Inorganic Mercury Concentrations Research Articles

Impact of mercury discharged from submarine volcano on inner bay ecosystems

Organic mercury, inorganic mercury and total mercury concentrations in phytoplankton (<0.1 mm) and zooplankton (>0.1 mm) collected in Kagoshima Bay, Japan were measured from 2017 to 2019 to estimate the impact of mercury discharged from submarine volcanoes on ecosystems; submarine volcanic activity continues at a depth of 200 m in the inner part of Kagoshima Bay. The total mercury concentrations in phyto- and zooplankton collected by vertical hauling at 0–200 m at just above the submarine volcano were in the range of 0.11–2.0 mg kg−1 (avg. 0.67 mg kg−1) and 0.090–0.56 mg kg−1 (avg. 0.21 mg kg−1), respectively. These values were one order of magnitude higher than the values in plankton collected in the central part of Kagoshima Bay. Organic mercury concentrations in phyto- and zooplankton were <0.010–0.071 mg kg−1 (avg. 0.028 mg kg−1) and 0.012–0.25 mg kg−1 (avg. 0.10 mg kg−1), respectively, for the inner part, and <0.010–0.040 mg kg−1 (avg. 0.010 mg kg−1) and <0.010–0.025 mg kg−1 (avg. 0.012 mg kg−1), respectively, for the central part. The values obtained in the inner part of the bay increased in summer and decreased in winter, which was consistent with changes in seawater mercury concentrations affected by volcanic activity. The organic mercury concentration in zooplankton collected just above the submarine volcano showed a size dependency, and a higher value was observed in the larger size, which suggested that the discharged mercury from the volcano was absorbed and concentrated through the ecosystem.

Effect of mercury in the influx and efflux of nutrients in the microalga Desmodesmus armatus

Anthropogenic activities such as mining and the metallurgical industry are the main sources of mercury contamination. Mercury is one of the most serious environmental problems in the world. This study aimed to investigate, using experimental kinetic data, the effect of different inorganic mercury (Hg2+) concentrations on the response of microalga Desmodesmus armatus stress. Cell growth, nutrients uptake and mercury ions from the extracellular medium, and oxygen production were determined. A Compartment Structured Model allowed elucidating the phenomena of transmembrane transport, including influx and efflux of nutrients, metal ions and bioadsorption of metal ions on the cell wall, which are difficult to determine experimentally. This model was able to explain two tolerance mechanisms against mercury, the first one was the adsorption of Hg2+ions onto the cell wall and the second was the efflux of mercury ions. The model predicted a competition between internalization and adsorption with a maximum tolerable concentration of 5.29 mg/L of HgCl2. The kinetic data and the model showed that mercury causes physiological changes in the cell, which allow the microalga to adapt to these new conditions to counteract the toxic effects. For this reason, D. armatus can be considered as a Hg-tolerant microalga. This tolerance capacity is associated with the activation of the efflux as a detoxification mechanism that facilitates the maintenance of the osmotic balance for all the modeled chemical species. Furthermore, the accumulation of mercury in the cell membrane suggests the presence of thiol groups associated with its internalization, leading to the conclusion that metabolically active tolerance mechanisms are dominant over passive ones.

Assessing and predicting the changes for inorganic mercury and methylmercury concentrations in surface waters of a tidal estuary (Adour Estuary, SW France)

Total and dissolved concentrations of inorganic mercury (IHg) and methylmercury (MeHg) in water (Adour Estuary) were determined during three sampling campaigns and related to biogeochemical variables (nutrients, organic matter). Factors (sampling time, sample type) were included in analysis of covariance with effect separation. The urban estuary suffered historically from anthropogenic sources, however, decreased emissions have reduced Hg concentrations. Total IHg (0.51–3.42 ng L−1) and MeHg (25–81 pg L−1) concentrations are additively described by suspended particulate matter and particulate organic carbon. Higher total concentrations, carried by organic-rich particles, were found near specific discharge points (0.79–8.02 ng L−1 and 34–235 pg L−1 for IHg and MeHg, respectively). The associated high dissolved MeHg concentrations could not be explained only by biogeochemical variables. Better efficiency of the models is found for total than for dissolved concentrations. Models should be checked with other contaminants or with estuaries, suffering from downstream contamination.

