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Berlin Brandenburg

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  • 1
    Language: English
    In: Environmental science & technology, 18 February 2014, Vol.48(4), pp.2281-9
    Description: Organosulfur-coordinated As(III) and realgar (α-As4S4) have been identified as the dominant As species in the naturally As-enriched minerotrophic peatland Gola di Lago, Switzerland. In this study, we explored their oxidation kinetics in peat exposed to atmospheric O2 for up to 180 days under sterile and nonsterile conditions (25 °C, ∼ 100% relative humidity). Anoxic peat samples were collected from a near-surface (0-38 cm) and a deep peat layer (200-250 cm) and studied by bulk As, Fe, and S K-edge X-ray absorption spectroscopy as well as selective extractions as a function of time. Over 180 days, only up to 33% of organosulfur-coordinated As(III) and 44% of realgar were oxidized, corresponding to half-life times, t1/2, of 312 and 215 days, respectively. The oxidation of both As species was mainly controlled by abiotic processes. Realgar was oxidized orders of magnitude slower than predicted from published mixed-flow reactor experiments, indicating that mass-transfer processes were rate-limiting. Most of the As released (〉97%) was sequestered by Fe(III)-(hydr)oxides. However, water-extractable As reached concentrations of 0.7-19 μmol As L(-1), exceeding the WHO drinking water limit by up to 145 times. Only a fraction (20-36%) of reduced S(-II to I) was sensitive to oxidation and was oxidized faster (t1/2 = 50-173 days) than organosulfur-coordinated As(III) and realgar, suggesting a rapid loss of reactive As-sequestering S species following a drop in the water table. Our results imply that wetlands like Gola di Lago can serve as long-term sources for As under prolonged oxidizing conditions. The maintenance of reducing conditions is thus regarded as the primary strategy in the management of this and other As-rich peatlands.
    Keywords: Arsenic -- Chemistry ; Arsenicals -- Chemistry ; Soil -- Chemistry ; Sulfides -- Chemistry ; Sulfur Compounds -- Chemistry
    ISSN: 0013936X
    E-ISSN: 1520-5851
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  • 2
    Language: English
    In: Environmental Science and Technology, 01 April 2016, Vol.50(8)
    Description: Here, peatlands have received significant atmospheric inputs of As and S since the onset of the Industrial Revolution, but the effect of S deposition on the fate of As is largely unknown. It may encompass the formation of As sulfides and organosulfur-bound As, or the indirect stimulation of As biotransformation processes, which are presently not considered as important As immobilization pathways in wetlands. To investigate the immobilization mechanisms of anthropogenically derived As in peatlands subjected to long-term atmospheric pollution, we explored the solid-phase speciation of As, Fe, and S in English peat bogs by X-ray absorption spectroscopy. Additionally, we analyzed the speciation of As in pore- and streamwaters. Linear combination fits of extended X-ray absorption fine structure (EXAFS) data imply that 62–100% (average: 82%) of solid-phase As (Astot: 9–92 mg/kg) was present as organic As(V) and As(III). In agreement with appreciable concentrations of organoarsenicals in surface waters (pH: 4.0–4.4, Eh: 165–190 mV, average Astot: 1.5–129 μg/L), our findings reveal extensive biotransformation of atmospheric As and the enrichment of organoarsenicals in the peat, suggesting that the importance of organometal(loid)s in wetlands subjected to prolonged air pollution is higher than previously assumed.
