Phosphorus adsorption on iron-coated sand under reducing conditions.

Mitigation measures are needed to prevent large loads of phosphate originating in agriculture from reaching surface waters. Iron-coated sand (ICS) is a residual product from drinking water production. It has a high phosphate adsorption capacity and can be placed around tile drains, taking no extra space, which increases the farmers' acceptance. The main concern regarding the use of ICS filters below groundwater level is that limited oxygen supply and high organic matter concentrations may lead to the reduction and dissolution of iron (hydr)oxides present and the release of previously adsorbed phosphate. This study aimed to investigate phosphate adsorption on ICS at the onset of iron reduction. First, we investigated whether simultaneous metal reduction and phosphate adsorption were relevant at two field sites in the Netherlands that use ICS filters around tile drains. Second, the onset of microbially mediated reduction of ICS in drainage water was mimicked in complementary laboratory microcosm experiments by varying the intensity of reduction through controlling the oxygen availability and the concentration of degradable organic matter. After 3 yr, ICS filters in the field removed phosphorus under low redox conditions. Over 45 d, the microbial reduction of manganese and iron oxides did not lead to phosphate release, confirming field observations. Electron microscopy and X-ray absorption spectroscopy did not evince systematic structural or compositional changes; only under strongly reducing conditions did iron sulfides form in small percentages in the outer layer of the iron coating. Our results suggest that detrimental effects only become relevant after long periods of operation.

Spatiotemporal Mineral Phase Evolution and Arsenic Retention in Microfluidic Models of Zerovalent Iron-Based Water Treatment.

Arsenic (As) is a toxic element, and elevated levels of geogenic As in drinking water pose a threat to the health of several hundred million people worldwide. In this study, we used microfluidics in combination with optical microscopy and X-ray spectroscopy to investigate zerovalent iron (ZVI) corrosion, secondary iron (Fe) phase formation, and As retention processes at the pore scale in ZVI-based water treatment filters. Two 250 µm thick microchannels filled with single ZVI and quartz grain layers were operated intermittently (12 h flow/12 h no-flow) with synthetic groundwater (pH 7.5; 570 µg/L As(III)) over 13 and 49 days. Initially, lepidocrocite (Lp) and carbonate green rust (GRC) were the dominant secondary Fe-phases and underwent cyclic transformation. During no-flow, lepidocrocite partially transformed into GRC and small fractions of magnetite, kinetically limited by Fe(II) diffusion or by decreasing corrosion rates. When flow resumed, GRC rapidly and nearly completely transformed back into lepidocrocite. Longer filter operation combined with a prolonged no-flow period accelerated magnetite formation. Phosphate adsorption onto Fe-phases allowed for downstream calcium carbonate precipitation and, consequently, accelerated anoxic ZVI corrosion. Arsenic was retained on Fe-coated quartz grains and in zones of cyclic Lp-GRC transformation. Our results suggest that intermittent filter operation leads to denser secondary Fe-solids and thereby ensures prolonged filter performance.

Thallium adsorption onto phyllosilicate minerals.

The adsorption of thallium (Tl) onto phyllosilicate minerals plays a critical role in the retention of Tl in soils and sediments and the potential transfer of Tl into plants and groundwater. Especially micaceous minerals are thought to strongly bind monovalent Tl(I), in analogy to their strong binding of Cs. To advance the understanding of Tl(I) adsorption onto phyllosilicate minerals, we studied the adsorption of Tl(I) onto Na- and K-saturated illite and Na-saturated smectite, two muscovites, two vermiculites and a naturally Tl-enriched soil clay mineral fraction. Macroscopic adsorption isotherms were combined with the characterization of the adsorbed Tl by X-ray absorption spectroscopy (XAS). In combination, the results suggest that the adsorption of Tl(I) onto phyllosilicate minerals can be interpreted in terms of three major uptake paths: (i) highest-affinity inner-sphere adsorption of dehydrated Tl+ on a very low number of adsorption sites at the wedge of frayed particle edges of illite and around collapsed zones in vermiculite interlayers through complexation between two siloxane cavities, (ii) intermediate-affinity inner-sphere adsorption of partially dehydrated Tl+ on the planar surfaces of illite and muscovite through complexation onto siloxane cavities, (iii) low-affinity adsorption of hydrated Tl+, especially in the hydrated interlayers of smectite and expanded vermiculite. At the frayed edges of illite particles and in the vermiculite interlayer, Tl uptake can lead to the formation of new wedge sites that enable further adsorption of dehydrated Tl+. On the soil clay fraction, a shift in Tl(I) uptake from frayed edge sites (on illite) to planar sites (on illite and muscovite) was observed with increasing Tl(I) loading. The results from this study show that the adsorption of Tl(I) onto phyllosilicate minerals follows the same trends as reported for Cs and Rb and thus suggests that concepts to describe the retention of (radio)cesium by different types of phyllosilicate minerals in soils, sediments and rocks are also applicable to Tl(I).

