Biosorption of <Superscript>241</Superscript>Am by <Emphasis Type="Italic">Saccharomyces cerevisiae</Emphasis>: Preliminary investigation on mechanism

As an important radioisotope in nuclear industry and other fields, ²⁴¹Am is one of the most serious contamination concerns due to its high radiation toxicity and long half-life. The encouraging biosorption of ²⁴¹Am from aqueous solutions by free or immobilized Saccharomyces cerevisiae (S. cerevisiae) has been observed in our previous experiments. In this study, the preliminary evaluation on mechanism was further explored via chemical or biological modification of S. cerevisiae, and using europium as a substitute for americium. The results indicated that the culture times of more than 16 hours for S. cerevisiae was suitable and the efficient adsorption of ²⁴¹Am by the S. cerevisiae was able to achieve. The pH value in solutions decreased gradually with the uptake of ²⁴¹Am in the S. cerevisiae, implying that H⁺ released from S. cerevisiae via ion-exchange. The biosorption of ²⁴¹Am by the decomposed cell wall, protoplasm or cell membrane of S. cerevisiae was same efficient as by the intact fungus. However, the adsorption ratio for ²⁴¹Am by the deproteinized or deacylated S. cerevisiae dropped obviously, implying that protein or carboxyl functional groups of S. cerevisiaece play an important role in the biosorption of ²⁴¹Am. Most of the investigated acidic ions have no significant influence on the ²⁴¹Am adsorption, while the saturated EDTA can strong inhibit the biosorption of ²⁴¹Am on S. cerevisiae. When the concentrations of coexistent Eu³⁺, Nd³⁺ were 100 times more than that of ²⁴¹Am, the adsorption ratios would decrease to 65% from more than 95%. It could be noted by transmission electron microscope (TEM) analysis that the adsorbed Eu is almost scattered in the whole fungus, while Rutherford backscattering spectrometry (RBS) analysis indicated that Ca in S. cerevisiae have been replaced by Eu via ion-exchange. All the results implied that the adsorption mechanism of ²⁴¹Am on S. cerevisiae is very complicated and at least involved in ion exchange, complexation process as well as well as nonspecific adsorption in cell wall because of static electricity.     

Sorption of 241Am by Aspergillus nigerspore and hyphae

Biosorption of ²⁴¹Am by a fungus A. niger, including the spore and hyphae, was investigated. The preliminary results showed that the adsorption of ²⁴¹Am by the microorganism was efficient. More than 96% of the total ²⁴¹Am could be removed from ²⁴¹Am solutions of 5.6-111 MBq/l (C _o) by spore and hyphaeof A. niger, with adsorbed ²⁴¹Am metal (Q) of 7.2-142.4 MBq/g biomass, and 5.2-106.5 MBq/g, respectively. The biosorption equilibrium was achieved within 1 hour and the optimum pH range was pH 1-3. No obvious effects on ²⁴¹Am adsorption by the fungus were observed at 10-45 °C, or in solutions containing Au³⁺ or Ag⁺, even 2000 times above the ²⁴¹Am concentration. The ²⁴¹Am biosorption by the fungus obeys the Freundlich adsorption equation. There was no significant difference between the adsorption behavior of A. nigerspore and hyphae. This revised version was published online in July 2006 with corrections to the Cover Date.     

Biosorption of americium-241 by Saccharomyces cerevisiae

The biosorption of radionuclide ²⁴¹Am from solution by Saccharomyces cerevisiae (S. cerevisiae), and the effects of experimental conditions on the adsorption were investigated. The preliminary results showed thatS. cerevisiae is a very efficient biosorbent. An average of more than 99% of the total ²⁴¹Am could be removed by S. cerevisiae of 2.1 g/l (dry weight) from ²⁴¹Am solutions of 17.54–4386.0 mg/l (2.22 MBq/l–555 MBq/l) with adsorption capacities of 7.45–1880.0 mg/g biomass (dry weight) (0.94 MBq/g–237.9 MBq/g). The adsorption equilibrium was achieved within 1 hour and the optimum pH ranged 1–3. No significant differences on ²⁴¹Am adsorption were observed at 10–45 °C, or in solutions containing Au³⁺ or Ag⁺, even 2000 times above ²⁴¹Am concentration. The relationship between concentrations and adsorption capacities of ²⁴¹Am indicated the biosorption process should be described by the Freundlich adsorption isotherm.     

