| 1. |
- Adediran, Gbotemi A., et al.
(författare)
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Microbial Biosynthesis of Thiol Compounds : Implications for Speciation, Cellular Uptake, and Methylation of Hg(II)
- 2019
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Ingår i: Environmental Science and Technology. - : American Chemical Society (ACS). - 0013-936X .- 1520-5851. ; 53:14, s. 8187-8196
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Tidskriftsartikel (refereegranskat)abstract
- Cellular uptake of inorganic divalent mercury (Hg(II)) is a key step in microbial formation of neurotoxic methylmercury (MeHg), but the mechanisms remain largely unidentified. We show that the iron reducing bacterium Geobacter sulfurreducens produces and exports appreciable amounts of low molecular mass thiol (LMM-RSH) compounds reaching concentrations of about 100 nM in the assay medium. These compounds largely control the chemical speciation and bioavailability of Hg(II) by the formation of Hg(LMM-RS)2 complexes (primarily with cysteine) in assays without added thiols. By characterizing these effects, we show that the thermodynamic stability of Hg(II)-complexes is a principal controlling factor for Hg(II) methylation by this bacterium such that less stable complexes with mixed ligation involving LMM-RSH, OH-, and Cl- are methylated at higher rates than the more stable Hg(LMM-RS)2 complexes. The Hg(II) methylation rate across different Hg(LMM-RS)2 compounds is also influenced by the chemical structure of the complexes. In contrast to the current perception of microbial uptake of Hg, our results adhere to generalized theories for metal biouptake based on metal complexation with cell surface ligands and refine the mechanistic understanding of Hg(II) availability for microbial methylation.
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| 2. |
- Bergknut, Magnus, et al.
(författare)
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Molecular characterization of brominated persistent pollutants using extended X-ray absorption fine structure (EXAFS) spectroscopy
- 2008
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Ingår i: Analytical and Bioanalytical Chemistry. - : Springer. - 1618-2642 .- 1618-2650. ; 390:3, s. 921-928
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Tidskriftsartikel (refereegranskat)abstract
- X-ray absorption fine structure (EXAFS) spectroscopy spectra were collected for three brominated persistent pollutants: 6-bromo-2,4,5-trichlorophenol (BrTriClP), pentabromophenol (PentaBrP) and 3,3',5,5'-tetrabromobisphenol A (TBBA). The substances were selected to be symmetrical (BrTriClP and TBBA) or asymmetrical (PentaBrP) with respect to the atomic Br positions and to differ in the number of bromine and other halide atoms, as well as their relative positions. The asymmetrical PentaBrP was modelled with special detail as not all bromine atoms have identical coordination environments. The studied substances displayed unique EXAFS spectra, which could be used to determine the molecular structure in fair detail. We conclude that EXAFS spectroscopy is a suitable technique for molecular characterization of the comparatively complex molecules within the class of compounds of brominated organic persistent pollutants. A detailed understanding of the EXAFS spectra of the pure compounds opens up possibilities to study the interactions with soil and sediment matrices by means of EXAFS spectroscopy. Figure Brominated organic persistent pollutants are characterized by EXAFS spectroscopy.
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| 3. |
- Bishop, Kevin, et al.
(författare)
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The Effects of Forestry on Hg Bioaccumulation in Nemoral/Boreal Waters and Recommendations for Good Silvicultural Practice
- 2009
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Ingår i: Ambio. - : Royal Swedish Academy of Sciences. - 0044-7447 .- 1654-7209. ; 38:7, s. 373-380
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Tidskriftsartikel (refereegranskat)abstract
- Mercury (Hg) levels are alarmingly high in fish from lakes across Fennoscandia and northern North America. The few published studies on the ways in which silviculture practices influence this problem indicate that forest operations increase Hg in downstream aquatic ecosystems. From these studies, we estimate that between one-tenth and one-quarter of the Hg in the fish of high-latitude, managed forest landscapes can be attributed to harvesting. Forestry, however, did not create the elevated Hg levels in the soils, and waterborne Hg/MeHg concentrations downstream from harvested areas are similar to those from wetlands. Given the current understanding of the way in which silviculture impacts Hg cycling, most of the recommendations for good forest practice in Sweden appear to be appropriate for high-latitude regions, e.g., leaving riparian buffer zones, as well as reducing disturbance at stream crossings and in moist areas. The recommendation to restore wetlands and reduce drainage, however, will likely increase Hg/MeHg loadings to aquatic ecosystems
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| 4. |
- Björn, Erik, et al.
(författare)
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Recent Advances in Mercury Speciation Analysis with Focus on Spectrometric Methods and Enriched Stable Isotope Applications
- 2007
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Ingår i: Ambio. - 0044-7447 .- 1654-7209. ; 36:6, s. 443–51-
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Tidskriftsartikel (refereegranskat)abstract
- This paper discusses some recent advances in spectrometric methods and approaches for mercury speciation analysis of environmental samples with focus on isotope dilution techniques for determination of mercury species' concentrations in gaseous samples and reaction rates in soils and sediments. Such analytical data is important inter alia in fundamental research on mercury biogeochemistry and for risk assessments of mercury-contaminated soils and sediments and for designing effective remedial actions. The paper describes how the use of enriched stable isotope tracers in mercury speciation analysis can improve the traceability and accuracy of results, facilitate rational method developments, and be useful for studying biogeochemical processes, i.e. rate of reactions and fluxes, of mercury species. In particular the possibilities to study and correct for unwanted species transformation reactions during sample treatment and to study “natural” transformations of species in environmental samples, or micro- and mesocosm ecosystems, during incubations are highlighted. Important considerations to generate relevant data in isotope tracer experiments as well as reliability and quality assurance of mercury speciation analysis in general are also discussed.
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| 5. |
- Clarholm, Marianne, et al.
(författare)
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Organic acid induced release of nutrients from metal-stabilized soil organic matter - The unbutton model
- 2015
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Ingår i: Soil Biology and Biochemistry. - : Elsevier BV. - 0038-0717 .- 1879-3428. ; 84, s. 168-176
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Forskningsöversikt (refereegranskat)abstract
- Processes of soil organic matter (SOM) stabilization and the reverse, destabilization of SOM resulting in subsequent release and mobilization of nutrients from SOM, remain largely unresolved. The perception of SOM as supramolecular aggregates built of low molecular mass biomolecules is currently emerging. Polyvalent metal cations contribute to SOM tertiary structure by bridging functional groups of such molecules (Simpson et al., 2002). The strong bond to metals protects high quality organic material from being immediately accessed and decomposed. Here we propose a three-step process by which low molecular mass organic acids (LMMOAs) and hydrolytic enzymes act in series to destabilize SOM supramolecules to release organic nitrogen (N) and phosphorus (P) for local hyphal and root uptake. Complexation of the stabilizing metals by fungal-released LMMOA gives fungal-root consortia direct access to organic substrates of good quality. Because of their small sizes and carboxyl group configuration, citric and oxalic acids are the most effective LMMOAs forming stable complexes with the main SOM bridging metals Ca and Al in SOM. Citrate, forming particularly strong complexes with the trivalent cations Al and Fe, is dominant in soil solutions of low-productive highly acidic boreal forest soils where mycorrhizal associations with roots are formed predominantly by fungi with hydrophobic hyphal surfaces. In these systems mycelia participate in the formation of N-containing SOM with a significant contribution from strong Al bridges. In less acidic soils of temperate forests, including calcareous influenced soils, SOM is stabilized predominantly by Ca bridges. In such systems mycorrhizal fungi with more hydrophilic surfaces dominate, and oxalic acid, forming strong bidentate complexes with Ca, is the most common LMMOA exuded. A plant-fungus driven biotic mechanism at the supramolecular aggregate level (10(3)-10(5) Da) resolves micro-spatial priming of SOM, where the destabilization step is prerequisite for subsequent release of nutrients. (C) 2015 Elsevier Ltd. All rights reserved.
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| 6. |
- Clarholm, Marianne, et al.