Use of iron-coated sand for removing soluble phosphorus from drainage water.

Mitigation measures are needed for reducing chronic dissolved phosphorus (P) losses from agricultural soils with a legacy of excessive P inputs to surface waters. Since pipe drains are an important pathway for P transport from agricultural soils to surface waters in flat areas, removing P from drainage water can be an effective measure. During a 4.5 year-field experiment, we tested the performance of a pipe drain enveloped with Fe-coated sand for removing soluble P from drainage water. Iron-coated sand is a by-product of the drinking water industry and has a high ability to bind P. The P concentration in the effluent from the enveloped pipe drain remained at a very low level over the entire monitoring period, with a removal percentage amounting to 93% for total P. During the field experiment, the enveloped pipe drain was below the groundwater level for a prolonged time. Nevertheless, no reduction of Fe(III) in the Fe-coated sand occurred during the first two years, most likely due to preferential reduction of Mn oxides present in the coatings of the sand particles, as reflected in elevated effluent Mn concentrations. Thereafter, reductive dissolution of Fe oxides in the coatings caused a gradual increase in the Fe concentration in the enveloped pipe drain effluent over time. Concomitantly, the dissolved Mn concentration decreased, most probably due to the depletion in easily accessible Mn oxides in the Fe-coated sand. The Fe in the Fe-coated sand was identified as silicate-containing ferrihydrite (Fh). The submerged conditions of the enveloped pipe drain neither affected the stability of Fh in the Fe-coated sand nor the ability of this measure to capture P from drainage water. Enveloping pipe drains with Fe-coated sand is an effective method for reducing dissolved P inputs from agricultural soils to surface waters and holds great promise for implementation in practice.

Thermodynamic controls on rates of iron oxide reduction by extracellular electron shuttles.

Anaerobic microbial respiration in suboxic and anoxic environments often involves particulate ferric iron (oxyhydr-)oxides as terminal electron acceptors. To ensure efficient respiration, a widespread strategy among iron-reducing microorganisms is the use of extracellular electron shuttles (EES) that transfer two electrons from the microbial cell to the iron oxide surface. Yet, a fundamental understanding of how EES-oxide redox thermodynamics affect rates of iron oxide reduction remains elusive. Attempts to rationalize these rates for different EES, solution pH, and iron oxides on the basis of the underlying reaction free energy of the two-electron transfer were unsuccessful. Here, we demonstrate that broadly varying reduction rates determined in this work for different iron oxides and EES at varying solution chemistry as well as previously published data can be reconciled when these rates are instead related to the free energy of the less exergonic (or even endergonic) first of the two electron transfers from the fully, two-electron reduced EES to ferric iron oxide. We show how free energy relationships aid in identifying controls on microbial iron oxide reduction by EES, thereby advancing a more fundamental understanding of anaerobic respiration using iron oxides.

Evaluation of thallium isotopic fractionation during the metallurgical processing of sulfides: An update.

