Impact of water quality parameters on the sorption of U(VI) onto hematite

In this study, the sorption of U(VI) from aqueous solution on hematite was studied as a function of various water quality parameters such as contact time, pH, ionic strength, soil humic acid (HA) or fulvic acid (FA), solid content and temperature by using a batch technique. The results demonstrated that the sorption of U(VI) was strongly dependent on ionic strength at pH < 6.0, and outer-sphere surface complexation may be the main sorption mechanism. The sorption was independent of ionic strength at pH > 6.0 and the sorption was mainly dominated by inner-sphere surface complexation. The presence of HA/FA increases U(VI) sorption at low pH, whereas decreases U(VI) sorption at high pH. The thermodynamic parameters (ΔH⁰, ΔS⁰, and ΔG⁰) were calculated from the temperature dependent sorption isotherms, and the results suggested that U(VI) sorption was a spontaneous and endothermic process. The results might be important for the application of hematite in U(VI) pollution management.     

Removal of uranium (VI) from aqueous solution by adsorption of hematite

Hematite, a type of inorganic-sorptive medium, was used for the removal of U (VI) from aqueous solutions. Variables of the batch experiments including solution pH, contact time, initial concentration, temperature, calcium and magnesium ions were studied. The results indicated that the adsorption capacities are strongly affected by the solution pH, contact time and initial concentration. A higher pH favors higher U (VI) removal. The adsorption was also affected by temperature and calcium and magnesium ions, but the effect is very weak. The maximum adsorption capacity (q_m) only increased from 3.36 mg g⁻¹ to 3.54 mg g⁻¹ when the temperature was increased from 293 K to 318 K. A two-stage kinetic behavior was observed in the adsorption of uranium (VI): very rapid initial adsorption in a few minutes, followed by a long period of slower uptake. It was found that an increase in temperature resulted in a higher uranium (VI) loading per unit weight of the sorbent. The adsorption of uranium by hematite had good efficiency, and the equilibrium time of adsorbing uranium (VI) was about 6 h. The isothermal data were fitted with both Langmuir and Freundlich equations, but the data fitted the former better than the latter. The pseudo-first-order kinetic model, pseudo-second-order kinetic model and intraparticle diffusion model were used to describe the kinetic data, but the pseudo-second-order kinetic model was the best. The thermodynamic parameter ΔG⁰ were calculated, the negative ΔG⁰ values of uranium (VI) at different temperatures confirmed the adsorption processes were spontaneous.     

Plutonium(VI) accumulation and reduction by lichen biomass: correlation with U(VI)

The uptake of plutonium(VI) and uranium(VI) by lichen biomass was studied in the foliose lichen Parmotrema tinctorum to elucidate the migration behavior of Pu and U in the terrestrial environment. Pu and U uptake by P. tinctorum averaged 0.040+/-0.010 and 0.055+/-0.015 g gdry (-1), respectively, after 96 h incubation with 4.0 x 10(14) mol 1(-1) Pu solutions of pH 3, 4 and 5. SEM observations showed that the accumulated Pu is evenly distributed on the upper and lower surfaces of P. tinctorum, in contrast to U(VI), which accumulated in both cortical and medullary layers. UV/VIS absorption spectroscopy demonstrates that a fraction of Pu(VI) in the solution is reduced to Pu(V) by the organic substances released from P. tinctorum, and the accumulated Pu on the surface is reduced to Pu(IV), while U(VI) keeps the oxidation state of VI. Since the solubility of Pu(IV) hydroxides is very low, reduced Pu(VI) does not penetrate to the medullary layers, but is probably precipitated as Pu(IV) hydroxides on the cortical lichen surface. It is concluded that the uptake and reduction of Pu(VI) by lichens is important to determine the mobilization and oxidation states of Pu in the terrestrial environment.     