Mercury, silver and selenium in serum before and after removal of amalgam restorations: results from a prospective cohort study in Norway

Objective A prospective cohort study on changes of health complaints after removal of amalgam restorations was carried out at the request of the Norwegian Directorate of Health. The aim was to provide and evaluate experimental treatment to patients with health complaints attributed to dental amalgam fillings. Methods Patients (n = 32) with medically unexplained physical symptoms (MUPS), which were attributed to dental amalgam restorations had all their amalgam restorations removed and replaced with other dental restorative materials. Samples of blood were collected before and 1 year after removal of the fillings, and concentration of inorganic mercury (I-Hg), methylmercury (MeHg), silver (Ag) and selenium (Se) in serum was determined by inductively coupled plasma–sector field mass spectrometry. The comparison groups (one with MUPS but without attribution to amalgam [n = 28] and one group of healthy individuals [n = 19]) received no treatment. The participants responded to questionnaires at baseline and at follow-up after 1 and 5 years. Results Concentration of I-Hg and Ag in serum decreased significantly after removal of all amalgam restorations. Concentration of MeHg and Se in serum were not changed. Intensity of health complaints was significantly reduced after amalgam removal, but there were no statistically significant correlations between exposure indicators and health complaints. Conclusions Removal of all amalgam restorations is followed by a decrease of concentration of I-Hg and Ag in serum. The results support the hypothesis that exposure to amalgam fillings causes an increase of the daily dose of both I-Hg and Ag. Even though intensity of health complaints decreased after removal of all amalgam restorations there was no clear evidence of a direct relationship between exposure and health complaints. Trial registration: The project is registered at Clinicaltrials.gov (NCT01682278).

Mercury speciation in estuarine water using dithiol-based magnetic solid-phase extraction and cold vapor atomic fluorescence spectrometry

In this work, a method for mercury speciation using magnetic nanoparticles (MNPs) coated with dithiol and detection by cold vapor atomic fluorescence spectrometry (CV AFS) was developed. The magnetic Fe3O4 nanoparticles were coated with Al2O3 and sodium dodecyl sulfate (SDS) and functionalized with 1,3,4-thiadiazole-2,5-dithiol (TDT). The resulting functionalized MNPs (FMNPs, Fe3O4@Al2O3-TDT) were dispersed in the water samples, and the sorption performance with different mercury species was investigated. Once retained on the surface of Fe3O4@ Al2O3-TDT MNPs, the mercury species were magnetically separated from the sample and eluted with HCl. The organic mercury species were oxidized employing KBr-KBrO3 (100 and 17 mM, respectively) in an acid medium (HCl 1.0 M), and the results were expressed considering the total inorganic mercury concentration. It was successfully applied in mercury speciation analysis in the estuarine water, followed by CV AFS determination. In the proposed method under optimal conditions (pH 6), inorganic mercury was quantified in a linear range from 10 to 2000 ng L−1, with a limit of detection of 0.55 ng L−1, relative standard deviation (RSD) < 1.62%, and an enrichment factor of twelve. The recoveries in spiked estuarine water samples ranged from 94 to 106% for Hg(II), 85–91% for MeHg, 83–94% for EtHg, and 84–95% (PhHg) using two levels of concentration (100 and 500 ng L−1). The method is accurate, precise, and efficiently applied in mercury species determination in a complex matrix without laborious and time-consuming sample preparation.

