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.     

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.     

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.     

The combined effect of uranium and gamma radiation on biological responses and oxidative stress induced in Arabidopsis thaliana

Uranium never occurs as a single pollutant in the environment, but always in combination with other stressors such as ionizing radiation. As effects induced by multiple contaminants can differ markedly from the effects induced by the individual stressors, this multiple pollution context should not be neglected. In this study, effects on growth, nutrient uptake and oxidative stress induced by the single stressors uranium and gamma radiation are compared with the effects induced by the combination of both stressors. By doing this, we aim to better understand the effects induced by the combined stressors but also to get more insight in stressor-specific response mechanisms. Eighteen-day-old Arabidopsis thaliana seedlings were exposed for 3 days to 10 μM uranium and 3.5 Gy gamma radiation. Gamma radiation interfered with uranium uptake, resulting in decreased uranium concentrations in the roots, but with higher transport to the leaves. This resulted in a better root growth but increased leaf lipid peroxidation. For the other endpoints studied, effects under combined exposure were mostly determined by uranium presence and only limited influenced by gamma presence. Furthermore, an important role is suggested for CAT1/2/3 gene expression under uranium and mixed stressor conditions in the leaves.     

Biomonitoring of environmental pollution by thorium and uranium in selected regions of the Republic of Kazakhstan

Two former uranium mines and a uranium reprocessing factory in the city of Aktau, Kazakhstan, may represent a risk of contaminating the surrounding areas by uranium and its daughter elements. One of the possible fingerprinting tools for studying the environmental contamination is using plant samples, collected in the surroundings of this city in 2007 and 2008. The distribution pattern of environmental pollution by uranium and thorium was evaluated by determining the thorium and uranium concentrations in plant samples (Artemisia austriaca) from the city of Aktau and comparing these results with those obtained for the same species of plants from an unpolluted area (town of Kurchatov). The determination of the uranium and thorium concentrations in different parts of A. austriaca plants collected from the analyzed areas demonstrated that the main contamination of the flora in areas surrounding the city of Aktau was due to dust transported by the wind from the uranium mines. The results obtained demonstrate that all the areas surrounding Aktau have a higher pollution level due to thorium and uranium than the control area (Kurchatov). A few “hot points” with high concentrations of uranium and thorium were found near the uranium reprocessing factory and the uranium mines.     

Bioaccumulation and biological effects in the earthworm Eisenia fetida exposed to natural and depleted uranium

The accumulations of both natural (U) and depleted (DU) uranium in the earthworms (Eisenia fetida) were studied to evaluate corresponding biological effects. Concentrations of metals in the experimental soil ranged from 1.86 to 600 mg kg⁻¹. Five biological endpoints: mortality, animals’ weight increasing, lysosomal membrane stability by measuring the neutral red retention time (the NRRT), histological changes and genetic effects (Comet assay) were used to evaluate biological effects in the earthworms after 7 and 28 days of exposure. No effects have been observed in terms of mortality or weight reduction. Cytotoxic and genetic effects were identified at quite low U concentrations. For some of these endpoints, in particular for genetic effects, the dose (U concentration)-effect relationships have been found to be non-linear. The results have also shown a statistically significant higher level of impact on the earthworms exposed to natural U compared to depleted U.     

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.     

Bioavailability of sediment-associated and low-molecular-mass species of radionuclides/trace metals to the mussel Mytilus edulis

Sediments can act as a sink for contaminants in effluents from industrial and nuclear installations or when released from dumped waste. However, contaminated sediments may also act as a potential source of radionuclides and trace metals to the water phase due to remobilisation of metals as dissolved species and resuspension of particles. The marine mussel Mytilus edulis is a filter-feeding organism that via the gills is subjected to contaminants in dissolved form and from contaminants associated to suspended particles via the digestive system. In this paper the bioavailability of sediment-associated and seawater diluted Cs, Co, Cd and Zn radioactive tracers to the filtering bivalve M. edulis has been examined. The mussels were exposed to tracers diluted in ultrafiltered (<10 kDa) seawater (Low Molecular Mass form) or to tracers associated with sediment particles from the Stepovogo Fjord at Novaya Zemlya in short-term uptake experiments, followed by 1-month depuration experiments in flow-through tanks. A toxicokinetic model was fitted to the uptake and depuration data, and the obtained parameters were used to simulate the significance of the two uptake pathways at different suspended sediment loads and sediment-seawater distribution coefficients. The results of the model simulations, assuming steady state conditions, suggest that resuspended particles from contaminated sediments can be a highly significant pathway for mussels in the order ¹⁰⁹Cd ≌ ⁶⁵Zn < ¹³⁴Cs < ⁶⁰Co. The significance increases with higher suspended sediment load and with higher K_d. Furthermore, the experimental depuration data suggest that Cs is retained longer and Co, Cd and Zn shorter by the mussels when associated with ingested sediments, than if the metals are taken up from the low molecular mass (LMM) phase.     

