Se Sorption Research Articles

Effect of Pyrolysis Temperature on the Sorption of Cd(II) and Se(IV) by Rice Husk Biochar

This study investigated the removal of metal cations (Cd(II)) and metalloid anions (Se(IV)) from their aqueous solution by using agricultural waste (rice husk biochar). Rice husk biochar samples were prepared under 300, 500, and 700 °C pyrolysis conditions and their physicochemical properties were characterized. Aqueous Cd(II) and Se(IV) sorption kinetics and isotherms of rice husk biochar were studied. The results showed that the yield of rice husk biochar decreased from 41.6% to 33.3%, the pH increased from 7.5 to 9.9, and the surface area increased from 64.8 m2/g to 330.0 m2/g as the pyrolysis temperature increased from 300 °C to 700 °C. Under the experimental conditions, at increasing preparation temperatures of rice husk biochar, the sorption performance of Cd(II) and Se(IV) was enhanced. The sorption capability and sorption rate were considerably higher and faster for Cd(II) ions than for Se(IV) ions. Cd(II) sorption was found to reach equilibrium faster, within 150 min, while Se(IV) sorption was slower and reached equilibrium within 750 min. The maximum sorption capacities of cadmium and selenium by rice husk biochar were 67.7 mg/g and 0.024 mg/g, respectively, according to Langmuir model fitting.

Upscaling of Se(IV) sorption coefficients with hierarchical mineral characterization in multi-scale fractured granite

Upscaling of Se(IV) sorption coefficients with hierarchical mineral characterization in multi-scale fractured granite

Breakthrough Curves Prediction of Selenite Adsorption on Chemically Modified Zeolite Using Boosted Decision Tree Algorithms for Water Treatment Applications

This work describes an experimental and machine learning approach for the prediction of selenite removal on chemically modified zeolite for water treatment. Breakthrough curves were constructed using iron-coated zeolite adsorbent and the adsorption behavior was evaluated as a function of an initial contaminant concentration as well as the ionic strength. An elevated selenium concentration in water threatens human health and aquatic life. The migration of this metalloid from the contaminated sites and the problems associated with its high releases into the water has become a major environmental concern. The mobility of this emerging metalloid in the contaminated water prompted the development of an efficient, cost-effective adsorbent for its removal. Selenite [Se(IV)] removal from aqueous solutions was studied in laboratory-scale continuous and packed-bed adsorption columns using iron-coated natural zeolite adsorbents. The proposed adsorbent combines iron oxide and natural zeolite’s ability to bind contaminants. Breakthrough curves were initially obtained under variable experimental conditions, including the change in the initial concentration of Se (IV), and the ionic strength of solutions. Investigating the effect of these parameters will enhance selenite mobility retardation in contaminated water. Continuous adsorption experiment findings will evaluate the efficiency of this economical and naturally-based adsorbent for selenite removal and fate in water. Multilinear and non-linear regressions approaches were utilized, yet low coefficients of determination values were respectively obtained. Then, a comparative analysis of five boosted regression tree algorithms for a selenite breakthrough curve prediction was performed. AdaBoost, Gradient boosting, XGBoost, LightGBM, and CatBoost models were analyzed using the experimental data of the packed-bed columns. The performance of these models for the breakthrough curve prediction under different operation conditions, such as initial selenite concentration and ionic strength, was discussed. The applicability of these models was evaluated using performance metrics (i.e., Mean Absolute Error (MAE), Root Mean Square Error (RMSE), Mean Absolute Percentage Error (MAPE), and coefficient of determination (R2). The CatBoost model provided the best fit for a breakthrough prediction with a coefficient of determination R2 equal to 99.57. The k-fold cross-validation technique and the statistical metrics verify this model’s accurateness. A feature importance assessment indicated that Se (IV) initial concentration was the most influential experimental variable, while the ionic strength had the least effect. This finding was consistent with the column transport results, which observed Se (IV) sorption dependency on its inlet concentration; simultaneously, the ionic strength effect was negligible. This work proposes implementing machine learning-based approaches for predicting water remediation-associated processes. The significance of this work was to provide an alternative method for investigating selenite adsorption behavior and predicting the breakthrough curves using a machine-based approach. This work also highlighted the importance of management practices of adsorption processes involved in water remediation.

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.

