Sofi Jonsson

Mercury Methylation Rates for Geochemically Relevant HgII Species in Sediments

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.

Differentiated availability of geochemical mercury pools controls methylmercury levels in estuarine sediment and biota

Neurotoxic methylmercury (MeHg) formed from inorganic divalent mercury (Hg(II)) accumulates in aquatic biota and remains at high levels worldwide. It is poorly understood to what extent different geochemical Hg pools contribute to these levels. Here we report quantitative data on MeHg formation and bioaccumulation, in mesocosm water-sediment model ecosystems, using five Hg(II) and MeHg isotope tracers simulating recent Hg inputs to the water phase and Hg stored in sediment as bound to natural organic matter or as metacinnabar. Calculations for an estuarine ecosystem suggest that the chemical speciation of Hg(II) solid/adsorbed phases control the sediment Hg pools contribution to MeHg, but that input of MeHg from terrestrial and atmospheric sources bioaccumulates to a substantially greater extent than MeHg formed in situ in sediment. Our findings emphasize the importance of MeHg loadings from catchment runoff to MeHg content in estuarine biota and we suggest that this contribution has been underestimated.

Mercury isotope signatures in contaminated sediments as a tracer for local industrial pollution sources.

Mass-dependent fractionation (MDF) and mass-independent fractionation (MIF) may cause characteristic isotope signatures of different mercury (Hg) sources and help understand transformation processes at contaminated sites. Here, we present Hg isotope data of sediments collected near industrial pollution sources in Sweden contaminated with elemental liquid Hg (mainly chlor-alkali industry) or phenyl-Hg (paper industry). The sediments exhibited a wide range of total Hg concentrations from 0.86 to 99 μg g(-1), consisting dominantly of organically-bound Hg and smaller amounts of sulfide-bound Hg. The three phenyl-Hg sites showed very similar Hg isotope signatures (MDF δ(202)Hg: -0.2‰ to -0.5‰; MIF Δ(199)Hg: -0.05‰ to -0.10‰). In contrast, the four sites contaminated with elemental Hg displayed much greater variations (δ(202)Hg: -2.1‰ to 0.6‰; Δ(199)Hg: -0.19‰ to 0.03‰) but with distinct ranges for the different sites. Sequential extractions revealed that sulfide-bound Hg was in some samples up to 1‰ heavier in δ(202)Hg than organically-bound Hg. The selectivity of the sequential extraction was tested on standard materials prepared with enriched Hg isotopes, which also allowed assessing isotope exchange between different Hg pools. Our results demonstrate that different industrial pollution sources can be distinguished on the basis of Hg isotope signatures, which may additionally record fractionation processes between different Hg pools in the sediments.

Enhanced availability of mercury bound to dissolved organic matter for methylation in marine sediments

The forms of inorganic mercury (HgII) 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 HgII atom to divalent metal transporters, or by binding HgII 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 HgII complexed with DOM of marine origin was up to 2.7 times more available for methylation in sediments than HgII added as a dissolved inorganic complex (HgII(aq)). We argue that the DOM used to complex HgII directly facilitated the bacterial uptake of HgII whereas the inorganic dissolved HgII-complex adsorbed to the sediment matrix before forming bioavailable dissolved HgII 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 HgII binding capacities between sediments.

Terrestrial discharges mediate trophic shifts and enhance methylmercury accumulation in estuarine biota

Terrestrial discharge can cause pelagic zone trophic shifts and enhance methylmercury accumulation in plankton three- to sixfold. 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.

Substantial emission of gaseous monomethylmercury from contaminated water-sediment microcosms.

