Effect of uranium(VI) speciation on simultaneous microbial reduction of uranium(VI) and iron(III)

Uranium is a pollutant of concern to both human and ecosystem health. Uranium's redox state often dictates whether it will reside in the aqueous or solid phase and thus plays an integral role in the mobility of uranium within the environment. In anaerobic environments, the more oxidized and mobile form of uranium (UO2(2+) and associated species) may be reduced, directly or indirectly, by microorganisms to U(IV) with subsequent precipitation of UO. However, various factors within soils and sediments, such as U(VI) speciation and the presence of competitive electron acceptors, may limit biological reduction of U(VI). Here we examine simultaneous dissimilatory reduction of Fe(III) and U(VI) in batch systems containing dissolved uranyl acetate and ferrihydrite-coated sand. Varying amounts of calcium were added to induce changes in aqueous U(VI) speciation. The amount of uranium removed from solution during 100 h of incubation with S. putrefaciens was 77% in absence of Ca or ferrihydrite, but only 24% (with ferrihydrite) and 14% (without ferrihydrite) were removed for systems with 0.8 mM Ca. Dissimilatory reduction of Fe(III) and U(VI) proceed through different enzyme pathways within one type of organism. We quantified the rate coefficients for simultaneous dissimilatory reduction of Fe(III) and U(VI) in systems varying in Ca concecentration (0-0.8 mM). The mathematical construct, implemented with the reactive transport code MIN3P, reveals predominant factors controlling rates and extent of uranium reduction in complex geochemical systems.     

Reduction of copper(II) by iron(II)

Laboratory and field investigations have clearly demonstrated the important role of reduced iron (Fe(II)) in reductive transformations of first-row transition metal species. However, interactions of Fe(II) and copper (Cu) are not clearly understood. This study examined the reduction of Cu(II) by Fe(II) in stirred-batch experiments at pH 5.2 and 5.5 as influenced by chloride (Cl-) concentration (0.002-0.1 M), initial metal concentration (0.1-9.1 mM), and reaction time (1-60 min) under anoxic conditions. Reduction of Cu(II) to Cu(I) by dissolved Fe(II) was rapid under all experimental conditions and the stability of the products explains the driving force for the redox reaction. Under conditions of low [Cl-] and high initial metal concentration, >40% of total Cu and Fe were removed from solution after 1 min, which accompanied formation of a brownish-red precipitate. X-ray diffraction (XRD) patterns of the precipitates revealed the presence of cuprite (Cu2O), a Cu(I) mineral, based on d-spacings located at 0.248, 0.215, 0.151, and 0.129 nm. Fourier transform infrared (FTIR) spectroscopy corroborated XRD data for the presence of Cu2O, with features located at 518, 625, and 698 cm(-1). Increasing [Cl-] stabilized the dissolved Cu(I) product against Cu2O precipitation and resulted in more Fe precipitated from solution (relative to Cu) that appears to be present as poorly crystalline lepidocrocite (gamma-FeOOH). This process may be important in anoxic soil environments, where dissolved Fe(II) levels can accumulate.     

Quantifying constraints imposed by calcium and iron on bacterial reduction of uranium(VI)

