Distribution and partitioning of mercury in a river catchment impacted by former mercury mining activity

Mercury distribution and partitioning was studied in the River Idrijca system, draining the area of the former Idrija mercury mine, Slovenia. Mercury dynamics were assessed by speciation analysis of mercury in water and river bed sediment samples during a 2-year study at locations on the River Idrijca and its major tributaries. Simultaneously, the influence of some major physico-chemical parameters that influence the fate of mercury in the aquatic environment was investigated. The distribution of mercury species in the River Idrijca catchment indicated contamination from mine tailings distributed in the town of Idrija and erosion of contaminated soils. The partitioning between dissolved and particulate mercury phases in river water was found to be mostly controlled by the variable content of suspended solids resulting from changing hydrological conditions and complexation with various ligands present in river water, among which dissolved organic carbon (DOC) seems to be the most important. Overall results indicate that mercury is transported downstream from the mining area mainly as finely suspended material including colloids rather than in the dissolved phase. This riverine transport occurs mostly during short, but extreme hydro-meteorological conditions when remobilization of mercury from the river bed sediments occurs. A significant part of the mercury particulate phase in water corresponds to cinnabar particles. During its transport, important Hg transformation mechanisms that increase the risk of mercury uptake by biota take place, evidenced by the increase in the relative contribution of reactive mercury (Hg_R), dissolved gaseous mercury (DGM) and monomethylmercury (MeHg) downstream from the Idrija mine. However, our data revealed relatively low methylation efficiency in this contaminated river system. We attribute this to the site specific physico-chemical conditions responsible for making inorganic mercury unavailable and limiting the capacity of methylating bacteria.     

Potential causes of enhanced transfer of mercury to St. Lawrence River Biota: implications for sediment management strategies at Cornwall, Ontario, Canada

We examined factors and pathways involved in the transfer of mercury (Hg) to the food web in St. Lawrence River embayments near Cornwall, Ontario, where natural remediation of contaminated sediments (eventual burial by settling of cleaner sediments) has been adopted as a management strategy. Yellow perch (Perca flavescens) from one of the study zones (Zone 1) along the river by Cornwall contained significantly higher total mercury (THg) concentrations than perch from other equally contaminated zones. While THg concentrations in benthic invertebrates did not vary among contaminated zones, THg concentrations in yellow perch and invertebrate prey recovered from the perch stomachs were 1.5–2.5 times higher in Zone 1 than those from other zones, suggesting that prey selection affects THg accumulation more than habitat location. No significant differences were found in THg concentrations among different prey species within Zone 1, although there were significant differences in THg concentrations in the same prey species within Zone 1. In contrast, THg concentrations among different prey species increased significantly with trophic level in other contaminated and reference zones. The lack of correspondence between trophic position and THg accumulation in Zone 1 suggests two possibilities: (1) yellow perch in Zone 1 are highly mobile and are assimilating THg from a wide range of prey across Zone 1 with variable THg concentrations and (2) there may be an important non-dietary source of THg to the Zone 1 food web. Potential waterborne Hg sources to Zone 1 were investigated. Whereas THg and MeHg values in discharges from a disused canal were similar to Zone 1 surface water values (0.97 and 0.04 ng l^?1, respectively), concentrations in storm sewer and combined sewer overflows discharging in the vicinity of Zone 1 were 19–45-fold (THg) and 2–4-fold (MeHg) higher than upstream river water. Contributions of Hg to the water column from sediment–water diffusion, estimated using a simple, well-mixed reactor model, ranged 0.05–0.1% of the surface water THg concentration and 1–2% of the MeHg concentration measured in summer months in Zone 1. Although not investigated in the other zones, a strong correlation (r ² = 0.82) was found between MeHg in porewater and amphipod concentrations in Zone 1, indicating that the sediment porewater is bioavailable and likely an important pathway for transfer of sediment Hg to the foodweb. Large areas of Zone 1 contain bark deposits and produce high rates of gas ebullition, and may not provide favourable conditions for progressive burial with clean sediments and attenuation of Hg transfer to biota through natural remediation. Careful monitoring of surface sediment concentrations and biota is required in these areas. Failure to reduce concentrations of Hg in these media would indicate alternative or additional management measures are required.     