    Keywords: Environmental Sciences ; Engineering ; Environmental Sciences
    ISSN: 0013-936X
    E-ISSN: 1520-5851
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  • 3
    Language: English
    In: Environmental science & technology, 07 October 2014, Vol.48(19), pp.11320-9
    Description: Elevated solution concentrations of As in anoxic natural systems are usually accompanied by microbially mediated As(V), Mn(III/IV), and Fe(III) reduction. The microbially mediated reductive dissolution of Fe(III)-(oxyhydr)oxides mainly liberates sorbed As(V) which is subsequently reduced to As(III). Manganese oxides have been shown to rapidly oxidize As(III) and Fe(II) under oxic conditions, but their net effect on the microbially mediated reductive release of As and Fe is still poorly understood. Here, we investigated the microbial reduction of As(V)-bearing ferrihydrite (molar As/Fe: 0.05; Fe tot: 32.1 mM) by Shewanella sp. ANA-3 (10(8) cells/mL) in the presence of different concentrations of birnessite (Mn tot: 0, 0.9, 3.1 mM) at circumneutral pH over 397 h using wet-chemical analyses and X-ray absorption spectroscopy. Additional abiotic experiments were performed to explore the reactivity of birnessite toward As(III) and Fe(II) in the presence of Mn(II), Fe(II), ferrihydrite, or deactivated bacterial cells. Compared to the birnessite-free control, the highest birnessite concentration resulted in 78% less Fe and 47% less As reduction at the end of the biotic experiment. The abiotic oxidation of As(III) by birnessite (k initial = 0.68 ± 0.31/h) was inhibited by Mn(II) and ferrihydrite, and lowered by Fe(II) and bacterial cell material. In contrast, the oxidation of Fe(II) by birnessite proceeded equally fast under all conditions (k initial = 493 ± 2/h) and was significantly faster than the oxidation of As(III). We conclude that in the presence of birnessite, microbially produced Fe(II) is rapidly reoxidized and precipitates as As-sequestering ferrihydrite. Our findings imply that the ability of Mn-oxides to oxidize As(III) in water-logged soils and sediments is limited by the formation of ferrihydrite and surface passivation processes.
    Keywords: Arsenic -- Chemistry ; Ferric Compounds -- Chemistry ; Iron -- Chemistry ; Oxides -- Chemistry ; Shewanella -- Metabolism
    ISSN: 0013936X
    E-ISSN: 1520-5851
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  • 4
    Language: English
    In: Environmental science & technology, 2013, Vol.47(21), pp.12165-73
    Description: The speciation of As in wetlands is often controlled by natural organic matter (NOM), which can form strong complexes with Fe(III). Here, we elucidated the molecular-scale interaction of arsenite (As(III)) with Fe(III)-NOM complexes under reducing conditions. We reacted peat (40-250 μm size fraction, 1.0 g Fe/kg) with 0-15 g Fe/kg at pH 〈2, removed nonreacted Fe, and subsequently equilibrated the Fe(III) complexes formed with 900 mg As/kg peat at pH 7.0, 8.4, and 8.8. The solid-phase speciation of Fe and As was studied by electron paramagnetic resonance (Fe) and X-ray absorption spectroscopy (As, Fe). Our results show that the majority of Fe in the peat was present as mononuclear Fe(III) species (RFe-C = 2.82-2.88 Å), probably accompanied by small Fe(III) clusters of low nuclearity (RFe-Fe = 3.25-3.46 Å) at high pH and elevated Fe contents. The amount of As(III) retained by the original peat was 161 mg As/kg, which increased by up to 250% at pH 8.8 and an Fe loading of 7.3 g/kg. With increasing Fe content of peat, As(III) increasingly formed bidentate mononuclear (RAs-Fe = 2.88-2.94 Å) and monodentate binuclear (RAs-Fe = 3.35-3.41 Å) complexes with Fe, thus yielding direct evidence of ternary complex formation. The ternary complex formation went along with a ligand exchange reaction between As(III) and hydroxylic/phenolic groups of the peat (RAs-C = 2.70-2.77 Å). Our findings thus provide spectroscopic evidence for two yet unconfirmed As(III)-NOM interaction mechanisms, which may play a vital role in the cycling of As in sub- and anoxic NOM-rich environments such as peatlands, peaty sediments, swamps, or rice paddies.