Determination of Mercury in Artificial Saliva Extract of Chewing Tobacco by Dispersive Liquid–Liquid Micro-Extraction Using Electrothermal Atomic Absorption Spectrometry (ETAAS)

An enrichment method was developed for the determination of inorganic mercury (Hg) in artificial saliva extracts (ASE) of frequently consuming chewing tobacco products (CTP). The artificial saliva extracts of the mainpuri and gutkha chewing tobacco were subjected to dispersive liquid-liquid micro-extraction (DLLµE) based on the ultrasound based back extraction of hydrophobic complex of inorganic mercury (iHg) separately by L-cysteine and hydrochloric acid. The total Hg, extractable Hg (EHg), and enriched inorganic mercury in artificial saliva extracts of chewing tobacco were determined by electrothermal atomic absorption spectrometry (ETAAS) and inductively coupled plasma – optical emission spectrometry (ICP-OES). The results obtained by these techniques were not significantly different (p > 0.05). Factors affecting the extraction efficiency of inorganic mercury such as concentration of the ligand, pH, disperser/extracting solvent, sonication time, and back extracting reagents were optimized by multivariate techniques. The precision and accuracy of total mercury (tHg) was confirmed by analyzing a tobacco certified reference material, while the validity of the proposed method (DLLµE) was ensured by spiking inorganic mercury in artificial saliva extracts of the chewing tobacco products. Using the optimized conditions for developed method, the limit of detection and enrichment factor for inorganic mercury were 0.17 μg/L and 96.2, respectively. The extractable Hg in artificial saliva extracts of chewing tobacco was from 35 to 48% of the total content. However, the concentration of inorganic mercury was between 68 and 80% of the total extractable concentration in artificial saliva extracts of the chewing tobacco.

Selective organomercury determination by ICP-MS made easy

A fast and cost-effective procedure based on Inductively Coupled Plasma – Mass Spectrometry (ICP-MS) for the selective determination of methylmercury (MeHg) is proposed and validated for fish tissue analysis. Selectivity for MeHg is achieved by simply inserting a strong anion exchange resin to block inorganic mercury as negatively charged chloride species, leaving MeHg unretained. The procedure features a 15 min extraction time followed by a 100 s analysis time achieving a limit of detection of 1.6 μg kg−1 on solid samples. The effect of the solution composition and inorganic mercury concentration were extensively studied to fully assess the selectivity of the procedure: Hg(II):MeHg ratios up to 50 are tolerated and cause systematic errors lower than 15%. The entire procedure was successfully validated by standard reference material from the marine food web, namely fish muscle and liver plus zooplankton. The method was finally applied to the detection of MeHg in the marine trophic web of Djibouti (Gulf of Aden): a trophic magnification factor of 13.5 proved the high risk associated with the biomagnification of methylmercury.

Indices of the DNA repair system in the brain of fish as a biomarker of inorganic mercury burden

Mercury is a widespread heavy metal that causes a stable and prolonged environmental pollution. Low concentrations of inorganic and organic mercury compounds are found in almost all water bodies. The high level of mercury bioaccumulation is a cause of tissue-specific toxicity, including neurotoxicity. Absorbed in nervous tissue mercury can cause brain disorders both in neural and glial cells. The brain of fish is considered one of the most susceptible targets for cytotoxicity of mercury in aquatic ecosystems. Taking into account that different forms of mercury have widespread distribution and exhibit a strong neurotoxic effect, the assessment of mercury cytotoxicity in the brain of fish is relevant and extremely important. Rainbow trout Oncorhynchus mykiss was exposed to mercury chloride in the dose range of 5-20 μg/L for 60 days to study the chronic exposure of low doses. In this paper, we studied the influence of inorganic mercury on oxidative stress, DNA repair proteins – ERCC1 and PARP1 in the trout’s brain. The results obtained have shown that the chronic effect of inorganic mercury causes dose-dependent oxidative stress in the fish brain. In addition, low concentrations of mercury (10 and 20 μg/L) caused a decrease in the content of ERCC1 in the brain of fish. On the contrary, the same doses have caused an increase in PARP1 expression. That is the chronic influence of low concentrations of inorganic mercury has a negative effect in the fish brain. Observed results showed that inorganic mercury has a potential for suppressing DNA repair and, therefore, increases the instability of genome. Thus, ERCC1 and PARP1 can be considered as the sensitive biomarkers of mercury cytotoxicity in the fish brain. A further study of mercury neurotoxicity is needed to find out the hazard of mercury environmental pollution as well as a validation of biomarkers of their impact.

