Selenium Sorption Research Articles

Sorption of Selenium(IV) and Selenium(VI) onto Iron Oxide/Hydroxide-Based Carbon Materials: Activated Carbon and Carbon Foam

Selenium pollution in water is a worldwide issue. Se(IV) and Se(VI) are mainly found in contaminated water due to their high solubility and mobility; their presence poses a serious risk as they can severely harm human health. Although iron oxide and hydroxide nanoparticles can be efficient candidates for the removal of selenium oxyanions due to their high adsorption capacity, the role of each iron species has not been fully elucidated. Furthermore, iron species are often found to be less effective for Se(VI) than Se(IV). The challenge and novelty of this study was to develop a carbon material impregnated with different iron phases, including oxides (magnetite/hematite) and hydroxides (goethite/lepidocrocite) capable of removing both Se(IV) and Se(VI). Since the phase and morphology of the iron nanoparticles play a significant role in Se adsorption, the study evaluated both characteristics by modifying the impregnation method, which is based on an oxidative hydrolysis with FeSO4 7H2O and CH3COONa, and the type of carbonaceous support (activated carbon or sucrose-based carbon foam). Impregnated activated carbons provide better removal efficiencies (70–80%) than carbon foams (<40%), due to their high surface areas and point zero charges. These results show that the adsorption of Se(VI) is more favorable on magnetic oxides (78%) and hydroxides (71%) than in hematite (<40%). In addition, the activated carbon decorated with magnetite showed a high adsorption capacity for both selenium species, even in alkaline conditions, when the sorbent surface is negatively charged. A mechanism based on the adsorption of inner-sphere complexes was suggested for Se(IV) immobilization, whereas Se(VI) removal occurred through the formation of outer-sphere complexes and redox processes.

The uptake of selenium by perennial ryegrass in soils of different organic matter contents receiving sheep excreta

Background and aimsThe intake of selenium, an essential element for animals and humans, in ruminants is largely determined by selenium concentration in ingested forages, which take up selenium mainly from soil. Ruminant excreta is a common source of organic fertilizer, which provides both nutrients and organic matter. This study aims to unentangle the unclear effect of applying different types of ruminant excreta in soils of different organic matter contents on selenium uptake by forage.MethodsPerennial ryegrass (Lolium perenne) was grown in soils of different organic matter contents. Urine and/or feces collected from sheep fed with organic or inorganic mineral supplements, including selenium, were applied to the soils. The selenium in the collected samples were analyzed using ICP-MS. The associated biogeochemical reactions were scrutinized by wet chemistry.ResultsThe application of urine and/or feces resulted in either the same or lower selenium concentrations in perennial ryegrass. The excreta type did not affect total selenium accumulation in grass grown in low organic matter soil, whereas in high organic matter soil, feces resulted in significantly lower total selenium accumulation than urine, which was attributed to a possible interaction of selenium sorption in soil and microbial reduction of Se.ConclusionThis one-time excreta application did not increase, but further decrease in some treatments, selenium concentration and accumulation in the perennial ryegrass. Consequently, to increase ruminant selenium intake, supplementing selenium directly to animals is more recommended than applying animal manure to soil, which might drive selenium reduction and decrease selenium uptake by grass.