A dynamic integrated model for mercury bioaccumulation in marine organisms

A novel integrated dynamic model, the Integrated Fish Model (INTFISH), incorporating mercury (Hg) dynamics at non-steady state in marine organisms, is presented and is applied to the benthic food web in a polluted area. The integrated Fish model represents the dynamics of inorganic mercury (Hg^II) and methyl‑mercury (MeHg) in a real marine ecosystem including environmental (seawater and sediments) and biota compartments. Mercury concentration in fish is estimated using the INTFISH model coupled, in real-time, with results from i) the seawater and sediments modules computed using the HR3DHG model, ii) a dedicated Phytoplankton model and iii) six modules for Hg fluxes within the invertebrate compartment, incorporating the main organisms included in fish diet preferences, whose variations during the whole life cycle are also taken into account to verify the sensitivity of the integrated model to the core set of parameters. The simulated total mercury concentrations (Hg^TOT) in specimens of red mullet (Mullus barbatus), selected as target species for the Fish model, are in excellent agreement with field observations reported from the investigated area. The intrinsic modularity of the model offers the opportunity to extend simulations to other fish species (which are part of the diet of human populations of interest) and predict Hg concentration in food. A natural extension of the model will allow to evaluate the health risks related to human consumption of contaminated fish.     

The effect of aqueous speciation and cellular ligand binding on the biotransformation and bioavailability of methylmercury in mercury-resistant bacteria

Mercury resistant bacteria play a critical role in mercury biogeochemical cycling in that they convert methylmercury (MeHg) and inorganic mercury to elemental mercury, Hg(0). To date there are very few studies on the effects of speciation and bioavailability of MeHg in these organisms, and even fewer studies on the role that binding to cellular ligands plays on MeHg uptake. The objective of this study was to investigate the effects of thiol complexation on the uptake of MeHg by measuring the intracellular demethylation-reduction (transformation) of MeHg to Hg(0) in Hg-resistant bacteria. Short-term intracellular transformation of MeHg was quantified by monitoring the loss of volatile Hg(0) generated during incubations of bacteria containing the complete mer operon (including genes from putative mercury transporters) exposed to MeHg in minimal media compared to negative controls with non-mer or heat-killed cells. The results indicate that the complexes MeHgOH, MeHg-cysteine, and MeHg-glutathione are all bioavailable in these bacteria, and without the mer operon there is very little biological degradation of MeHg. In both Pseudomonas stutzeri and Escherichia coli, there was a pool of MeHg that was not transformed to elemental Hg(0), which was likely rendered unavailable to Mer enzymes by non-specific binding to cellular ligands. Since the rates of MeHg accumulation and transformation varied more between the two species of bacteria examined than among MeHg complexes, microbial bioavailability, and therefore microbial demethylation, of MeHg in aquatic systems likely depends more on the species of microorganism than on the types and relative concentrations of thiols or other MeHg ligands present.     

Methylmercury concentrations and production rates across a trophic gradient in the northern Everglades