Metabolomic Responses of Green Alga Chlamydomonas reinhardtii Exposed to Sublethal Concentrations of Inorganic and Methylmercury.

Metabolomics characterizes low-molecular-weight molecules involved in different biochemical reactions and provides an integrated assessment of the physiological state of an organism. By using liquid chromatography-mass spectrometry targeted metabolomics, we examined the response of green alga Chlamydomonas reinhardtii to sublethal concentrations of inorganic mercury (IHg) and monomethylmercury (MeHg). We quantified the changes in the levels of 93 metabolites preselected based on the disturbed metabolic pathways obtained in a previous transcriptomics study. Metabolites are downstream products of the gene transcription; hence, metabolite quantification provided information about the biochemical status of the algal cells exposed to Hg compounds. The results showed that the alga adjusts its metabolism during 2 h exposure to 5 × 10-9 and 5 × 10-8 mol L-1 IHg and MeHg by increasing the level of various metabolites involved in amino acid and nucleotide metabolism, photorespiration, and tricarboxylic acid (TCA) cycle, as well as the metabolism of fatty acids, carbohydrates, and antioxidants. Most of the metabolic perturbations in the alga were common for IHg and MeHg treatments. However, the exposure to IHg resulted in more pronounced perturbations in the fatty acid and TCA metabolism as compared with the exposure to MeHg. The observed metabolic perturbations were generally consistent with our previously published transcriptomics results for C. reinhardtii exposed to the comparable level of IHg and MeHg. The results highlight the potential of metabolomics for toxicity evaluation, especially to detect effects at an early stage of exposure prior to their physiological appearance.

Distribution of mercury species in different tissues and trophic levels of commonly consumed fish species from the south Bay of Biscay (France)

Mercury (Hg) is a contaminant of global concern in marine ecosystems, notably due to its ability to accumulate and concentrate in food webs. Concentrations of total mercury (THg), methylmercury (MeHg) and inorganic mercury (IHg) were assessed and compared in different tissues (liver, muscle, and gonads) of three common fish species (hake Merluccius merluccius, red mullet Mullus surmuletus, and sole Solea solea) from the continental shelf from the southern part of the Bay of Biscay. Several studies investigated Hg concentration in fish muscle, but few assessed concentrations in other organs, despite the importance of such data to understand contaminant organotropism and metabolization. Results showed that trophic position and feeding habitat are required to understand the variability of Hg concentration in muscle between fish species. In addition, high MeHg/THg ratio in muscle could be explained by the predatory behavior of the studied fish species and the biomagnification of this Hg species within the food web, MeHg. Despite differences between species, Hg concentration was always higher in muscle (from 118 ± 64 to 338 ± 101 ng g−1 w.w.) and liver (from 122 ± 108 to 271 ± 95 ng g−1 w.w.). These results can be related to physiological processes especially the MeHg detoxification strategies.

Relationship Between Hg Speciation and Hg Methylation/Demethylation Processes in the Sulfate-Reducing Bacterium Pseudodesulfovibrio hydrargyri: Evidences From HERFD-XANES and Nano-XRF.