Impact of fracture filling materials on selenium sorption in granite

Selenium (Se) sorption behaviors have been widely studied for evaluating radionuclide reactive transport in fractured granite. However, with disparate mineral compositions, the impact of fracture filling materials (FFMs) is often ignored in characterizing radionuclide sorption and migration. This study aims to investigate the contribution of FFMs to the sorption of radionuclide by conducting flow-through experiments with granite, FFMs, and their mixtures (GFMs) separately. The relative contribution of major minerals in these materials is further identified by column experiments with pure minerals. Taking the granite core samples collected from a potentialrepositorysite as an example, the Se(IV) sorption and migration is mainly influenced by biotite and albite in granite samples, and is controlled by smectite and illite in FFMs. The sorption distribution coefficient (Kd) estimated from the individual mineral experiments decreased in the following order: smectite > illite > biotite > K-feldspar > albite > quartz > calcite. When all minerals were mixed, the sorption ability increased with the mass fraction of FFMs. The component additivity model (CAM) was further tested by predicting Kd in different mineral mixtures. The calculated Kd values were lower than those obtained from experimental fitting results. The largest discrepancy occurred when the mass fractions of the granite and FFMs were equal. This implies that CAM has certain limitations in upscaling Kd directly from individual minerals to mineral mixtures, especially when the mass fraction of FFMs is larger than 0.2. The results from this study provide valuable insights for understanding the sorption behaviors of radionuclides in fractured granite.

Ex and In Situ Reactivity and Sorption of Selenium in Opalinus Clay in the Presence of a Selenium Reducing Microbial Community

79Se is a critical radionuclide concerning the safety of deep geological disposal of certain radioactive wastes in clay-rich formations. To study the fate of selenium oxyanions in clayey rocks in the presence of a selenium reducing microbial community, in situ tests were performed in the Opalinus Clay at the Mont Terri Rock Laboratory (Switzerland). Furthermore, biotic and abiotic batch tests were performed to assess Se(VI) and Se(IV) reactivity in the presence of Opalinus Clay and/or stainless steel, in order to support the interpretation of the in situ tests. Geochemical modeling was applied to simulate Se(VI) reduction, Se(IV) sorption and solubility, and diffusion processes. This study shows that microbial activity is required to transform Se(VI) into more reduced and sorbing Se species in the Opalinus Clay, while in abiotic conditions, Se(VI) remains unreactive. On the other hand, Se(IV) can be reduced by microorganisms but can also sorb in the presence of clay without microorganisms. In situ microbial reduction of Se oxyanions can occur with electron donors provided by the clay itself. If microorganisms would be active in the clay surrounding a disposal facility, microbial reduction of leached Se could thus contribute to the overall retention of Se in clayey host rocks.

Sorption of Heavy Metal Ions of Chromium, Manganese, Selenium, Nickel, Cobalt, Iron from Aqueous Acidic Solutions in Batch and Dynamic Conditions on Natural and Synthetic Aluminosilicate Sorbents.

Zeolites are materials with known sorption properties. The sorption is thought to progress mainly by ion exchange with Na+, K+, Mg2+, Ca2+ or H+ from the zeolite exchange sites. The aim of the study was to compare the sorption properties of natural and synthetic zeolites on the example of the removal of selected metals from aqueous acidic solutions. Uptake experiments for selected ions of chromium, manganese, selenium, nickel, cobalt, and iron were performed using the batch and kinetic column methods. The sorption of the individual metal ions in mg per 1g of sorbent was determined for each sorbent. The relative affinity sequence of the examined cations toward the various sorbent was presented. The Langmuir model was used to model the adsorption equilibrium. Vermiculite under 1 mm of diameter (SF), Na-X, and Na-A were proved to be the most suitable for the individual uptake of studied metal ions. It was observed that the behavior of selenium ions differed from the remaining ones which was interpreted that selenium undergoes adsorption in the anionic form. The fixed-bed column studies were performed using Na-A, ensuring the sorption of selenium in the presence of iron(III) ions. The experiments were conducted using Na-X zeolite pre-loaded by Fe(III) as well as unmodified sorbent eluted by an equimolar mixture containing 100 ppm of Fe and Se. Obtained results prove that selenium sorption improves if other metal ions such as iron appear in the acidic solution. That efficient selenium sorption conditions can be applied to remove selenium which was recognized as toxic at higher levels.

