| 1. |
- Bouchet, Sylvain, et al.
(författare)
-
Analytical developments for the determination of monomethylmercury complexes with low molecular mass thiols by reverse phase liquid chromatography hyphenated to inductively coupled plasma mass spectrometry
- 2014
-
Ingår i: Journal of Chromatography A. - : Elsevier BV. - 0021-9673 .- 1873-3778. ; 1339, s. 50-58
-
Tidskriftsartikel (refereegranskat)abstract
- The behavior of monomethylmercury (MMHg) is markedly influenced by its distribution among complexes with low molecular mass (LMM) thiols but analytical methodologies dedicated to measure such complexes are very scarce up to date. In this work, we selected 15 LMM thiols often encountered in living organisms and/or in the environment and evaluated the separation of the 15 corresponding MMHg-thiol complexes by various high performance liquid chromatography (HPLC) columns. Two C18 (Phenomenex Synergi Hydro-RP and LunaC18(2)), two phenyl (Inertsil Ph 3 and 5 mu m) and one mixed-mode (Restek Ultra IBD) stationary phases were tested for their retention and resolution capacities of the various complexes. The objective was to find simple separation conditions with low organic contents in the mobile phase to provide optimal conditions for detection by inductively coupled plasma mass spectrometry (ICPMS). The 15 complexes were synthesized in solution and characterized by electrospray ionization-mass spectrometry (ESI-MS). The C18 columns tested were either not resolutive enough or too retentive. The 3 pm phenyl stationary phase was able to resolve 10 out of the 15 complexes in less than 25 min, under isocratic conditions. The mixed-mode column was especially effective at separating the most hydrophilic complexes (6 complexes out of the 15), corresponding to the main LMM thiols found in living organisms. The detection limits (DLs) for these two columns were in the low nanomolar range and overall slightly better for the phenyl column. The possibilities offered by such methodology were exemplified by monitoring the time-course concentrations of four MMHg-thiol complexes within a phytoplankton incubation containing MMHg in the presence of an excess of four added thiols.
|
|
| 2. |
- Bouchet, Sylvain, et al.
(författare)
-
Mercury sources and fate in a large brackish ecosystem (the Baltic Sea) depicted by stable isotopes
- 2023
-
Ingår i: Environmental Science and Technology. - : American Chemical Society (ACS). - 0013-936X .- 1520-5851. ; 57:38, s. 14340-14350
-
Tidskriftsartikel (refereegranskat)abstract
- Identifying Hg sources to aquatic ecosystems and processes controlling the levels of monomethylmercury (MMHg) is critical for developing efficient policies of Hg emissions reduction. Here we measured Hg concentrations and stable isotopes in sediment, seston, and fishes from the various basins of the Baltic Sea, a large brackish ecosystem presenting extensive gradients in salinity, redox conditions, dissolved organic matter (DOM) composition, and biological activities. We found that Hg mass dependent fractionation (Hg-MDF) values in sediments mostly reflect a mixing between light terrestrial Hg and heavier industrial sources, whereas odd Hg isotope mass independent fractionation (odd Hg-MIF) reveals atmospheric inputs. Seston presents intermediate Hg-MDF and odd Hg-MIF values falling between sediments and fish, but in northern basins, high even Hg-MIF values suggest the preferential accumulation of wet-deposited Hg. Odd Hg-MIF values in fish indicate an overall low extent of MMHg photodegradation due to limited sunlight exposure and penetration but also reveal large spatial differences. The photodegradation extent is lowest in the central basin with recurrent algal blooms due to their shading effect and is highest in the northern, least saline basin with high concentrations of terrestrial DOM. As increased loads of terrestrial DOM are expected in many coastal areas due to global changes, its impact on MMHg photodegradation needs to be better understood and accounted for when predicting future MMHg concentrations in aquatic ecosystems.
|
|
| 3. |
- Bravo, Andrea Garcia, et al.