Radioactivity measurements in moss (Hypnum cupressiforme) and lichen (Cladonia rangiformis) samples collected from Marmara region of Turkey

The present study was conducted to compare the ¹³⁷Cs, ⁴⁰K, ²³²Th, and ²³⁸U activity concentrations in epigeic moss (Hypnum cupressiforme) and lichen (Cladonia rangiformis). The activity levels in 37 moss and 38 lichen samples collected from the Marmara region of Turkey were measured using a gamma spectrometer equipped with a high purity germanium (HPGe) detector. The activity concentrations of ¹³⁷Cs, ⁴⁰K, ²³²Th, and ²³⁸U in the moss samples were found to be in the range of 0.36-8.13, 17.1-181.1, 1.51-6.17, and 0.87-6.70 Bq kg⁻¹ respectively, while these values were below detection limit (BDL)-4.32, 16.6-240.0, 1.32-6.47, and BDL-3.57 Bq kg⁻¹ respectively in lichen. The average moss/lichen activity ratios of ¹³⁷Cs, ⁴⁰K, ²³²Th, and ²³⁸U were found to be 1.32 ± 0.57, 2.79 ± 1.67, 2.11 ± 0.82, and 2.19 ± 1.02, respectively. Very low ¹³⁷Cs concentrations were observed in moss and lichen samples compared to soil samples collected from the same locations in a previous study. Seasonal variations of the measured radionuclide activities were also examined in the three sampling stations.     

Dose assessment for marine biota and humans from discharge of (131)I to the marine environment and uptake by algae in Sydney, Australia

Iodine-131 reaches the marine environment through its excretion to the sewer by nuclear medicine patients followed by discharge through coastal and deepwater outfalls. ¹³¹I has been detected in macroalgae, which bio-accumulate iodine, growing near the coastal outfall of Cronulla sewage treatment plant (STP) since 1995. During this study, ¹³¹I levels in liquid effluent and sludge from three Sydney STPs as well as in macroalgae (Ulva sp. and Ecklonia radiata) growing near their shoreline outfalls were measured. Concentration factors of 176 for Ulva sp. and 526 for E. radiata were derived. Radiation dose rates to marine biota from ¹³¹I discharged to coastal waters calculated using the ERICA dose assessment tool were below the ERICA screening level of 10 μGy/hr. Radiation dose rates to humans from immersion in seawater or consumption of Ulva sp. containing ¹³¹I were three and two orders of magnitude below the IAEA screening level of 10 μSv/year, respectively.     

Microdistribution of Am in structures of submerged macrophyte Elodea canadensis growing in the Yenisei River

A submerged macrophyte of the Yenisei River, Elodea canadensis, was used to study the microdistribution of the artificial radionuclide ²⁴¹Am among different components of the plant. The total amount of ²⁴¹Am added to the experimental system was 1850 ± 31 Bq/L. The total amount of ²⁴¹Am accumulated by the plants was 182 Bq per sample, or 758,333 ± 385 Bq/kg dry mass. It has been found that the major portion of ²⁴¹Am accumulated by E. canadensis, up to 85%, was bound to solid components of the cells. It is observed that the microdistribution of ²⁴¹Am within different components of the submerged plant E. canadensis was not uniform. ²⁴¹Am distribution vary depending on the age of the leaf blades, the state of the cells and morphological features of the plant stem.     

Microbial removal of uranyl by sulfate reducing bacteria in the presence of Fe (III) (hydr)oxides

Microbiological reduction of uranyl by sulfate reducing bacteria (SRB) has been proposed as a promising method for removal of radionuclide from groundwater. In this study, we examined the effect of two naturally occurring Fe(III) (hydr)oxides, hematite and goethite, on the bioreduction of U(VI) by a mixed culture of SRB via laboratory batch experiments. The biogenic precipitate from U(VI) bioreduction was determined using X-ray absorption near edge structure (XANES) analysis, showing a typical feature of uraninite (UO₂). In the presence of either hematite or goethite-containing Fe(III) ranging from 10 to 30 mM, the reduction of U(VI) was retarded by both minerals and the retardatory effect was enhanced with increasing amount of Fe(III) (hydr)oxide. When exposed to a mixture of hematite and goethite with the total Fe(III) kept constant at 20 mM, the retardatory effect on U(VI) reduction by the minerals were directly correlated with the fraction of hematite present. A slow increase in U(VI) concentration was also found in all Fe(III) (hydr)oxide treatments after 10-13 days, accompanied by the release of Fe(II) into the solution. The presence of Fe(III) (hydr)oxide can cause the eventual incomplete bioreduction of U(VI). However, it was not the case for the control without minerals. When mixing biogenic uraninite with hematite or goethite without SRB, Fe(II) was also detected in the solution. These findings suggest that the U(VI) remobilization after 10～13 days may be due to reoxidation of the uraninite by the solid-phase Fe(III) (hydr)oxide.     