Influence of silicate on the structural memory effect of layered double hydroxides for the immobilization of selenium

The influence of silicate on the structural memory effect of layered double hydroxides (LDHs) has been rarely reported. In this study, five kinds of calcined LDHs (CLDHs) were synthesized and used as adsorbents for the sorption of selenium with or without silicate, under the initial pH 10 and 13, respectively, characterized by X-ray diffraction (XRD), scanning electron microscope (SEM), infrared spectroscopy (IR), nuclear magnetic resonance (NMR), X-ray photoelectron spectroscopy (XPS), and N2 adsorption-desorption isotherm. The results indicated that silicate can significantly affect the phase transformation of CLDHs, and the sorption amounts of selenite and selenate dramatically decreased in the presence of silicate. Specifically, silicate can react with MgO and Al2O3 in CLDHs to generate magnesium silicate hydrate and geopolymer-like substance which were covered on the surface of particles, blocking the hydroxylation of metal oxides. However, higher pH suppressed the interaction between MgO and silicate and enhanced the formation of geopolymer-like substance, which promoted the regeneration of LDHs. Al in CLDHs plays a critical role in the regeneration of LDHs. Besides, the ternary oxides (CLDH-2, Mg2Al0.75Fe0.25-oxide; CLDH-3, Mg2Al0.5Fe0.5-oxide) possessed larger specific surface areas (127.7 and 158.2 m2/g) and consequently presented more resistance to the effect of silicate.

Tellurium and selenium sorption kinetics and solid fractionation under contrasting estuarine salinity and turbidity conditions

Tellurium (Te) is a Technology Critical Element (TCE) and a relevant product of nuclear fission. It has an unknown environmental biogeochemical cycle, mostly related to current analytical challenges in measuring its ultra-trace dissolved concentrations in complex environmental matrices. It is therefore generally compared to its geochemical pair selenium (Se), which shows a narrow range between diet essentiality and toxicity properties. Batch experiments using isotopically-labelled stable Te and Se were performed with fresh suspended particulate matter (SPM) from the fluvial part of the Gironde Estuary, simulating both estuarine salinity (S = 0 vs S = 32) and turbidity (100 mg L−1 vs 1000 mg L−1) gradients to understand the importance of the particulate phases in Te reactivity under estuarine conditions and verify the resemblance to Se behaviour. These experiments addressed sorption kinetics, sorption isotherms and fractionation from selective extractions of final equilibrated SPM. Results showed a strong, salinity-independent affinity of Te for the particulate phases (log10 Kd ~ 4.9 L kg−1), following a Langmuir-type isotherm. Contrastingly, Se adsorbs clearly less to estuarine SPM (log10 Kd ~ 2.5 L kg−1), following a Freundlich-type isotherm. Both isotherms and selective extractions highlighted differences between Te and Se sequestration. Selective extractions suggested higher mobility of particulate Se in contrast to Te. Based on these results the paper sets a first dispersion scenario on the environmental fate of radioactive Te and Se after hypothetical nuclear power plant accidental releases in coastal aquatic systems such as the Garonne-Gironde fluvial-estuarine system.

Toward Realizing Multifunctionality: Photoactive and Selective Adsorbents for the Removal of Inorganics in Water Treatment.

