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Wetlands are common sites of active Hg methylation by anaerobic microbes; however, the amount of methylmercury produced varies greatly, as Hg methylation is dependent upon both the availability of Hg and the composition and activity of the microbial community involved. In this study, we identified the major microbial guilds responsible for Hg methylation along a trophic gradient composed of two sites and three different types of wetlands: a bog-fen peatland gradient and a black alder swamp, serving as net sources and a sink for methylmercury respectively. Iron-reducing bacteria in the Geobacteraceae were important Hg methylators across all wetlands and seasons examined, as evidenced by abundant 16S rRNA and hgcA transcripts clustering with this family. Molybdate inhibited Hg methylation more efficiently in the peatlands than in the swamp, suggesting an increasing role of sulfate-reducing bacteria and/or related syntrophs in the methylation of Hg with decreasing trophic status. Sulfate addition failed to increase Hg methylation rates in the peatlands, suggesting that SRBs/syntrophs were instead likely metabolizing alternative substrates such as syntrophic fermentation of organic compounds with methanogens. These results highlight the interconnectivity of anaerobic metabolism and importance of community dynamics on the methylation of Hg in wetlands with different trophic status.

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

The chemical speciation of mercury (Hg), methyl mercury (MeHg), sulfur and iron was investigated in the sediment and porewater of Lake Angessjon, a boreal, shallow (maximum depth 2.5 m), oligo-/dystrophic lake in northern Sweden. The lake receives terrestrial stream runoff from surrounding coniferous forest soils and peatlands having a low pH (4.6) and high concentrations of dissolved organic matter (DOM, annual average: 45 mg L−1), Fe (60 µM), sulfate (105 µM), inorganic Hg (1200 pM) and MeHg (250 pM). Sulfur K-edge XANES and Hg LIII-edge EXAFS spectroscopic measurements were used to characterize and quantify the sulfur speciation in the lake sediment at nine occasions, covering different seasons in the years of 2007 and 2009. In the surface sediment (0–3 cm) sulfate is reduced to zero-valent S and inorganic sulfide, that in turn reacts with Fe to form FeSm (mackinawite) and FeS2 (framboidal pyrite). The latter mineral becomes increasingly dominant by depth in the sediment. Thermodynamic modeling successfully predicted measured porewater concentrations of Hg in the sediment. Metacinnabar (β-HgS) and Hg(NOM-RS)2 complexes (the latter formed as a reaction between Hg(II) and thiol groups associated with natural organic matter, NOM-RSH) were the dominant forms of Hg(II) in the solid phase of sediments and Hg(II)-polysulfides (aq) dominated in the porewater. We argue that FeSm is a key component that indirectly controlled the Hg(II) speciation in the sediment by keeping the aqueous phase concentration of inorganic sulfide in the 0.5–2 µM range throughout the year. Besides providing a pool of readily soluble inorganic sulfide for formation of β-HgS(s), as demonstrated by previously reported EXAFS experiments, we further suggest FeSm may serve as a precursor for the formation of a more crystalline (less soluble) β-HgS(s) phase than present in environments devoid of FeSm. Support for this was provided by comparing our results with previously reported thermodynamic modelling results of Hg(II) and MeHg solubility in organic soils devoid of FeSm. In more general terms, we suggest the presence or absence of FeSm, through its influence on the chemical speciation of Hg and MeHg, may be a key factor behind the variability in rates of Hg(II) and MeHg transformation processes, such as methylation, reduction and demethylation, reported for different environmental settings.