(författare)
-
High methylmercury production under ferruginous conditions in sediments impacted by sewage treatment plant discharges
- 2015
-
Ingår i: Water Research. - : Elsevier BV. - 0043-1354 .- 1879-2448. ; 80, s. 245-255
-
Tidskriftsartikel (refereegranskat)abstract
- Sewage treatment plants (STPs) are important point sources of mercury (Hg) to the environment. STPs are also significant sources of iron when hydrated ferric oxide (HFO) is used as a dephosphatation agent during water purification. In this study, we combined geochemical and microbiological characterization with Hg speciation and sediment amendments to evaluate the impact of STP's effluents on monomethylmercury (MMHg) production. The highest in-situ Hg methylation was found close to the discharge pipe in subsurface sediments enriched with Hg, organic matter, and iron. There, ferruginous conditions were prevailing with high concentrations of dissolved Fe2+ and virtually no free sulfide in the porewater. Sediment incubations demonstrated that the high MMHg production close to the discharge was controlled by low demethylation yields. Inhibition of dissimilatory sulfate reduction with molybdate led to increased iron reduction rates and Hg-methylation, suggesting that sulfate-reducing bacteria (SRB) may not have been the main Hg methylators under these conditions. However, Hg methylation in sediments amended with amorphous Fe(III)-oxides was only slightly higher than control conditions. Thus, in addition to iron-reducing bacteria, other non-SRB most likely contributed to Hg methylation. Overall, this study highlights that sediments impacted by STP discharges can become local hot-spots for Hg methylation due to the combined inputs of i) Hg, ii) organic matter, which fuels bacterial activities and iii) iron, which keeps porewater sulfide concentration low and hence Hg bioavailable.
|
|
| 4. |
- Bravo, Andrea G., et al.
(författare)
-
Methanogens and iron-reducing bacteria : the overlooked members of mercury-methylating microbial communities in boreal lakes
- 2018
-
Ingår i: Applied and Environmental Microbiology. - : American Society for Microbiology. - 0099-2240 .- 1098-5336. ; 84:23
-
Tidskriftsartikel (refereegranskat)abstract
- 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.
|
|
| 5. |
- Bravo, Andrea Garcia, et al.
(författare)
-
Methanogens and Iron-Reducing Bacteria : the Overlooked Members of Mercury-Methylating Microbial Communities in Boreal Lakes
- 2018
-
Ingår i: Applied and Environmental Microbiology. - 0099-2240 .- 1098-5336. ; 84:23
-
Tidskriftsartikel (refereegranskat)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 di- versity of these mercury-methylating microbial communities remains largely unex- plored. Previous studies have implicated sulfate-reducing bacteria as the main mer- cury methylators in aquatic ecosystems. In the present study, we characterized the diversity of mercury-methylating microbial communities of boreal lake sediments us- ing high-throughput sequencing of 16S rRNA and hgcA genes. Our results show that in the lake sediments, Methanomicrobiales and Geobacteraceae also represent abun- dant members of the mercury-methylating communities. In fact, incubation experi- ments with a mercury isotopic tracer and molybdate revealed that only between 38% and 45% of mercury methylation was attributed to sulfate reduction. These re- sults suggest that methanogens and iron-reducing bacteria may contribute to more than half of the mercury methylation in boreal lakes.
|
|
| 6. |
- Bravo, Andrea G., et al.
(författare)
-
Molecular composition of organic matter controls methylmercury formation in boreal lakes
- 2017
-
Ingår i: Nature Communications. - : Springer Science and Business Media LLC. - 2041-1723. ; 8
-
Tidskriftsartikel (refereegranskat)abstract
- A detailed understanding of the formation of the potent neurotoxic methylmercury is needed to explain the large observed variability in methylmercury levels in aquatic systems. While it is known that organic matter interacts strongly with mercury, the role of organic matter composition in the formation of methylmercury in aquatic systems remains poorly understood. Here we show that phytoplankton-derived organic compounds enhance mercury methylation rates in boreal lake sediments through an overall increase of bacterial activity. Accordingly, in situ mercury methylation defines methylmercury levels in lake sediments strongly influenced by planktonic blooms. In contrast, sediments dominated by terrigenous organic matter inputs have far lower methylation rates but higher concentrations of methylmercury, suggesting that methylmercury was formed in the catchment and imported into lakes. Our findings demonstrate that the origin and molecular composition of organic matter are critical parameters to understand and predict methylmercury formation and accumulation in boreal lake sediments.
|
|
| 7. |
- Drott, Andreas, et al.
