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Mono‐ and dimethylmercury (MMHg and DMHg, respectively) are the two primary organic forms of mercury (Hg) found in natural waters. While experimental approaches to characterize the environmental behavior of MMHg and inorganic forms of Hg are widely used today, few laboratories conduct experimental studies entailing the use of DMHg. In this paper, we have evaluated and developed different analytical and experimental approaches to quantify and use DMHg in laboratory studies. We demonstrate that DMHg can be analyzed from samples where MMHg is derivatized using sodium tetraethyl borate and where the matrix effects of dissolved sulfide are masked using copper sulfate. Tests, where the calibration curves of MMHg and DMHg were used, showed that MMHg may be used to calibrate for DMHg. For the pre‐concentration of DMHg, both traps filled with Tenax® TA and Bond Elut ENV were found suitable. We observed good recoveries of DMHg added to different types of natural waters or purified water containing aquarium salt, sodium chloride and dissolved sulfide, iron sulfide, and cadmium sulfide at DMHg : sulfide molar ratios > 10−6. In addition to evaluating these analytical aspects, we present suitable subsampling techniques for DMHg‐containing solutions, the recovery of DMHg when filtering DMHg through different types of filters, and experimental data on the long‐term stability of DMHg added to different types of waters and stored at different temperatures. Finally, we present and discuss a new synthetization protocol for preparing aqueous solutions containing DMHg free of organic solvents and where handling DMHg in a pure form is prevented. [ABSTRACT FROM AUTHOR]

Anoxic microniches in sinking particles in lakes have been identified as important water phase production zones of monomethylmercury (MeHg). However, the production and decay of MeHg during organic matter (OM) decomposition in the water column and its relation to the total Hg concentration in seston are poorly understood. We investigated total Hg and MeHg in relation to chemical changes in sinking seston and hydrochemical settings in a small and shallow (12 m deep) eutrophic lake during phytoplankton blooms from April to November 2019. The results show that MeHg proportions reach up to 22 % in seston in oxygen super saturation at the water surface and highest values (up to 26 %) at the oxic–suboxic redox boundary. MeHg concentrations were highest in May and November when algal biomass production was low and seston were dominated by zooplankton. Biodilution of MeHg concentrations could not be observed in the months of the highest algal biomass production; instead, MeHg and THg concentrations in seston were comparatively high. During suboxic OM decomposition and with decreasing redox potential (Mn and nitrate reduction), the concentration and proportion of MeHg in seston strongly decreased (<0.5 %), whereas total Hg concentrations show a 3.8- to 26-fold increase with water depth. Here, it remains unclear to which extent biodilution on the one hand and OM decomposition on the other alter the MeHg and THg concentration in seston. Changes in OM quality were most intense within or slightly below the redox transition zone (RTZ). The concentrations of MeHg and THg in seston from the RTZ were comparable to those found in the sediment trap material which integrated the changes in seston composition during the entire sampling period, suggesting that changes in the MeHg and THg content in the hypolimnion below the RTZ are comparatively small. Our study suggests that, in shallow eutrophic lakes, the water phase formation and decomposition of MeHg is intense and controlled by the decomposition of algal biomass and is, assumedly, largely disconnected from Hg methylation in sediments, similar to what has been observed in deep oligotrophic lakes. [ABSTRACT FROM AUTHOR]

Anoxic microniches in sinking particles in lakes have been identified as important water phase production zones of monomethylmercury (MeHg) (endogenic MeHg). However, the production and decay of MeHg during organic matter (OM) decomposition in the water column and its relation to the total Hg concentration in seston are poorly understood. We investigated Hg speciation and chemical changes in sinking seston in a small and shallow (12-m-deep) eutrophic lake during phytoplankton blooms from April to November 2019. The results show that MeHg proportions are high in seston at the water surface (up to 22 %) and at the oxic-suboxic redox boundary (up to 26 %). During suboxic OM decomposition, and with decreasing redox-potential, the concentration and proportion of MeHg in seston strongly decrease (< 0.5 %) as the water depth increases. Under these conditions, total Hg concentrations show a 3.8 to 26-fold increase. In the hypolimnion environment, changes in MeHg proportions were minimal in sinking seston, and samples collected by sediment traps had MeHg values similar to those measured at the sediment-water interface, though higher MeHg concentrations were found deeper in the sediment. Our results indicate that cycling of MeHg and total Hg (THg) in seston within small productive lakes is largely controlled by the decomposition processes of settling seston and that the endogenic MeHg pool appears to be largely disconnected from the sedimentary MeHg pool. [ABSTRACT FROM AUTHOR]