Persistent and potentially toxic inorganic oxoanions (e.g., arsenic and selenium) are one class of contaminants of concern in drinking water for which treatment technologies must be improved. Effective removal of these oxoanions is made difficult by the varying adsorption affinity of the different oxidation states, as well as the presence of background ions with similar chemical structure and behavior that strongly compete for adsorption sites, greatly reducing removal efficiencies. Recent studies pointing to the negative health effects of inorganic oxoanion contaminants have resulted or are expected to result in new regulations lowering their allowable maximum concentration level (MCL) in drinking water. While these regulations are intended to protect human and environmental health, they must also allow for balanced economic costs. As such, the MCLs are often set at levels that are not as health protective due to high treatment costs that continue to present a significant challenge for small (500-3300 people) to very small (25-500 people) communities. In this Account, we focus on the development of novel cost-effective, sustainable, and efficient multifunctional and selective adsorbents that offer solutions to the above challenges through two platforms: nanoenabled and transition-metal cross-linked chitosan (TMCC) and crystal facet engineered nanometal oxides (NMO). These complementary platforms offer treatment solutions at different scales and flow rates (e.g., in a point-of-use device versus a small-scale community system). Multifunctional adsorbents combine processes that traditionally require multiple steps offering the potential for reducing treatment time and costs. Development of selective adsorbents can greatly increase removal efficiencies of target contaminants by either promoting their adsorption or hindering adsorption of competitive ions. The following sections describe (1) synthesis of novel nanoenabled waste sourced bioadsorbents; (2) development of multifunctional adsorbents to simultaneously photo-oxidize arsenite and adsorb arsenate; (3) development of a selective adsorbent for removal of arsenate and selenite over phosphate; (4) investigations of the conventional wisdom that increased surface area yields increased oxoanion removal using selenium sorption on nanohematite as a case study; and (5) crystal engineering of nanohematite to promote selenite adsorption. The novel technologies developed through these research efforts can serve as templates for the creation of future adsorbents tailored for use targeting other oxoanion contaminants of interest.

Soil management and ionic strength on selenite retention in oxidic soils

ABSTRACT Sorption of selenium (Se) on soils may be influenced by factors that are changed though agricultural practices usually performed for crop production, such as soil pH, competing anion and organic matter contents, among others. This study aimed to evaluate the influence of soil management and ionic strength (IS) on Se retention in Brazilian soils, which is important to predict Se availability in both systems, native and cultivated soils. For that, adsorption and desorption reactions of Se were evaluated in 16 soil samples (eight from cultivated soils and eight from native soils), using solutions containing 100 and 500 µg L-1 Se in the form of sodium selenate and in two IS, 15 and 150 mM. Se adsorption varied as a function of IS for most soils, which may indicate that the adsorption mechanism by outer-sphere complex is important for selenate retention in the studied soils, but future studies involving other techniques, such as spectroscopic studies, are needed to more clearly confirm the adsorption mechanism. In general, adsorption varied in relation to soil characteristics, and native soils adsorbed larger Se amounts than the cultivated soils. In terms of desorption, soils which had larger Se adsorbed amounts also presented larger desorbed amounts. Finally, IS and soil management influenced the availability of selenate in the studied soils.

Selenium(IV) Sorption Onto γ-Al2O3: A Consistent Description of the Surface Speciation by Spectroscopy and Thermodynamic Modeling.

The sorption processes of Se(IV) onto γ-Al2O3 were studied by in situ Infrared spectroscopy, batch sorption studies, zeta potential measurements and surface complexation modeling (SCM) in the pH range from 5 to 10. In situ attenuated total reflection fourier-transform infrared (ATR FT-IR) spectroscopy revealed the predominant formation of a single inner-sphere surface species at the alumina surface, supporting previously reported EXAFS results, irrespective of the presence or absence of atmospherically derived carbonate. The adsorption of Se(IV) decreased with increasing pH, and no impact of the ionic strength was observed in the range from 0.01 to 0.1 mol L-1 NaCl. Inner-sphere surface complexation was also suggested from the shift of the isoelectric point of γ-Al2O3 observed during zeta potential measurements when Se(IV) concentration was 10-4 mol L-1. Based on these qualitative findings, the acid-base surface properties of γ-Al2O3 and the Se(IV) adsorption edges were successfully described using a 1-pK CD-MUSIC model, considering one bidentate surface complex based on previous EXAFS results. The results of competitive sorption experiments suggested that the surface affinity of Se(IV) toward γ-Al2O3 is higher than that of dissolved inorganic carbon (DIC). Nevertheless, from the in situ experiments, we suggest that the presence of DIC might transiently impact the migration of Se(IV) by reducing the number of available sorption sites on mineral surfaces. Consequently, this should be taken into account in predicting the environmental fate of Se(IV).