In this study, we report combined Tl isotopic and Tl mineralogical and speciation data from a set of Tl-rich sulfide concentrates and technological wastes from hydrometallurgical Zn extraction. We also present the first evaluation of Tl isotopic ratios over a cycle of sulfide processing, from the ore flotation to pyro- and hydrometallurgical stages. The results demonstrate that the prevailing Tl form in all samples is Tl(I), without any preferential incorporation into sulfides or Tl-containing secondary phases, indicating an absence of Tl redox reactions. Although the Tl concentrations varied significantly in the studied samples (~9-280 mg/kg), the overall Tl isotopic variability was small, in the range of -3.1 to -4.4 ± 0.7 (2σ) ε205Tl units. By combining present ε205Tl results with the trends first found for a local roasting plant, it is possible to infer minimum Tl isotopic effects throughout the studied industrial process. As a result, the use of Tl isotopic ratios as a source proxy may be complicated or even impossible in areas with naturally high/extreme Tl background contents. On the other hand, areas with two or more isotopically contrasting Tl sources allow for relatively easy tracing, i.e., in compartments which do not suffer from post-depositional isotopic redistributions.

Release of gold (Au), silver (Ag) and cerium dioxide (CeO2) nanoparticles from sewage sludge incineration ash.

Engineered nanoparticles (NPs) that are released into wastewater are retained by wastewater treatment plants (WWTPs) and accumulate in sewage sludge. Increasing shares of sludge are incinerated and landfilled, especially in industrialized countries. It is debated whether certain types of NPs can outlive the incineration process and subsequently be released from sewage sludge ash (SSA) landfills. To investigate the release of different types of NPs from SSA, we spiked gold (Au), silver (Ag) and cerium dioxide (CeO2) NPs to a pilot WWTP increasing the Au, Ag and Ce concentrations to 30, 43 and 389 mg kg-1 (dry matter basis) in the digested sludge. The spiked sludge was incinerated in a pilot fluidized bed reactor resulting in SSA with Au, Ag and Ce concentrations of 61, 103 and 854 mg kg-1. In addition, two sludge samples from a full-scale WWTP with Au concentrations of 5 and 16 mg kg-1 were incinerated, resulting in SSA with 9 mg kg-1 and 30 mg kg-1 Au. The spiked Au-NPs remain largely unaltered during the wastewater treatment and incineration process, whereas Ag-NPs and CeO2-NPs undergo transformation. During simulated landfill leaching in columns flushed with 400 to 500 pore volumes of artificial rainwater, Ag and Ce were retained in the ash, whereas about 17% of the spiked Au was released, mainly in particulate form. Lower fractions of mostly particulate Au were released from the ashes (3 and 9%) of unspiked SSA. In conclusion, unaltered Au-NPs significantly leach from landfilled SSA, whereas the incorporation of Ag-NPs and CeO2-NPs as transformed species into the SSA matrix limits the leaching of (nano)particulate and dissolved Ag and Ce compounds.

Transformation of TiO2 (nano)particles during sewage sludge incineration.

Titanium dioxide (TiO2) (nano)particles are produced in large quantities and their potential impacts on ecosystems warrants investigations into their fate after disposal. TiO2 particles released into wastewater are retained by wastewater treatment plants and accumulate in digested sludge, which is increasingly incinerated in industrialized countries. Therefore, we investigated the changes of the Ti-speciation during incineration of as-received sludge and of sludge spiked with anatase (d=20-50 nm) or rutile (d=200-400 nm) using X-ray absorption spectroscopy (XAS) and transmission electron microscopy (TEM). In the as-received sludge, rutile and anatase were the dominant Ti bearing minerals and both remained unaffected by the anaerobic treatment. During incineration, Ti reacts with hematite to members of the hematite-ilmenite solid solution series (Hem-Ilm). Up to 80% of the Ti spiked as anatase transformed into Hem-Ilm, a distorted 6-fold coordinated Ti (Ti(IV)sulfate) and rutile during incineration. Up to 30% and 60% of rutile transformed into Hem-Ilm and Ti(IV)sulfate represented phases in fly and bottom ash, respectively. Fe and Ti were spatially correlated in ash derived from as-received and anatase spiked sludge, whereas only a thin layer of the spiked rutile reacted with Fe, in line with XAS data. This study highlights the transient nature of nano-Ti species during sewage sludge incineration.

Quantification of individual Rare Earth Elements from industrial sources in sewage sludge.