Modified <Emphasis Type="Italic">Rhizopus arrhizus</Emphasis> biomass for sorption of <Superscript>241</Superscript>Am and other radionuclides

The improvement and the refinement of non-viable Rhizopus arrhizus biomass were investigated via immobilization. Immobilization was carried out by using sodium alginate/CaCl₂ solution and formaldehyde/HCl cross-linking with dead Rhizopus arrhizus biomass and were used for the sorption of radionuclides from low level effluent wastes. The sodium alginate/CaCl₂ immobilized biomass (ratio 1:2) showed about 86% sorption for ²⁴¹Am activity but due to its soft nature and tendency to undergo distortion in shape, is unsuitable for practical applications. The biomass cross-linked with 15% formaldehyde/0.1 M HCl solution has a relatively high mechanical strength and rigidity. It was showing a sorption of >99% for ²⁴¹Am activity and has the sorption capacity of ~65 mg/g for americium and uranium. Hence, it can be utilized for the removal of radionuclides from radioactive waste effluents.     

Simultaneous determination of 152Eu and 241Am in liquid solution by liquid scintillation counting

¹⁵²Eu and ²⁴¹Am are the most frequently used radiotracers in the separation studies on trivalent minor actinides and lanthanides. In almost all those studies, the determination of ¹⁵²Eu and ²⁴¹Am has been based on measuring their γ radiation by using a NaI(Tl) scintillation detector and/or a germanium detector. In this study, based on measuring the β particles and mono-energy electrons from ¹⁵²Eu and the α particles from ²⁴¹Am, we provide a new option to simultaneously determine the radioactivities of ¹⁵²Eu and ²⁴¹Am by liquid scintillation counting (LSC) with the aid of α/β discrimination. If the count rate ratio of ²⁴¹Am to ¹⁵²Eu is within the range of 100:1–1:100, the radioactivities of ¹⁵²Eu and ²⁴¹Am in mixed samples can be simultaneously determined by LSC with the errors less than 5 %. In addition, the interferences of ²⁴¹Am on Eu are divided into two parts: inside and outside the ²⁴¹Am region of interest. Only if the count rate ratio of ²⁴¹Am to Eu is more than 10:1, should the latter interference be in consideration.     

Migration mechanisms of 237Np and 241Am through loess media

Migration experiments with ²³⁷Np(V) and ²⁴¹Am(III) have been performed using a column system, packed with loess, taken from Shanxi, China. The adsorption mechanism of ²³⁷Np and ²⁴¹Am on the loess was examined by a chemical extraction method. Most of ²³⁷Np was adsorbed on the influent edge of the column, and the adsorbtion was mainly controlled by surface complexation. However, the migration of ²³⁷Np in loess media could be roughly evaluated by the distribution coefficient. In the case of ²⁴¹Am, particulate, the ²⁴¹Am species was formed in the influent solution and moved in the column. The ²⁴¹Am adsorbed on loess was controlled by irreversible reactions. The migration behavior of particulate ²⁴¹Am in loess media could be expressed by the filtration theory.     

Adsorption and migration of <Superscript>241</Superscript>Am in aerated zone soil