Methylmercury (MeHg) is a neurotoxin formed from inorganic divalent mercury (Hg-II) via microbial methylation, and boreal wetlands have been identified as major sources of MeHg. There is however a lack of studies investigating the relationship between the chemical speciation of Hg-II and MeHg formation in such environments, in particular regarding to role of thiol compounds. We determined Hg-II methylation potentials, k(meth), in boreal wetland soils using two Hg-II isotope tracers: Hg-198(OH)(2)(aq) and Hg-II bonded to thiol groups in natural organic matter, Hg-200(II)-NOM(ads), representing Hg-II sources with high and low availability for methylation. The Hg-198(OH)(2)(aq) tracer was consistently methylated to a 5-fold higher extent than Hg-200(II)-NOM(ads), independent of environmental conditions. This suggests that the concentration of Hg-II in porewater was a decisive factor for Hg-II methylation. A comprehensive thermodynamic speciation model (including Hg-II complexes with inorganic sulfide (H2S), polysulfides (H2Sn), thiols associated with natural organic matter (NOM-RSH) and specific low molecular mass thiols (LMM-RSH) provided new insights on the speciation of Hg-II in boreal wetland porewaters, but did not demonstrate any clear relationship between k(meth) and the calculated chemical speciation. In contrast, significant positive relationships were observed between k(meth) and the sum of LMM thiol compounds of biological origin. We suggest two possible mechanisms underlying these correlations: 1) LMM thiols kinetically control the size and composition of the HgII pool available for microbial uptake, and/or 2) LMM thiols are produced by microbes such that the correlation reflects a relation between microbial activity and MeHg formation. (C) 2020 The Author(s). Published by Elsevier B.V.

13 pages, 4 figures, 3 tables, supporting information https://doi.org/10.1038/s41598-018-37383-z, The formation of the potent neurotoxic methylmercury (MeHg) is a microbially mediated process that has raised much concern because MeHg poses threats to wildlife and human health. Since boreal forest soils can be a source of MeHg in aquatic networks, it is crucial to understand the biogeochemical processes involved in the formation of this pollutant. High-throughput sequencing of 16S rRNA and the mercury methyltransferase, hgcA, combined with geochemical characterisation of soils, were used to determine the microbial populations contributing to MeHg formation in forest soils across Sweden. The hgcA sequences obtained were distributed among diverse clades, including Proteobacteria, Firmicutes, and Methanomicrobia, with Deltaproteobacteria, particularly Geobacteraceae, dominating the libraries across all soils examined. Our results also suggest that MeHg formation is also linked to the composition of non-mercury methylating bacterial communities, likely providing growth substrate (e.g. acetate) for the hgcA-carrying microorganisms responsible for the actual methylation process. While previous research focused on mercury methylating microbial communities of wetlands, this study provides some first insights into the diversity of mercury methylating microorganisms in boreal forest soils, This project was carried out within the Swedish-Sino SMaREF (2013-6978) funded by the Swedish Research Council. This study was also supported by the Swedish Energy Agency (grant number 36155-1) and the Swedish Research Council (Grants 2011-7192 and 2012-3892)

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.

9 pages, 5 figures, 2 tables, supplementary material https://doi.org/10.1016/j.scitotenv.2020.137306, Peatlands are abundant elements of boreal landscapes where inorganic mercury (IHg) can be transformed into bioaccumulating and highly toxic methylmercury (MeHg). We studied fifteen peatlands divided into three age classes (young, intermediate and old) along a geographically constrained chronosequence to determine the role of biogeochemical factors and nutrient availability in controlling the formation of MeHg. In the 10 cm soil layer just below the average annual growing season water table, concentrations of MeHg and %MeHg (of total Hg) were higher in younger, more mesotrophic peatlands than in older, more oligotrophic peatlands. In contrast, total mercury (THg) concentrations were higher in the older peatlands. Partial least squares (PLS) analysis indicates that the net MeHg production was positively correlated to trophic demands of vegetation and an increased availability of potential electron acceptors and donors for Hg methylating microorganisms. An important question for further studies will be to elucidate why there is less THg in the younger peatlands compared to the older peatlands, even though the age of the superficial peat itself is similar for all sites. We hypothesize that ecosystem features which enhance microbial processes involved in Hg methylation also promote Hg reduction that makes previously deposited Hg more available for evasion back to the atmosphere, This work was supported by the China Scholarship Council (CSC, 2015–2018), the Sino-Swedish Mercury Management Research Framework (SMaReF: VR2013-6978), the National Natural Science Foundation of China (No. 41573078 and 41303098) and the Swedish Research Council Formas (2106-00896), With the funding support of the ‘Severo Ochoa Centre of Excellence’ accreditation (CEX2019-000928-S), of the Spanish Research Agency (AEI)