(författare)
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Translocation of metals by trees and fungi regulates pH, soil organic matter turnover and nitrogen availability in acidic forest soils
- 2013
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Ingår i: Soil Biology and Biochemistry. - : Elsevier BV. - 0038-0717 .- 1879-3428. ; 63, s. 142-153
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Forskningsöversikt (refereegranskat)abstract
- In this paper we provide support for the hypothesis that trees and fungi modify their physical environment in acidic forest soils by actively translocating metal cations from the mineral to the organic horizon. We suggest that pH buffering and soil organic matter (SOM) turnover in organic horizons are regulated by Ca and Mg cycling via the tree canopy and litter fall and by fungal translocation of Al from mineral soil. Fungi in addition translocate Fe from mineral to organic horizons to enhance the degradation of aromatic structures in SOM. Together these processes are in control of N bioavailability, including new inputs via N fixation. Cycling of Ca and Mg via tree canopy typically increase the base saturation and pH towards the surface of organic forest soil horizons. This process is most clearly depicted at sites with laterally moving groundwater. An up-transport of Al from mineral to the organic horizon is most important as a pH buffering process in less productive, acid soils having a pH below approximately 4.5. At this pH, the non-acidic properties of organically complexed Al keep pH at a level sufficiently high for maintained microbial activity. Furthermore, the formation of bridging bonds between major organic functional groups (carboxyls and phenols) and di- and trivalent metal cations of Ca, Al and Fe possesses a strong influence on the tertiary structure of SOM and its persistence to degradation and delivery of N. (C) 2013 Elsevier Ltd. All rights reserved.
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| 7. |
- Drott, Andreas, et al.
(författare)
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Do Potential Methylation Rates Reflect Accumulated Methyl Mercury in Contaminated Sediments?
- 2008
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Ingår i: Environmental Science and Technology. - : American Chemical Society (ACS). - 0013-936X .- 1520-5851. ; 42:1, s. 153-158
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Tidskriftsartikel (refereegranskat)abstract
- Relationships between the short-term mono-methyl mercury (MeHg) production, determined as the specific, potential methylation rate constant Km (day−1) after 48 h of incubation with isotope-enriched 201Hg(II) at 23 °C, and the long-term accumulation of ambient MeHg, were investigated in contaminated sediments. The sediments covered a range of environments from small freshwater lakes to large brackish water estuaries and differed with respect to source and concentration of Hg, salinity, primary productivity, quantity and quality of organic matter, and temperature climate. Significant (p < 0.001), positive relationships were observed between Km (day−1) and the concentration of MeHg normalized to total Hg (%MeHg) for surface sediments (0–10, 0–15, and in one case 0–20 cm) across all environments, and across subsets of organic and minerogenic freshwaters. This suggests that the methylation process (MeHg production) overruled demethylation and net transport processes in the surface sediments. The lack of a relationship between Km and %MeHg in two brackish water sediment depth profiles (0–100 cm) indicates that demethylation and the net effect of input−output are relatively more important at greater depths. Differences in the primary production and subsequent availability of easily degradable organic matter (serving as electron donor for methylating bacteria) was indicated to be the most important factor behind observed differences in %MeHg and Km among sites. In contrast, concentrations of sulfate were not correlated to Km, %MeHg, or absolute concentrations of MeHg. We conclude that total concentrations of Hg are of importance for the long-term accumulation of MeHg, and that %MeHg in surface sediments can be used as a proxy for the rate of methylation, across a range of sites from different environments.
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| 8. |
- Drott, Andreas, et al.
(författare)
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Effects of oxic and anoxic filtration on determined methyl mercury concentrations in sediment pore waters
- 2007
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Ingår i: Marine Chemistry. - : Elsevier BV. - 0304-4203. ; 103, s. 76-83
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Tidskriftsartikel (refereegranskat)abstract
- Accurate determination of methyl mercury (MeHg) concentrations in sediment pore waters is crucial for an improved understanding of mercury (Hg) biogeochemistry, and for improved risk assessment of Hg contaminated sites. In the present study, effects of oxic (air) and anoxic (N2) filtration (after centrifugation) on determined pore water MeHg concentrations were investigated in severely Hg contaminated pulp fibre sediments from two estuaries of the Bothnian Sea, Sweden. MeHg was determined in the filtrate using species-specific isotope dilution gas chromatography inductively coupled plasma mass spectrometry (SSID–GC–ICPMS), after ethylation with sodium tetraethylborate. Determined concentrations of MeHg were greater after anoxic filtration than after oxic filtration for all samples investigated, with MeHg(N2)/MeHg(air) ratios ranging between 3.4 and 343. Adsorption to newly formed Fe(III)/Mn(III/IV)-oxy/hydroxide surfaces is proposed as the main mechanism responsible for MeHg removal during oxic filtration. This is supported by decreases in dissolved Fe and Mn concentrations during oxic filtration, and by decreases in dissolved sulphur concentrations during oxic filtration in the samples with largest effect on MeHg concentrations. The latter is explained by adsorption of SO42− to newly formed Fe(III)/Mn(III/IV)-oxy/hydroxide surfaces. The effect of oxidation during filtration on pore water MeHg concentrations was largest in samples in which FeS(s) was not present, but with calculated pe-values below − 3. Thus, our results indicate that the largest errors with respect to pore water MeHg concentrations when filtering in air can be expected in samples with an intermediate redox potential, possibly buffered by a mixture of oxidation sensitive Fe(II/III) minerals.
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| 9. |
- Drott, Andreas, et al.
(författare)
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Importance of Dissolved Neutral Mercury Sulfides for Methyl Mercury Production in Contaminated Sediments
- 2007
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Ingår i: Environmental Science and Technology. - : American Chemical Society (ACS). - 0013-936X .- 1520-5851. ; 41:7, s. 2270-6
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Tidskriftsartikel (refereegranskat)abstract
- Biotic transformation of inorganic mercury, Hg(II), to mono methyl mercury (MeHg) is proposed to be largely controlled by passive uptake of neutral Hg complexes by sulfate reducing bacteria (SRB). In this study, the chemical speciation of Hg(II) in seven locally contaminated sediments covering environments such as (i) brackish water, (ii) low-productivity freshwater, and, (iii) high-productivity freshwater was related to potential Hg methylation rates, determined by incubation at 23 C for 48 h under N2(g), and to total MeHg concentrations in sediments. Pore water speciation was modeled considering Hg complexes with halides, organic thiols [Hg(SR)2(aq), associated to dissolved organic matter], monosulfides, and bisulfides. The sum of neutral mercury sulfides [Hg(SH)20(aq)] and [HgS0(aq)] was significantly, positively (p < 0.001, n = 20) correlated to the specific methylation rate constant (Km, day-1) at depths of 5-100 cm in two brackish water sediments. Total Hg, total mercury sulfides or Hg(SR)2(aq) in pore water gave no significant relationships with Km. In two sub-sets of freshwater sediments, neutral mercury sulfides were positively correlated to total Hg in pore water, and therefore, total Hg also gave significant relationships with Km. The sum of [Hg(SH)20(aq)] and [HgS0(aq)] was significantly, positively correlated to total sediment MeHg (g kg-1) in brackish waters (p < 0.001, n = 23), in southern, high-productivity freshwaters (p < 0.001, n = 20), as well as in northern, low-productivity freshwater (p = 0.048, n = 6). The slopes (b, b') of the relationships Km (day-1) = a + b([Hg(SH)20(aq)] + [HgS0(aq)]) and MeHg (g kg-1) = a' + b'([Hg(SH)20(aq)] + [HgS0(aq)]) showed an inverse relationship with the C/N ratio, supposedly reflecting differences in primary production and energy-rich organic matter availability among sites. We conclude that concentrations of neutral inorganic mercury sulfide species, together with the availability of energy-rich organic matter, largely control Hg methylation rates in contaminated sediments. Furthermore, Hg(SH)20(aq) is suggested to be the dominant species taken up by MeHg producing bacteria in organic-rich sediments without formation of HgS(s).
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| 10. |
- Drott, Andreas, et al.
(författare)
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Potential demethylation rate determinations in relation to concentrations of MeHg, Hg and pore water speciation of MeHg in contaminated sediments
- 2008
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Ingår i: Marine Chemistry. - : Elsevier. - 0304-4203 .- 1872-7581. ; 112:1-2, s. 93-101
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Tidskriftsartikel (refereegranskat)abstract
- Specific, potential demethylation rate constants (kd, day− 1) were determined in fresh and brackish water sediments from seven different sites in Sweden originally contaminated with either Hg0(l) or phenyl-Hg. Variations in kd among and within sites were related to ambient concentrations of Hg (1–1143 nmol g− 1) and MeHg (4.4–575pmol g− 1), and to pore water speciation of MeHg. Chemical speciation modeling revealed that MeHgSH(aq), MeHgS−(aq) and MeHg–thiol complexes [MeHgSR(aq)] associated to dissolved organic matter were the dominant MeHg species in the sediment pore water at all sites. Potential rates of MeHg demethylation were determined as the decomposition of isotopically enriched Me204HgCl during 48 h of incubation in darkness under N2(g) at 23 °C. There was a significant (p < 0.001) positive relationship between ambient MeHg concentrations in sediments and kd across all sites, but no significant relationship between ambient Hg and kd. At the three sites with the highest ambient Hg concentrations in sediments (average ± SD, 185 ± 249 nmol g− 1), kd was not significantly correlated with pore water MeHg speciation. At sites with lower concentrations of ambient Hg in sediments (average ± SD, 11 ± 8.4 nmol g− 1), there was a significant (p = 0.02) positive relationship between calculated concentrations of MeHgSH(aq), MeHgS−(aq), or the sum of these two species, and kd. If it is assumed that an oxidative demethylation process dominated at sites with lower concentrations of ambient Hg in sediments, the results suggest that it may be dependent on a passive uptake of inorganic MeHgSH molecules. It was shown that additions of different amounts of MeHg and Hg tracers, in relation to the ambient concentrations of MeHg and Hg, could result in dramatically different kd values within and between sites. At one brackish water site, both absolute demethylation rates and kds were significantly, inversely related to ambient concentrations of MeHg (and Hg). In contrast, at another brackish water site with generally less kds, samples with low ambient MeHg experienced toxic effects and demethylation was not detected. This implies that added (and possibly ambient) MeHg/Hg, depending on the environmental conditions, may have either stimulating or inhibitory effects on demethylation processes.
