Chemical composition of aquatic dissolved organic matter in five boreal forest catchments sampled in spring and fall seasons

The chemical composition and carbon isotope signature of aquatic dissolved organic matter (DOM) in five boreal forest catchments in Scandinavia were investigated. The DOM was isolated during spring and fall seasons using a reverse osmosis technique. The DOM samples were analyzed by elemental analysis, FT-IR, solid-state CP-MAS 13C-NMR, and C-1s NEXAFS spectroscopy. In addition, the relative abundance of carbon isotopes (12C, 13C, 14C) in the samples was measured. There were no significant differences in the chemical composition or carbon isotope signature of the DOM sampled in spring and fall seasons. Also, differences in DOM composition between the five catchments were minor. Compared to reference peat fulvic and humic acids, all DOM samples were richer in O-alkyl carbon and contained less aromatic and phenolic carbon, as shown by FT-IR, 13C-NMR, and C-1s NEXAFS spectroscopy. The DOM was clearly enriched in 14C relative to the NBS oxalic acid standard of 1950, indicating that the aquatic DOM contained considerable amounts of organic carbon younger than about 50years. The weight-based C:N ratios of 31 ± 6 and the $$\delta^{13}\hbox{C}$$ values of -29\pm2\permille indicate that the isolated DOM is of terrestrial rather than aquatic origin. We conclude that young, hydrophilic carbon compounds of terrestrial origin are predominant in the samples investigated, and that the composition of the aquatic DOM in the studied boreal forest catchments is rather stable during low to intermediate flow condition

Origin of high Zn contents in Jurassic limestone of the Jura mountain range and the Burgundy: evidence from Zn speciation and distribution

In order to better understand the origin and enrichment mechanisms leading to elevated Zn concentrations in Jurassic limestone of the Jura mountain range (JMR) and the Burgundy (B), we investigated four locations of Bajocian age (JMR: Lausen-Schleifenberg, Gurnigel; B: Vergisson-Davayé, Lucy-le-Bois) and two locations of Oxfordian age (JMR: Dornach, Pichoux) for their Zn distribution and speciation. Measurements of the acid-extractable and bulk Zn contents showed that Zn is stratigraphically and spatially heterogeneously distributed, in association with permeable carbonate levels. Up to 3,580 and 207mg/kg Zn was detected in Bajocian and Oxfordian limestone, respectively, with numerous limestone samples having Zn contents above 50mg/kg. Using X-ray absorption near edge structure spectroscopy and micro-X-ray fluorescence spectrometry, the speciation and micro-scale distribution of Zn was investigated for selected limestone samples. In Bajocian limestone sphalerite and/or Zn-substituted goethite and a minor fraction of Zn-bearing carbonates were identified. In contrast, Zn-bearing carbonates (Zn-substituted calcite and hydrozincite) were accounting for most of the total Zn in Oxfordian limestone. The micro-scale distribution of Zn for Bajocian and Oxfordian limestone was however similar with localized Zn-rich zones in the limestone cement and at the rim of oolites. The stratigraphic sporadicity and microscale heterogeneity of the Zn distribution together with the Zn speciation results point to a hydrothermal origin of Zn. Occurence of Zn-goethite is probably linked to the oxidative transformation of framboidal pyrite and hydrothermal sphalerite in contact with meteoritic waters. Difference in speciation between Bajocian limestone and Oxfordian limestone may be related to differences in rock permeability and/or to various hydrothermal events. Isotopic dating of the different mineralizations will be needed to decipher differences in Zn speciation and the precise chronology of hydrothermal episode

Interactions of ferrous iron with clay mineral surfaces during sorption and subsequent oxidation

In submerged soils and sediments, clay minerals are often exposed to anoxic waters containing ferrous iron (Fe2+). Here, we investigated the sorption of Fe2+ onto a synthetic montmorillonite (Syn-1) low in structural Fe (<0.05 mmol Fe per kg) under anoxic conditions and the effects of subsequent oxidation. Samples were prepared at two Fe-loadings (0.05 and 0.5 mol Fe added per kg clay) and equilibrated for 1 and 30 days under anoxic conditions (O2 < 0.1 ppm), followed by exposure to ambient air. Iron solid-phase speciation and mineral identity was analysed by 57Fe Mössbauer spectroscopy and synchrotron X-ray absorption spectroscopy (XAS). Mössbauer analyses showed that Fe(ii) was partially oxidized (14-100% of total added Fe2+) upon sorption to Syn-1 under anoxic conditions. XAS results revealed that the added Fe2+ mainly formed precipitates (layered Fe minerals, Fe(iii)-bearing clay minerals, ferrihydrite, and lepidocrocite) in different quantities depending on the Fe-loading. Exposing the suspensions to ambient air resulted in rapid and complete oxidation of sorbed Fe(ii) and the formation of Fe(iii)-phases (Fe(iii)-bearing clay minerals, ferrihydrite, and lepidocrocite), demonstrating that the clay minerals were unable to protect ferrous Fe from oxidation, even when equilibrated 30 days under anoxic conditions prior to oxidation. Our findings clarify the role of clay minerals in the formation and stability of Fe-bearing solid phases during redox cycles in periodically anoxic environments.ISSN:2050-7887ISSN:2050-789