(författare)
-
Refining Thermodynamic Constants for Mercury(II)-Sulfides in Equilibrium with Metacinnabar at Sub-Micromolar Aqueous Sulfide Concentrations
- 2013
-
Ingår i: Environmental Science and Technology. - : American Chemical Society (ACS). - 0013-936X .- 1520-5851. ; 47:9, s. 4197-4203
-
Tidskriftsartikel (refereegranskat)abstract
- An important issue in mercury (Hg) biogeochemistry is to explore the influence of aqueous Hg(II) forms on bacterial uptake, and subsequent methyl mercury formation, under iron(III) and sulfate reducing conditions. The success of this is dependent on relevant information on the thermodynamic stability of Hg-sulfides. In the present study, we determined the solubility of a commercially available HgS(s) phase, which was shown by X-ray diffraction to be a mixture of 83% metacinnabar and 17% cinnabar. At aqueous sulfide concentrations between 0.060 and 84 µM, well below levels in previous studies, we report a solubility product (log Ksp±SE) of -36.8±0.3 (HgS(s) + H+ = Hg2+ + HS-, I=0, T=25°C, pH 6-10, n=20) for metacinnabar. This value is 0.7 log units higher than previous estimates. Complementing our data with data from Paquette and Helz (1997), we took advantage of a large data set (n=65) covering a wide range of aqueous sulfide (0.06 µM-140 mM), and pH (1-11). Based on this we report refined formation constants (±SE) for the three aqueous Hg(II)-sulfide species proposed by Schwarzenbach and Widmer (1963): Hg2+ + 2HS- = Hg(SH)20; log K = 39.1±0.1, Hg2+ + 2HS- = HgS2H- + H+; log K = 32.5±0.1, Hg2+ + 2HS- = HgS22- + 2H+; log K = 23.2±0.1. Our refined log K values differ from previous estimates by 0.2-0.6 log units. Furthermore, at the low sulfide concentrations in our study we could rule out the value of -10.0 for the reaction HgS(s) + H2O = HgOHSH(aq), as reported by Dyrssén and Wedborg (1991). By establishing a solubility product for the most environmentally relevant HgS(s) phase, metacinnabar, and extending the range of aqueous sulfide concentrations to sub-µM levels, relevant for soils, sediments and waters, this study decreases the uncertainty in stability constants for Hg-sulfides, thereby improving the basis for understanding the bioavailability and mobility of Hg(II) in the environment.
|
|
| 8. |
- Gascon Diez, Elena, et al.
(författare)
-
Role of settling particles on mercury methylation in the oxic water 1 column of freshwater systems
- 2016
-
Ingår i: Environmental Science and Technology. - : American Chemical Society (ACS). - 0013-936X .- 1520-5851. ; 50:21, s. 11672-11679
-
Tidskriftsartikel (refereegranskat)abstract
- As the methylation of inorganic divalent mercury (HgII) to neurotoxic methylmercury (MeHg) has been attributed to the activity of anaerobic bacteria, the formation of MeHg in the oxic water column of marine ecosystems has puzzled scientists over the past years. Here we show for the first time that MeHg can be produced in particles sinking through oxygenated water column of lakes. Total mercury (THg) and MeHg concentrations were measured in settling particles and in surface sediments of the largest freshwater lake in Western Europe (Lake Geneva). Whilst THg concentration differences between sediments and settling particles were not significant, MeHg concentrations were up to ten-fold greater in settling particles. MeHg demethylation rate constants (kd) were of similar magnitude in both compartments. In contrast, Hg methylation rate constants (km) were one order of magnitude greater in settling particles. The net potential for MeHg formation, assessed by the ratio between the two rate constants (km kd-1), was therefore up to ten times higher in settling particles, denoting that in situ transformations likely contributed to the high MeHg concentrations found in settling particles. Hg methylation was inhibited ( 80 %) in settling particles amended with molybdate, demonstrating the prominent role of biological sulfate-reduction in the process.
|
|
| 9. |
- Höög, Johanna L, 1979, et al.