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| 11. |
- Drott, Andreas, et al.
(författare)
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Refining Thermodynamic Constants for Mercury(II)-Sulfides in Equilibrium with Metacinnabar at Sub-Micromolar Aqueous Sulfide Concentrations
- 2013
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Ingår i: Environmental Science and Technology. - : American Chemical Society (ACS). - 0013-936X .- 1520-5851. ; 47:9, s. 4197-4203
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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.
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| 12. |
- Eklöf, Karin, et al.
(författare)
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Formation of mercury methylation hotspots as a consequence of forestry operations
- 2018
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Ingår i: Science of the Total Environment. - : Elsevier BV. - 0048-9697 .- 1879-1026. ; 613-614, s. 1069-1078
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Tidskriftsartikel (refereegranskat)abstract
- 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.
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| 13. |
- Eklöf, Karin, et al.
(författare)
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Stubbskördens bidrag till kvicksilver i sjöar och vattendrag
- 2017
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Ingår i: Stubbskörd - hur påverkas klimat och miljö?. - 9789157694546 ; , s. 49-51
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Bokkapitel (övrigt vetenskapligt/konstnärligt)abstract
- Tidigare studier har visat att avverkning kan leda till ökad avrinning av kvicksilver (Hg), både totalt och biotillgängligt metyl-Hg. I en ny studie skapade stubbskörd miljöer där det bildades mycket metyl-Hg, främst i vattenfyll - da körskador och håligheter efter borttagna stubbar. Trots detta ökade inte koncentratio - nen av metyl-Hg i avrinnande bäckvatten från detta område.
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| 14. |
- Eriksson, Johan, et al.
(författare)
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Aniline and 2,4,6-trinitrotoluene associate preferentially to low molecular weight fractions of dissolved soil organic matter
- 2009
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Ingår i: Environmental Pollution. - : Elsevier BV. - 0269-7491 .- 1873-6424. ; 157, s. 3010-3015
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Tidskriftsartikel (refereegranskat)abstract
- Aniline and 2,4,6-trinitrotoluene (TNT) were equilibrated with particulate (POM) and dissolved organic matter (DOM) from an organic soil at different compositions of adsorbed major cations (Na, Al) and pH (aniline: 3.7-5.1, TNT: 4.8-5.0). After separation of POM, concentrations of (14)C-labelled aniline and TNT* (including TNT degradation products) were determined in DOM size fractions using size-exclusion chromatography (SEC) and UV-detection. Concentrations in the <3.5 kDa size fraction were 2.8-6.0 and 8.5-9.5 times higher for aniline and TNT*, respectively, as compared to the >40 kDa fraction. Thus, both aniline and TNT* were preferentially associated to the smallest DOM size fraction. The significant binding to DOM (similar extent as to POM) and the fact that the <3.5 kDa DOM fraction was less susceptible to flocculation by major metals suggests that the mobility of aniline and TNT is highly affected by the solubility of soil organic matter. (C) 2009 Elsevier Ltd. All rights reserved.
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| 15. |
- Eriksson, Johan, et al.
(författare)
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Binding of 2,4,6-Trinitrotoluene, Aniline, and Nitrobenzene to Dissolved and Particulate Soil Organic Matter
- 2004
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Ingår i: Environmental Science & Technology. - : American Chemical Society (ACS). - 0013-936X .- 1520-5851. ; 38:11, s. 3074-80
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Tidskriftsartikel (refereegranskat)abstract
- The distribution of TNT* (the sum of TNT and its degradation products), aniline, and nitrobenzene between particulate organic matter (POM), dissolved soil organic matter (DOM), and free compound was studied in controlled kinetic (with and without irradiation) and equilibrium experiments with mixtures of POM and DOM reflecting natural situations in organic rich soils. The binding of TNT* to POM was fast, independent of irradiation, and adsorption isotherms had a great linear contribution (as determined by a mixed model), indicative of a hydrophobic partitioning mechanism. The binding of TNT* to DOM was slower, strongly enhanced under nonirradiated conditions, and adsorption isotherms were highly nonlinear, indicative of a specific interaction between TNT derivatives and functional groups of DOM. Nitrobenzene was associated to both POM and DOM via hydrophobic partitioning, whereas aniline binding was dominated by specific binding to POM and DOM functional groups. On the basis of nitrobenzene and TNT* adsorption parameters determined by a mixed Langmuir + linear model, POM had 2-3 times greater density of hydrophobic moieties as compared to DOM. This difference was reflected by a greater (O + N)/C atomic ratio for DOM. The sum of C-C and C-H moieties, as determined by X-ray photoelectron spectroscopy (XPS), and the sum of aryl-C and alkyl-C, as determined by solid-state cross-polarization magic-angle spinning (CP-MAS) 13C NMR, could only qualitatively account for differences in adsorption parameters. Aliphatic C was found to be more important for the hydrophobic partitioning than aromatic C. On the basis of nonlinear adsorption parameters, the density of functional groups reactive with aniline and TNT derivatives was 1.3-1.4 times greater in DOM than in POM, which was in fair agreement with 13C NMR and XPS data for the sum of carboxyl and carbonyl groups as potential sites for electrostatic and covalent bonding. We conclude that in contaminated soils characterized by continuous leaching of DOM, formation of TNT derivatives (via biotic and abiotic reductive degradation) and their preference for specific functional groups in DOM may contribute to a significant transportation of potentially toxic TNT compounds into surface waters and groundwaters.
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| 16. |
- Fernández-Gómez, Cristal, et al.
(författare)
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Towards Universal Wavelength-Specific Photodegradation Rate Constants for Methyl Mercury in Humic Waters, Exemplified by a Boreal Lake-Wetland Gradient.
- 2013
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Ingår i: Environmental Science and Technology. - : American Chemical Society (ACS). - 0013-936X .- 1520-5851. ; 47:12, s. 6279-6287
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Tidskriftsartikel (refereegranskat)abstract
- We report experimentally determined first-order rate constants of MeHg photolysis in three waters along a Boreal lake-wetland gradient covering a range of pH (3.8-6.6), concentrations of total organic carbon (TOC 17.5-81 mg L(-1)), total Fe (0.8-2.1 mg L(-1)), specific UV254 nm absorption (3.3-4.2 L mg(-1) m(-1)) and TOC/TON ratios (24-67 g g(-1)). Rate constants determined as a function of incident sunlight (measured as cumulative photon flux of photosynthetically active radiation, PAR) decreased in the order dystrophic lake > dystrophic lake/wetland > riparian wetland. After correction for light attenuation by dissolved natural organic matter (DOM), wavelength-specific (PAR: 400-700 nm, UVA: 320-400 nm and UVB: 280-320 nm) first-order photodegradation rate constants (kpd) determined at the three sites were indistinguishable, with average values (±SE) of 0.0023 ± 0.0002, 0.10 ± 0.024 and 7.2 ± 1.3 m(2) E(-1) for kpdPAR, kpdUVA, and kpdUVB, respectively. The relative ratio of kpdPAR, kpdUVA, and kpdUVB was 1:43:3100. Experiments conducted at varying MeHg/TOC ratios confirm previous suggestions that complex formation with organic thiol groups enhances the rate of MeHg photodegradation, as compared to when O and N functional groups are involved in the speciation of MeHg. We suggest that if the photon fluxes of PAR, UVA, and UVB radiation are separately determined and the wavelength-specific light attenuation is corrected for, the first-order rate constants kpdPAR, kpdUVA, and kpdUVB will be universal to waters in which DOM (possibly in concert with Fe) controls the formation of ROS, and the chemical speciation of MeHg is controlled by the complexation with DOM associated thiols.