Methylmercury (MeHg) concentrations and production rates were examined along with sulfur biogeochemistry in Everglades sediments in March, July and December, 1995, as part of a large, multi-investigator study, the Aquatic Cycling of Mercury in the Everglades (ACME) project. The sites examined constitute a trophic gradient, generated from agricultural runoff, across the Everglades Nutrient Removal (ENR) Area, which is a re-constructed wetland, and Water Conservation Areas (WCA) 2A, 2B and 3 in the northern Everglades. MeHg concentrations and %MeHg (MeHg as a percent of total Hg) were lowest in the more eutrophic areas and highest in the more pristine areas in the south. MeHg concentrations ranged from <0.1 ng gdw^-1 sediment in the ENR to 5 ng gdw^-1 in WCA3 sediments; and MeHg constituted <0.2% of total Hg (Hg_T) in ENR, but up to about 2% in two sites in WCA2B and WCA3. Methylation rates in surficial sediments, estimated using tracer-level injections of²⁰³ Hg(II) into intact sediment cores, ranged from 0 to 0.12 d^-1, or about 1 to 10 ng g^-1 d^-1when the per day values are multiplied by the ambient total Hg concentration. Methylation was generally maximal at or within centimeters of the sediment surface, and was never observed in water overlying cores. The spatial pattern of MeHg production generally matched that of MeHg concentration. The coincident distributions of MeHg and its production suggest that in situ production controls concentration, and that MeHg concentration can be used as an analog for MeHg production. In addition, the spatial pattern of MeHg in Everglades sediments matches that in biota, suggesting that MeHg bioaccumulation may be predominantly a function of the de novo methylation rate in surficial sediments.Sulfate concentrations in surficial pore waters (up to 400 µm), microbial sulfate-reduction rates (up to 800 nm cc^-1 d^-1) and resultant pore water sulfide concentrations (up to 300 µm) at the eutrophic northern sites were all high relative to most freshwater systems. All declined to the south, and sulfate concentrations in WCA2B and in central WCA3 resembled those in oligotrophic lakes (50–100 µm). MeHg concentration and production were inversely related to sulfate reduction rate and pore water sulfide. Control of MeHg production in the northern Everglades appears to mimic that in an estuary, where sulfate concentrations are high and where sulfide produced by microbial sulfate reduction inhibits MeHg production.     

Trophic transfer of methyl mercury in the northern Florida Everglades

There are spatial differences in methyl mercury (MeHg) concentrations in biota in Water Conservation Areas 2 and 3 in the Everglades, with higher concentrations generally found in the southern areas. Fish and hemipterans had the most MeHg on a wet weight basis, with levels exceeding 30 ng g^-1. The magnitude of MeHg accumulation in biota varies seasonally and does not always appear to be associated with changes in water column concentration. This is exemplified by periphyton, the base of the foodweb in the Everglades, at a high nutrient sampling site. Although limited in scope, MeHg concentrations presented for biota provide insight into beginning to understand the dynamic nature of Hg transfer in the Everglades foodweb on a spatial and temporal basis.     

An Investigation of Total Mercury in Sediments and Interstitial Water in the North Fork Holston River below Saltville,Virginia, USA

The North Fork Holston River (NFHR) is historically renowned for having one of the most diversity rich unionid populations (Unionidae) worldwide; however, in recent decades, drastic reductions in mussel diversity, abundance, and recruitment have been documented. Unionid declines have been blamed on anthropogenic influences, specifically mercury-contaminated wastewater from a now closed chlorine-alkali plant in Saltville, VA. The objective of this research was to evaluate total mercury (Hg) contamination of sediments and interstitial waters in the NFHR beginning below Saltville and downstream for approximately 50 river miles. Mercury contaminated sediments and interstitial water were found downstream of the closed plant with the highest sediment concentration of 2.82 mg/kg dry weight total Hg found at river mile (rm) 80 and the highest interstitial water value at rm 30.4 with 2.1 μg/l. After 60-d in situ testing, total Hg concentrations in Asian clam (Corbicula fluminea) tissues were found to range from 0.016 to 0.13 mg/kg, while resident clams had Hg concentrations of 0.094 and 0.11 mg/kg wet weight. Although chronic toxicity was not observed, based on Corbicula growth and survival tests, nor in testing with cladocerans, mercury contamination is still a persistent problem at sites in the NFHR below the closed plant with negative correlations between mean clam growth and sediment Hg concentrations.     

Phytoremediation of mercury- and methyl mercury-contaminated sediments by water hyacinth (Eichhornia crassipes)

Phytoremediation has the potential for implementation at mercury- (Hg) and methylHg (MeHg)-contaminated sites. Water hyacinths (Eichhornia crassipes) were investigated for their ability to assimilate Hg and MeHg into plant biomass, in both aquatic and sediment-associated forms, over a 68-day hydroponic study. The suitability of E. crassipes to assimilate both Hg and MeHg was evaluated under differing phosphate (PO4) concentrations, light intensities, and sediment:aqueous phase contamination ratios. Because aquatic rhizospheres have the ability to enhance MeHg formation, the level of MeHg in water, sediment, and water hyacinth was also measured. Hg and MeHg were found to concentrate preferentially in the roots of E. crassipes with little translocation to the shoots or leaves of the plant, a result consistent with studies from similar macrophytes. Sediments were found to be the major sink for Hg as they were able to sequester Hg, making it non-bioavailable for water hyacinth uptake. An optimum PO4 concentration was observed for Hg and MeHg uptake. Increasing light intensity served to enhance the translocation of both Hg and MeHg from roots to shoots. Assimilation of Hg and MeHg into the biomass of water hyacinths represents a potential means for sustainable remediation of contaminated waters and sediments under the appropriate conditions.     