Uranium is a redox active contaminant of concern to both human health and ecological preservation. In anaerobic soils and sediments, the more mobile, oxidized form of uranium (UO(2)(2+) and associated species) may be reduced by dissimilatory metal-reducing bacteria. Despite rapid reduction in controlled, experimental systems, various factors within soils or sediments may limit biological reduction of U(VI), inclusive of competing electron acceptors and alterations in uranyl speciation. Here we elucidate the impact of U(VI) speciation on the extent and rate of reduction, and we examine the impact of Fe(III) (hydr)oxides (ferrihydrite, goethite, and hematite) varying in free energies of formation. Observed pseudo first-order rate coefficients for U(VI) reduction vary from 12 +/- 0.60 x 10(-3) h(-1) (0 mM Ca in the presence of goethite) to 2.0 +/- 0.10 x 10(-3) h(-1) (0.8 mM Ca in the presence of hematite). Nevertheless, dissolved Ca (at concentrations from 0.2 to 0.8 mM) decreases the extent of U(VI) reduction by approximately 25% after 528 h relative to rates without Ca present. Imparting an important criterion on uranium reduction, goethite and hematite decrease the dissolved concentration of calcium through adsorption and thus tend to diminish the effect of calcium on uranium reduction. Ferrihydrite, in contrast, acts as a competitive electron acceptor and thus, like Ca, decreases uranium reduction. However, while ferrihydrite decreases U(VI) in solutions without Ca, with increasing Ca concentrations U(VI) reduction is enhanced in the presence of ferrihydrite (relative to its absence)-U(VI) reduction, in fact, becomes almost independent of Ca concentration. The quantitative framework described herein helps to predict the fate and transport of uranium within anaerobic environments.     

Lability of drinking water treatment residuals (WTR) immobilized phosphorus: aging and pH effects

Time constraints associated with conducting long-term (>20 yr) field experiments to test the stability of drinking water treatment residuals (WTR) sorbed phosphorus (P) inhibit improved understanding of the fate of sorbed P in soils when important soil properties (e.g., pH) change. We used artificially aged samples to evaluate aging and pH effects on lability of WTR-immobilized P. Artificial aging was achieved through incubation at elevated temperatures (46 or 70 degrees C) for 4.5 yr, and through repeated wetting and drying for 2 yr. Using a modified isotopic ((32)P) dilution technique, coupled with a stepwise acidification procedure, we monitored changes in labile P concentrations over time. This technique enabled evaluation of the effect of pH on the lability of WTR-immobilized P. Within the pH range of 4 to 7, WTR amendment, coupled with artificial aging, ultimately reduced labile P concentrations by > or = 75% relative to the control (no-WTR) samples. Soil samples with different physicochemical properties from two 7.5-yr-old, one-time WTR-amended field sites were utilized to validate the trends observed with the artificially aged samples. Despite the differences in physicochemical properties among the three (two field-aged and one artificially aged) soil samples, similar trends of aging and pH effects on lability of WTR-immobilized P were observed. Labile P concentrations of the WTR-amended field-aged samples of the two sites decreased 6 mo after WTR amendment and the reduction persisted for 7.5 yr, ultimately resulting in > or = 70% reduction, compared to the control plots. We conclude that WTR application is capable of reducing labile P concentration in P-impacted soils, doing so for a long time, and that within the commonly encountered range of pH values for agricultural soils WTR-immobilized P should be stable.     

Effect of sulfate on the simultaneous bioreduction of iron and uranium

The biogeochemistry related to iron- and sulfate-reducing conditions influences the fate of contaminants such as petroleum hydrocarbons, trace metals, and radionuclides (i.e., uranium) released into the subsurface. An understanding of these processes is imperative to successfully predict the fate of contaminants during bioremediation scenarios. A series of flow-through sediment column experiments were performed to determine if the commencement of sulfate-reducing conditions would occur while bioavailable Fe(III) was present and to determine how the bioreduction of a contaminant (uranium) was affected by the switch from iron-dominated to sulfate-dominated reducing conditions. The results presented herein demonstrated that, under biostimulation, sulfate reduction can commence even though a significant pool of bioavailable Fe(III) is present. In addition, the rate of U(VI) reduction was not negatively affected by the commencement of sulfate-reducing conditions.     