Biosorption of uranium (VI) by immobilized Aspergillus fumigatus beads

Biosorption of uranium (VI) ions by immobilized Aspergillus fumigatus beads was investigated in a batch system. The influences of solution pH, biosorbent dose, U (VI) concentration, and contact time on U (VI) biosorption were studied. The results indicated that the adsorption capacity was strongly affected by the solution pH, the biosorbent dose and initial U (VI) concentration. Optimum biosorption was observed at pH 5.0, biosrobent dose (w/v) 2.5%, initial U (VI) concentration 60 mg L⁻¹. Biosorption equilibrium was established in 120 min. The adsorption process conformed to the Freunlich and Temkin isothermal adsorption models. The dynamic adsorption model conformed to pseudo-second order model.     

Improved performance of a biomaterial-based cation exchanger for the adsorption of uranium(VI) from water and nuclear industry wastewater

The amine-modified polyhydroxyethylmethacrylate (poly(HEMA))-grafted biomaterial (tamarind fruit shell, TFS) carrying carboxyl functional groups at the chain end (PGTFS-COOH) was prepared and used as an adsorbent for the removal of uranium(VI) from water and nuclear industry wastewater. FTIR spectral analysis revealed that U(VI) ions and PGTFS-COOH formed a chelate complex. The adsorption process was relatively fast, requiring only 120 min to attain equilibrium. The adsorption kinetic data were best described by the pseudo-second-order equation. The equilibrium adsorption data were correlated with the Sips isotherm model. The maximum U(VI) ions uptake with PGTFS-COOH was estimated to be 100.79 mg/g. The complete removal of 10 mg/L U(VI) from simulated nuclear industry wastewater was achieved by 3.5 g/L PGTFS-COOH. The reusability of the adsorbent was demonstrated over 4 cycles using NaCl (1.0 M) + HCl (0.5 M) solution mixture to de-extract the U(VI). The results show that the PGTFS-COOH tested is very promising for the recovery of U(VI) from water and wastewater.     

Redox chemistry of sulphate and uranium in a phosphogypsum tailings dump

The present study aims to assess the effect of redox conditions existing within the tailings dump on the stability of phosphogypsum (e.g. sulphate reduction) and uranium(VI). Phosphogypsum sampling and in-situ measurements were carried out at a coastal tailings dump in Vasiliko Cyprus, pH, E_H and solubility experiments were performed in simulated laboratory systems and thermodynamic calculations using MINTEQA2. Generally, in the open tailings dump oxidizing conditions predominate stabilizing sulphur and uranium in their hexavalent oxidation states. On the other hand, after the application of a soil/vegetative cover and in the presence of natural organic matter, anoxic conditions prevail (E_H < −70 mV) resulting in S(VI) and U(VI) reduction to S(−II) and U(IV), respectively. Although, the sulphide anion can form very insoluble compounds with heavy metal ions (e.g. Cd(II), Pb(II) etc.) and U(IV) oxide has very low solubility, partial reduction of sulphate to sulphide within gypsum may affect the stability of phosphogypsum resulting in enhanced erosion of the material by rain- and seawater and washing out of contaminants in particulate/colloidal form.     

Removal of uranium(VI) from aqueous solutions and nuclear industry effluents using humic acid-immobilized zirconium-pillared clay

Removal of uranium [U(VI)] from aqueous solutions with humic acid-immobilized zirconium-pillared clay (HA-Zr-PILC) was investigated using a batch adsorption technique. The adsorbent was characterized using XRD, FTIR, SEM, TG/DTG, surface area analyzer and potentiometric titration. The effects of pH, contact time, initial concentration, adsorbent dose, and adsorption isotherm on the removal process were evaluated. A maximum removal of 97.6 ± 2.1 and 94.7 ± 3.3% was observed for an initial concentration of 50 and 100 mg L⁻¹, respectively at pH 6.0 and an adsorbent dose of 2.0 g L⁻¹. Equilibrium was achieved in approximately 180 min. The mechanism for the removal of U(VI) ions by HA-Zr-PILC was based on an ion exchange reaction. The experimental kinetic and isotherm data were analyzed using a second-order kinetic equation and Langmuir isotherm model, respectively. The monolayer adsorption capacity for U(VI) removal was found to be 132.68 ± 5.04 mg g⁻¹. An increase of temperature of the medium caused an increase in metal adsorption. Complete removal (≅100%) of U(VI) from 1.0 L of a simulated nuclear industry effluent sample containing 10.0 mg U(VI) ions was possible with 1.5 g of HA-Zr-PILC. The adsorbent was suitable for repeated use (over 4 cycles) without any noticeable loss of capacity.     