Torrefaction, pyrolysis and gasification are of interest to convert lignocellulosic biomass into fuels and chemicals. These techniques involve thermal treatment at low partial pressures of oxygen. However, little is known about the transformation of ash elements during these processes. The phase transition of the major ash element calcium (Ca) was therefore studied with powder from pine as biomass model treated at temperatures 300–800 °C under atmospheres of 100% N2, 3% O2 and 6% O2 and thermodynamic equilibrium modelling. For evaluation, X-ray powder diffraction and synchrotron Ca K-edge X-ray absorption near edge structure (XANES) spectroscopy in combination with linear combination fitting and reference compounds was used. The results indicated that the most abundant Ca-containing species in the untreated material was thermally unstable Ca oxalate (CaC2O4) primarily decomposing into Ca phases dominated by carbonates at temperatures up to 600 °C. Double carbonates of calcium and potassium were observed in the form of fairchildiite/butscheliite (K2Ca(CO3)2), and these phases were stable over the low temperature range studied. Hydroxyapatite (Ca5(PO4)3OH) was expected to be present and thermally stable over the entire temperature interval and was found in untreated material. At temperatures above 600 °C calcium oxide (CaO) was formed. The amount of oxygen had little effect on the phase transitions. The results of thermodynamic modeling were in agreement with XANES showing that this is a versatile technique that can be applied to systems as complex as Ca phase transitions in thermally treated lignocellulosic biomass at low partial pressures of oxygen.

Mercury (Hg) remains hazardous in aquatic environments because of its biomagnification in food webs. Nonetheless, Hg uptake and impact in primary producers is still poorly understood. Here, we compared the cellular toxicity of inorganic and methyl Hg (IHg and MeHg, respectively) in the aquatic plant Elodea nuttallii. IHg and MeHg regulated contigs involved in similar categories (e.g., energy metabolism, development, transport, secondary metabolism), but MeHg regulated more contigs, supporting a higher molecular impact than IHg. At the organism level, MeHg induced antioxidants, while IHg decreased chlorophyll content. The uptake of Hg and expression of a subset of contigs was subsequently studied in complex media. Measured uptake pointed to a contrasted impact of cell walls and copper (Cu) on IHg and MeHg. Using a speciation modeling, differences in uptake were attributed to the differences in affinities of IHg and MeHg to organic matter in relation to Cu speciation. We also identified a distinct gene expression signature for IHg, MeHg, and Cu, further supporting different molecular toxicity of these trace elements. Our data provided fundamental knowledge on IHg and MeHg uptake in a key aquatic primary producer and confirmed the potential of transcriptomics to assess Hg exposure in environmentally realistic systems.

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 (103–105 Da) resolves micro-spatial priming of SOM, where the destabilization step is prerequisite for subsequent release of nutrients.

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 × 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 RSHg OR / NRC = 1.9 − 2.1 × 10 −4 h −1 ) that were very similar for Soil and Peat HA.

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.

Boreal wetlands have been identified as environments in which inorganic divalent mercury (HgII) is transformed to methylmercury (MeHg) by anaerobic microbes. In order to understand this transformation and the mobility and transport of HgII and MeHg, factors and conditions in control of the solubility and chemical speciation of HgII and MeHg need to be clarified. Here we explore the ability of thermodynamic models to simulate measured solubility of HgII and MeHg in different types of boreal wetland soils. With the input of measured concentrations of MeHg, sulfide, eight low molecular mass thiols and thiol groups associated with natural organic matter (NOM), as determined by sulfur K-edge X-ray absorption near-edge structure (XANES) spectroscopy and Hg LIII-edge extended X-ray absorption fine structure spectroscopy (EXAFS), the model could accurately predict porewater concentrations of MeHg in the wetlands. A similar model for HgII successfully predicted the average level of its concentration in the porewat...

