Uranium chemistry in stack solutions and leachates of phosphogypsum disposed at a coastal area in Cyprus

The effect of the matrix composition (main constituents) on the concentration and chemical behavior of uranium in phosphogypsum stack solutions and leachates has been investigated. Solid and aqueous samples were taken from three different sub-areas of a phosphogypsum stack at a coastal area in Vasilikos (Cyprus). The sub-areas are characterized whether by their acidity (e.g. "aged" and "non-aged" phosphogypsum) or by their salt content, originating from pulping water during wet stacking or (after deposition) from the adjacent sea. Measurements in stack solutions and leachates showed that phosphogypsum characteristics affect both, the concentration and the chemical behavior of uranium in solution. Uranium concentration in solutions of increased salinity is up to three orders of magnitude higher than in solutions of low salinity and this is attributed to the effect of ionic strength on the solubility of phosphogypsum. Modelling showed that uranium in stack solutions is predominantly present in the form of uranium(VI) phosphate complexes (e.g. UO(2)(H(2)PO(4))(2), UO(2)HPO(4)), whereas in leachates uranium(VI) fluoro complexes (e.g. UO(2)F(2), UO(2)F(3)(-)) are predominant in solution. The latter indicates that elution of uranium from phosphogypsum takes places most probably in the form of fluoro complexes. Both, effective elution by saline water and direct migration of uranium to the sea, where it forms very stable uranium(VI) carbonato complexes, indicate that the adjacent sea will be the final receptor of uranium released from Vasilikos phosphogypsum.     

Nuclide migration and the environmental radiochemistry of Florida phosphogypsum

Phosphogypsum, a waste by-product derived from the wet process production of phosphoric acid, represents one of the most serious problems facing the phosphate industry in Florida today. This by-product gypsum precipitates during the reaction of sulfuric acid with phosphate rock and is stored at a rate of about 40 million tons per year on several stacks in central and northern Florida. The main problem associated with this material concerns the relatively high levels of natural uranium-series radionuclides and other impurities which could have an impact on the environment and prevent its commercial use. We have studied the potential release of radionuclides from phosphogypsum by: (i) analysis of stack fluids, groundwaters, and soils associated with gypsum stacks; and (ii) geochemical modeling. Stack fluids were observed to be very high in dissolved uranium and 210Pb with only moderate concentrations of 226Ra. Underlying soils tend to be enriched in U and 210Pb indicating precipitation when acidic stack fluids enter a buffered environment. Modeling results showed significant increases in radionuclide complexes with sulfate and phosphate, resulting in relatively mobile uncharged or negatively charged solution species within the stacks with likely precipitation of multicomponent solids with increasing pH below the stack. Our evidence thus suggests that, while phosphogypsum stacks do contain significant quantities of dissolved radionuclides, removal mechanisms appear to prevent large-scale migration of radionuclides to the underlying aquifer.     

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 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.     

Estimation of 222Rn release from the phosphogypsum board used in housing panels

Phosphogypsum board is a popular construction material used for housing panels in Korea. Phosphogypsum often contains (226)Ra which decays into (222)Rn through an alpha transformation. (222)Rn emanated from the (226)Ra-bearing phosphogypsum board has drawn the public concern due to its potential radiological impacts to indoor occupants. The emanation rate of (222)Rn from the board is estimated in this paper. A mathematical model of the emanation rate of (222)Rn from the board is presented and validated through a series of experiments. The back diffusion effect due to accumulation of (222)Rn-laden air was incorporated in the model and found to have a strong impact on the (222)Rn emanation characteristics.     