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| 17. |
- Frankki, Sofia, et al.
(författare)
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Mobility of Chloroaromatic Compounds in Soil: Case Studies of Swedish Chlorophenol-contaminated Sawmill Sites
- 2007
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Ingår i: AMBIO: A Journal of the Human Environment. ; 36:6, s. 452–7-
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Tidskriftsartikel (refereegranskat)abstract
- This paper summarizes recent studies on the environmental fate of chloroaromatic compounds in chlorophenol (CP)-contaminated soil and groundwater at Swedish sawmill sites. Relative proportions of CPs, polychlorinated phenoxy phenols (PCPPs), polychlorinated diphenyl ethers (PCDEs), polychlorinated dibenzo-p-dioxins (PCDDs), and polychlorinated dibenzofurans (PCDFs) were determined in preservatives, particulate organic matter (POM), dissolved organic matter (DOM), groundwater, and particles filtered from groundwater. All compound classes were found in the different compartments. The fraction of PCPPs, PCDEs, PCDDs, and PCDFs had increased in the soil samples relative to the proportions in the preservatives. This increase showed correlation with the hydrophobicity, that is, PCDDs had the largest increase. Similar correlation was found between hydrophobicity and the importance of partitioning to POM over DOM. The more water soluble compound group, CP, was found equally distributed between POM and DOM. For PCPPs, PCDEs, PCDDs, and PCDFs, the relative partitioning to POM increased with increased hydrophobicity. Despite the relative partitioning towards POM, compared with DOM, cotransport with DOM and suspended colloidal fractions was found to substantially increase the transport of these compounds in the groundwater samples.
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| 18. |
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| 19. |
- Frankki, Sofia, et al.
(författare)
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Partitioning of CPs, PCDEs, and PCDD/Fs between particulate and experimentally
- 2006
-
Ingår i: Environmental Science & Technology. - : American Chemical Society (ACS). - 0013-936X .- 1520-5851. ; 40:21, s. 6668-73
-
Tidskriftsartikel (refereegranskat)abstract
- We determined the distribution of hydrophobic organic contaminants (HOCs) to fractions of natural organic matter in a soil contaminated by chlorophenol wood preservatives more than 30 years ago. The concentration of dissolved organic matter (DOM) was enhanced in soil suspensions by raising pH to 6.8-9.1. After 48 h of desorption/equilibration, the DOM fraction was separated from the particulate organic matter (POM) of the soil by filtration. In the next step, DOM was flocculated by Al-nitrate, and free concentrations of HOCs were determined in the aqueous phase. The HOCs associated with DOM and POM were extracted with toluene. No significant differences in gross carbon chemistry were detected between DOM and POM, using X-ray photoelectron spectroscopy (XPS). Normalized to organic C, chlorophenols (CPs) showed a similar degree of partitioning between DOM and POM, whereas the partitioning of polychlorinated diphenyl ethers (PCDEs), polychlorinated dibenzo-p-dioxins, and furans (PCDD/Fs) was highly shifted toward POM. The partitioning to POM, relative to DOM, increased in the order PCDE < PCDF < PCDD, reflecting the hydrophobicity of the compounds.
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| 20. |
- Frankki, Sofia, et al.
(författare)
-
Partitioning of CPs, PCDEs, and PCDD/Fs between particulate and experimentally enhanced dissolved natural organic matter in a contaminated soil.
- 2006
-
Ingår i: Environmental Science and Technology. - : American Chemical Society. - 0013-936X .- 1520-5851. ; 40:21, s. 6668-73
-
Tidskriftsartikel (refereegranskat)abstract
- We determined the distribution of hydrophobic organic contaminants (HOCs) to fractions of natural organic matter in a soil contaminated by chlorophenol wood preservatives more than 30 years ago. The concentration of dissolved organic matter (DOM) was enhanced in soil suspensions by raising pH to 6.8-9.1. After 48 h of desorption/equilibration, the DOM fraction was separated from the particulate organic matter (POM) of the soil by filtration. In the next step, DOM was flocculated by Al-nitrate, and free concentrations of HOCs were determined in the aqueous phase. The HOCs associated with DOM and POM were extracted with toluene. No significant differences in gross carbon chemistry were detected between DOM and POM, using X-ray photoelectron spectroscopy (XPS). Normalized to organic C, chlorophenols (CPs) showed a similar degree of partitioning between DOM and POM, whereas the partitioning of polychlorinated diphenyl ethers (PCDEs), polychlorinated dibenzo-p-dioxins, and furans (PCDD/Fs) was highly shifted toward POM. The partitioning to POM, relative to DOM, increased in the order PCDE < PCDF < PCDD, reflecting the hydrophobicity of the compounds.
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| 21. |
- Gustavsson, Jenny, et al.
(författare)
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Bioavailability and chemical forms of Co and Ni in the biogasprocess : an evaluation based on sequential and acid volatile sulfide extractions
-
Annan publikation (övrigt vetenskapligt/konstnärligt)abstract
- Several previous studies report stimulatory effects on biogas process performance after trace element supplementation. However, the regulation of the bioavailability in relation to chemical speciation (e.g. the role of sulfide) is not fully understood. The objective of the present study was to determine the effect of sulfide on the chemical speciation and bioavailability of Co and Ni in lab-scale semi-continuously fed biogas tank reactors, digesting grain stillage. The chemical forms and potential bioavailability of Co and Ni in the reactors were determined by sequential extraction (SE), and analysis of acid volatile sulfide (AVS) together with simultaneously extracted metals (AVS-Me). The results for metal speciation analysis demonstrated that Ni was completely associated to the organic matter/sulfide fraction and AVS, suggesting low potential Ni-bioavailability. Cobalt was predominantly associated to organic matter/sulfide and AVS, but also to more soluble fractions which are considered to be more bioavailable. Process performance data showed that both Co and Ni were available for microbial uptake. Although the actual bioavailability of Co could be explained by association to more bioavailable chemical fractions as determined by SE, AVS and AVS-Me analysis, the complete association of Ni with organic matter/sulfides and AVS shows that Ni was taken up despite its expected low bioavailability. Thus, the results of the present study imply that Ni-sulfide precipitation does not prevent microbial uptake in the studied biogas reactors.
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| 22. |
- Gustavsson, Jenny, et al.
(författare)
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Bioavailability of cobalt and nickel during anaerobic digestion of sulfur-rich stillage for biogas formation
- 2013
-
Ingår i: Applied Energy. - : Elsevier. - 0306-2619 .- 1872-9118. ; 112, s. 473-477
-
Tidskriftsartikel (refereegranskat)abstract
- Addition of Co and Ni often improves the production of biogas during digestion of organic matter, i.e. increasing CH4-production, process stability and substrate utilization which often opens for higher organic loading rates (OLRs). The effect of Co and Ni addition was evaluated by measuring methane production, volatile solids reduction, pH and concentration of volatile fatty acids (VFAs). A series of six lab-scale semi-continuously fed biogas tank reactors were used for this purpose. The chemical forms and potential bioavailability of Co and Ni were examined by sequential extraction, acid volatile sulfide extraction (AVS) and simultaneously extracted metals. Furthermore, the sulfur speciation in solid phase was examined by sulfur X-ray absorption near edge structure spectroscopy. The effect of Co and Ni deficiency on the microbial community composition was analyzed using quantitative polymerase chain reaction and 454-pyrosequencing. The results showed that amendment with Co and Ni was necessary to maintain biogas process stability and resulted in increased CH4-production and substrate utilization efficiency. 10-20% of the total Co concentration was in dissolved form and should be regarded as easily accessible by the microorganisms. In contrast, Ni was entirely associated with organic matter/sulfides (mainly AVS) and regarded as very difficult to take up. Still Ni had stimulatory effects suggesting mechanisms such as dissolution of NiS to be involved in the regulation of Ni availability for the microorganisms. The microbial community structure varied in relation to the occurrence of Ni and Co. The acetate-utilizing Methanosarcinales dominated during stable process performance, i.e. when both Co and Ni were supplied, while hydrogenotrophic Methanomicrobiales increased together with VFA concentrations under Co or Ni deficiency. The increase was more pronounced at Co limitation. This study demonstrates that there are good possibilities to improve the performance of biogas processes digesting sulfur-rich substrates by supplementation of Co and Ni.
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| 23. |
- Gustavsson, Jenny, et al.