As an important radioisotope in nuclear industry and other fields, ²⁴¹ Am is one of the most serious contamination concerns due to its high toxicity and long half-life. In order to supply useful reference for disposal of ²⁴¹Am waste with low-medium radioactivity, the adsorption and migration behavior of ²⁴¹Am on aerated zone soil were investigated by the static experimental method and column experiments. The results showed that more than 98% of the total ²⁴¹Am could be adsorbed from ²⁴¹Am solution of 0.32·10⁻⁷−1.1·10⁻⁷ mol/l by the soil at pH 4–9. The adsorption of ²⁴¹Am on the soil was a pH-dependent process at pH<4, but for pH>4, the adsorption rate of ²⁴¹Am on the soil changed minutely. The adsorption equilibrium was achieved within 24 hours and no significant effect on adsorption of ²⁴¹Am was observed at liquid-solid ratios of 50:1–500:1. The relationship between concentration of ²⁴¹Am and adsorption capacities of ²⁴¹Am can be described by the Freundlich adsorption equation. Adsorption of ²⁴¹Am on the soil can be inhibited by humic acid, ferric hydroxide colloid, or some anions, such as citric acid anion, saturated EDTA solution, C₂O₄ ²⁻ and CO₃ ²⁻. It was also noted that the adsorption rate of ²⁴¹Am drops in solutions containing Eu³⁺ or Nd³⁺, even 0.5 times above the ²⁴¹Am concentration. A migration distance of 8 mm for ²⁴¹Am(III) is observed only in the aerated zone soil containing ferric colloid, while a migration distance of less than 2 mm is noted in other soil samples after more than 250 days. All these results indicate that the aerated zone soil is an efficient sorbent for ²⁴¹Am and can inhibit the migration of ²⁴¹Am.     

Autoradiographic study on the distribution of 241Am in the shell of the freshwater zebra mussel Dreissena polymorpha

Autoradiography was used to identify α-track distributions in a series of shell sections from live mussels Dreissena polymorpha Pallas and dissected shells of dead mussels obtained from laboratory experiments using relatively high concentrations of ²⁴¹Am in the exposure media, a required condition for successful use of this autoradiographic technique. A comparable distribution of α-tracks was recorded on autoradiographs from both live and dead shells suggesting that metabolism does not lead to any sizable changes in the process of ²⁴¹Am adsorption (present in the extrapallial fluid) onto the inner surface of shell. Autoradiographs showed a preferential accumulation of ²⁴¹Am in the organic periostracum, whereas the outer and inner shell layers were characterized by a relatively low α-tracks density. No α-tracks were observed in the central part of the shell in any of the samples. These observations will be useful for the development of a general model to explain bioaccumulation and biosorption processes of radionuclides into mollusk shells.     

Adsorption behavior of Me2-CA-BTP/SiO2-P adsorbent toward MA(III) and Ln(III) in nitrate solution

A porous Me₂-CA-BTP/SiO₂-P adsorbent was prepared to separate MA(III) from Ln(III) in high level liquid waste (HLLW). The adsorption behavior of Me₂-CA-BTP/SiO₂-P toward ²⁴¹Am(III) and Ln(III) in 0.01 M HNO₃-NaNO₃ solution was studied. Me₂-CA-BTP/SiO₂-P showed high adsorption and selectivity toward ²⁴¹Am(III) over Ln(III) fission products with the separation factor (SF) reaching to 557, 2355, 1952, 1082, 214, 105, 86, 14 for Y, La, Ce, Nd, Sm, Eu, Gd and Dy respectively in 0.01 M HNO₃-0.99 M NaNO₃ solution. The adsorption kinetics of both Dy(III) and Eu(III) on Me₂-CA-BTP/SiO₂-P was studied and followed pseudo-second-order rate equation indicating chemical sorption as the rate-limiting step of the adsorption, and the adsorption isotherm of Dy(III) and Eu(III) matched better with the Langmuir isotherm than the Freundlich isotherm with the adsorption amount around 0.22 and 0.20 mmol/g respectively. Thermodynamic study revealed that the adsorption of both Dy(III) and Eu(III) on Me₂-CA-BTP/SiO₂-P was spontaneous and endothermic processes with a positive entropy at 298, 308, 313 K.     

Extraction of Americium with Substituted Calix[4]Arenes from Alkaline Solutions

Extraction of ²⁴¹Am and ¹⁵²Eu from carbonate-alkaline medias with solutions of functionalized calix[4]arenes and their nonmacrocyclic analogs in m-nitrobenzotrifluoride was studied. The dependencies of the Am distribution ratios on pH of the aqueous phase in the range 10 -13.5 and on the position and nature of functional groups in the calixarene core were examined. The composition of extractable solvates of americium with functionalized calix[4]arenes was determined. Thiacalixarenes extract americium more efficiently from alkaline solutions, as compared to calixarenes, demonstrating higher Am/Eu separation factor. Functionalization of the calixarenes improves the Am extraction efficiency and Am/Eu separation factor as well. In the case of thiacalixarenes, functionalization considerably decreases the extraction efficiency and selectivity.     