    Keywords: Arsenites -- Metabolism ; Ferric Compounds -- Chemistry ; Soil -- Chemistry ; Soil Pollutants -- Metabolism
    ISSN: 0013936X
    E-ISSN: 1520-5851
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  • 5
    Language: English
    In: Environmental Science and Technology, 06 September 2016, Vol.50(17)
    Description: Reductive release of the potentially toxic metalloid As from Fe(III) (oxyhydr)oxides has been identified as an important process leading to elevated As porewater concentrations in soils and sediments. Despite the ubiquitous presence of Mn oxides in soils and their oxidizing power toward As(III), their impact on interrelated As, Fe, and Mn speciation under microbially reducing conditions remains largely unknown. For this reason, we employed a column setup and X-ray absorption spectroscopy to investigate the influence of increasing birnessite concentrations (molar soil Fe-to-Mn ratios: 4.8, 10.2, and 24.7) on As speciation and release from an As-contaminated floodplain soil (214 mg As/kg) under anoxic conditions. Our results show that birnessite additions significantly decreased As leaching. The reduction of both As and Fe was delayed, and As(III) accumulated in birnessite-rich column parts, indicating the passivation of birnessite and its transformation products toward As(III) oxidation and the precipitation of Fe(III)(oxyhydr)oxides. Microbial Mn reduction resulted in elevated soil pH values, which in turn lowered the microbial activity in the birnessite-enriched soil. We conclude that in Mn-oxide-rich soil environments undergoing redox fluctuations, the enhanced As adsorption to newly formed Fe(III) (oxyhydr)oxides under reducing conditions leads to a transient stabilization of As.
    Keywords: Engineering ; Environmental Sciences
    ISSN: 0013-936X
    E-ISSN: 1520-5851
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  • 6
    Language: English
    In: Environmental science & technology, 06 November 2012, Vol.46(21), pp.11788-97
    Description: Terrestrial ecosystems rich in natural organic matter (NOM) can act as a sink for As. Recently, the complexation of trivalent As by sulfhydryl groups of NOM was proposed as the main mechanism for As-NOM interactions in anoxic S- and NOM-rich environments. Here we tested the molecular-scale interaction of bisulfide (S(-II)) with NOM and its consequences for arsenite (As(III)) binding. We reacted 0.2 mol C/L peat and humic acid (HA) with up to 5.8 mM S(-II) at pH 7 and 5, respectively, and subsequently equilibrated the reaction products with 55 μM As(III) under anoxic conditions. The speciation of S and the local coordination environment of As in the solid phase were studied by X-ray absorption spectroscopy. Our results document a rapid reaction of S(-II) with peat and HA and the concomitant formation of reduced organic S species. These species were highly reactive toward As(III). Shell fits of As K-edge extended X-ray absorption fine structure spectra revealed that the coordination environment of trivalent As was progressively occupied by S atoms. Fitted As-S distances of 2.24-2.34 Å were consistent with sulfhydryl-bound As(III). Besides As(III) complexation by organic monosulfides, our data suggests the formation of nanocrystalline As sulfide phases in HA samples and an As sorption process for both organic sorbents in which As(III) retained its first-shell oxygens. In conclusion, this study documents that S(-II) reaction with NOM can greatly enhance the ability of NOM to bind As in anoxic environments.
    Keywords: Humic Substances ; Arsenites -- Chemistry ; Soil -- Chemistry ; Soil Pollutants -- Chemistry ; Sulfides -- Chemistry
    ISSN: 0013936X
    E-ISSN: 1520-5851
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  • 7
    Language: English
    In: Environmental Science and Technology, 04 October 2016, Vol.50(19)
    Description: Peatlands frequently serve as efficient biogeochemical traps for U. Mechanisms of U immobilization in these organic matter-dominated environments may encompass the precipitation of U-bearing mineral(oid)s and the complexation of U by a vast range of (in)organic surfaces. The objective of this work was to investigate the spatial distribution and molecular binding mechanisms of U in soils of an alpine minerotrophic peatland (pH 4.7-6.6, Eh = -127 to 463 mV) using microfocused X-ray fluorescence spectrometry and bulk and microfocused U L3-edge X-ray absorption spectroscopy. The soils contained 2.3-47.4 wt % organic C, 4.1-58.6 g/kg Fe, and up to 335 mg/kg geogenic U. Uranium was found to be heterogeneously distributed at the micrometer scale and enriched as both U(IV) and U(VI) on fibrous and woody plant debris (48 plus or minus 10% U(IV), x plus or minus s, n = 22). Bulk U X-ray absorption near edge structure (XANES) spectroscopy revealed that in all samples U(IV) comprised 35-68% of total U (x = 50%, n = 15). Shell-fit analyses of bulk U L3-edge extended X-ray absorption fine structure (EXAFS) spectra showed that U was coordinated to 1.3 plus or minus 0.2 C atoms at a distance of 2.91 plus or minus 0.01 A (x plus or minus s), which implies the formation of bidentate-mononuclear U(IV/VI) complexes with carboxyl groups. We neither found evidence for U shells at ~3.9 A, indicative of mineral-associated U or multinuclear U(IV) species, nor for a substantial P/Fe coordination of U. Our data indicates that U(IV/VI) complexation by natural organic matter prevents the precipitation of U minerals as well as U complexation by Fe/Mn phases at our field site, and suggests that organically complexed U(IV) is formed via reduction of organic matter-bound U(VI).
