should not be readily used as a direct surrogate for in vivo studies and that, in contrast with the in vitro results, the cooking of fish muscle did not decrease the exposure of the consumer to MeHg.

Stable mercury concentrations of tropical tuna in the south western Pacific ocean: An 18-year monitoring study

Global anthropogenic mercury (Hg) emissions to the atmosphere since industrialization are widely considered to be responsible for a significant increase in surface ocean Hg concentrations. Still unclear is how those inputs are converted into toxic methylmercury (MeHg) then transferred and biomagnified in oceanic food webs. We used a unique long-term and continuous dataset to explore the temporal Hg trend and variability of three tropical tuna species (yellowfin, bigeye, and skipjack) from the southwestern Pacific Ocean between 2001 and 2018 (n = 590). Temporal trends of muscle nitrogen (δ15N) and carbon (δ13C) stable isotope ratios, amino acid (AA) δ15N values and oceanographic variables were also investigated to examine the potential influence of trophic, biogeochemical and physical processes on the temporal variability of tuna Hg concentrations. For the three species, we detected significant inter-annual variability but no significant long-term trend for Hg concentrations. Inter-annual variability was related to the variability in tuna sampled lengths among years and to tuna muscle δ15N and δ13C values. Complementary AA- and model-estimated phytoplankton δ15N values suggested the influence of baseline processes with enhanced tuna Hg concentrations observed when dinitrogen fixers prevail, possibly fuelling baseline Hg methylation and/or MeHg bioavailability at the base of the food web. Our results show that MeHg trends in top predators do not necessary capture the increasing Hg concentrations in surface waters suspected at the global oceanic scale due to the complex and variable processes governing Hg deposition, methylation, bioavailability and biomagnification. This illustrates the need for long-term standardized monitoring programs of marine biota worldwide.

Five decades of declining methylmercury concentrations in boreal foodwebs suggest pivotal role for sulphate deposition

Widespread declines in mercury (Hg) in fish in pristine lakes in Fennoscandia since the 1970s are unexplained. Interactions between climate, atmospheric deposition, and elemental cycling of carbon (C), sulphur (S) and Hg are complex and affect Hg bioaccumulation. A parallel significant decline in methyl-Hg (MeHg) concentrations in aquatic macroinvertebrates (Chironomidae) was found between 1976–78 and 2004–15 in an intensely studied, pristine boreal lake (Langtjern, boreal Fennoscandia). Monitoring at Langtjern demonstrated a four-fold decrease in aqueous sulphate concentrations (SO4, 50-year record), significant lake browning (30-year records), increasing sediment Hg concentrations (50-year record), warming (45-year record) and increased runoff (40-year record). Contrasting Hg trends in biota (downward) and sediment (upward) indicated a disconnect between lake Hg loading and foodweb Hg bioaccumulation. We suggest that reduced SO4-deposition has 1) constrained substrate availability for SO4-reducing methylating bacteria (causing reduced foodweb MeHg exposure despite increased Hg loading to the lake), and 2), increased the binding affinity between aqueous organic matter and Hg species (leading to reduced MeHg bioavailability). The downward MeHg trend at the base of the foodweb at Langtjern is mirrored at higher trophic levels by strong declines in perch (Perca fluviatilis) and pike (Esox lucius) Hg concentrations in boreal Fennoscandia. A plausible explanation is that declining SO4-deposition, rather than climate change or reduced atmospheric Hg, is currently driving reduced MeHg contamination in northern freshwater foodwebs.

Dragonfly larvae as biosentinels of Hg bioaccumulation in Northeastern and Adirondack lakes: relationships to abiotic factors.