Biosorption of Cu(II), Zn(II), Ni(II) and Pb(II) ions by cross-linked metal-imprinted chitosans with epichlorohydrin

Cross-linked metal-imprinted chitosan microparticles were prepared from chitosan, using four metals (Cu(II), Zn(II), Ni(II), and Pb(II)) as templates, and epichlorohydrin as the cross-linker. The microparticles were characterized by Fourier transform infrared spectroscopy, solid state (13)C nuclear magnetic resonance spectroscopy, and energy-dispersive X-ray spectroscopy. They were used for comparative biosorption of Cu(II), Zn(II), Ni(II) and Pb(II) ions in an aqueous solution. The results showed that the sorption capacities of Cu(II), Zn(II), Ni(II), and Pb(II) on the templated microparticles increased from 25 to 74%, 13 to 46%, 41 to 57%, and 12 to 43%, respectively, as compared to the microparticles without metal ion templates. The dynamic study showed that the sorption process followed the second-order kinetic equation. Three sorption models, Langmuir, Freundlich, and Dubinin-Radushkevich, were applied to the equilibrium isotherm data. The result showed that the Langmuir isotherm equation best fitted for monolayer sorption processes. Furthermore, the microparticles can be regenerated and reused for the metal removal.     

Soil sorption of acidic pesticides: modeling pH effects

A model of acidic pesticide sorption in soils was developed from theoretical modeling and experimental data, which initially considered a combination of a strongly acidic pesticide and a variable-charge soil with high clay content. Contribution of 2,4-D [(2,4-dichlorophenoxy) acetic acid] anionic-form sorption was small when compared with molecular sorption. Dissociation of 2,4-D was not sufficient to explain the variation in Kd as a function of pH. Accessibility of soil organic functional groups able to interact with the pesticide (conformational changes) as a function of organic matter dissociation was proposed to explain the observed differences in sorption. Experimental 2,4-D sorption data and K(oc) values from literature for flumetsulam [N-(2,6-difluorophenyl)-5-methyl [1,2,4] triazolo [1,5-a] pyrimidine-2-sulfonamide] and sulfentrazone [N-[2,4-dichloro-5-[4-(difluromethyl)-4,5-dihydro-3-methyl-5-oxo-1H-1,2,4-triazol-1-yl] phenyl] methanesulfonamide] in several soils fit the model.     

Kinetic and equilibrium characterization of uranium(VI) adsorption onto carboxylate-functionalized poly(hydroxyethylmethacrylate)-grafted lignocellulosics

This study investigated the feasibility of using a new adsorbent prepared from coconut coir pith, CP (a coir industry-based lignocellulosic residue), for the removal of uranium [U(VI)] from aqueous solutions. The adsorbent (PGCP-COOH) having a carboxylate functional group at the chain end was synthesized by grafting poly(hydroxyethylmethacrylate) onto CP using potassium peroxydisulphate-sodium thiosulphite as a redox initiator and in the presence of N,N'-methylenebisacrylamide as a crosslinking agent. IR spectroscopy results confirm the graft copolymer formation and carboxylate functionalization. XRD studies confirm the decrease of crystallinity in PGCP-COOH compared to CP, and it favors the protrusion of the functional group into the aqueous medium. The thermal stability of the samples was studied using thermogravimetry (TG). Surface charge density of the samples as a function of pH was determined using potentiometric titration. The ability of PGCP-COOH to remove U(VI) from aqueous solutions was assessed using a batch adsorption technique. The maximum adsorption capacity was observed at the pH range 4.0-6.0. Maximum removal of 99.2% was observed for an initial concentration of 25mg/L at pH 6.0 and an adsorbent dose of 2g/L. Equilibrium was achieved in approximately 3h. The experimental kinetic data were analyzed using a first-order kinetic model. The temperature dependence indicates an endothermic process. U(VI) adsorption was found to decrease with an increase in ionic strength due to the formation of outer-sphere surface complexes on PGCP-COOH. Equilibrium data were best modeled by the Langmuir isotherm. The thermodynamic parameters such as DeltaG(0), DeltaH(0) and DeltaS(0) were derived to predict the nature of adsorption. Adsorption experiments were also conducted using a commercial cation exchanger, Ceralite IRC-50, with carboxylate functionality for comparison. Utility of the adsorbent was tested by removing U(VI) from simulated nuclear industry wastewater. Adsorbed U(VI) ions were desorbed effectively (about 96.2+/-3.3%) by 0.1M HCl. The adsorbent was suitable for repeated use (more than four cycles) without any noticeable loss of capacity.     