Distribution and behavior of some radionuclides associated with the Trinity nuclear test

The activities of ¹³³Ba, ¹³⁷Cs, ¹⁵²Eu, ¹⁵⁴Eu, ¹⁵⁵Eu, ²³⁹Pu, and ²⁴¹Am were determined by gamma spectroscopy on the largest sample set (n = 49) of bulk trinitite to date. The range in activity for all isotopes is large. For example, the activity of ²⁴¹Am (normalized to the time of detonation) ranges between 1 and 42 Bq/g. Comparison of activities for isotopes derived from the device, ²⁴¹Am versus ¹³⁷Cs, ¹⁵⁵Eu, and ²³⁹Pu, indicate positive trends. Correlations were not observed between the activities of the soil-derived activation products ¹⁵²Eu and ¹⁵⁴Eu and the radioisotopes from the device. The calculated ratio of fission products (¹⁵⁵Eu/¹³⁷Cs) is 0.012 ± .006 (1σ, n = 3), which is lower than predicted for the thermal neutron-induced fission of ²³⁹Pu (~0.03). This discrepancy may be attributed to the spontaneous fission of the natural U tamper resulting in mixing between fission products from ²³⁹Pu and ²³⁵U. The spatial distribution of the trinitite samples relative to ground zero has been modeled based on the activity of ¹⁵²Eu. The calculated distances do not correlate with any of the activities for the radioisotopes investigated here, and suggest a relatively homogeneous distribution. However, trinitite samples with the highest activities for ¹³⁷Cs, ²³⁹Pu, and ²⁴¹Am yield the shortest calculated distances of 50–60 m away from ground zero.     

Complexation of Eu(III), Am(III) and Cm(III) with Dicarboxylates: Thermodynamics and Structural Aspects of the Binary and Ternary Complexes

The complexation of Eu(III), Am(III) and Cm(III) with dicarboxylate anions with O, N or S donor groups was measured in I=6.60 mol⋅kg⁻¹ (NaClO₄) at temperatures of 0–60 °C by potentiometry and solvent extraction. The complexation thermodynamics of these complexes show that their stability is due to highly favorable complexation entropies because the complexation enthalpies are endothermic. Luminescence studies with Eu(III) and Cm(III) were used to measure the hydration numbers of the complexes. NMR spectra of ¹H and ¹³C were used to determine the binding modes of La(III) with the ligands. The formation of 1:1:1 ternary complexes of M(EDTA)⁻ with the dicarboxylate ligands was studied to determine changes in coordination of the metal cation with formation of the ternary species. The complexation of ternary complexes changes from bidentate to monodentate as the chain length between the binding sites of the dicarboxylates increases from 1 (malonate) to 4 (adipate). DFT computations were used to confirm the structural aspects of the interaction of these complexes.     

Biosorption of uranium(VI) by a mangrove endophytic fungus <Emphasis Type="Italic">Fusarium sp</Emphasis>. #ZZF51 from the South China Sea

The uranium(VI) accumulation was studied in detail by using the biomass of mangrove endophytic fungus Fusarium sp.#ZZF51 from the South China Sea. The uranium(VI) biosorption process onto the tested fungus powders was optimized at pH 4.0, adsorption time 60 min, and uranium(VI) initial concentration 50 mg L⁻¹ with 61.89% of removal efficiency. According to Fourier transform infrared spectra for the tested fungus before and after loaded with uranium(VI), the results showed that both of hydroxyl and carboxyl groups acted as the important roles in the adsorption process. In addition, the experimental data were analyzed by using parameter and kinetic models, and it was obtained that the Langmuir isotherm model and the pseudo-second-order kinetic model provided better correlation with the experimental data for adsorption of uranium(VI).     