Mercury (Hg) is a toxic pollutant, widespread in northeastern US ecosystems. Resource managers' efforts to develop fish consumption advisories for humans and to focus conservation efforts for fish-eating wildlife are hampered by spatial variability. Dragonfly larvae can serve as biosentinels for Hg given that they are widespread in freshwaters, long-lived, exhibit site fidelity, and bioaccumulate relatively high mercury concentrations, mostly as methylmercury (88% ± 11% MeHg in this study). We sampled lake water and dragonfly larvae in 74 northeastern US lakes that are part of the US EPA Long-Term Monitoring Network, including 45 lakes in New York, 43 of which are in the Adirondacks. Aqueous dissolved organic carbon (DOC) and total Hg (THg) were strongly related to MeHg in lake water. Dragonfly larvae total mercury ranged from 0.016-0.918 μg/g, dw across the study area; Adirondack lakes had the minimum and maximum concentrations. Aqueous MeHg and dragonfly THg were similar between the Adirondack and Northeast regions, but a majority of lakes within the highest quartile of dragonfly THg were in the Adirondacks. Using landscape, lake chemistry, and lake morphometry data, we evaluated relationships with MeHg in lake water and THg in dragonfly larvae. Lakewater DOC and lake volume were strong predictors for MeHg in water. Dragonfly THg Bioaccumulation Factors (BAFs, calculated as [dragonfly THg]:[aqueous MeHg]) increased as lake volume increased, suggesting that lake size influences Hg bioaccumulation or biomagnification. BAFs declined with increasing DOC, supporting a potential limiting effect for MeHg bioavailability with higher DOC.

The effects of climate, habitat, and trophic position on methylmercury bioavailability for breeding New York songbirds.

Mercury (Hg) is a global pollutant that affects songbird populations across a variety of ecosystems following conversion to methylmercury (MeHg)-a form of Hg with high potential for bioaccumulation and bioavailability. The amount of bioavailable MeHg in an ecosystem is a function of the amount of total Hg present as well as Hg methylation rates, which vary across the landscape in space and time, and trophic transfer. Using songbirds as an indicator of MeHg bioavailability in terrestrial ecosystems, we evaluated the role of habitat, climate, and trophic level in dictating MeHg exposure risk across a variety of ecosystems. To achieve this objective, 2243 blood Hg samples were collected from 81 passerine and near-passerine species in New York State, USA, spanning 10 different sampling regions from Long Island to western New York. Using a general linear mixed modeling framework that accounted for regional variation in sampling species composition, we found that wetland habitat area within 100 m of capture location, 50-year average of summer maximum temperatures, and trophic position inferred using stable isotope analysis were all correlated with songbird blood Hg concentrations statewide. Moreover, these patterns had a large degree of spatial variability suggesting that the drivers of MeHg bioavailability differed significantly across the state. Mercury deposition, land cover, and climate are all expected to change throughout the northeastern United States in the coming decades. Terrestrial MeHg bioavailability will likely respond to these changes. Focused research and monitoring efforts will be critical to understand how exposure risk responds to global environmental change across the landscape.

Factors affecting MeHg bioaccumulation in stream biota: the role of dissolved organic carbon and diet

The bioaccumulation of the neurotoxin methylmercury (MeHg) in freshwater ecosystems is thought to be mediated by both water chemistry (e.g., dissolved organic carbon [DOC] and dissolved mercury [Hg]) and diet (e.g., trophic position and diet composition). Hg in small streams is of particular interest given their role as a link between terrestrial and aquatic processes. Terrestrial processes determine the quantity and quality of streamwater DOC, which in turn influence the quantity and bioavailability of dissolved MeHg. To better understand the effects of water chemistry and diet on Hg bioaccumulation in stream biota, we measured DOC and dissolved Hg in stream water and mercury concentration in three benthic invertebrate taxa and three fish species across up to 12 tributary streams in a forested watershed in New Hampshire, USA. As expected, dissolved total mercury (THg) and MeHg concentrations increased linearly with DOC. However, mercury concentrations in fish and invertebrates varied non-linearly, with maximum bioaccumulation at intermediate DOC concentrations, which suggests that MeHg bioavailability may be reduced at high levels of DOC. Further, MeHg and THg concentrations in invertebrates and fish, respectively, increased with δ15N (suggesting trophic position) but were not associated with δ13C. These results show that even though MeHg in water is strongly determined by DOC concentrations, mercury bioaccumulation in stream food webs is the result of both MeHg availability in stream water and trophic position.