Partitioning of radionuclides and trace elements in phosphogypsum and its source materials based on sequential extraction methods

Phosphogypsum is a waste produced by the phosphate fertilizer industry. Although phosphogypsum is mainly calcium sulphate dihydrate, it contains elevated levels of impurities, which originate from the source phosphate rock used in the phosphoric acid production. Among these impurities, radionuclides from 238U and 232Th decay series are of most concern due to their radiotoxicity. Other elements, such as rare earth elements (REE) and Ba are also enriched in the phosphogypsum. The bioavailability of radionuclides (226Ra, 210Pb and 232Th), rare earth elements and Ba to the surrounding aquatic system was evaluated by the application of sequential leaching of the phosphogypsum samples from the Brazilian phosphoric acid producers. The sequential extraction results show that most of the radium and lead are located in the "iron oxide" (non-CaSO4) fraction, and that only 13-18% of these radionuclides are distributed in the most labile fraction. Th, REE and Ba were found predominantly in the residual phase, which corresponds to a small fraction of the phosphate rock or monazite that did not react and to insoluble compounds such as sulphates, phosphates and silicates. It can be concluded that although all these elements are enriched in the phosphogypsum samples they are not associated with CaSO4 itself and therefore do not represent a threat to the surrounding aquatic environment.     

Study of Ni adsorption on NKF-6 zeolite

The adsorption of ⁶³Ni from aqueous solutions using NKF-6 zeolite was investigated by a batch technique under ambient conditions. The adsorption was investigated as a function of contact time, pH, ionic strength, foreign ions, humic substances (FA/HA) and temperature. The kinetic adsorption was well described by the pseudo-second-order rate equation. The adsorption of ⁶³Ni on NKF-6 zeolite was strongly dependent on pH and ionic strength, and the adsorption of ⁶³Ni increased with increasing NKF-6 zeolite content. At low pH values, the presence of FA enhanced the adsorption of ⁶³Ni on NKF-6 zeolite, but the presence of HA had no drastic effect. At high pH values, the presence of FA or HA decreased the adsorption of ⁶³Ni on NKF-6 zeolite. The adsorption isotherms were well represented by the Langmuir model. The thermodynamic parameters (i.e., ΔH⁰, ΔS⁰and ΔG⁰) for the adsorption of ⁶³Ni were determined from the temperature dependent isotherms at 293.15, 313.15 and 333.15 °K, respectively, and the results indicate that the adsorption reaction was favored at high temperature. The results suggest that the adsorption process of ⁶³Ni on NKF-6 zeolite is spontaneous and endothermic.     

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.     

Natural radioactivity in phosphates, phosphogypsum and natural waters in Morocco

The contents of natural radionuclides (uranium, actinium and thorium series) were measured in sedimentary phosphate rock samples using high-resolution gamma spectrometry. Data obtained for uranium content (ppm) were compared with the results obtained by a method based on the measurements using solid-state nuclear track detectors (SSNTD) in the same samples. The potential leaching of radionuclides from sedimentary phosphate rock during the industrial production of the phosphoric acid was studied. The process of leaching of the radioisotopes from phosphogypsum was discussed. A method for the direct alpha counting of 226Ra thin source, elaborated by the deposition of Ra from aqueous solutions on manganese oxides film deposited on polyvinyl support, have been developed and applied for the determination of 226Ra in natural water samples. The results show that only the water sample from the mine area reveals the presence of 226Ra at a level of about 0.2 Bq l-1.     

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.     

In vitro dissolution studies of uranium bearing material in simulated lung fluid

Inhaled uranium (U) bearing material will partially dissolve in the fluid lining of the lung, followed by a combination of retention, re-distribution, and excretion of the U. The rate of dissolution influences the retention time at the site of deposition, and the extent to which the material is available for re-distribution to other tissues. The consequential radiation dose is dependent upon the material distribution in the body and the exposure time to various tissues. The International Commission on Radiological Protection, ICRP 66 [International Commission on Radiological Protection (ICRP), 1994. Human Respiratory Tract Model for Radiological Protection. ICRP Publication 66] recommends the use of experimentally determined solubility coefficients in dose modelling. Material specific absorption parameters allow for better dose estimation than using ICRP default values for F (fast), M (moderate) and S (slow) classifications of U compounds. In vitro dissolution tests were carried out on U material collected from two U mines located in Australia. A static technique was designed in which particle samples were sandwiched between two 0.1-mum pore size membrane filters. The filter sandwich was exposed to a solvent (simulated lung fluid) for selected time intervals, at controlled test conditions for temperature and pH. The collected solution was analysed for U concentration using ICP-MS. The resulting dissolution curves were fitted with a double or triple exponential equation to determine the dissolution coefficients.     

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.     

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.     

