We present a sensitive, selective and robust method for the determination of 14 thiol compounds in aqueous samples. Thiols were derivatized with omega-bromoacetonylquinolinium bromide (BQB) and its deuterium labeled equivalent D7-ω-bromoacetonylquinolinium bromide (D7). Derivatized thiols were preconcentrated by online solid-phase extraction (SPE) followed by liquid chromatography separation and electrospray ionization tandem mass spectrometry determination (SPE/LC-ESI-MS/MS). The robustness of the method was validated for wide ranges in pH, salinity, and concentrations of sulfide and dissolved organic carbon (DOC) to cover contrasting natural water types. The limits of detection (LODs) for the thiols were 3.1-66 pM. Between 6 and 14 of the thiols were detected in different natural sample types at variable concentrations: boreal wetland porewater (0.7-51 nM), estuarine sediment porewater (50 pM-11 nM), coastal sea water (60 pM-16 nM), and sulfate reducing bacterium cultures (80 pM-4 nM). MS/MS fragmentation of the compounds produces two pairs of common product ions, m/z 130.2/137.1 and 218.1/225.1, which enables scanning for unknown thiols in precursor ion scan mode. Using this approach, we identified cysteine, mercaptoacetic acid, N-acetyl-L-cysteine and sulfurothioic S-acid in boreal wetland porewater. The performance of the developed method sets a new state of the art for the determination of thiol compounds in environmental and biological samples.

The formation of the potent neurotoxic methylmercury (MeHg) is a microbially mediated process that has raised much concern because MeHg poses threats to wildlife and human health. Since boreal forest soils can be a source of MeHg in aquatic networks, it is crucial to understand the biogeochemical processes involved in the formation of this pollutant. High-throughput sequencing of 16S rRNA and the mercury methyltransferase, hgcA, combined with geochemical characterisation of soils, were used to determine the microbial populations contributing to MeHg formation in forest soils across Sweden. The hgcA sequences obtained were distributed among diverse clades, including Proteobacteria, Firmicutes, and Methanomicrobia, with Deltaproteobacteria, particularly Geobacteraceae, dominating the libraries across all soils examined. Our results also suggest that MeHg formation is also linked to the composition of non-mercury methylating bacterial communities, likely providing growth substrate (e.g. acetate) for the hgcA-carrying microorganisms responsible for the actual methylation process. While previous research focused on mercury methylating microbial communities of wetlands, this study provides some first insights into the diversity of mercury methylating microorganisms in boreal forest soils.

Oxygen-depleted areas are spreading in coastal and offshore waters worldwide, but the implication for production and bioaccumulation of neurotoxic methylmercury (MeHg) is uncertain. We combined observations from six cruises in the Baltic Sea with speciation modeling and incubation experiments to gain insights into mercury (Hg) dynamics in oxygen depleted systems. We then developed a conceptual model describing the main drivers of Hg speciation, fluxes, and transformations in water columns with steep redox gradients. MeHg concentrations were 2-6 and 30-55 times higher in hypoxic and anoxic than in normoxic water, respectively, while only 1-3 and 1-2 times higher for total Hg (THg). We systematically detected divalent inorganic Hg (Hg-II) methylation in anoxic water but rarely in other waters. In anoxic water, high concentrations of dissolved sulfide cause formation of dissolved species of Hg-II: HgS2H(aq)- and Hg (SH)(2)(0)((aq)). This prolongs the lifetime and increases the reservoir of Hg-II readily available for methylation, driving the high MeHg concentrations in anoxic zones. In the hypoxic zone and at the hypoxic-anoxic interface, Hg concentrations, partitioning, and speciation are all highly dynamic due to processes linked to the iron and sulfur cycles. This causes a large variability in bioavailability of Hg, and thereby MeHg concentrations, in these zones. We find that zooplankton in the summertime are exposed to 2-6 times higher MeHg concentrations in hypoxic than in normoxic water. The current spread of hypoxic zones in coastal systems worldwide could thus cause an increase in the MeHg exposure of food webs.