Effect of humic acid on absorption-release processes in the bottom sediments-Yenisei river water system as studied by dual-column ion chromatography and γ-ray spectrometry

The effect of humic acid on absorption-release processes in the bottom sediments-Yenisei river water system was studied by dual-column ion chromatography and γ-ray spectrometry. With the use of ion chromatography, it was found that processes related to the absorption of SO ₄ ^2? and Cl^? anions by a solid phase with the release of NO ₃ ^? , PO ₄ ^3? , and F^? to a liquid phase competed in the test systems as the concentration of water-soluble organic carbon (WSOC) was increased. Only the test anions were released in the systems without the introduction of an additional amount of WSOC as humic acid. With the use of γ-ray spectrometry, it was found that the release of ⁶⁰Co, ¹⁵²Eu, and ²⁴¹Am radionuclides to the liquid phase in the systems with added humic acid began much earlier than in the system without the addition of humic acid. In this case, the amount of released radionuclides was greater than the amount of radioisotopes released in the system without the addition of humic acid: ～25% ²⁴¹Am, ～3% ¹⁵²Eu, and ～0.8% ⁶⁰Co in the system with added humic acid or 0.8% ¹⁵²Eu and <0.1% ⁶⁰Co in the system without the addition of humic acid. The ²⁴¹Am radionuclide was not determined in the system without the addition of humic acid. An increase in the concentration of WSOC in the experimental system of bottom sediments-Yenisei river water initiated the release of ⁶⁰Co, ¹⁵²Eu, and ²⁴¹Am anthropogenic radionuclides from bottom sediments because of the formation of soluble complexes capable of migration. An increase in the concentration of WSOC had almost no effect on the release of ⁴⁰K and ¹³⁷Cs radionuclides.     

Entrapment of Lentinus sajor-caju into Ca-alginate gel beads for removal of Cd(II) ions from aqueous solution: preparation and biosorption kinetics analysis

A white rot fungus species Lentinus sajor-caju biomass was entrapped into alginate gel via a liquid curing method in the presence of Ca(II) ions. The biosorption of cadmium(II) by the entrapped live and dead fungal biomass has been studied in a batch system. The heat-treatment process enhanced the biosorption capacity of the immobilized fungal biomass. The effect of initial cadmium concentration, pH and temperature on cadmium removal has been investigated. The maximum experimental biosorption capacities for entrapped live and dead fungal mycelia of L. sajur-caju were found to be 104.8±2.7 mg Cd(II) g⁻¹ and 123.5±4.3 mg Cd(II) g⁻¹, respectively. The kinetics of cadmium biosorption was fast, approximately 85% of biosorption taking place within 30 min. The biosorption equilibrium was well described by Langmuir and Freundlich adsorption isotherms. The change in the biosorption capacity with time is found to fit pseudo-second-order equations. Cadmium binding properties of entrapped fungal preparations have been determined applying the Ruzic equations. Since the biosorption capacities are relatively high for both entrapped live and dead forms, they could be considered as suitable biosorbents for the removal of cadmium in wastewater treatment systems. The biosorbents were reused in three consecutive adsorption/desorption cycles without significant loss in the biosorption capacity.     

Determination of <Superscript>241</Superscript>Am/<Superscript>243</Superscript>Am ratios

Determination of ²⁴¹Am/²⁴³Am ratios is required for vanous purposes including assay of Am by isotope dilution techniques. Alpha-spectrometry on electrodeposited sources is a preferred technique for this determination. However, there is an inherent problem of tail contribution which necessitates the use of suitable algorithms to account for the same. Recently, in the frame of a Coordinated Research Program (CRP) of the International Atomic Energy Agency (IAEA), WinALPHA software has been developed which is a combination of an asymmetrical Gaussian for the main part of the peak and a low energy function. Therefore, it was of interest to compare the use of this algorithm with the routinely used method, in our laboratory, based on geometric progression (G. P.) decrease. Since, there are no reference materials available commercially for ²⁴¹Am/²⁴³Am ratios, synthetic mixtures covening a wide range (0.3 to 2.0) of ²⁴¹Am/²⁴³Am α-activity ratios were used and un-ignited electrodeposited sources were prepared for α-spectrometry. The α-spectra obtained using PIPS detector, were evaluated using the two algonthms The ²⁴¹Am/²⁴³Am α-activity ratios obtained were also compared with those determined by thermal ionization mass spectrometry (TIMS). An agreement of about 1% was obtained in the ²⁴¹Am/²⁴³Am ratios determined by the two methods and also by using the two algorithms for α-spectrum evaluation.     