Effect of pH on the sorption of uranium in soils

This work was undertaken to study the influence of soil type and chemical composition on uranium sorption ratios (SR in 1 kg-1) in order to reduce the uncertainty associated with this parameter in risk assessment models. Thirteen soil samples were collected from three different locations in France under different geological conditions. Clay content varied from 7.0 to 50.0%, pH ranged from 5.5 to 8.8 and organic matter content from 1.0 to 4.6%. Soils were incubated at room temperature in polyethylene packets for 28 days in the presence of 1 mg U kg-1 soil. Sorption ratio values varied from 0.9 to 3198 for all soils with no significant effect of soil texture or of organic matter. However, soil pH was highly linearly correlated with (log SR) as a probable consequence of the existence of different uranium complexes as a function of soil pH. The sorption behaviour differences between UO2(2+) and UO2(2+)-carbonate complexes are so great that any other effect of soil properties on U sorption is hidden. Thus, soil pH should be the focus variable for reduction of the uncertainty associated with the soil Kd value used in environmental risk assessments, even for reducing the uncertainty in site-specific Kd values.     

Diffusive gradient in thin FILMS (DGT) compared with soil solution and labile uranium fraction for predicting uranium bioavailability to ryegrass

The usefulness of uranium concentration in soil solution or recovered by selective extraction as unequivocal bioavailability indices for uranium uptake by plants is still unclear. The aim of the present study was to test if the uranium concentration measured by the diffusive gradient in thin films (DGT) technique is a relevant substitute for plant uranium availability in comparison to uranium concentration in the soil solution or uranium recovered by ammonium acetate. Ryegrass (Lolium perenne L. var. Melvina) is grown in greenhouse on a range of uranium spiked soils. The DGT-recovered uranium concentration (C_DGT) was correlated with uranium concentration in the soil solution or with uranium recovered by ammonium acetate extraction. Plant uptake was better predicted by the summed soil solution concentrations of UO₂²⁺, uranyl carbonate complexes and UO₂PO₄⁻. The DGT technique did not provide significant advantages over conventional methods to predict uranium uptake by plants.     

Exhalation of (222)Rn from phosphogypsum piles located at the Southwest of Spain

Phosphogypsum (PG) is a waste product of the phosphoric acid production process and contains, generally, high activity concentrations of uranium series radionuclides. It is stored in piles formed over the last 40 years close to the town of Huelva (Southwest of Spain). The very broad expanse of the PG piles (about 1200 ha) produces a local, but unambiguous, radioactive impact to their surroundings. In 1992, the regional government of Andalusia restored an area of 400 ha by covering it with a 25-cm thick layer of natural soil and, currently, there is an additional zone of 400 ha in course of restoration (unrestored) and the same area of active PG stacks. Due to the high activity concentration of (226)Ra in active PG stacks (average 647 Bq kg(-1)), a significant exhalation of (222)Rn could be produced from the surface of the piles. Measurements have been made of (222)Rn exhalation from active PG stacks and from restored and unrestored zones. The (222)Rn exhalation from unrestored zones is half of that of the active PG stacks. Following restoration, the (222)Rn exhalation is approximately eight times lower than the active PG stacks. The activity concentrations of natural radionuclides ((226)Ra, (40)K, (232)Th) in the mentioned zones have been determined. This study was also conducted to determine the effect of (226)Ra activity concentration on the (222)Rn exhalation, and a good correlation was obtained between the (222)Rn exhalation and (226)Ra activity, porosity and density of soil.     