Sorption of Se(-II) on illite, MX-80 bentonite, shale, and limestone in Na–Ca–Cl solutions

Selenium has been identified as an element of interest for the safety assessment of a deep geological repository (DGR) for used nuclear fuel. In Canada, groundwaters at DGR depths in sedimentary rocks have been observed to have a high ionic strength. This paper examines the sorption behavior of Se(-II) onto illite, MX-80 bentonite, Queenston shale, and argillaceous limestone in Na–Ca–Cl solutions of varying ionic strength (0.1–6 mol/kgw (m)) and across a pH range of 4–9. Little ionic strength dependence for Se(-II) sorption onto all solids was observed except that sorption at high ionic strength (6 m) was generally slightly lower than sorption at low ionic strength (0.1 m). Illite and MX-80 exhibited the expected results for anion sorption, while shale and limestone exhibited more constant sorption across the pH range tested. A non-electrostatic surface complexation model successfully predicted sorption of Se(-II) onto illite and MX-80 using the formation of an inner-sphere surface complex and an outer-sphere surface complex. Optimized values for the formation reactions of these surface species were proposed.

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.

Preparation of wheat bran-titanium dioxide (TiO2) composite and its application for selenium adsorption

Selenium is metabolically required by a variety of organisms, but it may induce toxicity at high doses. The removal of a high concentration of selenium from water with natural and biocompatible materials is a vital component in the reuse of selenium given that the process converts low-cost materials into value-added products. In this study, novel wheat bran-titanium dioxide (TiO2) composite was prepared through the in situ hydrolysis of titanium oxysulfate in the presence of wheat bran after destarching, and its sorption characteristics toward Se(IV) from aqueous solutions were investigated. Scanning electronic microscopy and X-ray diffraction results revealed that amorphous TiO2 particles dispersed in the fiber matrix and on the fiber surface. The sorption of Se(IV) on the wheat bran-TiO2 composite was fast and pH dependent. The wheat bran-TiO2 composite exhibited high sorption capacity for Se(IV) at high temperatures, and the Langmuir isotherm models were able to fit the experimental data. The presence of phosphate reduced the efficiency of Se(IV) adsorption, whereas other coexisting anions had slight effects on Se(IV) adsorption. Fourier transform infrared analysis showed that the hydroxyl groups of TiO2 on the composite surface were involved in Se(IV) adsorption. The hybrid wheat bran-TiO2 composite has a promising application for Se(IV) sorption and enrichment in aqueous solutions.

Exploring sorption behaviors of Se(IV) and Se(VI) on Beishan granite: Batch, ATR-FTIR, and XPS investigations

As the important anions in the high-level radioactive waste (HLRW), and the sorption behaviors of Se(VI) and Se(IV) on Beishan granite are important to the safe evaluation and performance assessment of the deep geological repository for HLRW in China. In this study, the sorption behaviors of Se(IV) and Se(VI) on Beishan granite were investigated under different environmental factors combining batch and spectroscopic approaches, such as X-ray photoelectron spectroscopy (XPS) and attenuated total reflection Fourier transformed infrared (ATR-FTIR). The results showed that Se(IV) sorption on Beishan granite was much higher than that of Se(VI) mainly due to their molecule charge densities and speciation in solution. The sorption of Se(IV) was independent of ionic strength, suggesting that the inner-sphere complexes (ISCs) was dominant for Se(IV) sorption on granite. However, Se(VI) sorption on Beishan granite was strongly dependent on ionic strength, which indicated that ion exchange and outer-sphere complexes (OSCs) dominated Se(VI) sorption. ATR-FTIR confirmed that Se(IV) and humic acid (HA) could form a soluble complex of HA-Se(IV) in solution. Therefore, under low pH and HA concentration conditions, the presence of HA could enhance Se(IV) sorption; while inhibited Se(IV) sorption on granite to some extent under high pH and HA concentration conditions. In case of Se(VI), the presence of HA greatly reduced the surface charge density of the Beishan granite, which in turn enhanced the electrostatic repulsion of Se(VI) and granite surfaces, thereby inhibiting Se(VI) sorption on granite surface. When Se(IV) coexisted with Eu (III), the sorption of Se(IV) on granite could be enhanced to a large extent, which might be due to the formation of Eu2(SeO3)3 complex with Se(IV) under alkaline condition (consistent with ATR-FTIR), or surface charge modifications of Beishan granite caused by Eu(III) sorption. Owing to the ISCs of Se(IV) on granite, the presence of anions almost no obvious effect on Se(IV) sorption except for SO32− and HPO42− in terms of the competitive sorption, which inhibited Se(IV) sorption to some extent. It was interesting that CO32− could enhance Se(IV) sorption to a large extent, however the mechanism was still not clear. Furthermore, XPS further confirmed that Se(IV) sorption on granite was dominated by Fe(II) and Fe(III), and the host mineral was biotite.