Adsorption characterization of Pb(II) and Cu(II) ions onto chitosan-tripolyphosphate beads: Kinetic,equilibrium and thermodynamic studies

Chitosan-tripolyphosphate (CTPP) beads were synthesized, characterized and were used for the adsorption of Pb(II) and Cu(II) ions from aqueous solution. The effects of initial pH, agitation period, adsorbent dosage, different initial concentrations of heavy metal ions and temperature were studied. The experimental data were correlated with the Langmuir, Freundlich and Dubinin-Radushkevich isotherm models. The maximum adsorption capacities of Pb(II) and Cu(II) ions in a single metal system based on the Langmuir isotherm model were 57.33 and 26.06 mg/g, respectively. However, the beads showed higher selectivity towards Cu(II) over Pb(II) ions in the binary metal system. Various thermodynamic parameters such as enthalpy (ΔH°), Gibbs free energy (ΔG°) and entropy (ΔS°) changes were computed and the results showed that the adsorption of both heavy metal ions onto CTPP beads was spontaneous and endothermic in nature. The kinetic data were evaluated based on the pseudo-first and -second order kinetic and intraparticle diffusion models. Infrared spectra were used to elucidate the mechanism of Pb(II) and Cu(II) ions adsorption onto CTPP beads.     

Removal of uranium(VI) from contaminated sediments by surfactants

Uranium(VI) sorption onto a soil collected at the Melton Branch Watershed (Oak Ridge National Laboratory, TN) is strongly influenced by the pH of the soil solution and, to a lesser extent, by the presence of calcium, suggesting specific chemical interactions between U(VI) and the soil matrix. Batch experiments designed to evaluate factors controlling desorption indicate that two anionic surfactants, AOK and T77, at concentrations ranging from 60 to 200 mM, are most suitable for U(VI) removal from acidic soils such as the Oak Ridge sediment. These surfactants are very efficient solubilizing agents at low uranium concentrations: ca. 100% U(VI) removal for [U(VI)]o,sorbed = 10(-6) mol kg-1. At greater uranium concentrations (e.g., [U(VI)]o,sorbed = ca. 10(-5) mol kg-1), the desorption efficiency of the surfactant solutions increases with an increase in surfactant concentration and reaches a plateau of 75 to 80% of the U(VI) initially sorbed. The most probable mechanisms responsible for U(VI) desorption include cation exchange in the electric double layer surrounding the micelles and, to a lesser extent, dissolution of the soil matrix. Limitations associated with the surfactant treatment include loss of surfactants onto the soil (sorption) and greater affinity between U(VI) and the soil matrix at large soil to liquid ratios. Parallel experiments with H2SO4 and carbonate-bicarbonate (CB) solutions indicate that these more conventional methods suffer from strong matrix dissolution with the acid and reduced desorption efficiency with CB due to the buffering capacity of the acidic soil.     

Immobilization of Pb(II), Cd(II) and Ni(II) ions on kaolinite and montmorillonite surfaces from aqueous medium