Storage and export of mercury from a contaminated bay (Ria de Aveiro,Portugal)

Mercury has been determined in water, suspended particulate matter (SPM)and sediments (solid fraction and pore water) collected in a heavilycontaminated confined area (Largo do Laranjo) of the Ria de Aveiro.Mercury has been analysed in seabass (Dicentrarchus labrax) capturedin several locations of the lagoon. The levels of mercury in water and SPMin the contaminated sampled places fluctuated daily with the tide (from 10to 53 ng.dm^-3 and 3.5 to 26 g.g^-1, respectively),indicating the export at the tidal rhythm. Bottom sediments exhibitedhigher concentrations, the maximum (48 g.g^-1) occurringnear the anthropogenic source at depths corresponding to the periods ofhigher industrial discharges. Mercury concentrations in pore waters (max.80 ng.dm^-3) exceed the values found in the water column and werehigher at depths where Acid Volatile Sulphides (AVS) presented broadmaximums. This implies a remobilization at anoxic conditions. However theexport across the sediment-water interface predicted through moleculardiffusion is low (between 1 to 4 × 10^-3 ng.cm^-2.h^-1) incomparison to the industrial input. The anthropogenic mercury appears tobe rapidly accumulated in seabass, a predator fish that enter seasonally inLargo do Laranjo.     

Effects of complexing agents on the distribution of Hg(II) species provided by food to starfish Leptasterias polaris

Abstract

Mature starfish Leptasterias polaris were exposed to labelled mercury (II) species via food contaminated at a level of 5.0 μg g^?1. The distribution of inorganic Hg and methylmercury (MeHg) in starfish organs and tissues and the effect of a series of complexing agents on mercury translocation between organs and tissues were examined over a 24-h period. The distribution of mercury species in coelomic fluid components, ammonia excretion rate and mercury excretion were also measured. The highest concentrations were observed in the stomach (the source organ) and in pyloric caecum (up to 0.32 μg g^?1 wet weight for inorganic Hg and 0.22 μg g^?1 for MeHg). Concentrations of MeHg in gonads ranged from ≤ 0.01 to 0.08 μg g^?1 whereas concentrations of inorganic Hg never exceeded 0.06 μg g^?1. In all studied cases, mercury concentration was very low the coelomic fluid (≤ 0.01 μg g^?1). The short-term distribution of Hg species via contaminated food in starfish L. polaris seems to be controlled by the haemal system, a primitive circulatory system responsible for the transport of soluble nutrients from the digestive track towards organs and tissues, but a possible role of the coelomic fluid can not be excluded. Very low Hg contents were observed in gonads and in the coelomic fluid which fills the general cavity. Except for mercaptoethanol (merOH) and dimercaptosuccinic acid (DMSA), the addition of complexing agents to the food had little effect on the distribution of Hg species. MerOH appeared as an efficient carrier for methylmercury transport through the digestive system. DMSA enhanced the translocation of inorganic mercury from stomach and pyloric caecum toward external tissues and markedly increased its excretion.     

Kinetic incorporation of mercury in Emerita portoricensis (Crustacea: Decapoda)

Benthic test species used in toxicity assays are the best indicators of sediment toxicity because they live in direct contact with sediments and the water column. Mercury chloride is one the most toxic metallic salts. Its strong affinity for particles explains the high Hg content found in benthic populations. The genus Emerita is abundantly found in Venezuelan coasts and is a good bioaccumulator of pollutants, but the toxicological assays performend on this genus are scarce. The present experimental test reports on the distribution of mercury in the water column and sediment, using static bioassay in short term (24 hr) and the ability of Emerita portoricensis to bioconcentrate mercury under experimental conditions. Our results suggest that the Hg transference from water to sediment is enhanced in the presence of Emerita. The kinetic uptake of Hg in Emerita portoricensis shows a mechanism of rapid absorption reaching high metal concentrations in short exposure times.     