Multi-site surface complexation modelling of Se(IV) sorption on biotite

A surface complexation model of Se(IV) sorption on biotite with one type of strong sorption sites and two types of weak sorption sites were developed based on experimental data obtained from titration, sorption edge and sorption isotherm experiments. Titration data was collected using a batch-wise manner together with backtitration to calibrate the effect of mineral dissolution in 0.01 M KClO4 background electrolytes from pH 3 to 11 in an inert atmosphere glovebox. Further calibrations of the titration curve include proton exchange and cation exchange in which the calculations of cation occupancies on biotite surfaces were taken into account. The sorption edge measurements were determined by measuring the sorption of 10−9 M total Se with a radioactive Se-75 tracer on converted biotite in 0.01 M KClO4 solution from pH 3 to 11. Se sorption was observed to be strongly dependent on pH. Surface complexation modelling was performed by deriving a set of optimized parameters that can fit titration, sorption edge and sorption isotherm (at pH ~7.7) experimental data. A CASTEP code implemented into Materials Studio was used to calculate the site densities and site types on the biotite surfaces. Weak sorption sites with site densities of 3.2 sites/nm2 and 1.4 sites/nm2 were derived from the codes and used in the sorption model. A computer code that coupled PHREEQC with Python was developed for the fitting and optimizing processes. The model was validated by sorption data at pH ~9.5. The results show that the model can provide quantitative predicts of Se(IV) sorption in groundwater conditions of a deep geological repository and help improve the performance assessments by giving more convincing estimates of the release of radionuclides towards aquifers and biosphere.

Se(VI) sorption from aqueous solution using alginate/polyethylenimine membranes: Sorption performance and mechanism

New high percolating alginate membranes are designed without using sophisticated drying methods: negatively charged alginate reacts with positively charged polyethylenimine (PEI), prior to be crosslinked with glutaraldehyde and air-dried. This is sufficient to obtain a highly macroporous structured membrane. Highly percolating properties of these new A-PEI membranes make the material applicable in natural drainage systems. The high density of amine groups in composite membranes explain their high affinity for anions in acidic solutions. FTIR, SEM-EDX and XPS analysis are used to explore the sorption mechanism. Se(VI) is sorbed through electrostatic attraction between positive amine groups and negative selenium anions; in a second step, bound Se(VI) is reduced by amine and hydroxyl groups in acidic conditions. A-PEI membranes are successfully used for recovering Se(VI) anions at pH 2. The maximum sorption capacity is close to 83 mg Se g−1; the sorption isotherm is described by the Sips and Langmuir equations. The membranes are poorly sensitive to flow rate in the range 15–50 mL min−1. The kinetic profiles are fitted by the pseudo-first order rate equation. Solute desorption is operated using NaOH solutions; the sorbent shows a remarkable stability in sorption and desorption properties for a minimum of 4 cycles.

Fast abiotic sorption of selenates (SeO42-) in soils: pitfalls of batch sorption data acquired by inductively coupled plasma quadrupole mass spectrometry (ICP-QMS)

ABSTRACTLow selenium (Se) dietary intake has encouraged the development of fortification strategies such as SeO42- application to arable land. Selenate is highly mobile in soil systems, but it is not known whether fast abiotic retention could reduce Se loss from topsoil after SeO42- fertilisation. This work explicitly aims at fast abiotic SeO42- sorption in three soils exposed to 20–1250 µg L−1 Se in a 24-h batch experiment. This study demonstrated the susceptibility of Se sorption data to distortion when inductively coupled plasma quadrupole mass spectrometry (ICP-QMS) measurements suffered from non-spectral interferences induced by concomitant elements in an aqueous soil-derived matrix. The distribution coefficient (Kd), not exceeding 2 L kg−1 at any Se level, was shown to be a useful indicator for the extent of ion competition for sorption sites depending on the SeO42- concentration employed. Sorption experiments conducted in the presence or absence of nitrate (10 mM), sulphate (0.52 mM) and phosphate (0.21 mM) allowed three phenomena explaining different SeO42- retention behaviours found even between similar Cambisols to be proposed. Finally, we showed that the co-application of sulphate or phosphate with SeO42- might decrease Se sorption from 150–170 µg kg−1 to a net release from native Se pool.Abbreviations: 1st IP: first ionisation potential; RSD: relative standard deviation

Effects of Mineral Compositions on Matrix Diffusion and Sorption of 75Se(IV) in Granite.