Thousands of dams are currently under construction or planned worldwide to meet the growing need for electricity. The creation of reservoirs could, however, lead to conditions that promote the accumulation of mercury (Hg) in surface sediments and the subsequent production of methylmercury (MeHg). Once produced, MeHg can bioaccumulate to harmful levels in organisms. It is unclear to what extent variations in physical features and biogeochemical factors of the reservoir impact Hg accumulation. The objective of this study was to identify key drivers of the accumulation of total Hg (THg) in tropical reservoir sediments. The concentration of THg in all analyzed depth intervals of 22 sediment cores from the five contrasting reservoirs investigated ranged from 16 to 310 ng g−1 (n = 212, in the different sediment cores, the maximum depth varied from 18 to 96 cm). Our study suggests reservoir size to be an important parameter determining the concentration of THg accumulating in tropical reservoir sediments, with THg ranging up to 50 ng g−1 in reservoirs with an area exceeding 400 km2 and from 100 to 200 ng g−1 in reservoirs with an area less than 80 km2. In addition to the reservoir size, the role of land use, nutrient loading, biome and sediment properties (e.g., organic carbon content) was tested as potential drivers of THg levels. The principal component analysis conducted suggested THg to be related to the properties of the watershed (high degree of forest cover and low degree of agricultural land use), size and age of the reservoir, water residence time and the levels of nutrients in the reservoir. A direct correlation between THg and tested variables was, however, only observed with the area of the reservoir. [ABSTRACT FROM AUTHOR]

The forms of inorganic mercury (Hg II ) taken up and methylated by bacteria in sediments still remain largely unknown. From pure cultures studies, it has been suggested that dissolved organic matter (DOM) may facilitate the uptake either by acting as a shuttle molecule, transporting the Hg II atom to divalent metal transporters, or by binding Hg II and then being transported into the cell as a carbon source. Enhanced availability of Hg complexed to DOM has however not yet been demonstrated in natural systems. Here, we show that Hg II complexed with DOM of marine origin was up to 2.7 times more available for methylation in sediments than Hg II added as a dissolved inorganic complex (Hg II (aq) ). We argue that the DOM used to complex Hg II directly facilitated the bacterial uptake of Hg II whereas the inorganic dissolved Hg II complex adsorbed to the sediment matrix before forming bioavailable dissolved Hg II complexes. We further demonstrate that differences in net methylation in sediments with high and low organic carbon content may be explained by differences in the availability of carbon to stimulate the activity of Hg methylating bacteria rather than, as previously proposed, be due to differences in Hg II binding capacities between sediments. [ABSTRACT FROM AUTHOR]

Net formation of methylmercury (MeHg) in sediments is known to be affected by the availability of inorganic divalent mercury (HgII) and by the activities of HgII methylating and MeHg demethylating bacteria. Enhanced autochthonous organic matter deposition to the benthic zone, following increased loading of nutrients to the pelagic zone, has been suggested to increase the activity of HgII methylating bacteria and thus the rate of net methylation. However, the impact of increased nutrient loading on the biogeochemistry of mercury (Hg) is challenging to predict as different geochemical pools of Hg may respond differently to enhanced bacterial activities. Here, we investigate the combined effects of nutrient (N and P) supply to the pelagic zone and the chemical speciation of HgII and of MeHg on MeHg formation and degradation in a brackish sediment-water mesocosm model ecosystem. By use of Hg isotope tracers added in situ to the mesocosms or ex situ in incubation experiments, we show that the MeHg formation rate increased with nutrient loading only for HgII tracers with a high availability for methylation. Tracers with low availability did not respond significantly to nutrient loading. Thus, both microbial activity (stimulated indirectly through plankton biomass production by nutrient loading) and HgII chemical speciation were found to control the MeHg formation rate in marine sediments [ABSTRACT FROM AUTHOR]