Terrestrial discharge can cause pelagic zone trophic shifts and enhance methylmercury accumulation in plankton three- to sixfold., The input of mercury (Hg) to ecosystems is estimated to have increased two- to fivefold during the industrial era, and Hg accumulates in aquatic biota as neurotoxic methylmercury (MeHg). Escalating anthropogenic land use and climate change are expected to alter the input rates of terrestrial natural organic matter (NOM) and nutrients to aquatic ecosystems. For example, climate change has been projected to induce 10 to 50% runoff increases for large coastal regions globally. A major knowledge gap is the potential effects on MeHg exposure to biota following these ecosystem changes. We monitored the fate of five enriched Hg isotope tracers added to mesocosm scale estuarine model ecosystems subjected to varying loading rates of nutrients and terrestrial NOM. We demonstrate that increased terrestrial NOM input to the pelagic zone can enhance the MeHg bioaccumulation factor in zooplankton by a factor of 2 to 7 by inducing a shift in the pelagic food web from autotrophic to heterotrophic. The terrestrial NOM input also enhanced the retention of MeHg in the water column by up to a factor of 2, resulting in further increased MeHg exposure to pelagic biota. Using mercury mass balance calculations, we predict that MeHg concentration in zooplankton can increase by a factor of 3 to 6 in coastal areas following scenarios with 15 to 30% increased terrestrial runoff. The results demonstrate the importance of incorporating the impact of climate-induced changes in food web structure on MeHg bioaccumulation in future biogeochemical cycling models and risk assessments of Hg.

Net formation of methylmercury (MeHg) in sediments is known to be affected by the availability of inorganic divalent mercury (Hg(II)) and by the activities of Hg(II) methylating and MeHg demethylating bacteria. Enhanced autochthonous organic matter deposition to the benthic zone, following increased loading of nutrients to the pelagic zone, has been suggested to increase the activity of Hg(II) methylating bacteria and thus the rate of net methylation. However, the impact of increased nutrient loading on the biogeochemistry of mercury (Hg) is challenging to predict as different geochemical pools of Hg may respond differently to enhanced bacterial activities. Here, we investigate the combined effects of nutrient (N and P) supply to the pelagic zone and the chemical speciation of Hg(II) and of MeHg on MeHg formation and degradation in a brackish sediment-water mesocosm model ecosystem. By use of Hg isotope tracers added in situ to the mesocosms or ex situ in incubation experiments, we show that the MeHg formation rate increased with nutrient loading only for Hg(II) tracers with a high availability for methylation. Tracers with low availability did not respond significantly to nutrient loading. Thus, both microbial activity (stimulated indirectly through plankton biomass production by nutrient loading) and Hg(II) chemical speciation were found to control the MeHg formation rate in marine sediments.

Four years of catchment export and wetland input-output mass balances are reported for inorganic Hg (Hg(inorg)), methyl mercury (MeHg), dissolved organic carbon (DOC), and sulfate in eight Swedish boreal wetlands. All wetlands had a history of artificial drainage and seven were subjected to small-scale flooding during the complete study period (two sites) or the two last years (five sites). We used an approach in which specific runoff data determined at hydrological stations situated at a distance from the studied sites were used in the calculation of water and element budgets. All wetlands except one were significant sinks for Hg(inorg). Seven wetlands were consistent sources of MeHg and one (an Alnus glutinosa swamp) was a significant sink. The pattern of MeHg yields was in good agreement with previously determined methylation and demethylation rates in the wetland soils of this study, with a maximum MeHg yield obtained in wetlands with an intermediate soil acidity (pH ∼5.0) and C/N ratio (∼20). We hypothesize that an increased nutrient status from poor to intermediate conditions promotes methylation over demethylation, whereas a further increase in nutrient status and trophy to meso- and eutrophic conditions promotes demethylation over methylation. Small-scale flooding showed no or moderate changes in MeHg yield, maintaining differences among wetlands related to nutrient status.

Despite methylmercury (MeHg) production in boreal wetlands being a research focus for decades, little is known about factors in control of methylation and demethylation rates and the effect of wetl ...

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).

Concentrations of inorganic, mercuric mercury (Hg(II)), methyl mercury (MeHg) and ancillary chemistry measured in first-order streams draining 0-4 (N = 20) and 4-10 (N = 27) year-old clear-cuts of former Norway Spruce Picea abies (Karst.) forest stands were compared with concentrations in streams draining70 year-old Norway Spruce reference stands (N = 10). Concentrations of MeHg, and ratios of MeHg TOC(-1) and Hg(II) TOC(-1), were significantly (p0.01) elevated in 0-4 year-old clear-cuts, as compared to references. The only ancillary variable showing a significant elevation for 0-4 year-old clear-cuts was Mn (p0.02). The 4-10 year-old clear-cuts showed intermediate concentrations with nonsignificant differences as compared to references. pH, nitrate, sulfate, Ca, Fe, TOC, TON, and the aromaticity of TOC (SUVA(254 nm)) showed nonsignificant differences between clear-cut age classes and references. Assuming that MeHg and Hg(II) are mobilized from soil to stream to a similar relative extent as a consequence of clear-cutting, a calculation showed that (1)/(6) of the elevated MeHg concentration was due to enhanced mobilization from soil and (5)/(6) was due to new methylation of Hg(II) 0-4 years after clear-cut. New methylation after clear-cut is suggested to be stimulated by an increased availability of electron donors for methylating bacteria, as a consequence of degradation of logging residue ("slash") and soil organic matter. A subdivision of sites situated above and below the highest postglacial coastline (HC) revealed a significant elevation of MeHg, MeHg TOC(-1) and Hg(II) TOC(-1) (p0.05) beyond their references in 0-4 year-old clear-cuts above (but not below) the HC. This suggests that postglacial deposits of FeS(s) and FeS(2)(s) were not an important factor for elevation of MeHg after clear-cut.