The present study investigates the immobilization of Pb(II), Cd(II) and Ni(II) on clays (kaolinite and montmorillonite) in aqueous medium through the process of adsorption under a set of variables (concentration of metal ion, amount of clay, pH, time and temperature of interaction). Increasing pH favours the removal of metal ions till they are precipitated as the insoluble hydroxides. The uptake is rapid with maximum adsorption being observed within 180 min for Pb(II) and Ni(II) and 240 min for Cd(II). A number of available models like the Lagergren pseudo first-order kinetics, second-order kinetics, Elovich equation, liquid film diffusion and intra-particle diffusion are utilized to evaluate the kinetics and the mechanism of the immobilization interactions. Two isotherm equations due to Langmuir and Freundlich showed good fits with the experimental data. Kaolinite and montmorillonite have considerable Langmuir monolayer capacity with respect to Pb(II), Cd(II) and Ni(II), the values being in the range of 6.8-11.5mg/g (kaolinite) and 21.1-31.1mg/g (montmorillonite). The Freundlich adsorption capacity follows a similar order. The thermodynamics of the immobilization process indicates the same to be exothermic with Pb(II) and Ni(II), but endothermic with Cd(II). The interactions with Pb(II) and Ni(II) are accompanied by decrease in entropy and Gibbs energy while the endothermic immobilization of Cd(II) is supported by an increase in entropy and an appreciable decrease in Gibbs energy. The results have established good potentiality for kaolinite and montmorillonite to remove heavy metals like Pb(II), Cd(II) and Ni(II) from aqueous medium through adsorption-mediated immobilization.     

Equilibrium and kinetic studies on biosorption of Hg(II), Cd(II) and Pb(II) ions onto microalgae Chlamydomonas reinhardtii

The microalgae Chlamydomonas reinhardtii was used for the biosorption of Hg(II), Cd(II) and Pb(II) ions. The maximum adsorption of Hg(II) and Cd(II) ions on Chlamydomonas reinhardtii biomass was observed at pH 6.0 and the corresponding value for Pb(II) ions was 5.0. The biosorption of Hg(II), Cd(II) and Pb(II) ions by microalgae biomass increased as the initial concentration of Hg(II), Cd(II) and Pb(II) ions increased in the biosorption medium. The maximum biosorption capacities of microalgae for Hg(II), Cd(II) and Pb(II) ions were 72.2+/-0.67, 42.6+/-0.54 and 96.3+/-0.86 mg/g dry biomass, respectively. The affinity order for algal biomass was Pb(II)>Hg(II)>Cd(II). FT-IR analysis of algal biomass revealed the presence of amino, carboxyl, hydroxyl and carbonyl groups, which were responsible for biosorption of metal ions. Biosorption equilibrium was established in about 60 min and the equilibrium was well described by the Freundlich biosorption isotherms. Temperature change in the range of 5-35 degrees C did not affect the biosorption capacity. The microalgae could be regenerated using 0.1 M HCl, with up to 98% recovery, which allowed the reuse of the biomass in six biosorption-desorption cycles without any considerable loss of biosorption capacity.     

Biosorption of copper(II) and lead(II) onto potassium hydroxide treated pine cone powder

Pine cone powder surface was treated with potassium hydroxide and applied for copper(II) and lead(II) removal from solution. Isotherm experiments and desorption tests were conducted and kinetic analysis was performed with increasing temperatures.As solution pH increased, the biosorption capacity and the change in hydrogen ion concentration in solution increased. The change in hydrogen ion concentration for lead(II) biosorption was slightly higher than for copper(II) biosorption. The results revealed that ion-exchange is the main mechanism for biosorption for both metal ions. The pseudo-first order kinetic model was unable to describe the biosorption process throughout the effective biosorption period while the modified pseudo-first order kinetics gave a better fit but could not predict the experimentally observed equilibrium capacities. The pseudo-second order kinetics gave a better fit to the experimental data over the temperature range from 291 to 347 K and the equilibrium capacity increased from 15.73 to 19.22 mg g^?1 for copper(II) and from 23.74 to 26.27 for lead(II).Activation energy was higher for lead(II) (22.40 kJ mol^?1) than for copper(II) (20.36 kJ mol^?1). The free energy of activation was higher for lead(II) than for copper(II) and the values of ΔH* and ΔS* indicate that the contribution of reorientation to the activation stage is higher for lead(II) than copper(II). This implies that lead(II) biosorption is more spontaneous than copper(II) biosorption.Equilibrium studies showed that the Langmuir isotherm gave a better fit for the equilibrium data indicating monolayer coverage of the biosorbent surface. There was only a small interaction between metal ions when simultaneously biosorbed and cation competition was higher for the Cu-Pb system than for the Pb-Cu system. Desorption studies and the Dubinin–Radushkevich isotherm and energy parameter, E, also support the ion-exchange mechanism.     