Exploring the migration behaviors of selenium in granite is critical for the safe disposal of radioactive waste. The matrix diffusion and sorption of 75Se(IV) (analogue for 79Se) in granite were systematically studied to set reliable parameters in this work. Through-diffusion and batch sorption experiments were conduct with four types of Beishan granite. The magnitudes of the obtained apparent diffusion coefficient (Da) values are of the following order: monzogranite > granodiorite-2 > granodiorite-1, which is opposite to the sequence of the Kd values obtained from both the diffusion model and batch sorption experiments. The EPMA results of the granitic flakes showed that there was no obvious enrichment of Se(IV) on quartz, microcline and albite. Only biotite showed a weak affinity for Se(IV). Macroscopic sorption behaviors of Se(IV) on the four types of granite were identical with the sequence of the granitic biotite contents. Quantitative fitting results were also provided. XPS and XANES spectroscopy data revealed that bidentate inner-sphere complexes were formed between Se(IV) and Fe(III). Our results indicate that biotite can be representative of the Se(IV) sorption in complex mineral assemblages such as granite, and the biotite contents are critically important to evaluate Se(IV) transport in granite.

Retention of selenium by calcium aluminate hydrate (AFm) phases under strongly-reducing radioactive waste repository conditions.

Safety assessment studies of future nuclear waste repositories carried out in many countries predict selenium-79 to be a critical radionuclide due to its presence as anion in three relevant oxidation states (vi, iv, -ii) resulting in weak retardation by most common rock minerals. This assumption, however, ignores its potential uptake by AFm phases, positively charged anion exchangers, which are present in significant quantities in the cementitious materials used in artificial barriers. Here we report for the first time wet chemistry and spectroscopic data on the interaction of the most relevant selenium anion species under the expected strongly reducing conditions, i.e. HSe-, with two AFm phases commonly found in cement, monocarbonate (AFm-MC) and hemicarbonate (AFm-HC). Batch sorption experiments showed that HSe- is retained much more strongly by AFm-HC (solid-liquid distribution ratio, Rd, of 100 ± 50 L kg-1) than by AFm-MC (Rd = 4 ± 2 L kg-1) at the equilibrium pH (∼12). X-ray absorption fine-structure (XAFS) spectroscopy revealed that the larger d-spacing in AFm-HC (d-spacing = 8.2 Å) provides easy access for HSe- to the AFm interlayer space for sorption, whereas the smaller d-spacing of AFm-MC (d-spacing = 7.55 Å) hinders interlayer access and limits HSe- sorption mostly to the outer planar surfaces and edges of the latter AFm phase. XAFS spectra further demonstrated that Se(-ii) prevalently sorbed in the interlayers of AFm-HC, is better protected from oxidation than Se(-ii) prevalently sorbed onto the outer surfaces of AFm-MC. The quantitative sorption data along with the molecular-scale process understanding obtained from this study provide crucial insight into the Se retention by the cementitious near-field of a radioactive waste repository under reducing conditions.

Adsorption of Selenite and Selenate on Ferrihydrite in the Presence and Absence of Dissolved Organic Carbon

This study examines selenite [Se(IV)] and selenate [Se(VI)] adsorption on two-line ferrihydrite in the presence and absence of two low-molecular-weight dissolved organic carbon (DOC) species, citric and salicylic acid. Ferrihydrite surface potential measurements were also examined to identify shifts in isoelectric points, which suggest possible adsorption mechanisms. Sorption was completed in batch reactor systems at environmentally relevant pH. Our results indicate citric acid suppressed both Se(IV) and Se(VI) sorption on ferrihydrite, which may be caused by competition. This was especially evident at pH 5 to 7 for Se(IV) and pH 5 to 6 for Se(VI). Little sorption suppression was observed for both Se species in the presence of salicylic acid. In the presence of Se(IV) and Se(VI), citric acid adsorption was reduced (pH 5-8). Salicylic acid sorption was almost completely suppressed in the presence of Se(IV) throughout the entire pH range examined, with minimal sorption occurring at pH 5. In the presence of Se(VI), the largest reduction in salicylic acid sorption occurred at pH 5 to 6. Small shifts in the surface potential of ferrihydrite at higher pH suggest that Se(VI) and salicylic acid form weak, outer-sphere complexes. However, at pH 5 and 6, there is a shift in the surface potential measurements to more negative values, indicating possible formation of stronger, inner-sphere complexes. Larger surface potential shifts for Se(IV) and citric acid suggest the formation of strong, inner-sphere complexes. This work demonstrates the ability of low-molecular-weight DOC species (particularly for citric acid) to increase Se(IV) and Se(VI) solubility through sorption suppression.