Properties,use and health effects of depleted uranium (DU): a general overview

Depleted uranium (DU), a waste product of uranium enrichment, has several civilian and military applications. It was used as armor-piercing ammunition in international military conflicts and was claimed to contribute to health problems, known as the Gulf War Syndrome and recently as the Balkan Syndrome. This led to renewed efforts to assess the environmental consequences and the health impact of the use of DU. The radiological and chemical properties of DU can be compared to those of natural uranium, which is ubiquitously present in soil at a typical concentration of 3 mg/kg. Natural uranium has the same chemotoxicity, but its radiotoxicity is 60% higher. Due to the low specific radioactivity and the dominance of alpha-radiation no acute risk is attributed to external exposure to DU. The major risk is DU dust, generated when DU ammunition hits hard targets. Depending on aerosol speciation, inhalation may lead to a protracted exposure of the lung and other organs. After deposition on the ground, resuspension can take place if the DU containing particle size is sufficiently small. However, transfer to drinking water or locally produced food has little potential to lead to significant exposures to DU. Since poor solubility of uranium compounds and lack of information on speciation precludes the use of radioecological models for exposure assessment, biomonitoring has to be used for assessing exposed persons. Urine, feces, hair and nails record recent exposures to DU. With the exception of crews of military vehicles having been hit by DU penetrators, no body burdens above the range of values for natural uranium have been found. Therefore, observable health effects are not expected and residual cancer risk estimates have to be based on theoretical considerations. They appear to be very minor for all post-conflict situations, i.e. a fraction of those expected from natural radiation.     

Radon exhalation from phosphogypsum building boards: symmetry constraints, impermeable boundary conditions and numerical simulation of a test case

Comprehensive understanding of (222)Rn exhalation from phosphogypsum-bearing building material and its accumulation in indoor air is likely to rely on numerical simulation, particularly if transient effects, three-dimensional domains and convection are to be included and investigated. Yet, experimental data and analytical results are helpful (if not crucial) as far as validation is concerned. Having in mind computational code simplicity and in the light of a recent experimental and theoretical report on (222)Rn release from phosphogypsum boards for housing panels, this paper presents and discusses an alternative testing set-up and the corresponding boundary conditions, namely one side of the panel bounded by impermeable wall. Although this is a new facility to be tested, the resultant steady-state one-dimensional diffusion-dominant analytical solution is shown to match the counterpart deduced in the aforementioned previous report, despite it relaxes the constraint of symmetry about the phosphogypsum board centerline, which is inferred in that prior experimental scenario. In addition, numerical results are conducted for a diffusion-dominant two-dimensional time-varying test case concerning (222)Rn accumulation in a closed chamber having an exhaling phosphogypsum board tightly placed at one wall.     

Characteristics of soil organic matter (SOM) extracted using base with subsequent pH lowering and sequential pH extraction

Humic substances from eight soils of varying properties were extracted by two different methods: (1) the traditional NaOH-extraction with subsequent acidification to different pH (approximately 1 to approximately 12) and sequential extractions using 0.01 M NaNO(3) at incremental pH (approximately 1 to approximately 11). Cumulative organic matter (OM) in the sequential extractions showed properties that were consistent with NaOH-extracted OM. The release of Al and Fe in the sequential extractions was closely related with the release of organic carbon (OC). The ratio of OC associated with humic acid (HA) and fulvic acid (FA) (the HA:FA ratio) varied widely among the soils indicating heterogeneity in their OM composition. However, a significant correlation between this HA:FA ratio and the NaOH extractable %OC content of the soils is indicative of the possible relationship between them. Between pH 5 and 7, which is a typical soil solution pH, a significant amount of HA-associated OC was soluble. In modeling metal speciation in soil solutions, it has been assumed that all dissolved organic carbon (DOC) that is active toward metal binding is associated with FA. The results of this study indicate that the validity of these assumptions based on model sensitivity alone is questionable.     

Biosorption of uranium by chemically modified Rhodotorula glutinis

The present paper reports the biosorption of uranium onto chemically modified yeast cells, Rhodotorula glutinis, in order to study the role played by various functional groups in the cell wall. Esterification of the carboxyl groups and methylation of the amino groups present in the cells were carried out by methanol and formaldehyde treatment, respectively. The uranium sorption capacity increased 31% for the methanol-treated biomass and 11% for the formaldehyde-treated biomass at an initial uranium concentration of 140 mg/L. The enhancement of uranium sorption capacity was investigated by Fourier transform infrared (FTIR) spectroscopy analysis, with amino and carboxyl groups were determined to be the important functional groups involved in uranium binding. The biosorption isotherms of uranium onto the raw and chemically modified biomass were also investigated with varying uranium concentrations. Langmuir and Freundlich models were well able to explain the sorption equilibrium data with satisfactory correlation coefficients higher than 0.9.