Microorganisms are key players in the transformation of mercury into neurotoxic methylmercury (MeHg). Nevertheless, this mechanism and the opposite MeHg demethylation remain poorly understood. Here, we explored the impact of inorganic mercury (IHg) and MeHg concentrations from 0.05 to 50 μM on the production and degradation of MeHg in two sulfate-reducing bacteria, Pseudodesulfovibrio hydrargyri BerOc1 able to methylate and demethylate mercury and Desulfovibrio desulfuricans G200 only able to demethylate MeHg. MeHg produced by BerOc1 increased with increasing IHg concentration with a maximum attained for 5 μM, and suggested a saturation of the process. MeHg was mainly found in the supernatant suggesting its export from the cell. Hg L3-edge High- Energy-Resolution-Fluorescence-Detected-X-ray-Absorption-Near-Edge-Structure spectroscopy (HERFD-XANES) identified MeHg produced by BerOc1 as MeHg-cysteine2 form. A dominant tetracoordinated βHgS form was detected for BerOc1 exposed to the lowest IHg concentrations where methylation was detected. In contrast, at the highest exposure (50 μM) where Hg methylation was abolished, Hg species drastically changed suggesting a role of Hg speciation in the production of MeHg. The tetracoordinated βHgS was likely present as nano-particles as suggested by transmission electron microscopy combined to X-ray energy dispersive spectroscopy (TEM-X-EDS) and nano-X ray fluorescence (nano-XRF). When exposed to MeHg, the production of IHg, on the contrary, increased with the increase of MeHg exposure until 50 μM for both BerOc1 and G200 strains, suggesting that demethylation did not require intact biological activity. The formed IHg species were identified as various tetracoordinated Hg-S forms. These results highlight the important role of thiol ligands and Hg coordination in Hg methylation and demethylation processes.

Internal dynamics of inorganic and methylmercury in a marine fish: Insights from mercury stable isotopes

Mercury isotope ratios in fish tissues have been used to infer sources and biogeochemical processes of mercury in aquatic ecosystems. More experimental studies are however needed to understand the internal dynamics of mercury isotopes and to further assess the feasibility of using fish mercury isotope ratios as a monitoring tool. We exposed Olive flounder (Paralichthys olivaceus) to food pellets spiked with varying concentrations (400, 1600 ng/g) of methylmercury (MeHg) and inorganic mercury (IHg) for 10 weeks. Total mercury (THg), MeHg concentrations, and mercury isotope ratios (δ202Hg, Δ199Hg, Δ200Hg) were measured in the muscle, liver, kidney, and intestine of fish. Fish fed mercury unamended food pellets and MeHg amended food pellets showed absence of internal δ202Hg and Δ199Hg fractionation in all tissue type. For fish fed IHg food pellets, the δ202Hg and Δ199Hg values of intestine equilibrated to those of the IHg food pellets. Kidney, muscle, and liver exhibited varying degrees of isotopic mixing toward the IHg food pellets, consistent with the degree of IHg bioaccumulation. Liver showed additional positive δ202Hg shifts (∼0.63‰) from the binary mixing line between the unamended food pellets and IHg food pellets, which we attribute to redistribution or biliary excretion of liver IHg with a lower δ202Hg to other tissues. Significant δ202Hg fractionation in the liver and incomplete isotopic equilibration in the muscle indicate that these tissues may not be suitable for source monitoring at sites heavily polluted by IHg. Instead, fish intestine appears to be a more suitable proxy for identifying IHg sources. The results from our study are essential for determining the appropriate fish tissues for monitoring environmental sources of IHg and MeHg.

Mercury bioaccumulation in stream fish from an agriculturally-dominated watershed

Bioaccumulation of mercury in freshwater fish is a complex process driven by environmental and biological factors. In this study, we assessed mercury in fish from four tributaries to the Red Deer River, Alberta, Canada, which are characterized by high surface water mercury concentrations. We used carbon (δ13C) and nitrogen (δ15N) stable isotopes to examine relationships between fish total mercury (THg) concentrations, food web dynamics and patterns in unfiltered THg and methylmercury (MeHg) concentrations. We found that THg concentrations exceeded the tissue residue quality guideline for the protection of wildlife consumers in 99.7% of fish sampled. However, while the surface water THg concentration was highest in Michichi Creek and the MeHg concentration was consistent across streams, patterns of fish THg concentrations varied depending on species. Furthermore, body size and trophic level were only correlated with THg concentrations in white sucker (Catostomus commersoni) and Prussian carp (Carrasius gibelio). The results of this study suggest that mercury poses a risk to the health of piscivorous wildlife in the Red Deer River watershed. Despite high THg concentrations in these streams, mercury bioaccumulation is not driven by environmental inorganic mercury concentrations. Additionally, commonly cited factors associated with mercury concentrations in fish, such as body size and trophic level, may not strongly influence bioaccumulation in these stream ecosystems.