Influence of Fe(II) on the Se(IV) sorption under oxic/anoxic conditions using bentonite

79Se, one of the key radionuclides for nuclear waste disposal, threatens the quality of the environment, as well as human health. Therefore, it needs to be permanently isolated from the biosphere. The aim of the study was to investigate the effects of Fe(II)/Fe(III) on the removal of 79Se using bentonite in the pH range of 2.0–10.0 under oxic/anoxic conditions. Under oxic conditions, Se(IV) prefers to form inner-sphere complexes with Fe(III)-oxyhydroxide, derived from the oxidization of Fe(II) using oxygen. Interestingly, Se(IV) will interact with Fe(III) and form a poorly soluble ferric selenite at pH ∼4 under oxic conditions. Under anoxic conditions, however, the concentration of Fe(II) is closely related to the sorption process of Se(IV) on bentonite. When the concentration of Fe(II) was less than 1%, Fe(II) combined with the hydroxyl, forming Fe(OH)2, which generated a disproportionation at pH ∼8 and formed a new sorbent, Fe3O4. However, when the concentration of Fe(II) was increased to 5%, reduction precipitation was the primary way to remove Se(IV) in aqueous solution. XANES (X-ray Absorption Near Edge Structure) spectra showed that higher pH values are beneficial for the formation of the final thermodynamic reduction product, Fe selenide. These results suggested that Fe(II) significantly affect the Se(IV) sorption. Overall, this study confirmed the significant role of Fe(II) on the retardation of 79Se and on remediation for Se(IV) contamination in the hydrosphere.

High performance preconcentration of inorganic Se species by dispersive micro-solid phase extraction with a nanosilica-ionic liquid hybrid material

A highly sensitive and efficient dispersive micro-solid phase extraction (D-μ-SPE) method was developed for inorganic Se speciation analysis. A novel ionic liquid (IL)-nanomaterial hybrid consisting of 1-dodecyl-3-methylimidazolium bromide-functionalized nanosilica was used for the efficient retention of Se(IV) complexed with ammonium pyrrolidine dithiocarbamate, followed by elution with an ethyl acetate/Triton X-114 mixture and determination by electrothermal atomic absorption spectroscopy. The Se(VI) species was selectively determined by difference between total inorganic Se and Se(IV) after pre-reduction. The IL-nanomaterial hybrid was characterized by Fourier transform infrared spectroscopy and transmission electronic microscopy. Likewise, Se(IV) sorption capacity of the retention material and maximum amount of IL loaded on its surface were determined. Several factors concerning the functionalization, extraction and elution steps were optimized, yielding a 100% extraction efficiency for Se(IV) under optimal conditions. A limit of detection of 1.1ngL−1, a relative standard deviation of 5.7% and a 110-fold enhancement factor were obtained. The D-μ-SPE method was successfully applied to several water samples from different origins and compositions, including rain, tap, underground, river and sea.

Influence of inherent iron and oxygen concentrations on selenite sorption process using bentonite

The oxygen concentration and inherent Fe in bentonite have a significant influence on the Se(IV) sorption process. In this study, the sorption of selenite on natural bentonite was investigated using a batch experiment method, and the distribution coefficient ( K d) values were obtained in the pH range from 2.0 to 10.0 under oxic/anoxic conditions. The K d values always reached a maximum value at a pH of 4 under oxic conditions and at a pH of 8 under anoxic conditions; meanwhile, the K d value under anoxic conditions was larger than the value under oxic conditions, especially in regard to the maximum K d values. The oxygen conditions have a significant influence on the ratio of redox-sensitive Fe2+/Fe3+, which was closely related to the difference in the K d values under both oxic/anoxic conditions. Ferric selenite and green rust could be responsible for the maximum K d values under oxic/anoxic conditions. In the leaching experiments, we found that the Fe2+ in bentonite could replace Mg2+ and Al3+ in the octahedral sheet. Spectroscopy methods, such as Fourier transform infrared spectroscopy (FTIR), X-ray diffraction (XRD) and X-ray absorption spectroscopy (XAS) were used to characterize the surface properties of the samples after reaction. Overall, this study shows that the addition of Fe2+-containing materials into backfill/buffer materials under anoxic condition could enhance the sorption of 79Se(IV).