Earlier studies have shown that boreal forest logging can increase the concentration and export of methylmercury (MeHg) in stream runoff. Here we test whether forestry operations create soil environments of high MeHg net formation associated with distinct microbial communities. Furthermore, we test the hypothesis that Hg methylation hotspots are more prone to form after stump harvest than stem-only harvest, because of more severe soil compaction and soil disturbance. Concentrations of MeHg, percent MeHg of total Hg (THg), and bacterial community composition were determined at 200 soil sampling positions distributed across eight catchments. Each catchment was either stem-only harvested (n = 3), stem-and stump-harvested (n = 2) or left undisturbed (n = 3). In support of our hypothesis, higher MeHg to THg ratios was observed in one of the stump-harvested catchments. While the effects of natural variation could not be ruled out, we noted that most of the highest % MeHg was observed in water-filled cavities created by stump removal or driving damage. This catchment also featured the highest bacterial diversity and highest relative abundance of bacterial families known to include Hg methylators. We propose that water-logged and disturbed soil environments associated with stump harvest can favor methylating microorganisms, which also enhance MeHg formation. 

Neurotoxic methylmercury causes adverse effects to ecosystem viability and human health. Previous studies have revealed that ponding alters natural organic matter (NOM) composition and increase methylmercury concentrations in rivers, especially in the first years after flooding. Here, we investigate the influence of NOM composition (i.e., sources and degradation status) on mercury methylation rate constants in nine boreal beaver ponds of different ages across Sweden. We show that increased methylmercury concentrations in surface waters is a consequence of enhanced mercury methylation in the pond sediments. Moreover, our results reveal that during the first years after the initial flooding, mercury methylation rates are fueled by the amount of fresh humic substances released from the flooded soils and by an increased production of algal-derived NOM triggered by enhanced nutrient availability. Our findings indicate that impoundment-induced changes in NOM composition control mercury methylation processes, causing the raise in MeHg levels in ponds.

Stable and efficient oxygen evolution reaction (OER) catalysts for the oxidation of water to dioxygen in highly acidic media are currently limited to expensive noble metal (Ir and Ru) oxides since presently known OER catalysts made of inexpensive earth-abundant materials generally suffer anodic corrosion at low pH. In this study, we report that a mixed-polymorph film comprising maghemite and hematite, prepared using spray pyrolysis deposition followed by low-temperature annealing, showed a sustained OER rate (>24 h) corresponding to a current density of 10 mA cm−2 at an initial overpotential of 650 mV, with a Tafel slope of only 56 mV dec−1 and near-100% Faradaic efficiency in 0.5 M H2SO4 (pH 0.3). This performance is remarkable, since iron (III) oxide films comprising only maghemite were found to exhibit a comparable intrinsic activity, but considerably lower stability for OER, while films of pure hematite were OER-inactive. These results are explained by the differences in the polymorph crystal structures, which cause different electrical conductivity and surface interactions with water molecules and protons. Our findings not only reveal the potential of iron (III) oxide as acid-stable OER catalyst, but also highlight the important yet hitherto largely unexplored effect of crystal polymorphism on electrocatalytic OER performance.