Emission rates of gaseous monomethylmercury (CH(3)Hg(II)), as well as elemental mercury (Hg(0)) and dimethylmercury [(CH(3))(2)Hg(II)], were determined in Hg-contaminated water-sediment microcosms (duplicates of three treatments) by gaseous species-specific isotope dilution analysis (SSIDA). Incubation of approximately 500 g (wet mass) of sediments containing 30 mumol of ambient Hg with an addition of 2.6 mumol of (201)Hg(II) tracer resulted in average (n = 6) gaseous emissions of 84 +/- 26, 100 +/- 37, and 830 +/- 380 pmol of ambient CH(3)Hg(II), CH(3)(201)Hg(II), and (201)Hg(0), respectively, during 108 days of incubation. In contrast to Hg(0), a transient temporal pattern was observed for measured CH(3)Hg(II) emission rates, which peaked at day 12 and decreased to much lower levels by the end of the experiments. At day 12, CH(3)Hg(II) 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 CH(3)Hg(II) did not reflect the accumulated CH(3)Hg(II) content in the sediment, suggesting that emissions mainly originated from newly methylated Hg(II). Speciation modeling of the pore water suggests that CH(3)Hg(II) was emitted as CH(3)HgSH(0)(g).

Dimethylmercury Formation Mediated by Inorganic and Organic Reduced Sulfur Surfaces

Underlying formation pathways of dimethylmercury ((CH3)2Hg) in the ocean are unknown. Early work proposed reactions of inorganic Hg (HgII) with methyl cobalamin or of dissolved monomethylmercury (CH3Hg) with hydrogen sulfide as possible bacterial mediated or abiotic pathways. A significant fraction (up to 90%) of CH3Hg in natural waters is however adsorbed to reduced sulfur groups on mineral or organic surfaces. We show that binding of CH3Hg to such reactive sites facilitates the formation of (CH3)2Hg by degradation of the adsorbed CH3Hg. We demonstrate that the reaction can be mediated by different sulfide minerals, as well as by dithiols suggesting that e.g. reduced sulfur groups on mineral particles or on protein surfaces could mediate the reaction. The observed fraction of CH3Hg methylated on sulfide mineral surfaces exceeded previously observed methylation rates of CH3Hg to (CH3)2Hg in seawaters and we suggest the pathway demonstrated here could account for much of the (CH3)2Hg found in the ocean.

Challenges and opportunities for managing aquatic mercury pollution in altered landscapes

The environmental cycling of mercury (Hg) can be affected by natural and anthropogenic perturbations. Of particular concern is how these disruptions increase mobilization of Hg from sites and alter the formation of monomethylmercury (MeHg), a bioaccumulative form of Hg for humans and wildlife. The scientific community has made significant advances in recent years in understanding the processes contributing to the risk of MeHg in the environment. The objective of this paper is to synthesize the scientific understanding of how Hg cycling in the aquatic environment is influenced by landscape perturbations at the local scale, perturbations that include watershed loadings, deforestation, reservoir and wetland creation, rice production, urbanization, mining and industrial point source pollution, and remediation. We focus on the major challenges associated with each type of alteration, as well as management opportunities that could lessen both MeHg levels in biota and exposure to humans. For example, our understanding of approximate response times to changes in Hg inputs from various sources or landscape alterations could lead to policies that prioritize the avoidance of certain activities in the most vulnerable systems and sequestration of Hg in deep soil and sediment pools. The remediation of Hg pollution from historical mining and other industries is shifting towards in situ technologies that could be less disruptive and less costly than conventional approaches. Contemporary artisanal gold mining has well-documented impacts with respect to Hg; however, significant social and political challenges remain in implementing effective policies to minimize Hg use. Much remains to be learned as we strive towards the meaningful application of our understanding for stakeholders, including communities living near Hg-polluted sites, environmental policy makers, and scientists and engineers tasked with developing watershed management solutions. Site-specific assessments of MeHg exposure risk will require new methods to predict the impacts of anthropogenic perturbations and an understanding of the complexity of Hg cycling at the local scale.

Effects of Nutrient Loading and Mercury Chemical Speciation on the Formation and Degradation of Methylmercury in Estuarine Sediment

Net formation of methylmercury (MeHg) in sediments is known to be affected by the availability of inorganic divalent mercury (Hg(II)) and by the activities of Hg(II) 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 Hg(II) 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 Hg(II) 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 Hg(II) 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 Hg(II) chemical speciation were found to control the MeHg formation rate in marine sediments.