In situ uranium stabilization by microbial metabolites

Microbial melanin production by autochthonous bacteria was explored in this study as a means to increase U immobilization in U contaminated soil. This article demonstrates the application of bacterial physiology and soil ecology for enhanced U immobilization in order to develop an in situ, U bio-immobilization technology. We have demonstrated microbial production of a metal chelating biopolymer, pyomelanin, in U contaminated soil from the Tims Branch area of the Department of Energy (DOE), Savannah River Site (SRS), South Carolina, as a result of tyrosine amendments. Bacterial densities of pyomelanin producers were >10(6) cells per g wet soil. Pyomelanin demonstrated U complexing and mineral binding capacities at pH 4 and 7. In laboratory studies, in the presence of goethite or illite, pyomelanin enhanced U sequestration by these minerals. Tyrosine amended soils in a field test demonstrated increased U sequestration capacity following pyomelanin production up to 13 months after tyrosine treatments.     

X-ray absorption spectroscopy studies of reactions of technetium, uranium and neptunium with mackinawite

Technetium, uranium and neptunium may all occur in the environment in more than one oxidation state (IV or VII, IV or VI and IV or V respectively). The surface of mackinawite, the first-formed iron sulfide phase in anoxic conditions, can promote redox changes so a series of laboratory experiments were carried out to explore the interactions of Tc, U and Np with this mineral. The products of reaction were characterised using X-ray absorption spectroscopy. Technetium, added as TcO4(-), is reduced to oxidation state IV and forms a TcS(2)-like species. On oxidation of the mackinawite in air to form goethite, Tc remains in oxidation state IV but in an oxide, rather than a sulfide environment. At low concentrations, uranium forms uranyl surface complexes on oxidised regions of the mackinawite surface but at higher concentrations, the uranium promotes surface oxidation and forms a mixed oxidation state oxide phase. Neptunium is reduced to oxidation IV and forms a surface complex with surface sulfide ions. The remainder of the Np coordination sphere is filled with water molecules or hydroxide ions.     

Sorption of selenium anionic species on apatites and iron oxides from aqueous solutions

The sorption of selenite and selenate ions from aqueous solutions was investigated on hydroxyapatite, fluorapatite, goethite and hematite, in order to simulate the behavior of radioactive selenium in natural or artificial sorbing media. Correlation studies with acido-basic properties and solubility of the solids were also performed. The sorption is pH dependant, but these solids are very efficient for retaining selenite at pH values generally encountered in natural waters, with however higher K(d) values for oxides than apatites. Selenate ions are much less sorbed than selenite. Several methods such as electron microscopy and spectroscopic techniques were used to identify the sorption mechanisms. In the case of hydroxyapatite, sorption proceeds by substitution of phosphate groups in the lattice of the apatite crystal in the superficial layers of the solid. In the case of goethite and hematite, sorption can be interpreted and modeled by a surface complexation process, but there is a discrepancy between sorption site densities for selenite and for protons.     

乌江流域石灰土中铀等元素形态与铀活性

以中国西南乌江流域石灰土为例，运用逐级提取(Sequential Extraction，SEE)技术，并结合化学成分和相关参数数据，研究了石灰土中铀(U)等元素的形态，并在此基础上探讨了石灰土中U的活动性及释放潜力，旨在增进对U等元素生物地球化学循环的了解，同时也为流域U污染防治提供科学依据。研究结果表明：①石灰土中Mn主要存在于锰(氢)氧化物中，Ca主要存在于碳酸盐和硅酸盐矿物中，P主要存在于硅酸盐矿物和有机质中，U主要赋存于硅酸盐等残留部分中，其次赋存于有机质结合部分和碳酸盐矿物中；②石灰土剖面中活动态U所占的比例为10%~30%，平均17%，说明石灰土中的部分U在酸性和氧化-还原界面等条件下具有一定的迁移活性，即在上述条件下，石灰土中的部分U可释放进入周围水体或植物中；③石灰土中U的潜在释放量为036~150 g/t，平均U潜在释放量为076 g/t，因此，在酸雨和侵蚀等作用下，石灰土U释放可显著提高乌江河水U通量。     