(författare)
-
3D Architecture of the Trypanosoma brucei Flagella Connector, a Mobile Transmembrane Junction : Electron Tomography of the Flagella Connector
- 2016
-
Ingår i: PLoS Neglected Tropical Diseases. - : Public Library of Science (PLoS). - 1935-2727 .- 1935-2735. ; 10:1
-
Tidskriftsartikel (refereegranskat)abstract
- Background Cellular junctions are crucial for the formation of multicellular organisms, where they anchor cells to each other and/or supportive tissue and enable cell-to-cell communication. Some unicellular organisms, such as the parasitic protist Trypanosoma brucei, also have complex cellular junctions. The flagella connector (FC) is a three-layered transmembrane junction that moves with the growing tip of a new flagellum and attaches it to the side of the old flagellum. The FC moves via an unknown molecular mechanism, independent of new flagellum growth. Here we describe the detailed 3D architecture of the FC suggesting explanations for how it functions and its mechanism of motility. Methodology/Principal Findings We have used a combination of electron tomography and cryo-electron tomography to reveal the 3D architecture of the FC. Cryo-electron tomography revealed layers of repetitive filamentous electron densities between the two flagella in the interstitial zone. Though the FC does not change in length and width during the growth of the new flagellum, the interstitial zone thickness decreases as the FC matures. This investigation also shows interactions between the FC layers and the axonemes of the new and old flagellum, sufficiently strong to displace the axoneme in the old flagellum. We describe a novel filament, the flagella connector fibre, found between the FC and the axoneme in the old flagellum. Conclusions/Significance The FC is similar to other cellular junctions in that filamentous proteins bridge the extracellular space and are anchored to underlying cytoskeletal structures; however, it is built between different portions of the same cell and is unique because of its intrinsic motility. The detailed description of its structure will be an important tool to use in attributing structure / function relationships as its molecular components are discovered in the future. The FC is involved in the inheritance of cell shape, which is important for the life cycle of this human parasite.
|
|
| 10. |
- Isidorova, Anastasija, et al.
(författare)
-
The effect of lake browning and respiration mode on the burial and fate of carbon and mercury in the sediment of two boreal lakes
- 2016
-
Ingår i: Journal of Geophysical Research - Biogeosciences. - 2169-8953 .- 2169-8961. ; 121:1, s. 233-245
-
Tidskriftsartikel (refereegranskat)abstract
- In many northern temperate regions, the water color of lakes has increased over the past decades (lake browning), probably caused by an increased export of dissolved organic matter from soils. We investigated if the increase in water color in two lakes in Norway has resulted in increased burial of organic carbon (OC) and mercury (Hg) in the sediments and if the Hg was prone to methylation. Lake Solbergvann experienced a threefold water color increase, and OC burial increased approximately twofold concomitant to the water color increase. This lake had prolonged periods of anoxic bottom water, and anoxic OC mineralization rates were only about half of the oxic OC mineralization rates (7.7 and 17.5g C m(-2)yr(-1), respectively), contributing to an efficient OC burial. In Lake Elvaga, where water color increase was only approximately twofold and bottom water was oxygenated, no recent increase in OC burial could be observed. Hg burial increased strongly in both lakes (threefold and 1.6-fold in Lake Solbergvann and Lake Elvaga, respectively), again concomitant to the recent water color increase. The proportion of methylated Hg (MeHg) in surficial sediment was 1 order of magnitude higher in Lake Elvaga (up to 6% MeHg) than in Lake Solbergvann (0.2-0.6% MeHg), probably related to the different oxygenation regimes. We conclude that lake browning can result in increased OC and Hg burial in lake sediments, but the extent of browning and the dominating mode of sediment respiration (aerobic or anaerobic) strongly affect burial and fate of OC and Hg in sediments.
|
|