Behavior of mercury in the Patuxent River estuary

An overview of a comprehensive study of the behavior and fate of mercury in the estuarine Patuxent River is presented. Total Hg (Hg_T) and methylmercury (MeHg) exhibited weakly non-conservative behavior in the estuary. Total Hg concentrations ranged from 6 ng L^-1 in the upper reaches of the sub-urbanized tidal freshwater river to <0.5 ng L^-1 in the mesohaline lower estuary. Filterable (0.2 µm) Hg_T ranged from 0.2 to 1.5 ng L^-1. On average, MeHg accounted for <5% of unfiltered Hg_T and <2% of filterable Hg_T. Dissolved gaseous section Hg (DGHg) concentrations were highest (up to 150 pg L^-1) in the summer in the mesohaline, but were not well correlated with primary production or chlorophyll a, demonstrating the complex nature of Hg⁰ formation and cycling in an estuarine environment. Organic matter content appeared to control the Hg_T content of sediments, while MeHg in sediments was positively correlated with Hg_T and organic matter, and negatively correlated with sulfide. MeHg in sediments was low (0.1 to 0.5% of Hg_T). Preliminary findings suggest that net MeHg production within sediments exceeds net accumulation. Although Hg_T in pore waters increased with increasing sulfide, bulk MeHg concentrations decreased. The concentration of MeHg in sediments was not related to the concentration of Hg_T in pore waters. These observations support the hypothesis that sulfide affects the speciation and therefore bioavailability of dissolved and/or solid-phase Hg for methylation. Comparison with other ecosystems, and the negative correlation between pore water sulfide and sediment MeHg, suggest that sulfide limits production and accumulation of MeHg in this system.     

Mercury-selenium interactions in relation to histochemical staining of mercury in the rat liver

Summary Selenium has been suggested to enhance the histochemical staining of mercury when sections of tissue are subjected to the silver-enhancement method. In the present study, histochemical staining patterns of mercury in tissue sections of rat livers were compared with the actual content of organic and inorganic Hg in the livers, in both the presence and the absence of Se. Rats were injected intravenously with 5g of Hgg^–1 body weight as methyl [²⁰³Hg] mercury chloride (MeHg) or as [²⁰³Hg]mercuric chloride (Hg²⁺). After 2h, half the rats received an additional intraperitoneal injection of 2g of Se g^–1 body weight as sodium [⁷⁵Se]selenite. All the rats were killed 1h later. Homogenized liver samples were prepared for mercury analysis by two different methods: alkaline digestion and ultrasonic disintegration. Quantitative chemical analysis based on benzene extrction of the radioactively labelled Hg compounds showed that the chemical form of mercury, either organic or inorganic, was preserved from its administration to its deposition in the liver. Light and electron microscopy demonstrated that no silver enhancement of Hg occurred when MeHg alone was present in the sections of tissue, whereas MeHg accompanied by Se induced a moderate deposition of silver grains. In contrast, sections containing Hg²⁺ alone yielded some staining, and the addition of Se increased the staining dramatically. The results of the present study show that acute selenite pretreatment is a prerequisite for the histochemical demonstration of methyl mercury, and greatly increases the staining of inorganic mercury when applying the silver-enhancement method.     