Geochemical speciation of heavy metals in semiarid soils of the central Ebro Valley (Spain)

This study describes the chemical speciation of Fe, Mn, Zn and Cr in four selected soil types representative of the more abundant agricultural soils in the central Ebro river valley in Aragón. Gypsisols, Calcisols, Solonchaks and Solonetzs represent around 20% of the total soil surface in the region. A total of 12 selected sites have been sampled and five subsamples were taken in each site to create a composite sample. The four elements have been analysed by the sequential extraction procedure of Tessier et al. [Anal. Chem. 51 (1979) 844.] by emission atomic spectrometry of solid state (ICP OES). Very little amounts of Fe and Mn were retrieved from the exchangeable phase, the ready available for biogeochemistry cycles in the ecosystems. Therefore, low quantities of Fe and Mn can be taken up by plants in these alkaline soils. Cr was not detected in the bioavailable forms as well as Zn that was only present in negligible amounts in very few samples. The absence of mobile forms of Cr in all soils eliminates the toxic risk both in the trophic chain and from its migration downwards the soil profile. The largest contents of Fe, Zn and Cr were retrieved from the residual phase where metals are strongly bound to minerals, whereas Mn from the carbonate and oxide phases amounts 80% of its total content. Gypsisols and Calcisols have the lowest metal contents while the highest are found in Solonetzs and Solonchaks.     

Application of a magnetic extraction technique to assess radionuclide-mineral association in Cumbrian shoreline sediments

An assessment has been made of the association of (239+240)Pu, 241Am and 210Po (in secular equilibrium with 210Pb) with iron minerals using a magnetic extraction technique. Grab samples of beach sand from the Cumbrian (UK) coastline were subjected to successive extractions with an approximately 0.1 T ferrite magnet and an approximately 0.3 T rare-earth magnet procedure to separate magnetic iron oxide minerals. Radionuclide concentrations in the magnetic extracts were enhanced (by approximately 4-6-fold) relative to the residue. Those in the approximately 0.1 T magnet extracts were broadly similar to those in the antiferromagnetic material extracted by the approximately 0.3 T magnet, despite the very large differences in magnetic property values between the two fractions (one to two orders of magnitude). The percentage of magnetic material in terms of mass was small and therefore, the majority of these radionuclides (on average 88%) were associated with the residue. Removal of stable Fe was incomplete. Given that the radionuclides may also bind to paramagnetic (nonmagnetic) Fe minerals, the data were extrapolated by normalising the results to quantitative Fe removal. This yielded average values of 37%, 45% and 46% for (239+240)Pu, 241Am and 210Po(210Pb), respectively, as upper limits for the fraction associated with magnetic + nonmagnetic Fe minerals. There are significant uncertainties inherent in quantifying data from this extraction technique. Nevertheless, it seems reasonable to conclude that radionuclide association with Fe minerals is unlikely to have a significant impact upon the physical dispersion of sediment contaminated by Sellafield discharges in the Irish Sea. However, it may be an important factor in governing Pu redox and redissolution behaviour.     

Removal of uranium(VI) from aqueous solutions by manganese oxide coated zeolite: discussion of adsorption isotherms and pH effect

This paper discusses the adsorption properties for uranium(VI) by manganese oxide coated zeolite (MOCZ). The removal of uranium(VI) from aqueous solution by adsorption onto MOCZ in a single-component system with various contact times, pH, competitive ions, temperatures and initial concentrations of uranium(VI) was investigated. The experimental results were fitted to the Langmuir, Freundlich and the three-parameter Redlich-Peterson model isotherms to obtain the characteristic parameters of each model. Both the Langmuir and Redlich-Peterson isotherms were found to best represent the measured adsorption data. According to the evaluation using the Langmuir equation, the maximum adsorption capacity of uranium(VI) ions onto MOCZ was 15.1 mg g(-1) at 293K and pH 4.0. Using the thermodynamic equilibrium constants obtained at different temperatures, various thermodynamic parameters, such as DeltaG(0), DeltaH(0) and DeltaS(0), have been calculated. The thermodynamics of uranium(VI) ion/MOCZ system indicates the spontaneous and endothermic nature of the process. It was noted that an increase in temperature resulted in a higher uranium loading per unit weight of the adsorbent.     