The origin and composition of dissolved organic matter (DOM) in porewater of lake sediments is intricate and decisive for fate of pollutants including mercury (Hg). While there are many reports on the relationship between dissolved organic carbon concentration (DOC) and mercury (Hg) concentrations in aquatic systems, there are few in which DOM compositional properties, that may better explain the fate of Hg, have been the focus. In this study, porewaters from sediments of three lakes, Caihai Lake (CH), Hongfeng Lake (HF) and Wujiangdu Lake (WJD), all located in southwest China, were selected to test the hypothesis that DOM optical properties control the fate of Hg in aquatic ecosystems. Porewater DOM was extracted and characterized by UV-Vis absorption and fluorescence spectroscopy. A two end-member (autochthonous and allochthonous DOM) mixing model was used to unveil the origin of DOM in porewaters of the three lakes. Our results show a higher input of terrestrial DOM in the pristine lake CH, as compared to lakes HF and WJD lakes, which were both influenced by urban environments and enriched in autochthonous DOM. While the relationships between the concentrations of DOC and the different chemical forms of Hg forms were quite inconsistent, we found important links between specific DOM components and the fate of Hg in the three lakes. In particular, our results suggest that allochthonous, terrestrial DOM inhibits Hg(II) availability for Hg methylating micro-organisms. In contrast, autochthonous DOM seems to have been stimulated MeHg formation, likely by enhancing the activity of microbial communities. Indeed, DOM biodegradation experiments revealed that differences in the microbial activity could explain the variation in the concentration of MeHg. While relationships between concentrations of DOC and Hg vary among different sites and provide little information about Hg cycling, we conclude that the transport and transformation of Hg (e.g. the methylation process) are more strongly linked to DOM chemical composition and reactivity.

Wetlands are common net producers of the neurotoxin monomethylmercury (MeHg) and are largely responsible for MeHg bioaccumulation in aquatic food-webs. However, not all wetlands net produce MeHg; notable exceptions are black alder (Alnus glutinosa) swamps, which net degrade MeHg. Here we report the mechanisms of MeHg demethylation in one such swamp (EHT), shown to be a sink for MeHg during four consecutive years. The potential demethylation rate constant (k(d) ) in soil incubations was similar to 3 times higher in the downstream (EHT-D: k(d) similar to 0.14 d(-1)) as compared to the upstream part of the swamp (EHT-U: k(d) 0.05 d(-1)). This difference concurred with increased stream and soil pH, and a change in plant community composition. Electron acceptor and inhibitor addition experiments revealed that abiotic demethylation dominated at EHT-U while an additional and equally large contribution from biotic degradation was observed at EHT-D, explaining the increase in MeHg degradation. Biotic demethylation (EHT-D) was primarily due to methanogens, inferred by a decrease in k(d) to autoclaved levels following selective inhibition of methanogens. Though methanogen-specific transcripts (mcrA) were found throughout the wetland, transcripts clustering with Methanosaetaceae were exclusive to EHT-D, suggesting a possible role for these acetoclastic methanogens in the degradation of MeHg.