Mercury and other heavy metals influence bacterial community structure in contaminated Tennessee streams

High concentrations of uranium, inorganic mercury [Hg(II)], and methylmercury (MeHg) have been detected in streams located in the Department of Energy reservation in Oak Ridge, TN. To determine the potential effects of the surface water contamination on the microbial community composition, surface stream sediments were collected 7 times during the year, from 5 contaminated locations and 1 control stream. Fifty-nine samples were analyzed for bacterial community composition and geochemistry. Community characterization was based on GS 454 FLX pyrosequencing with 235 Mb of 16S rRNA gene sequence targeting the V4 region. Sorting and filtering of the raw reads resulted in 588,699 high-quality sequences with lengths of >200 bp. The bacterial community consisted of 23 phyla, including Proteobacteria (ranging from 22.9 to 58.5% per sample), Cyanobacteria (0.2 to 32.0%), Acidobacteria (1.6 to 30.6%), Verrucomicrobia (3.4 to 31.0%), and unclassified bacteria. Redundancy analysis indicated no significant differences in the bacterial community structure between midchannel and near-bank samples. Significant correlations were found between the bacterial community and seasonal as well as geochemical factors. Furthermore, several community members within the Proteobacteria group that includes sulfate-reducing bacteria and within the Verrucomicrobia group appeared to be associated positively with Hg and MeHg. This study is the first to indicate an influence of MeHg on the in situ microbial community and suggests possible roles of these bacteria in the Hg/MeHg cycle.     

Arsenic transport between water and sediments

Arsenic discharged into the Moira River has accumulated in the sediments of Moira Lake during the past century. The chronology of arsenic concentrations in the sediments, established using Pb-210 dating, has a subsurface concentration maximum (> 1000 g g^–1) that reflects higher inputs to the lake 15 to 45 years ago. The distribution coefficient (K_d) of arsenic in the surficial sediments was low (4000–6000 L kg^–1) and decreased below the sediment water interface. Higher concentrations of exchangeable As also were extracted deeper in the sediments. As a result, arsenic is mobile in the sediment column and the flux of arsenic via diffusion and particle resuspension from the sediments into the water is greater than current external loading from the Moira River. Less than 20% of the external input of arsenic is buried in the lake sediments. Using these flux measurements and a one dimensional model of arsenic transport in the sediment column, we constructed the history of arsenic exchange between water and sediments throughout the past century. The simulations predict that arsenic input into the water from the sediments has been > 20 % of external loading for the past 25 years and will continue to be important in the future as diffusion and resuspension regenerate arsenic from the mixed layer of the sediments into the overlying water.     

Effects of environment and genotype on mercury and methylmercury accumulation in rice (<Emphasis Type="Italic">Oryza sativa</Emphasis> L.)

Background and aims

Rice grains contaminated by mercury (Hg) and methylmercury (MeHg) pose risks to human health. This study evaluated the relative importance of genotype, environment and genotype-environment interactions on the accumulation of total Hg (THg) and MeHg in brown rice.

Methods

A pot trial with four rice genotypes and 10 Hg-contaminated paddy soils was conducted under greenhouse conditions. The effects of genotype, environment and genotype-environment interactions on brown rice THg and MeHg accumulation were assessed by an Additive Main Effects and Multiplicative Interaction (AMMI) model.

Results

THg and MeHg concentrations in brown rice ranged from 20.5 to 75.5 μg kg^?1 and 2.24 to 54.7 μg kg^?1, respectively. The AMMI model indicated that genotype explained 41.1 and 19.6%, environment described 40.6 and 55.8%, and the genotype-environment interaction explained 11.9 and 20.0% of the variation in brown rice THg and MeHg levels, respectively. Brown rice THg positively correlated with water-soluble Hg and total potassium, but negatively correlated with total sulphur, iron, total organic carbon and nickel in soils. Brown rice MeHg negatively correlated with soil pH and selenium.

Conclusion

THg accumulation in brown rice was mainly affected by both genotype and environment, whereas MeHg accumulation was largely determined by environment.

     

Mercury and selenium interaction in vivo: effects on thioredoxin reductase and glutathione peroxidase