Rare Earth Elements (REEs) are used in increasing amounts in technical applications and consumer products. However, to date, the contribution of industrial sources to the loads of individual REEs in wastewater streams have not been quantified. Here, we determine the REE contents in sludge collected from 63 wastewater treatment plants (WWTPs) across Switzerland. To quantify the industrial fraction of individual REEs in the sewage sludge, we develop two complementary approaches, based on REE ratios and REE pattern fitting. Unspecific (background) inputs, with REE patterns similar to the averaged REE pattern of soils collected across Switzerland, dominate the REE budget of most WWTPs. A few WWTPs receive significant REE inputs from specific industrial sources. Based on population equivalents of Switzerland, we estimate a total annual load of 4200 kg Cerium (Ce, 0.5 g Ce year-1 capita-1), with an industrial contribution of 2000 kg year-1. The latter agrees with estimates of probabilistic mass flow models for engineered nanoscale CeO2 particles discharged to the sewer network. About 7 kg year-1 of Samarium (Sm,total for Switzerland: 184 kg year-1 or 0.02 g Sm year-1 capita-1) and 3 kg year-1 of Europium (Eu,total for Switzerland: 44 kg year-1 or 0.005 g Eu year-1 capita-1) are assigned to industrial inputs from single WWTPs. Gadolinium (Gd) is used in the form of a stable complex as contrast agent in magnetic resonance imaging. Assuming 10% removal of Gd during wastewater treatment, we calculate an annual discharge of 90 kg of Gd from one individual WWTP to surface waters. WWTPs with exceptionally high industrial inputs of specific REEs warrant detailed investigations to identify the respective sources and to assess whether REE concentrations in effluents are elevated to the same degree.

Transformation of Hexagonal Birnessite upon Reaction with Thallium(I): Effects of Birnessite Crystallinity, pH, and Thallium Concentration.

We examined the uptake of Tl(I) by two hexagonal birnessites and related phase transformations in laboratory experiments over 12 sequential additions of 0.01 M Tl(I)/Mn at pH 4.0, 6.0, and 8.0. The Tl-reacted Mn oxides were characterized for their structure, Tl binding, and morphology using X-ray diffraction, X-ray photoelectron and X-ray absorption spectroscopies, and transmission electron microscopy. Very limited Tl oxidation was observed in contrast to previous works, where equal Tl(I)/Mn was added in a single step. Instead, both birnessites transformed into a 2 × 2 tunneled phase with dehydrated Tl(I) in its tunnels at pH 4, but only partially at pH 6, and at pH 8.0 they remained layered. The first four to nine sequential Tl(I)/Mn additions resulted in lower residual dissolved Tl+ concentrations than when the same amounts of Tl(I)/Mn were added in single steps. This study thus shows that the repeated reaction of hexagonal birnessites with smaller Tl(I)/Mn at ambient temperature triggers a complete phase conversion with Tl(I) as the sole reacting cation. The novel pathway found may be more relevant for contaminated environments and may help explain the formation of minerals like thalliomelane [Tl+(Mn7.54+Cu0.52+)O16]; it also points to the possibility that other reducing species trigger similar Mn oxide transformation reactions.

Arsenic and Other Geogenic Contaminants in Groundwater - A Global Challenge.

Groundwater is a much safer and more dependable source of drinking water than surface water. However, natural (geogenic) hazardous elements can contaminate groundwater and lead to severe health problems in consumers. Arsenic concentrations exceeding the WHO drinking water guideline of 10 µg/L globally affect over 220 million people and can cause arsenicosis (skin lesions and cancers). Fluoride, while preventing caries at low concentrations, has detrimental effects when above the WHO drinking water guideline of 1.5 mg/L and puts several hundred million people at risk of dental and skeletal fluorosis. In this article, we report on the geochemistry and occurrence of arsenic and fluoride in groundwater and on the development of global and regional risk maps that help alert governments and water providers to take appropriate mitigation measures for the provision of safe drinking water. We then summarize research on the removal of arsenic and fluoride from drinking water, focusing on adapted technologies for water treatment. Finally, we discuss the applicability of various measures in a larger context and future challenges in reaching the goal of access to safe drinking water for all.

Quantification of anthropogenic and geogenic Ce in sewage sludge based on Ce oxidation state and rare earth element patterns.