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 degrees 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.

The retention and mobility of hydrophobic organic contaminants (HOCs) in soil is mainly determined by hydrophobic partitioning to dissolved and particulate organic matter (DOM and POM, respectively). The aqueous phase, DOM, and POM fractions were extracted and separated from soils at three sites contaminated with technical chlorophenol formulations. Concentrations of chlorophenols (CP), polychlorinated phenoxyphenols (PCPP), polychlorinated diphenyl ethers (PCDE) and polychlorinated dibenzo-p-dioxins and furans (PCDD/F) were determined. The partitioning to POM, in relation to DOM, increased in all three soils with increasing hydrophobicity in the order CPPCPP ~ PCDE ~ PCDFPCDD. Differences in partitioning to DOM (logK(DOC)) and POM (logK(POC)) could not be explained by differences in gross organic C chemistry. Black carbon did not contribute significantly to the sorption of PCDDs, whereas70% wood fibre in one soil resulted in a decrease of logK(POC) of 0.5 units for CPs and PCDDs. We conclude that logK(OC) for both DOM and POM need to be explicitly determined when the retention and mobility of HOCs is described and modelled in soils.

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.

Even if it is generally accepted that associations with natural organic matter (NOM) to a great extent determine the bioavailability and mobility of trace metals in soils and waters, the knowledge about the identity of NOM functional groups involved is still limited. In this study, extended X-ray absorption fine structure (EXAFS) spectroscopy was used to determine the coordination chemistry of zinc (Zn) in two organic soils (500-10,000 microg Zn g(-), pH 5.6-7.3). In both soils Zn was coordinated by a mixture of oxygen/nitrogen (O/N) and sulfur (S) ligands in the first coordination shell. In average, 0.4-0.9 S atoms were located at a distance of 2.29-2.33 angstom, well in agreement with a 4-fold coordination with thiolates (RS-) in proteins. In addition 2.7-3.7 O/N atoms were located at 1.99-2.04 angstrom. The improved merit of fit by inclusion of S atoms was shown to be significant after adjusting for the improvement caused merely by increasing the number of fitting parameters. Two second shell Zn-C distances were used in our model: 3.0-4.2 carbon (C) atoms, associated to first shell O/N, were encountered at an average distance of 2.84 amgstrom, and 0.4-0.9 C atoms, associated to first shell S, were encountered at an average distance of 3.32 angstrom. These Zn-C distances are well in agreement with distances determined in well-defined organic molecules. It is concluded that Zn forms mainly inner-sphere complexes with a mixture of 4-fold coordination with S and O/N ligands and 6-fold coordination with O ligands in organic soils.