Multiple regression analysis to assess the spatial distribution and speciation of mercury in surface sediments of a contaminated lagoon.

The concentrations of inorganic mercury (IHg) and methylmercury (MeHg) in surface sediments from the contaminated Aveiro Lagoon (Portugal) were determined by species-specific isotope dilution analysis. Different behaviour of IHg and MeHg was observed based upon multiple regression analysis, including geochemical characteristics of the surface sediments (fine fraction, concentrations of organic matter and metals) and non-Euclidean distances between sampling points. This data treatment method was valid over the entire concentration range of IHg and MeHg, allowing robust quantitative evaluation with respect to extrapolation. For IHg, there was statistical separation of the dispersion away from the contamination source and of Al concentration in the sediments. The MeHg concentrations followed those of IHg at high concentrations. The geochemical variables, such as concentrations of Ca (marine influence proxy), Mn and organic matter, were necessary to describe the behaviour of MeHg across the whole concentration range. The models for MeHg demonstrated that, close to the mouth of the lagoon, net production of MeHg was higher. In future, multiple regression analysis could be applied to separate and to evaluate quantitatively the effects of geochemistry and dispersion away from the contamination source in sediments contaminated with other substances.

Total, methyl and inorganic mercury concentrations in blood and environmental exposure sources in newcomer women in Toronto, Canada

Measurements of total blood Hg (tHg), often used as a proxy for methyl Hg (MeHg) concentrations, are most commonly the focus of population-based studies. Data on Hg species in biomarkers can allow for a more nuanced characterization of environmental exposure sources and risk but their availability is limited, especially for newcomer populations. The purpose of the Metals in Newcomer Women (MNW) study was to address existing data gaps on metal concentrations and exposure sources in newcomer women (19–45 years) and to examine tHg, MeHg and inorganic Hg (iHg) in the blood of East and South Asian women recently arrived to Toronto. Study participants were recruited in 2015 (n = 211). Total Hg concentrations were determined using both ICP-Q-MS and isotope dilution (ID)-SPME-GC-ICP-MS. A sample subset (n = 76) was chosen for the analysis of blood MeHg and iHg concentrations (also using ID-SPME-GC-ICP-MS). Hierarchical regression models were used to assess associations between blood tHg concentrations and environmental exposure factors for MNW participants. For the sample subset, a log-linear model was used to examine associations between blood iHg and MeHg concentrations and fish consumption patterns. The geometric mean (GM) blood tHg concentration was 1.05 µg/L (95% CI: 0.88–1.25), which was elevated compared to Canadian-born women (GM: 0.57 µg/L; 95% CI: 0.49–0.66), in a specialized data analysis of the Canadian Health Measures Survey (CHMS). GM concentrations for iHg and MeHg were 0.21 µg/L (95% CI: 0.16–0.28) and 2.66 µg/L (95% CI: 2.00–3.55), respectively. Significant distal determinants associated with blood tHg concentrations were: level of educational attainment, having lived in a coastal/fishing community prior to arrival, and global region of origin. Use of iron supplements and consumption of higher mercury fish species were also associated with tHg concentrations in the fully adjusted model. The study results demonstrate that blood Hg concentrations in newcomer women are slightly elevated, with some individuals in exceedance of recommended concentrations for women of reproductive age. The consumption of fish species low in Hg is recommended for newcomer women, especially those who consume fish frequently.