A soil column study to evaluate treatment of trace elements from saline industrial wastewater.

Industrial wastewater from the flue gas desulfurization (FGD) process is characterized by the presence of trace elements of concern, such as selenium (Se) and boron (B) and relatively high salinity. To simulate treatment that FGD wastewater undergoes during transport through soils in subsurface treatment systems, a column study (140-d duration) was conducted with native Kansas soil and saline FGD wastewater, containing high Se and B concentrations (170 μg/L Se and 5.3 mg/L B) and negligible arsenic (As) concentration (∼1.2 μg/L As). Se, B, and As, and dissolved organic carbon concentrations and organic matter spectroscopic properties were measured in the influent and outflow. Influent Se concentrations were reduced by only ∼half in all treatments, and results suggest that Se sorption was inhibited by high salinity of the FGD wastewater. By contrast, relative concentrations (C/Co) of B in the outflow were typically <10%, suggesting that B sequestration may have been enhanced by higher salinity. Unexpected elevated As concentrations in the outflow (at >150 μg/L in the treatment with labile organic carbon addition) suggest that soils not previously known to be geogenic arsenic sources have the potential to release As to groundwater in the presence of high salinity wastewater and under reducing conditions.

Sorption of Se(IV) and Se(VI) to coal fly ash/cement composite: Effect of Ca2 + and high ionic strength

The sorption behavior and mechanisms of Se from wastewater with high salinity are unclear, a scenario that can be encountered in the flue-gas-desulfurization (FGD) blowdown at coal-fired power plants. In this study, we investigated the uptake behavior and mechanisms of Se(IV) and Se(VI) by a coal fly ash/cement composite at high ionic strengths (IS) of up to 3.0M NaCl or CaCl2 using batch sorption experiments, Fourier-transform infrared spectroscopy, X-ray photoelectron spectroscopy, X-ray diffraction, and X-ray absorption spectroscopy. NaCl, regardless of IS, only caused slight changes in Se(IV) and Se(VI) uptake. Presence of CaCl2 significantly enhanced Se(IV) uptake, but had minor effect at low IS (≤0.3M) and no effect at high IS (>0.3M) on Se(VI) uptake. Both Se(IV) and Se(VI) mainly formed outer-sphere surface complexes in the presence of NaCl. The enhanced Se(IV) uptake by CaCl2 is likely due to the formation of Ca-SeO3 precipitate(s). Outer-sphere complexation is the main mechanism for Se(VI) sorption in the presence of CaCl2, with additional formation of minor amounts of inner-sphere complex at IS >0.3M. The results added new mechanistic insights for Se removal from industrial wastewaters with high salinity and will be useful for immobilization of Se in the co-management of FGD blowdown and coal fly ash wastes.

Immobilization of selenium by Mg-bearing minerals and its implications for selenium removal from contaminated water and wastewater

This study examines the possible immobilization of Se(VI) by Mg-bearing hydrotalcite and serpentine-like minerals. Selenate immobilization was carried out via adsorption and coprecipitation reactions under alkaline conditions. The effects of Mg/Al ratios, temperature and initial Se concentration on the adsorption and/or coprecipitation of Se6+ onto these Mg-bearing minerals were examined. The sorption mechanism of Se(VI) was examined by XAFS analysis to give account of its local coordination environment. The results showed that Se(VI) sorption behavior by hydrotalcite and serpentine-like minerals was mainly influenced by their Mg/Al ratio. Higher removal efficiency of Se(VI) (> 60 and 90% at 100 and 10ppm initial Se concentration) was observed during coprecipitation onto hydrotalcite and serpentine-like phases with Mg/Al ratios of 2 and 1.25, respectively. The formation of Mg-bearing minerals was enhanced at higher temperature (at 75°C) but the effect of temperature in Se(VI) immobilization was very minimal. Selenate was mainly retained via outer-sphere complexation but an irreversible fraction of sorbed selenate (about 20%) was observed in these mineral phases. In overall, this study has several important implications in the possible application of hydrotalcite and aluminian serpentine in Se(VI) immobilization.