Adsorptive removal of Cd(II) and Pb(II) ions from aqueous solutions by using Turkish illitic clay

The ability of Turkish illitic clay (TIC) in removal of Cd(II) and Pb(II) ions from aqueous solutions has been examined in a batch adsorption process with respect to several experimental conditions including initial solution pH, contact time, initial metal ions concentration, temperature, ionic strength, and TIC concentration, etc. The characterization of TIC was performed by using FTIR, XRD and XRF techniques. The maximum uptake of Cd(II) (11.25 mg g⁻¹) and Pb(II) (238.98 mg g⁻¹) was observed when used 1.0 g L⁻¹ of TIC suspension, 50 mg L⁻¹ of initial Cd(II) and 250 mg L⁻¹ of initial Pb(II) concentration at initial pH 4.0 and contact time of 240 min at room temperature. The experimental data were analyzed by the Langmuir, Freundlich, Temkin and Dubinin Radushkevich (D-R) isotherm models. The monolayer adsorption capacity of TIC was found to be 13.09 mg g⁻¹ and 53.76 mg g⁻¹ for Cd(II) and Pb(II) ions, respectively. The kinetics of the adsorption was tested using pseudo-first-order, pseudo-second-order, Elovich and intraparticle diffusion models. The results showed that the adsorption of Cd(II) and Pb(II) ions onto TIC proceeds according to the pseudo-second-order model. Thermodynamic parameters including the Gibbs free energy (ΔG), enthalpy (ΔH), and entropy (ΔS) changes indicated that the present adsorption process was feasible, spontaneous and endothermic in the temperature range of 5–40 °C.     

Electrochemical remediation of copper (II) from an industrial effluent Part II: three-dimensional foam electrodes

A batch recycle removal of copper ions from an industrial effluent by means of copper foam cathodes was tested. A constant current of 750 A was applied to the cell in order to perform the reduction. Copper depletion was investigated at different solution flow rates and a removal greater than 98% was obtained with a flow rate of 1000 l/h. The influence of initial metal concentration on copper deposition and current efficiency is also discussed.     

Effects of pH and cyclodextrins on pentachlorophenol degradation (mineralization) by white-rot fungi

White-rot fungi (WRF) such as Trametes hirsuta completely degrade (mineralize) pentachlorophenol (PCP) and many other organopollutants. This has led to them being used to decontaminate various substrates (e.g. soil) through biorememediation. However, because PCP is a biocide, it can inhibit fungal growth and thereby its own degradation. It was hypothesized that substrate pH might affect PCP degradation, because when the pH is lower than 4.7 (the pKa for PCP) the phenol predominates, while at higher pH the phenate does. These two PCP species differ markedly in physical and biological properties. The effect of cyclodextrins was also investigated since it is known that the inclusion complexes these form with PCP differ in bioavailability and toxicity from non-complexed PCP. Tests were first made in liquid and agar media (where conditions are relatively easy to control), and then in a sawdust, because it is a common target matrix for WRF bioremediation. Results with the liquid and agar media showed that growth in the presence of inhibitory PCP concentrations decreased as the pH decreased, consistent with the phenol being more toxic. Growth in sawdust was less affected by PCP regardless of the pH, presumably because the PCP sorbed to the wood which decreased its bioavailability. Some cyclodextrins markedly decreased the PCP's toxicity in liquid, agar and sawdust media. Rates of PCP mineralization (measured from production of (14)CO(2) from (14)C PCP) in liquid cultures containing 0.5 mgkg(-1) PCP (a sub-inhibitory concentration) were similar from pH 2.5-7.5, indicating that the phenol and the phenate were equally degradable. Degradation of a growth inhibiting concentration on sawdust (1,000 mgkg(-1)) could be increased slightly by lowering the pH below the pKa, this increasing sorption to the wood. Degradation increased more when the pH was raised well above the pKa, presumably due to the phenate being less toxic and more soluble, making it more available to the degradative system. Although some cyclodextrins decreased growth inhibition, they also interfered with degradation. If this interference could be overcome, cyclodextrins could be used to increase the maximal PCP concentration that could be treated by WRF bioremediation.     