Increasing terrestrial run-off from melting glaciers and thawing permafrost to Arctic coastal areas is expected to facilitate re-mobilization of stored legacy persistent organic pollutants (POPs) and mercury (Hg), potentially increasing exposure to these contaminants for coastal benthic organisms. We quantified chlorinated POPs and Hg concentrations, lipid content and multiple dietary markers, in a littoral deposit-feeding amphipod Gammarus setosus and sediments during the melting period from April to August in Adventelva river estuary in Svalbard, a Norwegian Arctic Aarchipelago. There was an overall decrease in concentrations of ∑POPs from April to August (from 58 ± 23 to 13 ± 4 ng/g lipid weight; lw), Hg (from 5.6 ± 0.7 to 4.1 ± 0.5 ng/g dry weight; dw) and Methyl Hg (MeHg) (from 5 ± 1 to 0.8 ± 0.7 ng/g dw) in G. setosus. However, we observed a seasonal peak in penta- and hexachlorobenzene (PeCB and HCB) in May (2.44 ± 0.3 and 23.6 ± 1.7 ng/g lw). Sediment concentrations of POPs and Hg (dw) only partly correlated with the contaminant concentrations in G. setosus. Dietary markers, including fatty acids and carbon and nitrogen stable isotopes, indicated a diet of settled phytoplankton in May–July and a broader range of carbon sources after the spring bloom. Phytoplankton utilization and chlorobenzene concentrations in G. setosus exhibited similar seasonal patterns, suggesting a dietary uptake of chlorobenzenes that is delivered to the aquatic environment during spring snowmelt. The seasonal decrease in contaminant concentrations in G. setosus could be related to seasonal changes in dietary contaminant exposure and amphipod ecology. Furthermore, this decrease implies that terrestrial run-off is not a significant source of re-mobilized Hg and legacy POPs to littoral amphipods in the Adventelva river estuary during the melt season. • Diet in Gammarus setosus changes from April to August. • Lipid-adjusted POP and Hg levels decrease in G. setosus from April to August. • Deposited phytoplankton is a source of chlorobenzenes to G. setosus. • Glacial meltwater is not a significant source of contamination to G. setosus. • POP and Hg levels in G. setosus reflect seasonality in both ecology and exposure. [ABSTRACT FROM AUTHOR]

Monomethylmercury (MeHg) in fish from freshwater, estuarine, and marine environments is a major global environmental issue. Mercury levels in biota are mainly controlled by the methylation of inorganic mercuric mercury (HgII) to MeHg in water, sediments, and soils. There is, however, a knowledge gap concerning the mechanisms and rates of methylation of specific geochemical HgII species. Such information is crucial for a better understanding of variations in MeHg concentrations among ecosystems and, in particular, for predicting the outcome of currently proposed measures to mitigate mercury emissions and reduce MeHg concentrations in fish. To fill this knowledge gap we propose an experimental approach using HgII isotope tracers, with defined and geochemically important adsorbed and solid HgII forms in sediments, to study MeHg formation. We report HgII methylation rate constants, km, in estuarine sediments which span over 2 orders of magnitude depending on chemical form of added tracer: metacinnabar (β-201HgS(s)) < cinnabar (α-199HgS(s)) < HgII reacted with mackinawite (=FeS-202HgII) < HgII bonded to natural organic matter (NOM-196HgII) < a typical aqueous tracer (198Hg(NO3)2(aq)). We conclude that a combination of thermodynamic and kinetic effects of HgII solid-phase dissolution and surface desorption control the HgII methylation rate in sediments and cause the large observed differences in km-values. The selection of relevant solid-phase and surface-adsorbed HgII tracers will therefore be crucial to achieving biogeochemically accurate estimates of ambient HgII methylation rates. [ABSTRACT FROM AUTHOR]

Emission rates of gaseous monomethylmercury (CH3HgII), as well as elemental mercury (Hg0) and dimethylmercury ([CH3)2HgII], were determined in Hg-contaminated water-sediment microcosms (duplicates of three treatments) by gaseous species-specific isotope dilution analysis (SSIDA). Incubation of ∼500 g(wet mass) of sediments containing 30 μmol of ambient Hg with an addition of 2.6 μmol of 201HgII tracer resulted in average (n = 6) gaseous emissions of 84 ± 26, 100 ± 37, and 830 ± 380 pmol of ambient CH3HgII, CH3201HgII, and 201HgD, respectively, daring 108 days of incubation. In contrast to Hg0, a transient temporal pattern was observed for measured CH3HgII emission rates, which peaked at day 12 and decreased to much lower levels by the end of the experiments. At day 12, CH3HgII constituted 30-50% of the total emitted gaseous Hg emphasizing the significance of this species to total Hg emissions from anoxic sediment-water systems. Emission rates of gaseous CH3HgII did not reflect the accumulated CH3HgII content in the sediment suggesting that emissions mainly originated from newly methylated HgII. Speciation modeling of the pore water suggests that CH3HgII was emitted as CH3HgSH0(g). [ABSTRACT FROM AUTHOR]