Source relationships between streambank soils and streambed sediments in a mercury-contaminated stream

PurposeIn contaminated streams, understanding the role of streambank and streambed source contributions is essential to developing robust remedial solutions. However, identifying relationships can be difficult because of the lack of identifying signatures in source and receptor pools. East Fork Poplar Creek (EFPC) in Oak Ridge, TN, USA received historical industrial releases of mercury that contaminated streambank soils and sediments. Here, we determined relationships between the contaminated streambank soils and sand-sized streambed sediments.Materials and methodsField surveys revealed the spatial trends of the concentrations of inorganic total mercury (Hg) and methyl mercury (MeHg), Hg lability as inferred by sequential extraction, particle size distribution, and total organic carbon. Statistical tests were applied to determine relationships between streambank soil and streambed sediment properties.Results and discussionConcentrations of Hg in streambank soils in the upper reaches averaged 206 mg kg−1 (all as dry weight) (n = 457), and 13 mg kg−1 in lower reaches (n = 321), while sand-sized streambed sediments were approximately 16 mg kg−1 (n = 57). Two areas of much higher Hg and MeHg concentrations in streambank soils were identified and related to localized higher Hg concentrations in the streambed sediments; however, most of the streambank soils have similar Hg concentrations to the streambed sediments. The molar ratio of Hg to organic carbon, correlation between MeHg and Hg, and particle size distributions suggested similarity between the streambank soils and the fine sand-sized fraction (125–250 μm) collected from the streambed sediments. Mercury in the fine sand-sized streambed sediments, however, was more labile than Hg in the streambank soils, suggesting an in-stream environment that altered the geochemistry of sediment-bound Hg.ConclusionsThis study revealed major source areas of Hg in streambank soils, identified possible depositional locations in streambed sediments, and highlighted potential differences in the stability of Hg bound to streambank soils and sediments. This work will guide future remedial decision making in EFPC and will aid other researchers in identifying source–sink linkages in contaminated fluvial systems.

Fifty years after its discharge, methylation of legacy mercury trapped in the Penobscot Estuary sustains high mercury in biota

Fifty years ago, the Penobscot Estuary was contaminated by mercury discharged from the chlor-alkali plant located in Orrington, Maine, USA. Almost all of the mercury was discharged from the plant during the late 1960s and early 1970s. Despite the much lower mercury discharges in recent decades, present-day concentrations in surface sediment remain high (averaging 350–1100 ng/g dw) and are still high in blood of marsh birds (up to 10.5 μg/g), black duck muscle (0.8 μg/g), and lobster muscle (0.4 μg/g). Methyl mercury (MeHg) concentrations in marsh birds exceed levels that impair reproduction. There are health advisories for duck hunters and closures of shellfish fisheries. These continuing high mercury concentrations are caused by the trapping of legacy mercury in a mobile pool of sediment that is retained in the upper estuary above a tidally forced salinity front, which travels up and down the estuary each tidal cycle - slowing the transport of particulate mercury to Penobscot Bay. The trapped legacy mercury continues to be available for methylation 50 years after it first entered the estuary. This is demonstrated by the fact that rates of MeHg production are positively related to the inorganic mercury concentration in parts of the estuary with elevated concentrations of legacy mercury. Thus, remediation measures that would lower the THg concentration in surface sediment would lower the MeHg in birds, fish and shellfish. All of this new information leads us to recommend two remediation options. Addition of mercury binding agents may lower mercury concentrations in birds in some wetland areas. System-wide, we also recommend Enhanced Natural Recovery (ENR), a novel approach that involves the partial removal of the contaminated mobile sediment pool followed by replacement with clean-clay particulates to dilute inorganic mercury concentrations, which would lower methylation rates and mercury concentrations in biota.

Mercury methylation in stormwater retention ponds at different stages in the management lifecycle.