Solution speciation controls mercury isotope fractionation of Hg(II) sorption to goethite

The application of Hg isotope signatures as tracers for environmental Hg cycling requires the determination of isotope fractionation factors and mechanisms for individual processes. Here, we investigated Hg isotope fractionation of Hg(II) sorption to goethite in batch systems under different experimental conditions. We observed a mass-dependent enrichment of light Hg isotopes on the goethite surface relative to dissolved Hg (ε(202)Hg of -0.30‰ to -0.44‰) which was independent of the pH, chloride and sulfate concentration, type of surface complex, and equilibration time. Based on previous theoretical equilibrium fractionation factors, we propose that Hg isotope fractionation of Hg(II) sorption to goethite is controlled by an equilibrium isotope effect between Hg(II) solution species, expressed on the mineral surface by the adsorption of the cationic solution species. In contrast, the formation of outer-sphere complexes and subsequent conformation changes to different inner-sphere complexes appeared to have insignificant effects on the observed isotope fractionation. Our findings emphasize the importance of solution speciation in metal isotope sorption studies and suggest that the dissolved Hg(II) pool in soils and sediments, which is the most mobile and bioavailable, should be isotopically heavy, as light Hg isotopes are preferentially sequestered during binding to both mineral phases and natural organic matter

Formation of Zn-rich phyllosilicate, Zn-layered double hydroxide and hydrozincite in contaminated calcareous soils

Recent studies demonstrated that Zn-phyllosilicate- and Zn-layered double hydroxide-type (Zn-LDH) precipitates may form in contaminated soils. However, the influence of soil properties and Zn content on the quantity and type of precipitate forming has not been studied in detail so far. In this work, we determined the speciation of Zn in six carbonate-rich surface soils (pH 6.2 to 7.5) contaminated by aqueous Zn in the runoff from galvanized power line towers (1322 to 30090 mg/kg Zn). Based on 12 bulk and 23 microfocused extended X-ray absorption fine structure (EXAFS) spectra, the number, type and proportion of Zn species were derived using principal component analysis, target testing, and linear combination fitting. Nearly pure Zn-rich phyllosilicate and Zn-LDH were identified at different locations within a single soil horizon, suggesting that the local availabilities of Al and Si controlled the type of precipitate forming. Hydrozincite was identified on the surfaces of limestone particles that were not in direct contact with the soil clay matrix. With increasing Zn loading of the soils, the percentage of precipitated Zn increased from {approx}20% to {approx}80%, while the precipitate type shifted from Zn-phyllosilicate and/or Zn-LDH at the lowest studied soil Zn contents over predominantly Zn-LDH at intermediate loadings to hydrozincite in extremely contaminated soils. These trends were in agreement with the solubility of Zn in equilibrium with these phases. Sequential extractions showed that large fractions of soil Zn ({approx}30% to {approx}80%) as well as of synthetic Zn-kerolite, Zn-LDH, and hydrozincite spiked into uncontaminated soil were readily extracted by 1 M NH{sub 4}NO{sub 3} followed by 1 M NH{sub 4}-acetate at pH 6.0. Even though the formation of Zn precipitates allows for the retention of Zn in excess to the adsorption capacity of calcareous soils, the long-term immobilization potential of these precipitates is limited

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

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

Kinetics of Hg(II) exchange between organic ligands, goethite, and natural organic matter studied with an enriched stable isotope approach