Different circulation history of mercury in aquatic biota from King George Island of the Antarctic

To trace the circulation history of aquatic bioavailable Hg in the Antarctic, the species and isotopic compositions of Hg in sediment, Archaeogastropoda (Agas), Neogastropoda (Ngas), and fish collected from King George Island were studied in detail. Positive mass independent fractionation (MIF) was observed and positively correlated with the percentages of methylmercury (MeHg%) in Agas and Ngas, suggesting an effect of MeHg accumulation during trophic transfer on MIF signatures. However, both the ratios of Δ199Hg/δ202Hg and Δ199Hg/Δ201Hg indicated different circulation histories of Hg in Agas, Ngas, and fish. The microbial methylation in sediment was the primary source of MeHg in Agas and Ngas (Δ199Hg/δ202Hg ∼0, Δ199Hg/Δ201Hg ∼1.00). In contrast, the MeHg in fish (Δ199Hg/δ202Hg = 0.55 ± 0.06, Δ199Hg/Δ201Hg = 1.19 ± 0.17) came from the combined sources of residual MeHg which had sunk from the surface water and microbial-methylated MeHg in sediments, and the bioavailable Hg in the sediments contributed to approximately 44% of the total Hg in fish. Subsequently, the Δ199Hg values of bioavailable MeHg and IHg in sediments were quantitatively calculated, which provided key end-member information for future source apportionment in the Antarctic and other pelagic regions. It was also found that the Hg accumulated in Agas and Ngas had no history of MeHg photo-degradation, indicating that the methylated Hg in benthic zones suffered little photo-degradation and thus presented high bioavailability and environmental risk.

Effect of lactic acid bacteria on mercury toxicokinetics

The capacity of two LAB strains to inhibit inorganic [Hg(II)] and organic (methyl-Hg; MeHg) mercury translocation through monolayers of co-cultures of NCM460 and HT29-MTX colonic cells was evaluated. Lactobacillus casei BL23 and Lactobacillus acidophilus ATCC4356 reduced the permeability of Hg(II) and MeHg from aqueous solutions through NCM460/HT29-MTX monolayers (20–94% reduction). However, assays using the bioaccessible (soluble) Hg fraction obtained by in vitro gastrointestinal digestion of Hg-contaminated swordfish only showed a reduction (42%) with the BL23 strain. In vivo experiments carried out in mice receiving an acute dose of Hg(II) or MeHg (0.5 mg/kg body weight/day) with or without lactobacilli resulted in significant decreases of the bioavailability of MeHg with both strains and increased excretion of Hg in feces after treatment with the lactobacilli. However, Hg(II) bioavailability or excretion was not affected. Hg accumulation in liver and kidney remained similar in LAB-treated or non-treated animals. This is the first study of the impact of LAB on Hg(II) and MeHg toxicokinetics and shows that some LAB strains have potential to diminish MeHg bioavailability. Furthermore, it has established the basis for new studies on the protective effect of LAB under conditions resembling subchronic and chronic Hg exposures.

Terrestrial organic matter increases zooplankton methylmercury accumulation in a brown-water boreal lake