Stormwater retention ponds effectively manage erosion, flooding, and pollutant loadings, but are also sources of methylmercury (MeHg), a bioaccumulative neurotoxin which is produced by anaerobic aquatic microorganisms. Stormwater retention ponds have a 10-15 year working life, after which they are dredged and reflooded. In this study, we related MeHg biogeochemistry to the different stages of the management lifecycle. In a new, a dredged, and a mature stormwater retention pond, we measured MeHg and inorganic mercury (IHg) concentrations, and the potential for MeHg formation (Kmeth), during the early summer, peak summer, and fall of 2013. In our study sites, MeHg concentrations appear to be driven by mercury (Hg) methylation, indicated by significant correlations between Kmeth values and MeHg concentrations and the percent of Hg present as MeHg. Relationships between Hg variables and ancillary biogeochemistry suggest that Hg methylation is carried out by sulfate reducing bacteria, but that the process is modulated by the supply of IHg substrate, sediment total and labile organic carbon, and possibly competition with nitrate reducers. Wetlands at different points in the management lifecycle differ in terms of their MeHg biogeochemistry. The organic matter-poor new wetland had low MeHg production (mean Kmeth 0.014 per day) and sediment concentrations (mean 0.015 ng g-1), while the mature wetland both produced and accumulated MeHg about five times more actively. Methylmercury production capacity was only temporarily reduced in the reflooded sediments of the dredged wetland, which experienced rapid increases in Kmeth values from low (mean 0.015 per day) immediately after dredging, to values similar to those in the mature wetland after five months. This pattern may have been related to recolonization of the sediments with mercury methylators or increased microbial activities in response to the addition of fresh organic matter. Additional studies should focus on the applicability of these patterns to stormwater retention ponds in other areas, and particularly investigate the effects of stormwater pond dredging on their microbial ecology and MeHg biogeochemistry.

Toxicity of Inorganic Mercury to Native Australian Grass Grown in Three Different Soils.

In this study, three native Australian grasses namely Iseilema membranaceum (Barcoo), Dichanthium sericeum (Queensland Blue) and Sporobolus africanus (Tussock) were grown in three different soils spiked with different concentrations of inorganic mercury and the root elongation was monitored up to 28 days following the germination. Results showed that mercury at certain concentrations significantly inhibited the root growth of all three tested native grasses grown in three soils, however, the toxicity was less in the soil with high organic carbon content and acidic pH. The calculated EC50 values ranged from 10 to 224mg/kg total Hg in soil. However, the EC10 values indicated that existing guideline values for mercury may be of protective to the native Australian vegetation. Considering their tolerance to soil mercury, these grass species have the potential for their use in rehabilitation of mercury contaminated sites.

Automated dispersive liquid-liquid microextraction coupled to high performance liquid chromatography - cold vapour atomic fluorescence spectroscopy for the determination of mercury species in natural water samples

An automated, home-constructed, and low cost dispersive liquid-liquid microextraction (DLLME) device that directly coupled to a high performance liquid chromatography (HPLC) – cold vapour atomic fluorescence spectroscopy (CVAFS) system was designed and developed for the determination of trace concentrations of methylmercury (MeHg+), ethylmercury (EtHg+) and inorganic mercury (Hg2+) in natural waters. With a simple, miniaturized and efficient automated DLLME system, nanogram amounts of these mercury species were extracted from natural water samples and injected into a hyphenated HPLC-CVAFS for quantification. The complete analytical procedure, including chelation, extraction, phase separation, collection and injection of the extracts, as well as HPLC-CVAFS quantification, was automated. Key parameters, such as the type and volume of the chelation, extraction and dispersive solvent, aspiration speed, sample pH, salt effect and matrix effect, were thoroughly investigated. Under the optimum conditions, linear range was 10–1200ngL−1 for EtHg+ and 5–450ngL−1 for MeHg+ and Hg2+. Limits of detection were 3.0ngL−1 for EtHg+ and 1.5ngL−1 for MeHg+ and Hg2+. Reproducibility and recoveries were assessed by spiking three natural water samples with different Hg concentrations, giving recoveries from 88.4–96.1%, and relative standard deviations <5.1%.