Emissions of Ce from anthropogenic activities (anthropogenic Ce) into urban wastewater systems and the environment result from its widespread industrial use (abrasives, catalysts, nanotechnology). Because Ce in sewage sludge can also be of geogenic origin, the quantification of anthropogenic Ce in sewage sludge remains elusive. In this study, we evaluated the suitability of Ce oxidation state and rare earth element (REE) patterns for the quantification of anthropogenic Ce fractions in sewage sludge. A diverse set of soil samples served to gain baseline information on geogenic Ce. Geogenic Ce in the soils was characterized by high Ce(III) fractions (≥70%) and their REE patterns were comparable to the REE patterns of the upper continental crust. The sewage sludges contained on average ∼80% Ce(IV) (range 18-108%), pointing to the importance of anthropogenic inputs of Ce(IV). The quantification of the anthropogenic Ce fraction based on Ce oxidation state, however, was associated with considerable uncertainty because geogenic and anthropogenic Ce cannot exclusively be assigned to Ce(III) and Ce(IV), respectively. The REE patterns of most sewage sludges indicated a clear enrichment of Ce compared to heavier REE. Based on the assumption that the industrially used Ce is free of (most) other REE, we estimated the fraction of anthropogenic Ce in the sludges based on individual Ce/REE ratios. For the individual sludges the anthropogenic contributions were very variable (10-100%) but consistent fractions were obtained for individual sludges when calculated based on Ce/Dy (dysprosium), Ce/Er (erbium) and Ce/Eu (europium) ratios. Electron microscopy analysis of sludges dominated by anthropogenic Ce revealed that the Ce was mostly contained in nanoscale particles devoid of elements characteristic of Ce-bearing minerals. Thus, anthropogenic Ce contents derived from REE patterns may be used to validate current mass flow models for engineered CeO2 nanoparticles.

Mercury loads and fluxes from wastewater: A nationwide survey in Switzerland.

Mercury (Hg) pollution threatens ecosystems and human health. Wastewater treatment plants (WWTPs) play a key role in limiting Hg discharges from wastewaters to rivers and lakes, but large-scale studies to estimate Hg loads and discharge at national levels are scarce. We assessed the concentration, flux, speciation, and removal of Hg in municipal wastewater throughout Switzerland by investigating 64 WWTPs in a pre-study and a subset of 28 WWTPs in the main study. We also studied the behavior and pathways of Hg along the various treatment steps in a state-of-the-art WWTP. The resulting dataset, representative of industrialized countries, provides an overview of (i) current Hg concentration ranges, (ii) average per capita loads, and (iii) wastewater Hg inputs into surface waters. The results allowed estimation of a total Hg (THg) load in Swiss wastewater of 130 ± 30 kg THg/year (15.7 mg/capita/y), of which 96 ± 4% is retained in sewage sludge. About 4.7 ± 0.5 kg THg/year (0.57 mg/capita/y) is discharged with the treated wastewater into surface waters. This corresponds to only 1.5-3% of the THg load carried by the major Swiss rivers, indicating that >95% of riverine Hg originates from other sources. Extrapolation to the population of Europe would yield a total amount of 11,700 kg THg/year in raw wastewater, with some 480 kg THg/year discharged to surface waters. Monomethyl mercury on average accounted for 0.23% of THg, and its fraction remained constant along the different treatment steps.

Thallium and co-genetic trace elements in hydrothermal Fe-Mn deposits of Central Spain.

Thallium (Tl) is a hazardous trace metal that can harm human and environmental health. Tl pollution can result from the mining and smelting of Tl-bearing minerals, but also the natural weathering of Tl-bearing sulfide minerals may induce Tl release to the environment. In this study, hydrothermal deposits hosted in dolostone rocks sited along fossil thermal springs in the Lodares region (Soria province, central Spain) were studied. In this hydrothermal mineralization zone, Tl association with primary minerals, identified Tl-bearing secondary products resulting from natural weathering of primary minerals, as well as the dispersion from its natural source along a seasonal small streambed were explored. Samples were analyzed by chemical, microscopic and spectroscopic techniques and epithermal pyrite, sphalerite, galena and barite and secondary gypsum, jarosite, scorodite, anglesite, goethite, epsomite and elemental sulfur produced by both inorganic and bacterial processes were found. The highest Tl contents were found in hydrothermal pyrite (188 mg kg-1), jarosite (142 mg kg-1), Mn-oxides (27 mg kg-1) or kerogen (13 mg kg-1). Feldspar was identified by electron probe microanalysis as potential host phase of Tl. XANES results confirmed the association of Tl(I) with metal sulfides in pyrite-rich samples and highlighted the role of jarosite-like minerals for Tl(I) sequestration upon pyrite oxidation, even in carbonate-rich samples at near-neutral pH. In addition to micaceous minerals, jarosite-group minerals and K-feldspars may contribute to the natural attenuation of Tl in soils and sediments.