(författare)
-
Potential bioavailability and chemical forms of Co and Ni in the biogas process-An evaluation based on sequential and acid volatile sulfide extractions
- 2013
-
Ingår i: Engineering in Life Sciences. - : WILEY-BLACKWELL, 111 RIVER ST, HOBOKEN 07030-5774, NJ USA. - 1618-0240 .- 1618-2863. ; 13:6, s. 572-579
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Tidskriftsartikel (refereegranskat)abstract
- Several previous studies reported stimulatory effects on biogas process performance after trace metal supplementation. However, the regulation of the bioavailability in relation to chemical speciation, e.g. the role of sulfide is not fully understood. The objective of the present study was to determine the effect of sulfide on chemical speciation and bioavailability of Co and Ni in lab-scale semicontinuous stirred biogas tank reactors treating stillage. The chemical forms and potential bioavailability of Co and Ni were studied by sequential extraction, analysis of acid-volatile sulfide (AVS), and simultaneously extracted metals. The results demonstrated that Ni was completely associated to the organic matter/sulfide fraction and AVS, suggesting low potential bioavailability. Cobalt was predominantly associated to organic matter/sulfide and AVS, but also to more soluble fractions, which are considered to be more bioavailable. Process data showed that both Co and Ni were available for microbial uptake. Although the actual bioavailability of Co could be explained by association to more bioavailable chemical fractions, the complete association of Ni with organic matter/sulfides and AVS implies that Ni was taken up despite its expected low bioavailability. It was concluded that extensive Co- and Ni-sulfide precipitation did not inhibit microbial uptake of Co and Ni in the reactors.
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| 24. |
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| 25. |
- Gutensohn, Mareike Franziska, 1992-
(författare)
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Unraveling the importance of thiol compounds on mercury speciation, uptake and transformation by the iron-reducer Geobacter sulfurreducens
- 2023
-
Doktorsavhandling (övrigt vetenskapligt/konstnärligt)abstract
- The biogenic methylation of inorganic, divalent mercury (Hg(II)) by methylating microorganisms leads to formation and bioaccumulation of monomethyl mercury (MeHg) in the environment and can cause severe damage to ecosystems and human health. Diverse microorganisms carry the gene sequence hgcAB and are able to methylate Hg(II) intracellularly. The interplay of biological, chemical and physical parameters is driving mercury (Hg) transformation by microorganisms. The chemical speciation of Hg(II) with thiol compounds, both with dissolved low molecular mass (LMM) thiols and thiols present on microbial membrane surfaces, is one key factor for Hg availability and transformation. In this work the role of thiol compounds with respect to Hg speciation, uptake and transformation was studied by the iron-reducing model organisms Geobacter sulfurreducens. The turnover of dissolved thiols and the role of outer and inner membrane thiols was studied with novel experimental strategies.In Paper I and II the formation of thiol compounds was studied under varying nutrient conditions. It was shown that the formation of LMM-thiol compounds was impacted by divalent iron, Fe(II). Furthermore, we showed the turnover of the small LMM-thiol cysteine to the branched LMM-thiol penicillamine, which was further amplified by the addition of exogenous cysteine or nutrients. This turnover of small to branched LMM-thiols impacted the Hg(II) speciation in methylation assays and the relative contribution between cysteine and penicillamine was important for Hg(II) availability, uptake and methylation. In addition, the partition of Hg(II) between the cell-adsorbed and dissolved phase was shifted towards the latter at higher LMM-thiol concentrations. Nutrient concentrations impacted cell physiology due to a shift to an active metabolism and a faster metabolization of LMM-thiols. We concluded that the interplay between thiol metabolism, Hg(II) speciation and cell physiology are key parameters for Hg(II) methylation by G. sulfurreducens. In Paper III The outer and inner membrane was characterized independently by two X-ray absorption spectroscopy techniques. The determination of the Hg speciation by both X-ray absorption spectroscopy techniques showed coherent results for both the outer and inner membrane of G. sulfurreducens. The concentration of thiol membrane groups was higher on the inner compared to the outer membrane. The differences between the outer and inner membrane suggested that thiol concentration and Hg coordination environment likely impact the Hg(II) internalization. The role of membrane thiols for Hg(II) uptake and transformation was further investigated in Paper IV by selectively blocking these functional groups. Partitioning and uptake of Hg was not affected by blocking the outer and inner membrane thiols of whole cell and spheroplast samples, respectively. However, the Hg(II) methylation was decreased by blocking thiols at the outer membrane, but no effect was observed by blocking thiols at the inner membrane. Blocking of membrane surface thiols changed the physiology in whole cells but not in spheroplasts. This result suggested weaknesses of the applied blocking approach. In addition, Hg(II) reduction was studied on the outer and inner membrane and showed the formation of liquid and gaseous elemental Hg, Hg(0), in Paper III and IV, respectively.Overall, this work showed the central role of dissolved and cell-associated thiol compounds for Hg(II) uptake and the transformation reactions. Herby, concentration, compositions and distribution of thiols are crucial and impact the Hg(II) speciation, partitioning, uptake and availability for Hg(II) methylation and reduction. In addition, cell physiology is impacting the methylation potential and the turnover of LMM-thiol compounds. The role of membrane surface thiols for Hg(II) uptake was not fully identified, however such thiols were for the first time characterized selectively for the outer and inner membrane by X-ray absorption spectroscopy.
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| 26. |
- Gutensohn, Mareike, et al.
(författare)
-
Metabolic turnover of cysteine-related thiol compounds at environmentally relevant concentrations by Geobacter sulfurreducens
- 2023
-
Ingår i: Frontiers in Microbiology. - : Frontiers Media S.A.. - 1664-302X. ; 13
-
Tidskriftsartikel (refereegranskat)abstract
- Low-molecular-mass (LMM) thiol compounds are known to be important for many biological processes in various organisms but LMM thiols are understudied in anaerobic bacteria. In this work, we examined the production and turnover of nanomolar concentrations of LMM thiols with a chemical structure related to cysteine by the model iron-reducing bacterium Geobacter sulfurreducens. Our results show that G. sulfurreducens tightly controls the production, excretion and intracellular concentration of thiols depending on cellular growth state and external conditions. The production and cellular export of endogenous cysteine was coupled to the extracellular supply of Fe(II), suggesting that cysteine excretion may play a role in cellular trafficking to iron proteins. Addition of excess exogenous cysteine resulted in a rapid and extensive conversion of cysteine to penicillamine by the cells. Experiments with added isotopically labeled cysteine confirmed that penicillamine was formed by a dimethylation of the C-3 atom of cysteine and not via indirect metabolic responses to cysteine exposure. This is the first report of de novo metabolic synthesis of this compound. Penicillamine formation increased with external exposure to cysteine but the compound did not accumulate intracellularly, which may suggest that it is part of G. sulfurreducens’ metabolic strategy to maintain cysteine homeostasis. Our findings highlight and expand on processes mediating homeostasis of cysteine-like LMM thiols in strict anaerobic bacteria. The formation of penicillamine is particularly noteworthy and this compound warrants more attention in microbial metabolism studies.
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| 27. |
- Gutensohn, Mareike, et al.
(författare)
-
The combined effect of Hg(II) speciation, thiol metabolism, and cell physiology on methylmercury formation by Geobacter sulfurreducens
- 2023
-
Ingår i: Environmental Science and Technology. - : American Chemical Society (ACS). - 0013-936X .- 1520-5851. ; 57:18, s. 7185-7195
-
Tidskriftsartikel (refereegranskat)abstract
- 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.
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| 28. |
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| 29. |
- Hu, Haiyan, et al.
(författare)
-
Shifts in mercury methylation across a peatland chronosequence : From sulfate reduction to methanogenesis and syntrophy
- 2020
-
Ingår i: Journal of Hazardous Materials. - : Elsevier. - 0304-3894 .- 1873-3336. ; 387
-
Tidskriftsartikel (refereegranskat)abstract
- 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.
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| 30. |
- Högberg, Mona N, et al.
(författare)
-
Does ectomycorrhiza have a universal key role in the formation of soil organic matter in boreal forests?