Kinetics of americium and europium extraction by tert-butylthiacalix[4]arene from alkaline media

Kinetics of ¹⁵²Eu and ²⁴¹Am extraction by nitrogen-bearing alkyl amino phenol oligomer YaRB and tert-butylthiacalix[4]arene TCA from carbonate-alkaline media was studied. Both extractants efficiently extract americium and europium in pH interval 12–14. The maximum of americium extraction is located at the lower values of pH, compared with europium. YaRB extracts americium and europium faster than TCA, and at the same time, americium is extracted faster than europium by both extractants. In general, thiacalixarene TCA is regarded as more efficient extractant than alkyl amino phenol oligomer YaRB.

     

Synthesis of core–shell structured Fe<Subscript>3</Subscript>O<Subscript>4</Subscript>@carboxymethyl cellulose magnetic composite for highly efficient removal of Eu(III)

In this work, a carboxymethyl cellulose (CMC)-modified Fe₃O₄ (denoted as Fe₃O₄@CMC) composite was synthesized via a simple co-precipitation approach. Fourier transform infrared spectroscopy, zeta potential and thermogravimetric analysis results indicated that CMC was successfully coated on the Fe₃O₄ surfaces with a weight percent of ~30 % (w/w). The prepared Fe₃O₄@CMC composite was stable in acidic solution and could be easily collected with the aid of an external magnet. A batch technique was adopted to check the ability of the Fe₃O₄@CMC composite to remove Eu(III) as a function of various environmental parameters such as contact time, solution pH, ionic strength, solid content and temperature. The sorption kinetics process achieved equilibrium within a contact time of 7 h. The sorption isotherms were well simulated by the Langmuir model, and the maximum sorption capacity at 293 K was calculated to be 2.78 × 10^?4 mol/g, being higher than the series of adsorbent materials reported to date. The ionic strength-independent sorption behaviors, desorption experiments by using ammonium acetate and disodium ethylenediamine tetraacetate as well as the spectroscopic characterization suggested that Eu(III) was sequestrated on the hydroxyl and carboxyl sites of Fe₃O₄@CMC via inner-sphere complexation. Overall, the Fe₃O₄@CMC composite could be utilized as a cost-effective adsorbent for the removal of trivalent lanthanide/actinides (e.g., ^152+154Eu, ²⁴¹Am and ²⁴⁴Cm) from radioactive wastewater.     

Characterization of an Irish Sea radioactively contaminated marine sediment core by radiometric and mass spectrometric techniques

Summary A radioactively contaminated marine sediment core stemming from Irish Sea has been characterized by radiometric and mass spectrometric techniques as for ²³⁷Np, ²⁴¹Am, ²³⁹Pu, ²⁴⁰Pu, ²⁴¹Pu, ¹³⁷Cs and ¹⁵⁴Eu. The data obtained with independent methods in the framework of a QA/QC program as compared with the source term discharges, as well as with those reported in literature, are in good agreement.     

In situ measurement of transuranics using a calcium fluoride scintillation detection system

A prototype scintillation spectrometer capable of measuring low energy photons from transuranic elements in groundwater has been developed for in situ applications. The detector is a CaF₂ (Eu) crystal enclosed in a stainless steel casing with a 19 mg·cm^-2 stainless steel entrance window. Evaluation of the system was performed in the laboratory by submersing the probe into a number of aqueous solutions containing varying concentrations of ²⁴¹Am in a simulated well environment. Spectra obtained had easily discernible peaks associated with the low energy L X-rays and the 60 keV gamma-ray photopeak of ²⁴¹Am.