    Keywords: Engineering ; Environmental Sciences
    ISSN: 0013-936X
    E-ISSN: 1520-5851
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  • 8
    Language: English
    In: Environ. Sci. Technol, 18 November 2014, Vol.48((22) ; 11, 2014)
    Description: Floodplain soils are frequently contaminated with metal(loid)s due to present or historic mining, but data on the bioaccessibility (BA) of contaminants in these periodically flooded soils are scarce. Therefore, we studied the speciation of As and Fe in eight As-contaminated circumneutral floodplain soils ( less than or equal to 21600 mg As/kg) and their size fractions using X-ray absorption spectroscopy (XAS) and examined the BA of As in the solids by in-vitro gastrointestinal (IVG) extractions. Arsenopyrite and As(V)-adsorbed ferrihydrite were identified by XAS as the predominant As species. The latter was the major source for bioaccessible As, which accounted for 5-35% of the total As. The amount of bioaccessible As increased with decreasing particle size and was controlled by the slow dissolution kinetics of ferrihydrite in the gastric environment (pH 1.8). The relative BA of As (% of total) decreased with decreasing particle size only in a highly As-contaminated soil -- which supported by Fe XAS -- suggests the formation of As-rich hydrous ferric oxides in the gastric extracts. Multiple linear regression analyses identified Al, total As, Corg, and P as main predictors for the absolute BA of As (adjusted R2 less than or equal to 0.977). Health risk assessments for residential adults showed that (i) nearly half of the bulk soils may cause adverse health effects and (ii) particles 〈5 mu m pose the highest absolute health threat upon incidental soil ingestion. Owing to their low abundance, however, health risks were primarily associated with particles in the 5-50 and 100-200 mu m size ranges. These particles are easily mobilized from riverbanks during flooding events and dispersed within the floodplain or transported downstream.
    Keywords: Flood Plains ; Environmental Sciences ; Regression Analysis ; Spectroscopy ; Particle Size ; Rivers ; Flooded Soils ; Abundance ; Environmental Impact ; Particulates ; Ingestion ; Soil ; Health Risks ; Absorption Spectroscopy ; Flood Plains ; River Banks ; Kinetics ; Ph ; Flood Plains ; Speciation ; Risk ; Arsenic ; Public Health ; Assessments ; Soil Contamination ; Particle Size ; Solids ; Flood Plains ; Speciation ; Risk ; Arsenic ; Public Health ; Assessments ; Soil Contamination ; Particle Size ; Solids ; Freshwater Pollution ; Natural Hazards ; General (556) ; Toxicology & Environmental Safety ; Epidemiology and Public Health ; Water Resources and Supplies ; Data Acquisition;
    ISSN: 0013936X
    E-ISSN: 15205851
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  • 9
    Language: English
    In: Environ. Sci. Technol, 14 February 2014, Vol.48((1) ; 01, 2014)
    Description: Arsenic is a toxic trace element, which commonly occurs as contaminant in riverine floodplains and associated wetlands affected by mining and ore processing. In this study, we investigated the solid-phase speciation of As in river floodplain soils characterized by circumneutral pH (5.7-7.1) and As concentrations of up to 40.3 g/kg caused by former mining of arsenopyrite-rich ores. Soil samples collected in the floodplain of Ogosta River (Bulgaria) were size-fractionated and subsequently analyzed using a combination of X-ray fluorescence (XRF) spectrometry, powder X-ray diffraction (XRD), X-ray absorption spectroscopy (XAS), and selective chemical extraction of poorly crystalline mineral phases. Arsenic and Fe were found to be spatially correlated and both elements were strongly enriched in the fine soil particle size fractions (〈2 mu m and 2-50 mu m). Between 14 and 82% of the total As was citrate-ascorbate extractable. Molar As/Fe ratios were as high as 0.34 in the bulk soil extracts and increased up to 0.48 in extracts of the fine particle size fractions. Arsenic K-edge XAS spectra showed the predominance of As(V) and were well fitted with a reference spectrum of As(V) adsorbed to ferrihydrite. Whereas no As(III) was detected, considerable amounts of As(-I) were present and identified as arsenopyrite originating from the mining waste. Iron K-edge XAS revealed that in addition to As(V) adsorbed to ferrihydrite, X-ray amorphous As(V)-rich hydrous ferric oxides ("As-HFO") with a reduced number of corner-sharing FeO sub(6) octahedra relative to ferrihydrite were the dominating secondary As species in the soils. The extremely high concentrations of As in the fine particle size fractions (up to 214 g/kg) and its association with poorly crystalline Fe(III) oxyhydroxides and As-HFO phases suggest a high As mobilization potential under both oxic and anoxic conditions, as well as a high bioaccessibility of As upon ingestion, dermal contact, or inhalation by humans or animals.