- 2020
-
Ingår i: Soil Biology and Biochemistry. - : Elsevier BV. - 0038-0717 .- 1879-3428. ; 140
-
Tidskriftsartikel (refereegranskat)abstract
- Forest soil organic matter (SOM) is an important dynamic store of C and N, which releases plant available N and the greenhouse gases CO2 and N2O. Early stages of decomposition of recent plant litters are better known than the formation of older and more stable soil pools of N and C, in which case classic theory stated that selective preservation of more resistant plant compounds was important. Recent insights heighten that all plant matter becomes degraded and that older SOM consists of compounds proximally of microbial origin. It has been proposed that in boreal forests, ectomycorrhizal fungi (ECMF), symbionts of trees, are actively involved in the formation of slowly-degrading SOM.We characterized SOM in the mor-layer along a local soil N supply gradient in a boreal forest, a gradient with large variations in chemical and biological characteristics, notably a decline in the biomass of ECMF in response to increasing soil N supply.We found contrasting and regular patterns in carbohydrates, lignin, aromatic carbon, and in N-containing compounds estimated by solid-state C-13 and N-15 nuclear magnetic resonance (NMR) spectroscopy. These occurred along with parallel changes in the natural abundances of the stable isotopes C-13 and N-15 in both bulk SOM and extracted fractions of the SOM. The modelled "bomb-C-14" age of the lower layers studied ranged between 15 years at the N-poor end, to 70 years at the N-rich end of the gradient. On average half the increase in delta C-13 with soil depth (and hence age) of the mor-layer can be attributed to soil processes and the other half to changes in the isotopic composition of the plant C inputs. There was a decrease in carbohydrates (O-alkyl C) with increasing depth. This supports the classical hypothesis of declining availability of easily decomposable substrates to microorganisms with increasing soil depth and age. The observed increase in delta C-13 with depth, however, speaks against the idea of selective preservation of more resistant plant compounds like lignin. Furthermore, from the N-poor to the N-rich end the difference between N-15 in plant litter N and N in the deeper part of the mor-layer, the H-layer, decreased in parallel with a decline in ECMF.The latter provides evidence that the role of ECMF as major sink for N diminishes, and hence their potential role in SOM stabilization, when the soil N supply increases. At the N-rich end, where bacteria dominate over fungi, other agents than ECMF must be involved in the large build-up of the H-layer with the slowest turnover rate found along the gradient.
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| 31. |
- Jiang, Tao, et al.
(författare)
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Characteristics of dissolved organic matter (DOM) and relationship with dissolved mercury in Xiaoqing River-Laizhou Bay estuary, Bohai Sea, China
- 2017
-
Ingår i: Environmental Pollution. - : Elsevier. - 0269-7491 .- 1873-6424. ; 223, s. 19-30
-
Tidskriftsartikel (refereegranskat)abstract
- Abstract Because of heterogeneous properties, dissolved organic matter (DOM) is known to control the environmental fate of a variety of organic pollutants and trace metals in aquatic systems. Here we report absorptive and fluorescence properties of DOM, in concurrence with concentrations of dissolved mercury (Hg), along the Xiaoqing River-Laizhou Bay estuary system located in the Bohai Sea of China. A mixing model consisting of the two end-members terrestrial and aquatic DOM demonstrated that terrestrial signatures decreased significantly from the river into the estuary. Quasi-conservative mixing behavior of DOM sources suggests that the variations in the average DOM composition were governed by physical processes (e.g., dilution) rather than by new production and/or degradation processes. In contrast to some previous studies of river-estuary systems, the Xiaoqing River-Laizhou Bay estuary system displayed a non-significant correlation between DOM and Hg quantities. Based on this and the variation of Hg concentration along the salinity gradient, we concluded that Hg showed a non-conservative mixing behavior of suggested end-member sources. Thus, rather than mixing, Hg concentration variations seemed to be controlled by biogeochemical processes.
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| 32. |
- Jiang, Tao, et al.
(författare)
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Influence of dissolved organic matter (DOM) characteristics on dissolved mercury (Hg) species composition in sediment porewater of lakes from southwest China
- 2018
-
Ingår i: Water Research. - : Elsevier. - 0043-1354 .- 1879-2448. ; 146, s. 146-158
-
Tidskriftsartikel (refereegranskat)abstract
- 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.
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| 33. |
- Jiang, Tao, et al.
(författare)
-
Modeling of the structure-specific kinetics of abiotic, dark reduction of Hg(II) complexed by O/N and S functional groups in humic acids while accounting for time-dependent structural rearrangement
- 2015
-
Ingår i: Geochimica et Cosmochimica Acta. - : Elsevier BV. - 0016-7037 .- 0046-564X. ; 154, s. 151-167
-
Tidskriftsartikel (refereegranskat)abstract
- Dark reduction of Hg(II) to Hg(0) in deep waters, soils and sediments accounts for a large part of legacy Hg recycling back to the atmosphere. Natural organic matter (NOM) plays a dual role in the process, acting as an electron donor and complexation agent of Hg(II). Experimental determination of rates of dark Hg(II) reduction is complicated by the simultaneously ongoing kinetics of Hg(II) rearrangement from the abundant, relatively weakly bonding RO/N (carboxyl, amino) groups in NOM to the much stronger bonding RSH (thiol) group. In this study, kinetics of the rearrangement are accounted for and we report rates of dark Hg(II) reduction for two molecular structures in presence of humic acids (HA) extracted from three different sources. Values on the pseudo first-order rate constant for the proposed structure Hg(OR)(2) (k(red) (Hg(OR)2)) were 0.18, 0.22 and 0.35 h(-1) for Peat, Coal and Soil HA, respectively, and values on the constant for the proposed structure RSHgOR (k(red) (RSHgOR)) were 0.003 and 0.006 h(-1) for Peat and Soil HA, respectively. The Hg(SR)(2) structure is the thermodynamically most stable, but the limited time of the experiment (53 h) did not allow for a determination of the rate of the very slow reduction of Hg(II) in this structure. For two out of three HA samples the concentration of RSH groups optimized by the kinetic model (0.6 x 10(-3) RSH groups per C atoms) was in good agreement with independent estimates provided by sulfur X-ray absorption near-edge spectroscopy (S XANES). Experiments conducted at varying concentrations of Hg(II) and HA demonstrated a positive relationship between Hg(II) reduction and concentrations of specific Hg(II) structures and electron donor groups, suggesting first order in each of these two components. The limitation of the Hg(II) reduction by electron donating groups of HA, as represented by the native reducing capacity (NRC), was demonstrated for the Coal HA sample. Normalization to NRC resulted in pseudo second-order rate constants (k(red) (Hg(OR)2/NRC) = 0.012 h(-1), k(red) (RSHgOR/NRC) = 1.9 - 2.1 x 10(-4) h(-1)) that were very similar for Soil and Peat HA. (C) 2015 Elsevier Ltd. All rights reserved.
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| 34. |
- Jingying, Xu, 1984-, et al.
(författare)
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Mercury methylating microbial communities of boreal forest soils
- 2019
-
Ingår i: Scientific Reports. - : Springer Science and Business Media LLC. - 2045-2322. ; 9
-
Tidskriftsartikel (refereegranskat)abstract
- 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 linked to the composition of also 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.
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| 35. |
- Jonsson, Sofi, et al.
(författare)
-
Differentiated availability of geochemical mercury pools controls methylmercury levels in estuarine sediment and biota
- 2014
-
Ingår i: Nature Communications. - : Springer Science and Business Media LLC. - 2041-1723. ; 5, s. 4624-
-
Tidskriftsartikel (refereegranskat)abstract
- Neurotoxic methylmercury (MeHg) formed from inorganic divalent mercury (HgII) 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 HgII 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 HgII solid/adsorbed phases control the sediment Hg pool's 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.
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| 36. |
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| 37. |
- Jonsson, Sofi, 1984-, et al.
(författare)
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Geochemical and Dietary Drivers of Mercury Bioaccumulation in Estuarine Benthic Invertebrates
- 2022
-
Ingår i: Environmental Science and Technology. - : American Chemical Society (ACS). - 0013-936X .- 1520-5851. ; 56:14, s. 10141-10148
-
Tidskriftsartikel (refereegranskat)abstract
- Sediments represent the main reservoir of mercury (Hg) in aquatic environments and may act as a source of Hg to aquatic food webs. Yet, accumulation routes of Hg from the sediment to benthic organisms are poorly constrained. We studied the bioaccumulation of inorganic and methylmercury (HgII and MeHg, respectively) from different geochemical pools of Hg into four groups of benthic invertebrates (amphipods, polychaetes, chironomids, and bivalves). The study was conducted using mesocosm experiments entailing the use of multiple isotopically enriched Hg tracers and simulation of estuarine systems with brackish water and sediment. We applied different loading regimes of nutrients and terrestrial organic matter and showed that the vertical localization and the chemical speciation of HgII and MeHg in the sediment, in combination with the diet composition of the invertebrates, consistently controlled the bioaccumulation of HgII and MeHg into the benthic organisms. Our results suggest a direct link between the concentration of MeHg in the pelagic planktonic food web and the concentration of MeHg in benthic amphipods and, to some extent, in bivalves. In contrast, the quantity of MeHg in benthic chironomids and polychaetes seems to be driven by MeHg accumulation via the benthic food web. Accounting for these geochemical and dietary drivers of Hg bioaccumulation in benthic invertebrates will be important to understand and predict Hg transfer between the benthic and the pelagic food web, under current and future environmental scenarios.
