The Combined Effect of Hg(II) Speciation, Thiol Metabolism, and Cell Physiology on Methylmercury Formation by Geobacter sulfurreducens

The chemical and biological factors controlling microbial formation of methylmercury (MeHg) are widely studied separately, but the combined effects of these factors are largely unknown. We examined how the chemical speciation of divalent, inorganic mercury (Hg(II)), as controlled by low-molecular-mass thiols, and cell physiology govern MeHg formation by Geobacter sulfurreducens. We compared MeHg formation with and without addition of exogenous cysteine (Cys) to experimental assays with varying nutrient and bacterial metabolite concentrations. Cysteine additions initially (0-2 h) enhanced MeHg formation by two mechanisms: (i) altering the Hg(II) partitioning from the cellular to the dissolved phase and/or (ii) shifting the chemical speciation of dissolved Hg(II) in favor of the Hg(Cys)2 complex. Nutrient additions increased MeHg formation by enhancing cell metabolism. These two effects were, however, not additive since cysteine was largely metabolized to penicillamine (PEN) over time at a rate that increased with nutrient addition. These processes shifted the speciation of dissolved Hg(II) from complexes with relatively high availability, Hg(Cys)2, to complexes with lower availability, Hg(PEN)2, for methylation. This thiol conversion by the cells thereby contributed to stalled MeHg formation after 2-6 h Hg(II) exposure. Overall, our results showed a complex influence of thiol metabolism on microbial MeHg formation and suggest that the conversion of cysteine to penicillamine may partly suppress MeHg formation in cysteine-rich environments like natural biofilms

Sulfide in engineered methanogenic systems - Friend or foe?

Sulfide ions are regarded to be toxic to microorganisms in engineered methanogenic systems (EMS), where organic substances are anaerobically converted to products such as methane, hydrogen, alcohols, and carboxylic acids. A vast body of research has addressed solutions to mitigate process disturbances associated with high sulfide levels, yet the established paradigm has drawn the attention away from the multifaceted sulfide interactions with minerals, organics, microbial interfaces and their implications for performance of EMS. This brief review brings forward sulfide-derived pathways other than toxicity and with potential significance for anaerobic organic matter degradation. Available evidence on sulfide reactions with organic matter, interventions with key microbial metabolisms, and interspecies electron transfer are critically synthesized as a guidance for comprehending the sulfide effects on EMS apart from the microbial toxicity. The outcomes identify existing knowledge gaps and specify future research needs as a step forward towards realizing the potential of sulfide-derived mechanisms in diversifying and optimizing EMS applications

Mercury deposition and redox transformation processes in peatland constrained by mercury stable isotopes

Peatland vegetation takes up mercury (Hg) from the atmosphere, typically contributing to net production and export of neurotoxic methyl-Hg to downstream ecosystems. Chemical reduction processes can slow down methyl-Hg production by releasing Hg from peat back to the atmosphere. The extent of these processes remains, however, unclear. Here we present results from a comprehensive study covering concentrations and isotopic signatures of Hg in an open boreal peatland system to identify post-depositional Hg redox transformation processes. Isotope mass balances suggest photoreduction of HgII is the predominant process by which 30% of annually deposited Hg is emitted back to the atmosphere. Isotopic analyses indicate that above the water table, dark abiotic oxidation decreases peat soil gaseous Hg0 concentrations. Below the water table, supersaturation of gaseous Hg is likely created more by direct photoreduction of rainfall rather than by reduction and release of Hg from the peat soil. Identification and quantification of these light-driven and dark redox processes advance our understanding of the fate of Hg in peatlands, including the potential for mobilization and methylation of HgII.Mercury isotope signatures in groundwater, soil gas, solid peat, and atmosphere suggest that dark abiotic reduction of peat soil HgII to volatile Hg0 does not play a significant role in mobilizing Hg during peat mass los

Formation and mobilization of methylmercury across natural and experimental sulfur deposition gradients

We investigated the influence of sulfate (SO42-) 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 SO42- 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 SO42- in the experimental field study. The combined results from the experimental field study and deposition gradient accentuate the multiple, distinct and interacting roles of SO42- deposition in the formation and redistribution of MeHg in the environment. (c) 2020 The Authors. Published by Elsevier Ltd. This is an open access article under the CC BY-NC-ND license (http://creativecommons.org/licenses/by-nc-nd/4.0/)

Microbial communities mediating net methylmercury formation along a trophic gradient in a peatland chronosequence

Peatlands are generally important sources of methylmercury (MeHg) to adjacent aquatic ecosystems, increasing the risk of human and wildlife exposure to this highly toxic compound. While microorganisms play important roles in mercury (Hg) geochemical cycles where they directly and indirectly affect MeHg formation in peatlands, potential linkages between net MeHg formation and microbial communities involving these microorganisms remain unclear. To address this gap, microbial community composition and specific marker gene transcripts were investigated along a trophic gradient in a geographically constrained peatland chronosequence. Our results showed a clear spatial pattern in microbial community composition along the gradient that was highly driven by peat soil properties and significantly associated with net MeHg formation as approximated by MeHg concentration and %MeHg of total Hg concentration. Known fermentative, syntrophic, methanogenic and iron-reducing metabolic guilds had the strong positive correlations to net MeHg formation, while methanotrophic and methylotrophic microorganisms were negatively correlated. Our results indicated that sulfate reducers did not have a key role in net MeHg formation. Microbial activity as interpreted from 16S rRNA sequences was significantly correlated with MeHg and %MeHg. Our findings shed new light on the role of microbial community in net MeHg formation of peatlands that undergo ontogenetic change