Distribution of naturally occurring radionuclides (U, Th) in Timahdit black shale (Morocco)

Attention has been focused recently on the use of Moroccan black oil shale as the raw material for production of a new type of adsorbent and its application to U and Th removal from contaminated wastewaters. The purpose of the present work is to provide a better understanding of the composition and structure of this shale and to determine its natural content in uranium and thorium. A black shale collected from Timahdit (Morocco) was analyzed by powder X-ray diffraction and SEM techniques. It was found that calcite, dolomite, quartz and clays constitute the main composition of the inorganic matrix. Pyrite crystals are also present. A selective leaching procedure, followed by radiochemical purification and alpha-counting, was performed to assess the distribution of naturally occurring radionuclides. Leaching results indicate that 238U, 235U, 234U, 232Th, 230Th and 228Th have multiple modes of occurrence in the shale. U is interpreted to have been concentrated under anaerobic conditions. An integrated isotopic approach showed the preferential mobilization of uranium carried by humic acids to carbonate and apatite phases. Th is partitioned between silicate minerals and pyrite.     

Application of multivariate statistical analyses in the interpretation of geochemical behaviour of uranium in phosphatic rocks in the Red Sea,Nile Valley and Western Desert,Egypt

Factor and cluster analyses as well as the Pearson correlation coefficient have been applied to geochemical data obtained from phosphorite and phosphatic rocks of Duwi Formation exposed at the Red Sea coast. Nile Valley and Western Desert. Sixty-six samples from a total of 71 collected samples were analysed for SiO2, TiO2, Al203, Fe2O3, CaO, MgO, Na2O, K2O, P2O5, Sr, U and Pb by XRF and their mineral constituents were determined by the use of XRD techniques. In addition, the natural radioactivity of the phosphatic samples due to their uranium, thorium and potassium contents was measured by gamma-spectrometry. The uranium content in the phosphate rocks with P2O5 > 15% (average of 106.6 ppm) is higher than in rocks with P2O5 < 15% (average of 35.5 ppm). Uranium distribution is essentially controlled by the variations of P2O5 and CaO, whereas it is not related to changes in SiO2, TiO2, Al2O3, Fe2O3, MgO, Na2O and K2O concentrations.-Factor analysis and the Pearson correlation coefficient revealed that uranium belaves geochemically in different ways in the phosphatic sediments and phosphorites in the Red Sea, Nile Valley and Western Desert. In the Red Sea and Western Desert phosphorites, uranium occurs mainly in oxidized U6+ state where it seems to be fixed by the phosphate ion, forming secondary uranium phosphate minerals such as phosphuranylite. In the Nile Valley phosphorites, ionic substitution of Ca2+ by U4 is the main controlling factor in the concentration of uranium in phosphate rocks. Moreover, fixation of U6- by phosphate ion and adsorption of uranium on phosphate minerals play subordinate roles.     

Adsorption and desorption of 85Sr and 137Cs on reference minerals, with and without inorganic and organic surface coatings

The adsorption properties of reference minerals may be considerably modified by the presence of the inorganic and organic coatings that are ubiquitous in soils. It is therefore important to assess the effect of such coatings to evaluate the relevance of adsorption studies on pure minerals. The adsorption of trace amounts of (85)Sr and (137)Cs has been studied in dilute suspensions for various minerals that are common components of soils: quartz, calcium carbonate, kaolinite, montmorillonite and illite. We studied the effect of coatings with either Fe or Al oxide with varying additions of soil-extracted humic or fulvic acid. Both adsorption and desorption were measured and data presented as distribution coefficients, Kd. No adsorption was detected on quartz and it was not possible to coat this surface. Adsorption on calcium carbonate was small and not influenced by coatings. Adsorption of Sr on the three clay minerals was very similar, enhanced by the Al-coating, but not affected by Fe and organic coatings. The presence of organic coatings decreased Cs adsorption on illite. Similar but smaller effects were seen on montmorillonite and kaolinite. Aluminum coating enhanced Cs adsorption on illite, whereas both inorganic coatings caused decreases in adsorption on montmorillonite, and there was no effect on kaolinite. Effects were not additive with mixed, organic-inorganic coatings. Adsorption of both Cs and Sr on all minerals was strongly irreversible, with Kd (desorption) being up to four-times greater than adsorption Kd. The ratio of desorption and adsorption Cs Kd values (an assessment of irreversibility) was inversely related to adsorption Kd. This is consistent with a decreasing contribution of high-affinity adsorption as adsorption increases, but may also reflect the partial loss of organic coatings during desorption.     