Sorption and speciation of selenium in boreal forest soil

Sorption and speciation of selenium in the initial chemical forms of selenite and selenate were investigated in batch experiments on humus and mineral soil samples taken from a 4–m deep boreal forest soil excavator pit on Olkiluoto Island, on the Baltic Sea coast in southwestern Finland. The HPLC–ICP-MS technique was used to monitor any possible transformations in the selenium liquid phase speciation and to determine the concentrations of selenite and selenate in the samples for calculation of the mass distribution coefficient, Kd, for both species. Both SeO32− and SeO42− proved to be resistant forms in the prevailing soil conditions and no changes in selenium liquid phase speciation were seen in the sorption experiments in spite of variations in the initial selenium species, incubation time or conditions, pH, temperature or microbial activity. Selenite sorption on the mineral soil increased with time in aerobic conditions whilst the opposite trend was seen for the anaerobic soil samples. Selenite retention correlated with the contents of organic matter and weakly crystalline oxides of aluminum and iron, solution pH and the specific surface area. Selenate exhibited poorer sorption on soil than selenite and on average the Kd values were 27–times lower. Mineral soil was more efficient in retaining selenite and selenate than humus, implicating the possible importance of weakly crystalline aluminum and iron oxides for the retention of oxyanions in Olkiluoto soil. Sterilization of the soil samples decreased the retention of selenite, thus implying some involvement of soil microbes in the sorption processes or a change in sample composition, but it produced no effect for selenate. There was no sorption of selenite by quartz, potassium feldspar, hornblende or muscovite. Biotite showed the best retentive properties for selenite in the model soil solution at about pH 8, followed by hematite, plagioclase and chlorite. The Kd values for these minerals were 18, 14, 8 and 7 L/kg, respectively. It is proposed that selenite sorption is affected by the structural Fe(II) in biotite, which is capable of inducing the reduction of SeO32− to Se(0). Selenite probably forms a surface complex with Fe(III) atoms on the surface of hematite, thus explaining its retention on this mineral. None of the minerals retained selenate to any extent.

Thermodynamics of selenium sorption on alumina and montmorillonite

The effect of pH and temperature on the thermodynamics of selenium sorption on alumina and montmorillonite was investigated. The equilibrium constants were obtained from batch experiments carried out at 25 and 40°C, under acidic and near to neutral conditions. Microcalorimetry was used to measure directly the enthalpy change upon sorption. These data were analysed by taking into account the different reactions that occur during the sorption process (the acid–base equilibria in the bulk solution on the one hand and the complexation equilibria between surface sites of the solid and solution species on the other hand). This was done using a simple surface model which assumes that the thermodynamic properties of the aluminol surface sites of both alumina and montmorillonite are identical. Two of the considered reactions were found to predominate, one under acidic conditions and one at near neutral pH. The microcalorimetric data allowed to check that the temperature effect on selenium sorption on alumina and montmorillonite can be correctly predicted simply using the above assumption concerning the sorption sites and by applying van’t Hoff relation both to the homogeneous and heterogeneous reactions.

Adsorption of Se (IV) and Se (VI) Using Copper-Impregnated Activated Carbon and Fly Ash-Extracted Char Carbon

Surface and groundwater are often contaminated with toxic anions such as arsenic and selenium. Because of their large surface areas, selenium adsorption on carbon sorbents is considered an attractive water treatment technique. In this present work, selenium sorption on copper-impregnated activated carbon and fly ash-extracted char carbon was evaluated. Unburned carbon was extracted from fly ash using froth floatation techniques, and the carbon sorbents were modified using copper ions. Adsorption experiments confirmed the strong influence of electrostatic forces on equilibrium uptakes of selenite (Se (IV)) and selenate (Se (VI)). Selenium sorption on virgin char carbon was maximum only at acidic pH, i.e., at pH pHpzc, a two- to fourfold increase in sorption coverage and threefold increase in selenium percent removal was observed. Se (IV) sorption was higher compared to Se (VI) sorption. The effect of selenium concentrations and competing anions was studied to evaluate adsorbent performance. The order of maximum surface coverage followed the order: modified char carbon > modified activated carbon > char carbon. The main mechanism of selenium (Se) sorption appeared to be (1) electrostatic attraction of the Se ions to the modified carbon surface at acidic to neutral pH; (2) complexation of Se ions with the copper ions/oxides on the carbon surface; and (3) co-precipitation with copper hydroxides at alkaline pH.