Thallium Sorption onto Manganese Oxides.

The sorption of thallium (Tl) onto manganese (Mn) oxides critically influences its environmental fate and geochemical cycling and is also of interest in water treatment. Combined quantitative and mechanistic understanding of Tl sorption onto Mn oxides, however, is limited. We investigated the uptake of dissolved Tl(I) by environmentally relevant phyllo- and tectomanganates and used X-ray absorption spectroscopy to determine the oxidation state and local coordination of sorbed Tl. We show that extremely strong sorption of Tl onto vacancy-containing layered δ-MnO2 at low dissolved Tl(I) concentrations (log Kd ≥ 7.4 for ≤10-8 M Tl(I); Kd in (L/kg)) is due to oxidative uptake of Tl and that less specific nonoxidative Tl uptake only becomes dominant at very high Tl(I) concentrations (>10-6 M). Partial reduction of δ-MnO2 induces phase changes that result in inhibited oxidative Tl uptake and lower Tl sorption affinity (log Kd 6.2-6.4 at 10-8 M Tl(I)) and capacity. Triclinic birnessite, which features no vacancy sites, and todorokite, a 3 × 3 tectomanganate, bind Tl with lower sorption affinity than δ-MnO2, mainly as hydrated Tl+ in interlayers (triclinic birnessite; log Kd 5.5 at 10-8 M Tl(I)) or tunnels (todorokite). In cryptomelane, a 2 × 2 tectomanganate, dehydrated Tl+ replaces structural K+. The new quantitative and mechanistic insights from this study contribute to an improved understanding of the uptake of Tl by key Mn oxides and its relevance in natural and engineered systems.

Transformation of Nanoscale and Ionic Cu and Zn during the Incineration of Digested Sewage Sludge (Biosolids).

Engineered nanoparticles (NP) discharged to sewers are efficiently retained by wastewater treatment plants and accumulate in the sewage sludge, which is commonly digested. The resulting biosolids are either used as fertilizer or incinerated. In this study, we address the transformation of Cu and Zn during sewage sludge incineration and evaluate whether the form of Cu or Zn (nanoparticulate versus dissolved) added to the digested sewage sludge affects the fate of the metals during incineration. We spiked CuO-NP, dissolved CuSO4, ZnO-NP, or dissolved ZnSO4 into anaerobically digested sewage sludge to reach Cu and Zn concentrations of ≈2500 and ≈3700 mg/kg and maintained the sludge under mesophilic, anaerobic conditions for 24 h. Subsequently, the sludge was incinerated in a pilot fluidized bed reactor. The speciation of Cu and Zn in the sludge, derived from X-ray absorption spectroscopy measurements, was dominated by sulfidic species, with >90% of Cu and >60% of Zn coordinated to reduced sulfur groups. In the ash, both Cu (>60%) and Zn (≈100%) were coordinated to oxygen. The chemical speciation of Cu and Zn in the ashes was independent of whether they were spiked in the dissolved or nanoparticulate form and closely matched the speciation of Cu and Zn observed in ashes from full-scale incinerators.

Decreases in Iron Oxide Reducibility during Microbial Reductive Dissolution and Transformation of Ferrihydrite.