Mercury (Hg) contaminated sediments can be significant sources of Hg in aquatic ecosystems and, through re-emission processes, to the atmosphere. Transformation and release of Hg may be enhanced by various sediment perturbation processes, and controlling biogeochemical factors largely remain unclear. We investigated how rates of Hg transformations in pulp-fiber enriched sediment contaminated by Hg from chlor-alkali industry were controlled by (i) transient redox-changes in sulfur and iron chemistry, (ii) the chemical speciation and solubility of Hg, and (iii) the sources and characteristics of organic matter (OM). Sediment-bottom water microcosm systems were exposed to four combinations of air and nitrogen gas for a total time of 24 h. The treatments were: 24 h N-2, 0.5 h air + 23.5 h N-2, 4 h air + 20 h N-2 and 24 h of air exposure. As a result of these treatments, microcosms spanned a wide range of redox potential, as reflected by the dissolved sulfide concentration range of <= 0.3-97 mu M. Four different chemical species of inorganic divalent Hg (Hg-II) and methyl mercury (MeHg), enriched in different Hg isotope tracers, were added to the microcosms: 201 Hg(NO3)(2)(aq), Hg-202(II) adsorbed to OM (Hg-202(II)-OM(ads)), Hg-198(II) as microcrystalline metacinnabar (beta-(HgS)-Hg-198(s)) and (MeHgCl)-Hg-204(aq). Microcosm systems were composed of bottom water mixed with sediment taken at 0-2, 0-5 and 0-10 cm depth intervals. The composition of OM varied with sediment depth such that compared to deeper sediment, the 0-2 cm depth-interval had a 2-fold higher contribution of labile OM originating from algal and terrestrial inputs, serving as metabolic electron-donors for microorganisms. The potential methylation rate constant (k(meth)) of Hg tracers and net formation of ambient MeHg (MeHg/THg molar ratio) increased up to 50% and 400%, respectively at intermediate oxidative conditions, likely because of an observed 2-fold increase in sulfate concentration stimulating the activity of sulfate reducing bacteria with a capability of methylating Hg-II. Due to differences in Hg-II water-sediment partitioning, k(meth) varied by a factor of 11-70 for the different isotope-enriched Hg tracers. The chemical form of Hg-II was a major controlling factor for k(meth) and its response to the resuspension-oxidation of the system. The beta-(HgS)-Hg-198(s) tracer had the lowest k(meth) and it was mainly constrained by redox-driven Hg-II solubility. The Hg-202(II)-OM(ads) tracer showed an intermediate value on k(meth). It was controlled by both Hg-II solubility and availability of electron donors and acceptors, regulating bacterial activity. The Hg-201(NO3)(2)(aq) tracer had the highest value on k(meth) which was limited mainly by bacterial activity. The k(meth) was up to a factor of 3 higher in the 0-2 cm sediment depth-interval than in 0-5 and 0-10 cm intervals due to a larger contribution of labile OM in the 0-2 cm sediment. Reduction of Hg-II to Hg-0 followed by volatilization exclusively occurred at high sulfidic conditions in the top 0-2 cm sediment. Aromatic moieties of terrestrial OM, present mainly in the top sediment, is suggested to control the reduction of Hg-II. The Hg-0 volatilization rate constant for the Hg-202(II)-OM (ads) tracer exceeded that for beta-(HgS)-Hg-198(s) by one order of magnitude. Our results suggest that contaminated sediments posing a high risk for reactivation of legacy Hg following transient redox resuspension events are characterized by depletion of sulfate in the sediment porewater prior to resuspension, predominance of Hg-II species with solubility exceeding that of crystalline beta-HgS(s), and conditions promoting in situ formation and/ or import of labile OM from algal and terrestrial sources.

ABSTRACT: Methylmercury is a potent human neurotoxin which biomagnifies in aquatic food webs. Although anaerobic microorganisms containing the hgcA gene potentially mediate the formation of methylmercury in natural environments, the diversity of these mercury-methylating microbial communities remains largely unexplored. Previous studies have implicated sulfate-reducing bacteria as the main mercury methylators in aquatic ecosystems. In the present study, we characterized the diversity of mercury-methylating microbial communities of boreal lake sediments using high-throughput sequencing of 16S rRNA and hgcA genes. Our results show that in the lake sediments, Methanomicrobiales and Geobacteraceae also represent abundant members of the mercury-methylating communities. In fact, incubation experiments with a mercury isotopic tracer and molybdate revealed that only between 38% and 45% of mercury methylation was attributed to sulfate reduction. These results suggest that methanogens and iron-reducing bacteria may contribute to more than half of the mercury methylation in boreal lakes.

IMPORTANCE: Despite the global awareness that mercury, and methylmercury in particular, is a neurotoxin to which millions of people continue to be exposed, there are sizable gaps in the understanding of the processes and organisms involved in methylmercury formation in aquatic ecosystems. In the present study, we shed light on the diversity of the microorganisms responsible for methylmercury formation in boreal lake sediments. All the microorganisms identified are associated with the processing of organic matter in aquatic systems. Moreover, our results show that the well-known mercury-methylating sulfate-reducing bacteria constituted only a minor portion of the potential mercury methylators. In contrast, methanogens and iron-reducing bacteria were important contributors to methylmercury formation, highlighting their role in mercury cycling in the environment.