Selenium sorption on clays in synthetic groundwaters representing crystalline bedrock conditions

The sorption behaviour of selenium on kaolinite and illite minerals in synthetic groundwaters was evaluated using the mass distribution coefficient, R d, obtained in batch sorption experiments. The applied solutions were model solutions of fresh water, brackish water, saline water and glacial meltwater. The distribution coefficient values for illite varied between (0.4–60) × 10−3 and (11–720) × 10−3 m3 kg−1 for kaolinite. No clear effect of ionic strength or calcium concentration on the sorption was observed. The aqueous speciation calculations and the nonelectrostatic surface complexation model applied were in good accordance with the measured R d values at a neutral pH range.

Incorporation of selenium(IV) and selenium(VI) on uranyl peroxide

The sorption of Se(IV) and Se(VI) on uranium peroxide has been studied considering the sorption kinetics, the sorption isotherms and the effect of pH. Selenium sorption on studtite is fitted with a pseudosecond order reaction model; in addition, two different mechanisms seem to influence the sorption process: micropore diffusion and intra-particle diffusion. Both selenium(IV) and selenium(VI) are sorbed on studtite through a monolayer coverage. Sorption is higher at acidic pH than at alkaline pH. This behaviour is consistent with the chemical speciation of selenium in solution and with the acid–base properties of the solid.

Sorption of metals and metalloids from reverse osmosis concentrate on drinking water treatment solids

Drinking water treatment solids (DWTS) from coagulation processes could be a low-cost sorbent for selective removal of certain metals and metalloids from brine. In this study, continuous-flow sorption processes and factors affecting sorption of boron (III), copper (II), chromium (VI), lead (II), and selenium (VI) from reverse osmosis (RO) concentrate were investigated using different types of iron-derived DWTS. DWTS was demonstrated to be very effective in removal of copper and lead from RO concentrate, attributed to formation of strong inner-sphere complexes between the metal cations and Fe/Al oxide surface sites in the DWTS, as well as attractive electrostatic interactions with the negatively charged DWTS surface. Sorption of boron and selenium on the DWTS was lower. Boron exists primarily as nonionic boric acid at operating pH of 5.5–7.8, while selenate is a weakly bonding anion typically assumed to form outer-sphere surface complexes with Fe/Al oxides, both resulting in low removal. Sorption of the metals and metalloids was affected by their speciation and electrostatic interactions with DWTS. Higher influent pH increased boron and copper sorption but inhibited removal of chromium. Water temperature, solid moisture content, and loading rate did not have significant impact on sorption to the DWTS.

Two-stage biosorption of selenium from aqueous solution using dried biomass of the baker's yeast Saccharomyces cerevisiae