Mercury (Hg) pollution is a global environmental problem. The abiotic formation of dimethylmercury (DMeHg) from monomethylmercury (MMeHg) may account for a large portion of DMeHg in oceans. Previous experimental work has shown that abiotic formation of DMeHg from MMeHg can be facilitated by reduced sulfur groups on sulfide mineral surfaces. In that work, a mechanism was proposed in which neighboring MMeHg moieties bound to sulfide sites on a mineral surface react through an S N 2-type mechanism to form DMeHg and incorporate the remaining Hg atoms into the mineral surface. Here, we perform density functional theory calculations to explore the mechanisms of DMeHg formation on the 110 surface of a CdS(s) (hawleyite) nanoparticle. We show that coordination of MMeHg substituents to adjacent reduced sulfur groups protruding from the surface indeed facilitates DMeHg formation and that the reaction proceeds through direct transmethylation from one MMeHg substituent to another. Coordination of Hg by multiple S atoms provides a transition-state stabilization and activates a C-Hg bond for methyl transfer. In addition, solvation effects play an important role in the surface reconstruction of the nanoparticle and in decreasing the energetic barrier for DMeHg formation relative to the corresponding reaction in vacuo.

We investigated the influence of sulfate (SO 4 2- ) deposition and concentrations on the net formation and solubility of methylmercury (MeHg) in peat soils. We used data from a natural sulfate deposition gradient running 300 km across southern Sweden to test the hypothesis posed by results from an experimental field study in northern Sweden: that increased loading of SO 4 2- both increases net MeHg formation and redistributes methylmercury (MeHg) from the peat soil to its porewater. Sulfur concentrations in peat soils correlated positively with MeHg concentrations in peat porewater, along the deposition gradient similar to the response to added SO 4 2- in the experimental field study. The combined results from the experimental field study and deposition gradient accentuate the multiple, distinct and interacting roles of SO 4 2- deposition in the formation and redistribution of MeHg in the environment., Competing Interests: Declaration of interests The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2020 The Authors. Published by Elsevier Ltd.. All rights reserved.)

The input of mercury (Hg) to ecosystems is estimated to have increased two- to fivefold during the industrial era, and Hg accumulates in aquatic biota as neurotoxic methylmercury (MeHg). Escalating anthropogenic land use and climate change are expected to alter the input rates of terrestrial natural organic matter (NOM) and nutrients to aquatic ecosystems. For example, climate change has been projected to induce 10 to 50% runoff increases for large coastal regions globally. A major knowledge gap is the potential effects on MeHg exposure to biota following these ecosystem changes. We monitored the fate of five enriched Hg isotope tracers added to mesocosm scale estuarine model ecosystems subjected to varying loading rates of nutrients and terrestrial NOM. We demonstrate that increased terrestrial NOM input to the pelagic zone can enhance the MeHg bioaccumulation factor in zooplankton by a factor of 2 to 7 by inducing a shift in the pelagic food web from autotrophic to heterotrophic. The terrestrial NOM input also enhanced the retention of MeHg in the water column by up to a factor of 2, resulting in further increased MeHg exposure to pelagic biota. Using mercury mass balance calculations, we predict that MeHg concentration in zooplankton can increase by a factor of 3 to 6 in coastal areas following scenarios with 15 to 30% increased terrestrial runoff. The results demonstrate the importance of incorporating the impact of climate-induced changes in food web structure on MeHg bioaccumulation in future biogeochemical cycling models and risk assessments of Hg.

Monomethylmercury (MeHg) in fish from freshwater, estuarine, and marine environments is a major global environmental issue. Mercury levels in biota are mainly controlled by the methylation of inorganic mercuric mercury (Hg(II)) to MeHg in water, sediments, and soils. There is, however, a knowledge gap concerning the mechanisms and rates of methylation of specific geochemical Hg(II) species. Such information is crucial for a better understanding of variations in MeHg concentrations among ecosystems and, in particular, for predicting the outcome of currently proposed measures to mitigate mercury emissions and reduce MeHg concentrations in fish. To fill this knowledge gap we propose an experimental approach using Hg(II) isotope tracers, with defined and geochemically important adsorbed and solid Hg(II) forms in sediments, to study MeHg formation. We report Hg(II) methylation rate constants, k(m), in estuarine sediments which span over 2 orders of magnitude depending on chemical form of added tracer: metacinnabar (β-(201)HgS(s)) < cinnabar (α-(199)HgS(s)) < Hg(II) reacted with mackinawite (≡FeS-(202)Hg(II)) < Hg(II) bonded to natural organic matter (NOM-(196)Hg(II)) < a typical aqueous tracer ((198)Hg(NO(3))(2)(aq)). We conclude that a combination of thermodynamic and kinetic effects of Hg(II) solid-phase dissolution and surface desorption control the Hg(II) methylation rate in sediments and cause the large observed differences in k(m)-values. The selection of relevant solid-phase and surface-adsorbed Hg(II) tracers will therefore be crucial to achieving biogeochemically accurate estimates of ambient Hg(II) methylation rates.