Bioaccumulation and lack of oxidative stress response in the ragworm H. diversicolor following exposure to Ra in sediment

The main effluent from oil and gas production, produced water, from some platforms in the North Sea contains elevated concentrations of ²²⁶Ra. The aim of this study was to investigate whether ²²⁶Ra in sediment would accumulate in and affect sediment-dwelling organisms. In addition, we wanted to determine if the bioavailability would be modulated by the presence of a scale inhibitor which is used during oil and gas production. Hediste diversicolor was therefore exposed to different levels of ²²⁶Ra (30–6600 Bq kg⁻¹) in combination with scale inhibitor in the sediments in a flow through system. The levels of radioactivity in the exposures were close to levels that can be measured in proximity to oil/gas production facilities. ²²⁶Ra spiked to natural sediment partitioned into pore water and accumulated in the sediment-dwelling polychaete following a four-week exposure period. The results suggest that ²²⁶Ra did not bind strongly to sediment (low sediment:water partitioning coefficient), but it was not shown to bioaccumulate in any great extent (bioaccumulation factors of 0.019–0.022). Exposure of H. diversicolor in sediments with up to 6600 Bq kg⁻¹²²⁶Ra had no measurable effect on the total oxyradical scavenging capacity of the organisms compared to control. So although they accumulated the alpha-emitter, the treatments did not appear to cause oxidative stress in polychaete tissues.     

Determination of concentration factors for Cs-137 and Ra-226 in the mullet species Chelon labrosus (Mugilidae) from the South Adriatic Sea

Concentration factors for Cs-137 and Ra-226 transfer from seawater, and dried sediment or mud with detritus, have been determined for whole, fresh weight, Chelon labrosus individuals and selected organs. Cesium was detected in 5 of 22 fish individuals, and its activity ranged from 1.0 to 1.6 Bq kg⁻¹. Radium was detected in all fish, and ranged from 0.4 to 2.1 Bq kg⁻¹, with an arithmetic mean of 1.0 Bq kg⁻¹. In regards to fish organs, cesium activity concentration was highest in muscles (maximum - 3.7 Bq kg⁻¹), while radium was highest in skeletons (maximum - 25 Bq kg⁻¹). Among cesium concentration factors, those for muscles were the highest (from seawater - an average of 47, from sediment - an average of 3.3, from mud with detritus - an average of 0.8). Radium concentration factors were the highest for skeleton (from seawater - an average of 130, from sediment - an average of 1.8, from mud with detritus - an average of 1.5). Additionally, annual intake of cesium and radium by human adults consuming muscles of this fish species has been estimated to provide, in aggregate, an effective dose of about 4.1 μSv y⁻¹.     

Adsorption models of Cs radionuclide and Sr (II) on some Egyptian soils

Distribution of cesium (¹³⁴Cs and ¹³⁷Cs) and strontium (Sr-II) between soil/water phases depends on many factors such as concentration of these ions between phases, the cation exchange capacity (CEC) of the soil as well as its clay content, chemical composition (especially Na, K, Ca, and Mg ions), grain size distribution, calcite, iron oxide content, and organic coatings. Distribution coefficients (Kd) of cesium (labeled with ¹³⁷Cs) and strontium were measured on the grain size distributions ≥32 μm of four soil samples. These soils were obtained from four different locations within Inshas site in Egypt and three groundwater samples were obtained from the same site locations. X-ray diffraction showed that the soil samples consisted mainly of quartz mixed with the minor amounts of kaolonite and clay minerals. Sorption experiments were carried out at strontium aqueous concentrations range 10⁻⁷ to 10⁻⁴ mol l⁻¹. The CEC and Kds for cesium and strontium were measured at the same metal concentrations range. Distribution coefficients of cesium were found to be influenced by the composition of the soil, while the distribution coefficients of strontium were found to depend on calcium concentrations in the soil/groundwater system. The aim of this study was to determine the safety assessment of disposal ¹³⁷Cs radionuclide and Sr(II) in the aquifer regions inside the Inshas site. Sequential extraction tests showed that, strontium was associated with the carbonate fractions and majority of cesium was sorbed on the iron oxides and the residue.     

Evaluation of DNA damage in the root cells of Allium cepa seeds growing in soil of high background radiation areas of Ramsar – Iran

Plants are unique in their ability to serve as in situ monitors for environmental genotoxins. We have used the alkaline comet assay for detecting induced DNA damage in Allium cepa to estimate the impact of high levels of natural radiation in the soils of inhabited zones of Ramsar. The average specific activity of natural radionuclides measured in the soil samples for ²²⁶Ra was 12,766 Bq kg⁻¹ whereas in the control soils was in the range of 34–60 Bq kg⁻¹. A positive strong significant correlation of the DNA damage in nuclei of the root cells of A. cepa seeds germinated in the soil of high background radiation areas with ²²⁶Ra specific activity of the soil samples was observed. The results showed high genotoxicity of radioactively contaminated soils. Also the linear increase in the DNA damage indicates that activation of repair enzymes is not triggered by exposure to radiation in HBRA.