We determined the sorption of 2,4-dichlorophenol (DCP), 2,4,5-trichlorophenol (TCP) and pentachlorophenol (PCP) to dissolved (DOM) and particulate soil organic matter (POM) from the same soil in controlled equilibrium systems, using 14 C-labelled chlorophenols in combination with reversed-phase high-performance liquid chromatography (RP-HPLC) and liquid scintillation. Associations of DCP, TCP and PCP to DOM and POM were satisfactorily described by linear adsorption isotherms. Together with the absence of substantial competition between DCP and TCP for binding sites, this indicates a hydrophobic partitioning mechanism. The organic carbon normalized partitioning coefficient (K OC ) for the binding of DCP was similar in magnitude for POM (K POC ) and for DOM (K DOC ), whereas K POC for the more hydrophobic compounds TCP and PCP were approximately one order of magnitude greater than K DOC . On the basis of the relationships between log K OC and the organic carbon normalized partitioning coefficient (log K OW ), the extent of association to POM increases more with the hydrophobicity of the chlorophenol than the extent of association to DOM. This holds for our data obtained for DOM and POM of similar origin, as well as for various sources of POM and DOM reported in the literature. Differences in the magnitude of Kpoc and K DOC in our study could not be accounted for by differences in gross carbon chemistry of POM and DOM, as determined by nuclear magnetic resonance ( 13 C-NMR) and X-ray photoelectron spectroscopy (XPS). Thus, other factors such as the average size and capacity of hydrophobic moieties could explain differences in chlorophenol association between POM and DOM. We conclude that K POC and K DOC need to be determined explicitly, when the transport and retention'of chlorophenols is modelled, and not calculated from relationships between log K OC and log K OW .

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.

We combined synchrotron-based X-ray absorption near edge structure (XANES) spectroscopy, extended X-ray absorption fine structure (EXAFS) spectroscopy and binding affinity studies to determine the coordination, geometry, and strength of methyl mercury, CH3Hg (II), bonding in soil and stream organic matter. Samples of organic soil (OS), potentially soluble organic substances (PSOS) from the soil, and organic substances from a stream (SOS) draining the soil were taken along a short “hydrological transect.” We determined the sum of concentrations of highly reduced organic S groups (designated Org-SRED), such as thiol (RSH), disulfane (RSSH), sulfide (RSR), and disulfide (RSSR), using sulfur K-edge XANES. Org-SRED varied between 27% and 64% of total S in our samples. Hg LIII-edge EXAFS analysis were determined on samples added CH3Hg (II) to yield CH3Hg (II)/Org-SRED ratios in the range 0.01–1.62. At low ratios, Hg was associated to one C atom (the methyl group) at an average distance of 2.03 ± 0.02 A and to one S atom at an average distance of 2.34 ± 0.03 A, in the first coordination shell. At calculated CH3Hg(II)/Org-SRED ratios above 0.37 in OS, 0.32 in PSOS, and 0.24 in SOS, the organic S sites were saturated by CH3Hg+, and O (and/or N) atoms were found in the first coordination shell of Hg at an average distance of 2.09 ± 0.01 A. Based on the assumption that RSH (and possibly RSSH) groups take part in the complexation of CH3Hg+, whereas RSSR and RSR groups do not, approximately 17% of total organic S consisted of RSH (+ RSSH) functionalities in the organic soil. Corresponding figures for samples PSOS and SOS were 14% and 9%, respectively. Competitive complexation of CH3Hg+ by halide ions was used to determine the average binding strength of native concentrations of CH3Hg (II) in the OS sample. Using data for Org-SRED, calculated surface complexation constants were in the range from 1016.3 to 1016.7 for a model RSH site having an acidity constant of mercaptoacetic acid. These values compare favorably with identically defined stability constants (log K1) for the binding of methyl mercury to thiol groups in well-defined organic compounds.

Methyl mercury was determined by gas chromatography, microwave induced plasma, atomic emission spectrometry (GC-MIP-AES) using two different methods. One was based on extraction of mercury species into toluene, pre-concentration by evaporation and butylation of methyl mercury with a Grignard reagent followed by determination. With the other, methyl mercury was extracted into dichloromethane and back extracted into water followed by in situ ethylation, collection of ethylated mercury species on Tenax and determination. The accuracy of the entire procedure based on butylation was validated for the individual steps involved in the method. Methyl mercury added to various types of soil samples showed an overall average recovery of 87.5%. Reduced recovery was only caused by losses of methyl mercury during extraction into toluene and during pre-concentration by evaporation. The extraction of methyl mercury added to the soil was therefore quantitative. Since it is not possible to directly determine the extraction efficiency of incipient methyl mercury, the extraction efficiency of total mercury with an acidified solution containing CuSO4 and KBr was compared with high-pressure microwave acid digestion. The solvent extraction efficiency was 93%. For the IAEA 356 sediment certified reference material, mercury was less efficiently extracted and determined methyl mercury concentrations were below the certified value. Incomplete extraction could be explained by the presence of a large part of inorganic sulfides, as determined by x-ray absorption near-edge structure spectroscopy (XANES). Analyses of sediment reference material CRM 580 gave results in agreement with the certified value. The butylation method gave a detection limit for methyl mercury of 0.1 ng g(-1), calculated as three times the standard deviation for repeated analysis of soil samples. Lower values were obtained with the ethylation method. The precision, expressed as RSD for concentrations 20 times above the detection limit, was typically 5%.