Increases in terrestrial organic matter (tOM) transport from catchments to boreal lakes can affect methylmercury (MeHg) accumulation in aquatic biota both directly by increasing concentrations of aqueous MeHg, and indirectly through effects on MeHg bioavailability and on energy pathways in the lower food web. We carried out a detailed seasonal study of water chemistry, zooplankton diet, and MeHg accumulation in zooplankton in two lakes with contrasting tOM concentrations. Between-lake differences explained 51% of the variability in our water chemistry data, with no observed effect of season or sampling depth, contrary to our expectations. Higher tOM was correlated with higher aqueous Hg concentrations, lower areal pelagic primary productivity, and an increased contribution of terrestrial particles to pelagic particulate organic matter. Based on dietary marker analysis (δ13C, δ15N, and fatty acid [FA] composition), zooplankton diet was strongly linked to feeding mechanism, with dietary reliance on phytoplankton highest in the selective-feeding calanoid copepods, and lowest in filter feeding cladocerans. Zooplankton dietary reliance on phytoplankton and their concentrations of high-quality lipids, including polyunsaturated fatty acids, were higher in the clear-water lake than in the brown-water lake, where bacterial and terrestrial food sources were more prevalent. MeHg was highest in zooplankton from the brown-water lake, with highest concentrations in the 200–500 μm zooplankton size fraction for both lakes. Contrary to our expectations, there was no effect of season on zooplankton dietary markers or MeHg. Our results suggest that, overall, higher tOM results in higher MeHg concentrations in water and zooplankton, and reduces zooplankton dietary reliance on phytoplankton. Increased tOM thus leads to a decrease in the nutritional quality of zooplankton (i.e. higher MeHg concentrations, and lower concentrations of essential fatty acids), which may cascade up the food web with negative implications for higher trophic levels.

Lake sediment mercury biogeochemistry controlled by sulphate input from drainage basin

Mercury (Hg) and methyl mercury (MeHg) concentrations have never been measured in sediments of coastal lakes of Aquitaine, although high concentrations of Hg have been measured in fish. Our objective was to characterize benthic biogeochemical processes and the distribution of Hg in lake sediments and to connect these results with fish contamination. For this, we mapped and characterized sediments. We measured sediment Hg and MeHg content, and biogeochemical parameters. We identified organic deposits in deep areas, and sandy sediments in shallow areas. Sediments were anoxic below the sediment–water interface. The average Hg concentration in organic sediment was 213 μg kg−1 dry weight. Sandy sediments had an average Hg concentration of 4 μg kg−1 dw. We measured concentrations below 6 μg kg−1 dw in sediments from streams that drain the catchment. Similar concentrations in the four lakes suggest that the source of total Hg was not a point source in a given lake. The highest MeHg concentrations were found in the upper centimetres of organic sediments, where sulphate reduction occurred. MeHg represented 2.53% of total Hg for Lake Carcans-Hourtin, less in other lakes. The proportion of MeHg in sediment followed lake water sulphate concentrations. High sulphate concentrations resulted from agricultural activity in the Lake Carcans-Hourtin catchment. Our results corroborate the hypothesis that Hg methylation is linked to sulphate-reducing activity. High fluxes of sulphate from a drainage basin may induce large proportions of potentially bioavailable MeHg in lake sediment, even in non-polluted areas. The Hg methylation activity in the sediment reflected the exposure of predatory fish to MeHg.

Mercury speciation in various aquatic systems using passive sampling technique of diffusive gradients in thin-film

Mercury (Hg) is one of the primary health concerns in natural and urbanised environments due to past and present natural and anthropogenic emissions. Its environmental cycle is driven by redox reactions, microbial metabolism and organic matter (OM) interactions, which may all lead to formation of bioaccumulative organic Hg species; methylmercury (MeHg), with damaging consequences for human and ecosystem health. Hence, Hg lability and bioavailability has been the focus of many investigations and assessed with a variety of chemical proxies in order to improve understanding of the conditions that lead to enhanced bioavailability of Hg and its species. We investigated Hg labile species with Diffusive Gradient in Thin-film technique (DGT) in the water column and sediment of Zenne River (Brussels, Belgium) and Gulf of Trieste (North Adriatic). They represent two contemporary important Hg-impacted areas; the former by anthropogenic urban pollution, and the latter by historic pollution from Hg mining. Hg speciation of labile inorganic and methylmercury in these two environments was not yet investigated using DGT technique. The results show labile Hg species changing with season in the water column of Zenne River, while the sediments are the source of bioavailable MeHg to the water column that is transported further creating a halo effect in the region. Values of labile Hg species for water column and sediments in Gulf of Trieste differ from previous research, highlighting the need for more investigation into Hg bioavailability. MeHg/THg ratios were compared to other sampling methods for labile Hg species.