Mercury compounds exert toxic effects via interaction with many vital enzymes involved in antioxidant regulation, such as selenoenzymes thioredoxin reductase (TrxR) and glutathione peroxidase (GPx). Selenium supplementation can reactivate the mercury-inhibited TrxR and recover the cell viability in vitro. To gain an insight on how selenium supplementation affects mercury toxicity in vertebrates, we investigated the effects of selenium on the mercury accumulation and TrxR and GPx activities in a fish model. Juvenile zebra-seabreams were exposed either to methylmercury (MeHg) or inorganic mercury (Hg(2+)) in the presence or absence of sodium selenite (Se) for 28 days followed by 14 days of depuration. Mercury accumulation was found to be 10-fold higher under MeHg exposure than under Hg(2+) exposure. Selenium supplementation caused a half decrease of the accumulation of MeHg but did not influence Hg(2+) accumulation. Exposure to both mercurials led to a decrease of the activity of TrxR (<50% of control) in all organs. Se supplementation coincident with Hg(2+) exposure protected the thioredoxin system in fish liver. However, supplementation of Se during the depuration phase had no effects. The activity of GPx was only affected in the brain of fishes upon the exposure to MeHg and coexposure to MeHg and Se. Selenium supplementation has a limited capacity to prevent mercury effects in brain and kidney. These results demonstrate that Se supplementation plays a protective role in a tissue-specific manner and also highlight the importance of TrxR as a main target for mercurials in vivo.     

Dissolved and suspended mercury. species in the Wabigoon River (Ontario,Canada): seasonal and regional variations

Seasonal and regional variations in the speciation, sediment-water partitioning, and dynamics of mercury (Hg) were studied at selected sites along the Hg-polluted Wabigoon River, and at unpolluted headwater and tributary sites, during April–September, 1979. ‘Dissolved’ and ‘particulate’ forms of Hg in the water were separated by continuous-flow centrifugation in the field. The Hg and other pollutants such as wood chips and salt had been discharged from a chlor-alkali plant and paper mill at Dryden, Ontario. Concentrations and loadings of particulate methyl mercury (CH₃Hg⁺) and total particulate Hg (and loadings of total ‘dissolved’ Hg) were greatest during the spring flood (April-May) owing to accelerated resuspension and transport of sediments. Concentrations of ‘dissolved’ CH₃Hg⁺, however, were highest in the summer (July–September), probably reflecting stimulation of microbial methylating activity by elevated temperatures, together with factors such as reduced levels of metal-scavenging particulates and minimal dilution by runoff. Total dissolved Hg concentrations were relatively high in September at polluted sites only, possibly because of desorption from sediments due to elevated concentrations of Cl⁻ ions. Loadings of dissolved CH₃Hg⁺ tended to be high in the summer but were generally depressed (suggesting sorption by suspended particles) during the major spring-flood episode in May. During July–August dissolved CH₃Hg⁺ was a function of total dissolved Hg, suggesting rapid biomethylation of desorbed inorganic Hg; but in general dissolved and suspended CH₃Hg⁺ levels depended on environmental variables and were unrelated to total Hg concentrations. In the summer only, total dissolved Hg was a function of dissolved Cl⁻. Hg species in particulates were associated with sulfides, hydrated Fe and Mn oxides, organic matter (notably high molecular weight humic and humic-Fe components), and selenium (Se); but CH₃Hg⁺ and total Hg differed in their specific preferences for binding agents, implying that binding sites discriminate between CH₃Hg⁺ and Hg²⁺ ions. CH₃Hg⁺ was associated with sulfide and (in the spring only) with Fe oxides, whereas total Hg was associated with organic matter and Se and with DTPA- and NaOH-extractable Fe in the spring but with Mn oxide and NaOH-extractable organics in the summer. Sulfides were most abundant in May, indicating that they were eroded from bottom sediments, but Fe and Mn oxides were most abundant in the summer, probably owing to activities of filamentous iron bacteria and other micro-organisms. Particulate Hg was 98–100% nonextractable by mild solvents such as Ca acetate, CaCl₂, dilute acetic acid, and (at polluted sites only) DTPA solutions, suggesting that the particulate Hg mobilized in the spring may not be readily available to organisms; association with Se and high molecular weight humic matter also supports this hypothesis. Hg probably becomes more bio-available in the summer, as suggested by the upsurge in dissolved CH₃Hg⁺ and total dissolved Hg levels, and by increases in the solubility of particulate Hg in acetic acid, DTPA, H₂O₂, and NaOH solutions, as well as an increase in the relative importance of lower molecular weight fractions of NaOH-extractable Hg (in September). Regional variations in Hg speciation and partitioning reflected a gradient in sediment composition from wood chips near Dryden to silt-clay mud further downstream. Hg in silt-clay mud relatively far (> 35 km) downstream from the source of pollution or in unpolluted areas appeared to be more readily solubilized by Cl⁻ ions or chelators such as DTPA, more readily methylated (as indicated by downstream increases in dissolved CH₃Hg⁺ levels and CH₃Hg⁺/total Hg ratios), and was to a greater degree organically bound (H₂O₂-extractable), and thus was probably more bio-available, than Hg in wood-chip deposits. Possible explanations include weaker binding of Hg by the mud, the more finely divided state of the mud, and improved microbial growth at lower concentrations of toxic pollutants. Owing to enrichment in sulfides and Fe oxides, resuspended wood-chip sediments were especially efficient scavengers of CH₃Hg⁺. The results indicate that in any pollution abatement plan aimed at lowering the Hg levels in the biota of lakes fed by the Wabigoon River, immobilization, removal, or detoxification of dissolved as well as particulate forms of Hg in the river would probably have to be considered. Possibly, Hg species could be ‘scrubbed’ from the river water by increasing the suspended load and by sedimentation and treatment with Hg-binding agents in special receiving basins.     