Oxidation of inorganic contaminants by ferrates (VI, V, and IV)--kinetics and mechanisms: a review

Inorganic contaminants are found in water, wastewaters, and industrial effluents and their oxidation using iron based oxidants is of great interest because such oxidants possess multi-functional properties and are environmentally benign. This review makes a critical assessment of the kinetics and mechanisms of oxidation reactions by ferrates (Fe(VI)O(4)(2-), Fe(V)O(4)(3-), and Fe(IV)). The rate constants (k, M(-1) s(-1)) for a series of inorganic compounds by ferrates are correlated with thermodynamic oxidation potentials. Correlations agree with the mechanisms of oxidation involving both one-electron and two-electron transfer processes to yield intermediates and products of the reactions. Case studies are presented which demonstrate that inorganic contaminants can be degraded in seconds to minutes by ferrate(VI) with the formation of non-toxic products.     

Critical analysis of the waste management performance of two uranium production units in Brazil--part II: Caetite production center

This paper discusses the environmental waste management of the Heap-Leach Uranium Production Facility of Caetité located in a semi-arid region in Brazil. A comparison is made with the first uranium production site of the country located in Poços de Caldas. It is demonstrated that differences in the operational process along with different environmental conditions can lead to different impacts. In the present case groundwater is the potential most sensitive environmental medium despite the well-established consensus in the literature that radon and aerosol emissions may turn-out to be the most relevant environmental aspects of an installation located at this type of region. Most of the ²²⁶Ra content in the ore remains in the leached ore that is deposited with the waste rock. A lack in appropriate prediction of the hydrological balance has been causing unanticipated emissions of liquid effluents into the environment. Chemical treatment of this effluent may be needed. Contamination of groundwater in the short term by the waste ponds is not to be expected but it can be a relevant issue in the long term. As a consequence, careful closure schemes will need to be put in place. Finally, the overall costs with remediation in the Caetité production center are lower than those observed at the Poços de Caldas mining site.     

Removal of Se(IV) from aqueous solution using sulphuric acid-treated peanut shell

A carbonaceous sorbent was prepared from peanut shell via sulphuric acid treatment. Se(IV) removal from aqueous solution on the sorbent was studied varying time, pH, Se(IV) concentration, temperature and sorbent status (wet and dry). Se(IV) removal was faster using the wet sorbent than the dry sorbent following a pseudo-first-order model. Se(IV) removal increases at low pH values, and decreases as pH increases until pH 7. Sorption was found to fit the Langmuir equation and sorption capacity for the wet sorbent was higher than that for the dry one. Both sorbents showed an increased selenium sorption by rising the temperature. Redox processes between Se(IV) and the carbon sorbent are involved. Analysis by scanning electron microscope and X-ray powder diffraction for the sorbent after the reaction with acidified Se(IV) confirmed the availability of elemental selenium as particles on the sorbent surface as a result of Se(IV) reduction. Physicochemical tests showed an increase in sorbent acidity, cation exchange capacity (CEC) and surface functionality after the reaction with acidified Se(IV), indicating the oxidation processes occurring on the sorbent surface. Due to its reduction properties, the sorbent seems efficient for Se(IV) removal from aqueous solution.