Data from two Podzol O and E horizons, sampled in 1-cm layers at 13 points within 2 m × 2 m plots, were used to test the hypothesis that the composition of hydrogen ions (H) and aluminium (Al) adsorbed to the solid-phase soil organic matter (SOM) determines pH and Al solubility in organic-rich acidic forest soils. Organically adsorbed Al was extracted sequentially with 0.5 M CuCl 2 and organically adsorbed H was determined as the difference between total acidity titrated to pH 8.2 and Al extracted in 0.5 M CuCl 2 . The quotient between fractions of SOM sites binding Al and H (N Al /N H ) is shown to determine the variation in pH and Al solubility. It is furthermore shown that models in which pH and Al solubility are linked via a pH-dependent solubility of an Al hydroxide and in which cation exchange between Al 3+ and Ca 2+ , rather than cation exchange between Al 3+ and H + , is the main pH-buffering process cannot be used to simulate pH or Al solubility in O and E horizons. The fraction of SOM sites adsorbing Al increased by depth in the lower O and throughout the E horizon at the same magnitude as sites adsorbing H decreased. The fraction of sites binding the cations Ca 2+ + Mg 2+ + K + + Na + remained constant. It is suggested that a net reaction between Al silicates (proton acceptors) and protonated functional groups in SOM (proton donors) is the long-term chemical process determining the composition of organically adsorbed H and Al in the lower part of the O and in the E horizon of Podzols. Thus, in the long term, pH and Al solubility are determined by the interaction between organic acidity and Al alkalinity.

Sulfur K-edge x-ray absorption near-edge structure spectroscopy (XANES) was used to identify multiple organic S oxidation states in aquatic and soil humic substances. The XANES results suggest that S in humic substances exists in four major oxidation groups similar to sulfate ester, sulfonate, sulfoxide, and thiol-sulfide. Thiol S cannot be separated from sulfide X and must be considered as a single thiol-sulfide peak. The second derivative spectra suggest the existence of thiophene and sulfone S. The relative quantities of each major S form in humic samples were estimated based on the integrated cross section of each s {r_arrow} p transition peak corresponding to different S oxidation states in the S K-edge XANES spectra. The XANES results of the four humic samples used in this study appear to reflect the environmental settings where the humic substances originally formed. The percentage of the most reduced organic S (thiol-sulfide and possibly thiophene) in humic substances follows the sequence:aquatic samples > organic soil sample > mineral soil sample. The percentage of most oxidized S (sulfate group) was the greatest in the humic substance from a mineral soil and the lowest in the aquatic humic substances.

Neurotoxic methylmercury (MeHg) formed from inorganic divalent mercury (Hg(II)) accumulates in aquatic biota and remains at high levels worldwide. It is poorly understood to what extent different geochemical Hg pools contribute to these levels. Here we report quantitative data on MeHg formation and bioaccumulation, in mesocosm water-sediment model ecosystems, using five Hg(II) and MeHg isotope tracers simulating recent Hg inputs to the water phase and Hg stored in sediment as bound to natural organic matter or as metacinnabar. Calculations for an estuarine ecosystem suggest that the chemical speciation of Hg(II) solid/adsorbed phases control the sediment Hg 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.

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 ± 0.1 (HgS(s) + H(+) = Hg(2+) + 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). On the basis of this, we report refined formation constants (±SE) for the three aqueous Hg(II)-sulfide species proposed by Schwarzenbach and Widmer (1963): Hg(2+) + 2HS(-) = Hg(SH)2(0); log K = 39.1 ± 0.1, Hg(2+) + 2HS(-) = HgS2H(-) + H(+); log K = 32.5 ± 0.1, Hg(2+) + 2HS(-) = HgS2(2-) + 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-micromolar 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.