Decomposition of bisphenol-A (BPA) by radical oxygen.

A change in bisphenol-A (BPA) concentration leached from polycarbonate (PC) tube to the phosphatidyl ethanolamine (PhE)-containing water was compared to water only. Time-dependent increase in BPA concentration was observed in both samples at 37 degrees C. The leaching velocity of BPA to water was three times faster than that to PhE-containing water and BPA concentration in water reached to 55.8 ng/ml 5 weeks later. When BPA was determined immediately after BPA addition of various concentration of PhE up to 2.5mg/ml to water, the BPA recoveries were over 93%. But, when incubated at 37 degrees C for a special time, BPA concentration in PhE-containing water in glass tube decreased time-dependently. In the presence of H2O2, time and Fe3+ dose-dependent decrease in the BPA concentration particularly, a drastic decrease above 0.44 mM Fe3+ was observed. These results suggest that BPA would be decomposed by radical oxygen including lipoperoxides. An addition of serum prevented BPA decrease from radical oxygen to a great extent but could not recover the BPA decrease. Thiobarbituric acid (TBA) value, a good parameter of lipid oxidation, decreased gradually in the mixture of H9O2 and Fe3+ in the presence of BPA, implying an inhibition of lipid oxidation due to BPA oxidation by radical oxygen.     

Laboratory studies of the chemical behaviour of plutonium associated with contaminated estuarine sediments

Laboratory experiments, with contaminated Esk Estuary sediment and uncontaminated River Esk and North Sea waters, have provided detailed information on Pu remobilisation behaviour. Of the 977 mBq g⁻¹ Pu (III, IV) associated with the sediment, 2·6% is subject to a rapid reversible exchange reaction. Well-defined distribution coefficients (K_d) have been determined with respect to this labile fraction (e.g. 5 × 10³ litres kg⁻¹ for remobilisation into river water). A low level of Pu (III, IV) remobilisation can be maintained following complete removal of the labile fraction, probably through a rate-limited reaction involving a more strongly bound form of Pu. Plutonium (V, VI) remobilisation occurs both through rapid exchange of a comparable labile component and through a mechanism involving photo-oxidation of Pu (III, IV).A dominant proportion of the remobilised Pu (III, IV) in solution is anionic with a molecular weight1000 daltons, probably in the form of an organic complex. Remobilised Pu (V, VI) is mainly in true solution in variously charged forms. Addition of natural colloidal organic carbon (COC) to river water increased the level of labile Pu (III, IV) remobilisation. The effect can be described by two competing equilibria in which labile Pu (III, IV) (a) is complexed by COC, and (b) is adsorbed by the sediment. The same additions of COC reduced the level of Pu (V, VI) remobilisation, either through its action as a reducing agent or through the indirect effect of associated pH changes. Increasing the carbonate alkalinity (NaHCO₃) in river water decreases the remobilisation of both Pu (III, IV) and Pu (V, VI).     

Ecological-biogeochemical role of macrophytes in aquatic ecosystems of urbanized territories (an example of small water bodies of St. Petersburg)

The accumulation of heavy metals (Fe, Mn, Zn, Cu, Cr, Ni, Pb, Cd) and biogenic elements (P, S, K, Ca, Na) in leaves has been studied in macrophytes of different ecological groups growing in small water bodies of St. Petersburg. The ecogeological and biogeochemical role of macrophytes in the water-aquatic plants-bottom sediments system and their contribution to the stability of aquatic ecosystem functioning under conditions of a megalopolis are considered. Prospects for using macrophytes for bioindication and phytoremediation of polluted aquatic ecosystems are discussed.