Source tracing of natural organic matter bound mercury in boreal forest runoff with mercury stable isotopes

Terrestrial runoff represents a major source of mercury (Hg) to aquatic ecosystems. In boreal forest catchments, such as the one in northern Sweden studied here, mercury bound to natural organic matter (NOM) represents a large fraction of mercury in the runoff. We present a method to measure Hg stable isotope signatures of colloidal Hg, mainly complexed by high molecular weight or colloidal natural organic matter (NOM) in natural waters based on pre-enrichment by ultrafiltration, followed by freeze-drying and combustion. We report that Hg associated with high molecular weight NOM in the boreal forest runoff has very similar Hg isotope signatures as compared to the organic soil horizons of the catchment area. The mass-independent fractionation (MIF) signatures (Δ; 199; Hg and Δ; 200; Hg) measured in soils and runoff were in agreement with typical values reported for atmospheric gaseous elemental mercury (Hg; 0; ) and distinctly different from reported Hg isotope signatures in precipitation. We therefore suggest that most Hg in the boreal terrestrial ecosystem originated from the deposition of Hg; 0; through foliar uptake rather than precipitation. Using a mixing model we calculated the contribution of soil horizons to the Hg in the runoff. At moderate to high flow runoff conditions, that prevailed during sampling, the uppermost part of the organic horizon (Oe/He) contributed 50-70% of the Hg in the runoff, while the underlying more humified organic Oa/Ha and the mineral soil horizons displayed a lower mobility of Hg. The good agreement of the Hg isotope results with other source tracing approaches using radiocarbon signatures and Hg : C ratios provides additional support for the strong coupling between Hg and NOM. The exploratory results from this study illustrate the potential of Hg stable isotopes to trace the source of Hg from atmospheric deposition through the terrestrial ecosystem to soil runoff, and provide a basis for more in-depth studies investigating the mobility of Hg in terrestrial ecosystems using Hg isotope signatures

Shifts in mercury methylation across a peatland chronosequence: From sulfate reduction to methanogenesis and syntrophy

Peatlands are globally important ecosystems where inorganic mercury is converted to bioaccumulating and highly toxic methylmercury, resulting in high risks of methylmercury exposure in adjacent aquatic ecosystems. Although biological mercury methylation has been known for decades, there is still a lack of knowledge about the organisms involved in mercury methylation and the drivers controlling their methylating capacity. In order to investigate the metabolisms responsible for mercury methylation and methylmercury degradation as well as the controls of both processes, we studied a chronosequence of boreal peatlands covering fundamentally different biogeochemical conditions. Potential mercury methylation rates decreased with peatland age, being up to 53 times higher in the youngest peatland compared to the oldest. Methylation in young mires was driven by sulfate reduction, while methanogenic and syntrophic metabolisms became more important in older systems. Demethylation rates were also highest in young wetlands, with a gradual shift from biotic to abiotic methylmercury degradation along the chronosequence. Our findings reveal how metabolic shifts drive mercury methylation and its ratio to demethylation as peatlands age

Biogeochemical influences on net methylmercury formation proxies along a peatland chronosequence

A geographically constrained chronosequence of peatlands divided into three age classes (young, intermediate and old) was used to explore the role of biogeochemical influences, including electron donors and acceptors as well as chemical speciation of inorganic mercury (Hg(II)), on net formation of methylmercury (MeHg) as approximated by the fraction of MeHg to total mercury (THg) in the peat soil. We hypothesized that removing vascular plants would reduce availability of electron donors and thus net MeHg formation. However, we found no effect of the vascular plant removal. The sum of the potential electron donors (acetate, lactate, propionate and oxalate), the electron donation proxy organic C/Organic N, and the potential electron acceptors (Fe(III), Mn and sulfate) in porewater all showed significant correlations with the net MeHg formation proxies in peat soil (MeHg concentration and %MeHg of THg). Thus differences in both electron donor and acceptor availability may be contributing to the pattern of net MeHg formation along the chronosequence. In contrast, Hg(II) concentrations in peat porewater showed small differences along the gradient. A chemical speciation model successfully predicted the solubility of Hg and MeHg in the porewater. The modeling pointed to an enhanced concentration of Hg-polysulfide species in the younger peatlands as a potential factor behind increased Hg(II) solubility and methylation in the more nutrient-rich peatlands. This work contributes to the understanding of Hg and MeHg cycling in peatlands which can help guide mitigation measures to reduce aquatic MeHg biomagnification in peatland dominated landscapes. (C) 2021 The Authors. Published by Elsevier Ltd