    Keywords: Particle Size ; Absorption Spectroscopy ; Arsenic ; Flood Plains ; Ores ; River Discharge ; Wetlands ; Diffraction ; Mining ; Ph of Soil ; Flood Plains ; Trace Elements in Soil ; Environmental Sciences ; Weathering ; Wetlands ; Diffraction ; Spectroscopy ; Soil Particles ; Trace Elements in River Water ; Spectrometry ; Particle Size ; Arsenic ; Fluorescence ; Ingestion ; Trace Elements ; Soil ; Absorption Spectroscopy ; Flood Plains ; Mining Wastes ; Weathering ; Wetlands ; Mining ; Chemical Extraction ; Iron ; Rivers ; Flood Plains ; X-Rays ; Arsenic ; Soil Contamination ; Water Analysis ; Particle Size ; Wetlands ; Mine Wastes ; Rivers ; Flood Plains ; X-Rays ; Arsenic ; Soil Contamination ; Water Analysis ; Particle Size ; Wetlands ; Mine Wastes ; Bulgaria ; Freshwater ; Toxicology & Environmental Safety ; Runoff (556.16) ; Freshwater Pollution ; Water Resources and Supplies ; Data Acquisition ; Mechanical and Natural Changes;
    ISSN: 0013936X
    E-ISSN: 15205851
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  • 10
    Language: English
    In: Environmental science & technology, 03 July 2018, Vol.52(13), pp.7317-7326
    Description: In peatlands, arsenite was reported to be effectively sequestered by sulfhydryl groups of natural organic matter. To which extent porewater arsenite can react with reduced sulfur to form thioarsenates and how this affects arsenic sequestration in peatlands is unknown. Here, we show that, in the naturally arsenic-enriched peatland Gola di Lago, Switzerland, up to 93% of all arsenic species in surface and porewaters were thioarsenates. The dominant species, monothioarsenate, likely formed from arsenite and zerovalent sulfur-containing species. Laboratory incubations with sulfide-reacted, purified model peat showed increasing total arsenic sorption with decreasing pH from 8.5 to 4.5 for both, monothioarsenate and arsenite. However, X-ray absorption spectroscopy revealed no binding of monothioarsenate via sulfhydryl groups. The sorption observed at pH 4.5 was acid-catalyzed dissociation of monothioarsenate, forming arsenite. The lower the pH and the more sulfhydryl sites, the more arsenite sorbed which in turn shifted equilibrium toward further dissociation of monothioarsenate. At pH 8.5, monothioarsenate was stable over 41 days. In conclusion, arsenic can be effectively sequestered by sulfhydryl groups in anoxic, slightly acidic environments where arsenite is the only arsenic species. At neutral to slightly alkaline pH, monothioarsenate can form and its slow transformation into arsenite and low affinity to sulfhydryl groups suggest that this species is mobile in such environments.
    Keywords: Arsenic
    ISSN: 0013936X
    E-ISSN: 1520-5851
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