Ferrous iron formed during microbial ferric iron reduction induces phase transformations of poorly crystalline into more crystalline and thermodynamically more stable iron (oxyhydr)oxides. Yet, characterizing the resulting decreases in the reactivity of the remaining oxide ferric iron toward reduction (i.e., its reducibility) has been challenging. Here, we used the reduction of six-line ferrihydrite by Shewanella oneidensis MR-1 as a model system to demonstrate that mediated electrochemical reduction (MER) allows directly following decreases in oxide ferric iron reducibility during the transformation of ferrihydrite into goethite and magnetite which we characterized by X-ray diffraction analysis and transmission electron microscopy imaging. Ferrihydrite was fully reducible in MER at both pHMER of 5.0 and 7.5. Decreases in iron oxide reducibility associated with ferrihydrite transformation into magnetite were accessible at both pHMER because the formed magnetite was not reducible under either of these conditions. Conversely, decreases in iron oxide reducibility associated with goethite formation were apparent only at the highest tested pHMER of 7.5 and thus the thermodynamically least favorable conditions for iron oxide reductive dissolution. The unique capability to adjust the thermodynamic boundary conditions in MER to the specific reducibilities of individual iron (oxyhydr)oxides makes this electrochemical approach broadly applicable for studying changes in iron oxide reducibility in heterogeneous environmental samples such as soils and sediments.

Reductive dissolution of As(V)-bearing Fe(III)-precipitates formed by Fe(II) oxidation in aqueous solutions.

Iron(III)-precipitates formed by the oxidation of dissolved Fe(II) are important sorbents for major and trace elements in aquatic and terrestrial systems. Their reductive dissolution in turn may result in the release of associated elements. We examined the reductive dissolution kinetics of an environmentally relevant set of Fe(II)-derived arsenate-containing Fe(III)-precipitates whose structure as function of phosphate (P) and silicate (Si) content varied between poorly-crystalline lepidocrocite, amorphous Fe(III)-phosphate, and Si-containing ferrihydrite. The experiments were performed with 0.2-0.5 mM precipitate-Fe(III) using 10 mM Na-ascorbate as reductant, 5 mM bipyridine as Fe(II)-complexing ligand, and 10 mM MOPS/5 mM NaOH as pH 7.0 buffer. Times required for the dissolution of half of the precipitate (t50%) ranged from 1.5 to 39 h; spanning a factor 25 range. At loadings up to ~ 0.2 P/Fe (molar ratio), phosphate decreased the t50% of Si-free precipitates, probably by reducing the crystallinity of lepidocrocite. The reductive dissolution of Fe(III)-phosphates formed at higher P/Fe ratios was again slower, possibly due to P-inhibited ascorbate binding to precipitate-Fe(III). The slowest reductive dissolution was observed for P-free Si-ferrihydrite with ~ 0.1 Si/Fe, suggesting that silicate binding and polymerization may reduce surface accessibility. The inhibiting effect of Si was reduced by phosphate. Dried-resuspended precipitates dissolved 1.0 to 1.8-times more slowly than precipitates that were kept wet after synthesis, most probably because drying enhanced nanoparticle aggregation. Variations in the reductive dissolution kinetics of Fe(II) oxidation products as reported from this study should be taken into account when addressing the impact of such precipitates on the environmental cycling of co-transformed nutrients and contaminants.

Thallium stable isotope fractionation in white mustard: Implications for metal transfers and incorporation in plants.

We studied thallium (Tl) isotope fractionation in white mustard grown hydroponically at different Tl doses. Thallium isotope signatures in plants indicated preferential incorporation of the light 203Tl isotope during Tl uptake from the nutrient solution. Negative isotope fractionation was even more pronounced in dependence on how much the available Tl pool decreased. This finding corresponds to the concept of isotope overprinting related to a high contamination level in the growing media (solution or soil). Regarding Tl translocation in plants, we observed a large Tl isotope shift with an enrichment in the heavy 205Tl isotope in the shoots relative to the roots in treatments with low/moderate solution Tl concentrations (0.01/0.05 mg Tl/L), with the corresponding α205/203Tl fractionation factors of ˜1.007 and 1.003, respectively. This finding is probably a consequence of specific (plant) reactions of Tl replacing K in its cycle. The formation of the S-coordinated Tl(I) complexes, potentially affecting both Tl accumulation and Tl isotope fractionation in plants, however, was not proven in our plants, since we did not have indication for that on the basis of X-ray absorption spectroscopy, suggesting that Tl was mainly present as free/hydrated Tl+ ion or chemically bound to O-containing functional groups.