Knowledge about the chemical speciation of Hg(II) is a prerequisite for a proper understanding of biogeochemical processes in control of the transformation of Hg(II) into toxic and bioaccumulating monomethyl mercury. Of critical importance are structures and the stability of Hg(II)-complexes with inorganic and organic sulfur ligands in aqueous and solid phases of soils and sediments. On the basis of Hg L(III)-edge EXAFS experiments, we report Hg(II) to form a four-coordinated metacinnabar [beta-HgS(s)] phase when reacted with disordered FeS(s) (mackinawite), at pH 9.0 and a Hg(II) to FeS(s) molar ratio of 0.002-0.012. When Hg(II) (1000-20,000 microg Hg g(-1)) was added to mixtures of

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.

[1] Current research focus in mercury biogeochemistry is on the net production and accumulation of methyl mercury (MeHg) in organisms. The activity of iron- and sulfate-reducing bacteria (FeRB and SRB) has been identified as important for MeHg production. There are indications of a passive uptake of neutral Hg-sulfides by SRB, as well as of a facilitated bacterial uptake of Hg complexed by small organic molecules. In order to understand these processes, the chemical speciation of Hg and MeHg, and most important, the competition among organic thiols and inorganic sulfides and polysulfides, needs to be clarified under suboxic conditions (nM to low μM range of total sulfide concentrations) in wetland soils and sediments. In this paper the chemical speciation of Hg and MeHg is modeled at pH 4.0 and 7.0 in a conceptual wetland soil/sediment with typical concentrations of thiols, sulfides, Hg, and MeHg. Effects of precipitated HgS(s), the formation of Hg-polysulfides, and the size of the controversial stability constant for the formation of HOHgSH 0 (aq) are emphasized. The outcome of the modeling is discussed in light of chosen stability constants for Hg complexes with thiols, sulfides, and polysulfides. It is concluded that organic thiols are competitive with inorganic sulfides in the approximate total sulfide concentration range 0-1 μm. It is also concluded that increases in absolute aqueous concentrations of MeHg, or the molar ratio of dissolved MeHg/Hg, are not appropriate as indirect measures of MeHg net production, unless changes and differences in solubility of MeHg and Hg are corrected for.

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 the3.5 kDa size fraction were 2.8-6.0 and 8.5-9.5 times higher for aniline and TNT*, respectively, as compared to the40 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 the3.5 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.

Sediments contaminated by various sources of mercury (Hg) were studied at 8 sites in Sweden covering wide ranges of climate, salinity, and sediment types. At all sites, biota (plankton, sediment living organisms, and fish) showed enhanced concentrations of Hg relative to corresponding organisms at nearby reference sites. The key process determining the risk at these sites is the net transformation of inorganic Hg to the highly toxic and bioavailable methylmercury (MeHg). Accordingly, Hg concentrations in Perca fluviatilis were more strongly correlated to MeHg (p0.05) than to inorganic Hg concentrations in the sediments. At all sites, except one, concentrations of inorganic Hg (2-55 microg g(-1)) in sediments were significantly, positively correlated to the concentration of MeHg (4-90 ng g(-1)). The MeHg/Hg ratio (which is assumed to reflect the net production of MeHg normalized to the Hg concentration) varied widely among sites. The highest MeHg/Hg ratios were encountered in loose-fiber sediments situated in southern freshwaters, and the lowest ratios were found in brackish-water sediments and firm, minerogenic sediments at the northernmost freshwater site. This pattern may be explained by an increased MeHg production by methylating bacteria with increasing temperature, availability of energy-rich organic matter (which is correlated with primary production), and availability of neutral Hg sulfides in the sediment pore waters. These factors therefore need to be considered when the risk associated with Hg-contaminated sediments is assessed.

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.

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 degrees 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 (p0.001, 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 subsets 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 (microg kg-1) in brackish waters (p0.001, n = 23), in southern, high-productivity freshwaters (p0.001, 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 (microg 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).

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.

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(ll), 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 microg Cu g(-1) dryweight, pH 2.8-6.3), Cu(ll) was coordinated by 4 oxygen/ nitrogen (O/N) atoms at a distance of 1.92-1.95 angstroms 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 angstroms. 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 angstroms and multiple scattering at an average distance of 4.19 angstroms. Our results provide evidence for inner-sphere complexation of Cu(ll) in NOM and suggest that Cu(ll) 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.

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.