In the present study, the biosorption of selenium ion onto dried biomass of baker's yeast, Saccharomyces cerevisiae, in an aqueous system was investigated. An optimization of selenium biosorption was performed by varying the pH, the initial ion concentration and the biomass dosage. Selenium sorption isotherms were obtained at optimal conditions and the sorption equilibrium data fitted to the Sips isotherm model. The maximum uptake capacity by the Sips model was about 39.0mgg−1. The mass balance equations permitted a theoretical determination of the selenium concentration and the amount of biosorbent needed for achieving the required heavy metal removal. It was observed that two adsorption stages and 2g of baker's yeast biomass biosorbent were required to remove 96.10% of 50mgL−1 selenium from 100ml aqueous solution. In this condition, the percentage removal of selenium in stage one was 88.10% and stage two was 67.20%. The thermodynamic study revealed that the biosorption process of selenium has an endothermic and spontaneous nature and is promoted by increasing the temperature from 298 to 318K. The results also showed that the pseudo-second-order kinetic model correlated well with the experimental data, with an activation energy of 40.67kJmol−1. Based on the results of the percentage removal in the two-stage biosorption system, it could be concluded that the dried biomass of S. cerevisiae is a suitable sorbent for the removal of selenium ions from aqueous solution.

Anion-exchange separation of rhenium and selenium in schemes for obtaining ammonium perrhenate

Conditions for the quantitative separation of rhenium and selenium using anionites with isoporous structures are investigated with regard to the washing acid of the Balkhashskii Copper-Smelting Plant of KAZAKHMYS Corporation, which allows for the development of a unified technology for processing mixed rhenium-selenium solutions and obtaining end products, namely, high-clean ammonium perrhenate and elementary selenium. The completeness of metal separation is due to the development of methods for removing selenium both at the step of rhenium sorption and at the step of picking dynamic processes of impurities from the resin phase before rhenium desorption. Processes for the frontal-gradient removal of selenium from Purolite A170 weakly alkaline anionite have been developed, as well as marks of ionites for selective selenium sorption in order to obtain an associated product along with ammonium perrhenate.

Adsorption mechanism of selenium(VI) onto maghemite

In this study, the sorption properties of maghemite (γ-Fe2O3) towards selenium(VI) were studied for the first time both on the macroscopic and the molecular level. Using batch experiments, we found that the retention reaction was very fast. Both increase of pH and ionic strength led to a decrease of selenium(VI) sorption. Electrophoretic mobility measurements showed that selenium(VI) sorption had no significant effect on the isoelectric point of maghemite. These macroscopic results strongly suggested the formation of outer-sphere complexes across the investigated pH range (3.5–8.0). At the molecular level, the structure of the sorbed surface species was elucidated in situ using Attenuated Total Reflection Fourier-Transform Infrared (ATR FT-IR) spectroscopy and Extended X-ray Absorption Fine-Structure (EXAFS) spectroscopy. The ATR FT-IR results suggested the formation of outer-sphere complexes showing an unexpected bidentate symmetry, which possibly revealed the lack of accuracy of the actual widely-used classification of inner- and outer-sphere coordination for anionic species. EXAFS results revealed, that in addition to outer-sphere complexes, there is also a small (15%) contribution of an inner-sphere complex in binuclear corner-sharing geometry present.

Temperature impact on the sorption of selenium(VI) onto anatase

The impact of temperature (298K, 313K, and 333K) on the sorption of selenium(VI) onto anatase was investigated for the first time. At a macroscopic level, batch experiments showed a decrease of selenium(VI) retention with both increasing pH (3.5–7.0) and temperature. The thermodynamic parameters of the sorption reaction, i.e. the enthalpy ΔRH, entropy ΔRS, and the Gibbs free energy ΔRG, were determined from the temperature dependence sorption data using the van’t Hoff equation. The sorption process was found to be exothermic. Neither significant phase transformation nor a significant increase of anatase solubility could be detected with increasing temperature by XRD and ICP-MS. However, electrophoretic mobility measurements showed that both the zeta potential as well as the isoelectric point (pHIEP) of anatase were shifted to lower values with increasing temperature, leading to a decreased selenium(VI) sorption. At a microscopic level, the sorption mechanism of selenium(VI) onto anatase was elucidated at the three investigated temperatures by means of in situ Attenuated Total Reflection Fourier-Transform Infrared spectroscopy (ATR FT-IR). Results evidenced the formation of outer-sphere surface complexes, with no significant structural changes within the investigated temperature range.