The mobility and bioavailability of toxic Hg(II) in the environment strongly depends on its interactions with natural organic matter (NOM) and mineral surfaces. Using an enriched stable isotope approach, we investigated the exchange of Hg(II) between dissolved species (inorganically complexed or cysteine-, EDTA-, or NOM-bound) and solid-bound Hg(II) (carboxyl-/thiol-resin or goethite) over 30 days under constant conditions (pH, Hg and ligand concentrations). The Hg(II)-exchange was initially fast, followed by a slower phase, and depended on the properties of the dissolved ligands and sorbents. The results were described by a kinetic model allowing the simultaneous determination of adsorption and desorption rate coefficients. The time scales required to reach equilibrium with the carboxyl-resin varied greatly from 1.2 days for Hg(OH)2 to 16 days for Hg(II)-cysteine complexes and approximately 250 days for EDTA-bound Hg(II). Other experiments could not be described by an equilibrium model, suggesting that a significant fraction of total-bound Hg was present in a non-exchangeable form (thiol-resin and NOM: 53-58%; goethite: 22-29%). Based on the slow and incomplete exchange of Hg(II) described in this study, we suggest that kinetic effects must be considered to a greater extent in the assessment of the fate of Hg in the environment and the design of experimental studies, for example, for stability constant determination or metal isotope fractionation during sorption

Geochemical Soil Atlas of Switzerland - Distribution of Toxic Elements

Chemical elements such as copper and molybdenum are essential for animal and human health but may become toxic at elevated concentrations depending on the exposure and intake rate. Other elements such as mercury pose a threat to human health at already low concentrations. The soil acts as the main source of these elements for plant uptake and is thus driving accumulation along the food chain. However, in Switzerland, no nationwide information on elemental distributions in soils has existed up to now. The geochemical soil atlas of Switzerland will fill this gap by presenting the concentration ranges and the spatial distribution of 20 elements in the topsoil. In this summary, we present the methodological approaches and some main findings of the atlas with a focus on toxic elements as well as elements that can be or are toxic at higher concentrations

Isolation and purification of Cu-free methanobactin from Methylosinus trichosporium OB3b

<p>Abstract</p> <p>Background</p> <p>The isolation of highly pure copper-free methanobactin is a prerequisite for the investigation of the biogeochemical functions of this chalkophore molecule produced by methane oxidizing bacteria. Here, we report a purification method for methanobactin from <it>Methylosinus trichosporium </it>OB3b cultures based on reversed-phase HPLC fractionation used in combination with a previously reported resin extraction. HPLC eluent fractions of the resin extracted product were collected and characterized with UV-vis, FT-IR, and C-1s NEXAFS spectroscopy, as well as with elemental analysis and ESI-MS.</p> <p>Results</p> <p>The results showed that numerous compounds other than methanobactin were present in the isolate obtained with resin extraction. Molar C/N ratios, mass spectrometry measurements, and UV-vis spectra indicated that methanobactin was only present in one of the HPLC fractions. On a mass basis, methanobactin carbon contributed only 32% to the total organic carbon isolated with resin extraction. Our spectroscopic results implied that besides methanobactin, the organic compounds in the resin extract comprised breakdown products of methanobactin as well as polysaccharide-like substances.</p> <p>Conclusion</p> <p>Our results demonstrate that a purification step is indispensable in addition to resin extraction in order to obtain pure methanobactin. The proposed HPLC purification procedure is suitable for semi-preparative work and provides copper-free methanobactin.</p

Adsorption of hydroxamate siderophores and EDTA on goethite in the presence of the surfactant sodium dodecyl sulfate

Siderophore-promoted iron acquisition by microorganisms usually occurs in the presence of other organic molecules, including biosurfactants. We have investigated the influence of the anionic surfactant sodium dodecyl sulfate (SDS) on the adsorption of the siderophores DFOB (cationic) and DFOD (neutral) and the ligand EDTA (anionic) onto goethite (α-FeOOH) at pH 6. We also studied the adsorption of the corresponding 1:1 Fe(III)-ligand complexes, which are products of the dissolution process. Adsorption of the two free siderophores increased in a similar fashion with increasing SDS concentration, despite their difference in molecule charge. In contrast, SDS had little effect on the adsorption of EDTA. Adsorption of the Fe-DFOB and Fe-DFOD complexes also increased with increasing SDS concentrations, while adsorption of Fe-EDTA decreased. Our results suggest that hydrophobic interactions between adsorbed surfactants and siderophores are more important than electrostatic interactions. However, for strongly hydrophilic molecules, such as EDTA and its iron complex, the influence of SDS on their adsorption seems to depend on their tendency to form inner-sphere or outer-sphere surface complexes. Our results demonstrate that surfactants have a strong influence on the adsorption of siderophores to Fe oxides, which has important implications for siderophore-promoted dissolution of iron oxides and biological iron acquisition