Methylmercury and methane production potentials in North Carolina Piedmont stream sediments

Methylated mercury (MeHg) can be produced by all microbes possessing the genes hgcA and hgcB, which can include sulfate-reducing bacteria (SRB), iron-reducing bacteria (FeRB), methane-producing archaea (MPA), and other anaerobic microbes. These microbial groups compete for substrates, including hydrogen and acetate. When sulfate is in excess, SRB can outcompete other anaerobic microbes. However, low concentrations of sulfate, which often occur in stream sediments, are thought to reduce the relative importance of SRB. Although SRB are regarded as the primary contributors of MeHg in many aquatic environments, their significance may not be universal, and stream sediments are poorly studied with respect to microbial Hg methylation. We evaluated suppression of methanogenesis by SRB and the potential contributions from SRB, MPA and other MeHg producing microbes (including FeRB) to the production of MeHg in stream sediments from the North Carolina Piedmont region. Lower methanogenesis rates were observed when SRB were not inhibited, however, application of a sulfate-reduction inhibitor stimulated methanogenesis. Greater MeHg production occurred when SRB were active. Other MeHg producing microbes (i.e., FeRB) contributed significantly less MeHg production than SRB. MPA produced MeHg in negligible amounts. Our results suggest that SRB are responsible for the majority of MeHg production and suppress methanogenesis in mid-order stream sediments, similar to other freshwater sediments. Further investigation is needed to evaluate the generality of these findings to streams in other regions, and to determine the mechanisms regulating sulfate and electron acceptor availability and other potential factors governing Hg methylation and methane production in stream sediments.     

Role of Organic Carbon Sources and Sulfate in Controlling Net Methylmercury Production in Riverbank Sediments of the South River,VA (USA)

Mercury (Hg) transport and methylmercury (MeHg) production in riverbank sediments are complex processes influenced by site-specific physical and biogeochemical conditions. The South River watershed in VA, USA, contains elevated concentrations of Hg in riverbank and floodplain sediments, which has the potential to methylate. The role of specific organic carbon sources in promoting methylation reactions in natural sediments under dynamic flow conditions is not well understood. Four saturated column experiments were conducted, including a control column, which received South River water as an influent solution, and three columns that received South River water amended with: acetate (5.8 mM); lactate (5.7 mM); and lactate (5.7 mM) with SO₄^2? (10.1 mM). The amendments were selected to promote growth of different microorganisms to gain an understanding of the microbial processes, controlling rates of methylation. The column receiving lactate and SO₄^2? had the highest MeHg concentrations in the effluent and in the pore water near the effluent at 1.8 and 4.9 μg L^?1, respectively. At the cessation of the column experiments, the lactate–sulfate column sediments contained the highest populations of enumerable sulfur-reducing bacteria and the highest solid-phase MeHg at 530 ± 100 ng g^?1 dry wt. from the interval closest to the influent. The results suggest that the form and availability of electron donors and acceptors are primary factors controlling rates of methylation in the South River sediment.