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| 38. |
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| 39. |
- Jonsson, Sofi, 1984-, et al.
(författare)
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Mercury methylation rates for geochemically relevant HgII species in sediments
- 2012
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Ingår i: Environmental Science and Technology. - : American Chemical Society (ACS). - 0013-936X .- 1520-5851. ; 46:21, s. 11653-11659
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Tidskriftsartikel (refereegranskat)abstract
- Monomethylmercury (MeHg) in fish from freshwater, estuarine and marine environments are 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 two 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 causes 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.
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| 40. |
- Jonsson, Sofi, 1984-, et al.
(författare)
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Substantial emission of gaseous monomethylmercury from contaminated water-sediment microcosms
- 2010
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Ingår i: Environmental Science and Technology. - : American Chemical Society (ACS). - 0013-936X .- 1520-5851. ; 44:1, s. 278-283
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Tidskriftsartikel (refereegranskat)abstract
- 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).
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| 41. |
- Jonsson, Sofi, et al.
(författare)
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Terrestrial discharges mediate trophic shifts and enhance methylmercury accumulation in estuarine biota
- 2017
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Ingår i: Science Advances. - : American association for the advancement of science. - 2375-2548. ; 3:1
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Tidskriftsartikel (refereegranskat)abstract
- 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.
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| 42. |
- Jonsson, Sofi, 1984-
(författare)
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Unraveling the importance of solid and adsorbed phase mercury speciation for methylmercury formation, evasion and bioaccumulation
- 2013
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Doktorsavhandling (övrigt vetenskapligt/konstnärligt)abstract
- Monomethylmercury, MeHg, is formed under anoxic conditions in waters, sediments and soils and then bioaccumulated and biomagnified in aquatic food webs, negatively effecting both human and wildlife health. It is generally accepted that precipitation of mercury, Hg, and adsorption of Hg to e.g. organic matter and mineral surfaces are important processes limiting the reactivity of Hg mobilized in the environment by natural and anthropogenic activities. However, knowledge concerning the role of different solid and adsorbed chemical forms of Hg for MeHg formation, evasion and bioaccumulation is missing. Such information is vital for the understanding of environmental processes controlling MeHg formation and bioaccumulation, as well as for predicting how changes in e.g. loading rates of atmospheric Hg and the outcome of climate change scenarios and anthropogenic land use could alter Hg concentrations in biota.In this thesis, a novel experimental approach, using isotopically enriched solid and adsorbed phases of inorganic Hg, HgII, as tracers, was developed. Using this approach, we successfully determined rates of MeHg formation from solid and adsorbed Hg species in sediment slurries and in mesocosm systems under conditions closely resembling those in field. We conclude that the solid/adsorbed phase speciation of HgII is a major controlling factor for MeHg net formation rates. Microcosm experiments revealed that newly formed MeHg was a major contributor to the evasion of MeHg from the water‒sediment system, emphasizing the importance of MeHg formation rate, rather than MeHg concentration, in the sediment for this process. From mesocosm systems, we provide experimental evidence, as well as quantitate data, for that terrestrial and atmospheric sources of HgII and MeHg are more available for methylation and bioaccumulation processes than HgII and MeHg stored and formed in sediments. This suggests that the contribution from terrestrial and atmospheric sources to the accumulation of Hg in fish may have been underestimated. As a consequence, in regions where climate change is expected to further increase land runoff, terrestrial MeHg sources may have even higher negative effects on biota than previously thought. Data and concepts presented in this thesis lay the basis for unprecedented in-depth modeling of processes in the Hg biogeochemical cycle that will improve our understanding and the predicting power on how aquatic ecosystems may respond to environmental changes or differences in loading rates for atmospheric Hg.
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| 43. |
- Karlsson, Torbjörn, et al.
(författare)
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Complexation of cadmium to sulfur and oxygen functional groups in an organic soil
- 2007
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Ingår i: Geochimica et Cosmochimica Acta. - : Elsevier BV. - 0016-7037. ; 71, s. 604-14
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Tidskriftsartikel (refereegranskat)abstract
- Cadmium (Cd) is a toxic trace element and due to human activities soils and waters are contaminated by Cd both on a local and global scale. It is widely accepted that chemical interactions with functional groups of natural organic matter (NOM) is vital for the bioavailability and mobility of trace elements. In this study the binding strength of cadmium (Cd) to soil organic matter (SOM) was determined in an organic (49% organic C) soil as a function of reaction time, pH and Cd concentration. In experiments conducted at native Cd concentrations in soil (0.23 μg g−1 dry soil), halides (Cl, Br) were used as competing ligands to functional groups in SOM. The concentration of Cd in the aqueous phase was determined by isotope-dilution (ID) inductively-coupled-plasma-mass-spectrometry (ICP-MS), and the activity of Cd2+ was calculated from the well-established Cd–halide constants. At higher Cd loading (500–54,000 μg g−1), the Cd2+ activity was directly determined by an ion-selective electrode (ISE). On the basis of results from extended X-ray absorption fine structure (EXAFS) spectroscopy, a model with one thiolate group (RS−) was used to describe the complexation (Cd2+ + RS− two left arrows CdSR+; log KCdSR) at native Cd concentrations. The concentration of thiols (RSH; 0.047 mol kg−1 C) was independently determined by X-ray absorption near-edge structure (XANES) spectroscopy. Log KCdSR values of 11.2–11.6 (pKa for RSH = 9.96), determined in the pH range 3.1–4.6, compare favorably with stability constants for the association between Cd and well-defined thiolates like glutathione. In the concentration range 500–54,000 μg Cd g−1, a model consisting of one thiolate and one carboxylate (RCOO−) gave the best fit to data, indicating an increasing role for RCOOH groups as RSH groups become saturated. The determined log KCdOOCR of 3.2 (Cd2+ + RCOO− two left arrows CdOOCR+; log KCdOOCR; pKa for RCOOH = 4.5) is in accordance with stability constants determined for the association between Cd and well-defined carboxylates. Given a concentration of reduced sulfur groups of 0.2% or higher in NOM, we conclude that the complexation to organic RSH groups may control the speciation of Cd in soils, and most likely also in surface waters, with a total concentration less than 5 mg Cd g−1 organic C.
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| 44. |
- Karlsson, Torbjörn, et al.
(författare)
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Complexation of Copper(II) in Organic Soils and in Dissolved Organic Matter - EXAFS Evidence for Chelate Ring Structures
- 2006
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Ingår i: Environmental Science and Technology. - : American Chemical Society (ACS). - 0013-936X .- 1520-5851. ; 40:8, s. 2623-8
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Tidskriftsartikel (refereegranskat)abstract
- Associations with functional groups of natural organic matter (NOM) are of great importance for bioavailability, toxicity, and mobility of trace metals in soils and waters. In this study, the coordination chemistry of copper, Cu(II), in organic soils and dissolved organic matter (DOM) from soils and streams was investigated by extended X-ray absorption fine structure (EXAFS) spectroscopy. In both soil organic matter (SOM) and DOM (990-11 000 g Cu g-1 dry weight, pH 2.8-6.3), Cu(II) was coordinated by 4 oxygen/nitrogen (O/N) atoms at a distance of 1.92-1.95 Å in the first coordination shell. These four atoms are positioned in the equatorial plane of a Jahn-Teller distorted octahedron. In samples with a pH of 4.8-6.3, a second coordination shell with 2.0-3.8 C atoms was located at a distance of 2.76-2.86 Å. A significant improvement (19-39%) of the fit was obtained by including a third coordination shell with 2.0-3.8 O/C atoms involved in single scattering at an average distance of 3.69 Å and multiple scattering at an average distance of 4.19 Å. Our results provide evidence for inner-sphere complexation of Cu(II) in NOM and suggest that Cu(II) is complexed by either one or two five-membered chelate rings involving possible combinations of amino, carboxyl, or carbonyl functional groups. Ion activity measurements showed that less than 0.2% of total Cu was in the form of free Cu2+ in our samples at pH 4.8-6.3.
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| 45. |
- Karlsson, Torbjörn, et al.
(författare)
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Extended X-ray absorption fine structure spectroscopy evidence for the complexation of cadmium by reduced sulfur groups in natural organic matter
- 2005
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Ingår i: ENVIRONMENTAL SCIENCE & TECHNOLOGY. - : American Chemical Society (ACS). - 0013-936X .- 1520-5851. ; 39:9, s. 3048-55
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Tidskriftsartikel (refereegranskat)abstract
- It is widely accepted that the bioavaiiability, toxicity, and mobility of trace metals are highly dependent on complexation reactions with functional groups in natural organic matter (NOM). In this study, the coordination chemistry of Cd in NOM was investigated by extended X-ray absorption fine structure spectroscopy. Soil organic matter (SOM) from different types of organic soils and dissolved organic matter (DOM) from an organic and a mineral soil horizon of a Spodosol and aquatic DOM from Suwannee River were investigated. In SOM samples (1000-25000 mu g of Cd g(-1), pH 4.6-6.6), Cd was coordinated by 1.0-2.5 S atoms at a distance of 2.49-2.55 angstrom and by 3.0-4.5 O/N atoms at a distance of 2.22-2.25 angstrom. In DOM samples (1750-4250 mu g of Cd g(-1), pH 5.4-6.3), Cd was coordinated by 0.3-1.8 S atoms at a distance of 2.51-2.56 angstrom and 3.6-4.5 O/N atoms at a distance of 2.23-2.26 angstrom. In both SOM and DOM samples a second coordination shell of 1.7-6.0 carbon atoms was found at an average distance of 3.12 angstrom. This is direct evidence for inner-sphere complexation of Cd by functional groups in NOM. Furthermore, ion activity measurements showed that less than 1% of total Cd was in the form of free Cd2+ in our samples. Bond distances and coordination numbers suggest that Cd complexed in SOM and DOM is a mixture of a 4-coordination with S (thiols) and 4- and 6-coordinations with O/N ligands. Given that Cd-S associations on average are stronger than Cd-O/N associations, our results strongly indicate that reduced S ligands are involved in the complexation of Cd by NOM also at native concentrations of metal in oxidized organic-rich soils and in humic streams.
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| 46. |
- Karlsson, Torbjörn, et al.
(författare)
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Modeling Copper(II) Complexation in a Peat Soil Based on Spectroscopic Structural Information
- 2008
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Ingår i: Soil Science Society of America Journal. - : American Society of Agronomy. - 0361-5995 .- 1435-0661. ; 72:5, s. 1286-1291
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Tidskriftsartikel (refereegranskat)abstract
- The speciation of Cu in soils and surface waters is largely influenced by complexation reactions with natural organic matter (NOM). In this study, ion selective electrode data for the binding of Cu2+ to a forest peat soil were collected as a function of equilibration time, pH (2.4–6.6), and total Cu(II) concentration (1–54g Cu kg–1 dry soil). As a first step, a one-site Langmuir isotherm was successfully fitted to the Cu adsorption data for the complete concentration range at pH 4.6. In a second step, structural information extracted from extended x-ray absorption fine structure (EXAFS) spectroscopy, showing that Cu(II) forms five-membered rings with possible combinations of amine, carboxyl, and carbonyl functional groups in NOM, were used as input for chemical speciation calculations (using the chemical equilibrium model MINTEQA2). In agreement with the EXAFS results, a model consisting of one RNH2, forming monodentate complexes (Cu2+ + RNH2 RH2NCu2+; log stability constant KRH2NCu2+ = 9.2; –log acid dissociation constant [pKa] = 9.0 for RNH3+), and two adjacent RCOO– groups, forming bidentate complexes (Cu2+ + 2RCOO– Cu(OOCR)2; log stability constant β(RCOO)2Cu = 4.7; pKa = 4.5 for RCOOH), gave the best fit to the experimental data. Determined stability constants for Cu(II)–amine and Cu(II)–carboxyl complexes were in good agreement with well-defined Cu complexes with amino acids and carboxyls, respectively.
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| 47. |
- Karlsson, Torbjörn, et al.
(författare)
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Characterization of iron(III) in organic soils using extended X-ray absorption fine structure spectroscopy
- 2008
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Ingår i: Environmental Science and Technology. - : American Chemical Society (ACS). - 0013-936X .- 1520-5851. ; 42:15, s. 5449-5454
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Tidskriftsartikel (refereegranskat)abstract
- The distribution of different iron (Fe) species in soils, sediments, and surface waters has a large influence on the mobility and availability of Fe, other nutrients, and potentially toxic trace elements. However, the knowledge about the specific forms of Fe that occurs in these systems is limited, especially regarding associations of Fe with natural organic matter (NOM). In this study, extended X-ray absorption fine structure (EXAFS) spectroscopy was used to characterize Fe(III) in organic soils (pH 4.6-6.0) with varying natural Fe content. The EXAFS data were subjected to wavelet transform analysis, to facilitate the identification of the nature of backscattering atoms, and to conventional EXAFS data fitting. The collective results showed the existence of two pools of iron: mononuclear Fe(III)-NOM complexes and precipitated Fe(III) (hydr)oxides. In the soil with lowest pH (4.6) and Fe content mononuclear organic complexes were the completely dominating fraction whereas in soils with higher pH and Fe content increasing amounts of Fe (hydr)oxides were detected. These results are of environmental importance, as the different iron pools most likely have markedly different reactivities.
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| 48. |
- Kronberg, Rose-Marie, et al.
(författare)
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Detection of a key Hg methylation gene, hgcA, in wetland soils
- 2014
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Ingår i: Environmental Microbiology Reports. - : Wiley. - 1758-2229. ; 6, s. 441-447
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Tidskriftsartikel (refereegranskat)abstract
- The corrinoid protein, HgcA has been shown to be essential for Hg methylation in anaerobic bacteria. We investigated the diversity of hgcA from temperate and tropical wetland soils where Hg methylation is demonstrated. Sequences obtained from both environments clustered with those from the -Proteobacteria, Chloroflexi and Methanomicrobia with significant overlap in hgcA phylogeny between libraries. Clear differences in hgcA distribution were observed between two highly contrasting sites within a tropical wetland in Everglades National Park, USA. hgcA sequences obtained from the northern site clustered primarily with those of methanogens, while sequences from the estuarine site clustered primarily with sulphate-reducing bacteria and syntrophs in the -Proteobacteria. Libraries obtained from soils collected from a temperate swamp in Sweden were dominated by hgcA sequences within the -Proteobacteria with hgcA sequences clustering primarily with iron reducers in the upstream portion of the swamp and with sulphate reducers in the downstream portion of the swamp. Interestingly, enrichments prepared from the lower portion of this temperate wetland contained a high abundance of hgcA sequences clustering with methanogens. This first report on hgcA diversity in environmental samples suggests a role in Hg methylation for various phenotypic groups in different portions of wetlands.
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| 49. |
- Kronberg, Rose-Marie, et al.
(författare)
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Forest harvest contribution to Boreal freshwater methyl mercury load
- 2016
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Ingår i: Global Biogeochemical Cycles. - 0886-6236 .- 1944-9224. ; 30:6, s. 825-843
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Tidskriftsartikel (refereegranskat)abstract
- Effects of Boreal forest harvest on mercury (Hg) and methyl mercury (MeHg) soil pools and export by stream runoff were quantified by comparing 10 reference watersheds (REFs) covered by >80year old Norway spruce (Picea abies Karst.) forests with 10 similar watersheds subjected to clear-cutting (CCs). While total Hg soil storage did not change, MeHg pools increased seven times (p=0.006) in the organic topsoil 2 years after clear-cutting. In undulating terrain, situated above the postglacial marine limit (ML) of the ancient Baltic Sea, the mass ratio between flux-weighted MeHg and dissolved organic carbon (MeHg/DOC) in stream runoff increased 1.8 times (p<0.004) as a consequence of forest harvest. When recalculated to 100% clear-cutting of the watershed, the annual MeHg stream export increased 3.8 times (p=0.047). Below the ML, where the terrain was flatter, neither the MeHg/DOC ratio nor the annual export of MeHg differed between REFs and CCs, likely because of the larger contribution of MeHg exported from peaty soils and small wetlands. The most robust measure, MeHg/DOC, was used to calculate MeHg loadings to Boreal headwaters. If the forest harvest effect lasts 10years, clear-cutting increases MeHg runoff by 12-20% in Sweden and 2% in the Boreal zone as a whole. In Sweden, having intensely managed forests, 37% and 56% of MeHg are exported from peatlands and forest soils, respectively, and forest clear-cutting is adding another 6.6%. In the Boreal zone as a whole peatlands and forests soils contribute with 53% and 46%, respectively, and clear-cutting is estimated to add another 1.0%. An expected rapid increase in Boreal forest harvest and disturbance urge for inclusion of land use effects in mercury biogeochemical cycling models at different scales.
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| 50. |
- Kronberg, Rose-Marie, et al.
(författare)
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Mechanisms of Methyl Mercury Net Degradation in Alder Swamps : The Role of Methanogens and Abiotic Processes
- 2018
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Ingår i: Environmental Science and Technology Letters. - : American Chemical Society (ACS). - 2328-8930. ; 5:4, s. 220-225
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Tidskriftsartikel (refereegranskat)abstract
- 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.
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