A new method for the preconcentrations of U(VI) and Th(IV) by magnetized thermophilic bacteria as a novel biosorbent.

This paper proposes the use of Anoxybacillus flavithermus SO-15 immobilized on iron oxide nanoparticles (NPs) as a novel magnetized biosorbent for the preconcentrations of uranium (U) and thorium (Th). The SPE procedure was based on biosorption of U(VI) and Th(IV) on a column of iron oxide NPs loaded with dead and dried thermophilic bacterial biomass prior to U(VI) and Th(IV) measurements by ICP-OES. The biosorbent characteristicswere explored using FT-IR, SEM, and EDX. Significant operational factors such as solution pH, volume and flow rate of the sample solution, amounts of dead bacteria and iron oxide nanoparticles, matrix interference effect, eluent type, and repeating use of the biosorbent on process yield were studied. The biosorption capacities were found as 62.7 and 56.4 mg g-1 for U(VI) and Th(IV), respectively. The novel extraction process has been successfullyapplied to the tap, river, and lake water samples for preconcentrations of U(VI) and Th(IV).

[About the contents of 40K, 226Ra and 232Th in forest soils of the Republic of Belarus].

The specific activity of 40K, 232Th and 226Ra in forest soil ecotopes (A2-B2-C2-D2) has been investigated. When the fertility of the soil increases from A2 to D2, then the specific activity of 40K increases in the rooting zone of the soil from 275 ± 6.9 up to 499 ± 11 Bq/kg, 232Th--from 11.8 ± 0.5 to 17.1 ± 1.1 Bq/kg, 226Ra- from 19.2 γ 0.8 to 27.9 ± 1.5 Bq/kg. The calculated capacity of the absorbed dose of γ-radiation conditioned by 40K, 232Th and 226Ra increases from A2 to D2 from 27.5 ± 0.5 to 44.1 ± 1.1 nGy / h at the height of 1 m.

[Evaluation of the partial contribution of naturally occurring radionuclides and nonradioactive chemically toxic elements in formation of biological effects within the Vicia cracca population inhabiting the area contaminated with uranium-radium production wastes in the Komi Republic].

The site contaminated with uranium-radium production wastes in the Komi Republic was studied. The activity concentration of naturally occurring radionuclides (226Ra, 228Th, 238U, 230Th, 232Th, 210Po, and 210Pb), as well as concentrations of nonradioactive chemically toxic elements (Pb, Zn, Cu, As, V, Mo, Sr, Y, and Ba) in the soil samples from the experimental site is 10-183 times higher than reference levels. A chronic exposure to alpha-emitters and nonradioactive chemically toxic elements causes adverse effects in tufted vetch (Vacia cracca L.) both at the cellular (aberration of chromosomes) and population (decrease in the reproductive ability) levels. Radionuclides are the main contributors to the decrease in the reproductive capacity and an increase in the level of the cytogenetic damage in root tip cells of tufted vetch seedlings. As and Pb significantly influence the reproductive capacity of plants. Sr, Zn, Y and P modify the biological effects caused by exposure to radionuclides. Moreover, P and Zn reduce the adverse effects of radionuclides; however, Sr and Y enhance these effects.

Self-flocculating Chlorella vulgaris: A high-efficiency purification mechanism of radioactive Th4+ in an aquatic environment.

This study aimed to investigate the purification of radioactive thorium (Th4+) by Chlorella vulgaris in aquatic environments. Single-factor experiments and response surface optimization tests identified optimal purification conditions. The purification and metabolic response mechanisms of Chlorella to Th4+ were elucidated using physiological and biochemical analyses, three-dimensional excitation-emission matrix (3D-EEM) analysis, and metabolomic profiling. Increases in the Th4+ concentration caused Chlorella to self-flocculate, significantly improving the Th4+ purification efficiency. Under optimal conditions, the Th4+ purification efficiency for Th4+ in wastewater by Chlorella stabilized between 94.3 % and 98.2 %. Morphological analysis revealed that the purified Th4+ existed mainly in a stable residual state. Chlorella efficiently purified wastewater during treatment by regulating environmental pH, performing redox reactions, and utilizing extracellular polymeric substances (EPS) to interact with Th4+. Metabolomic analysis indicated that Chlorella adapted to the Th4+-contaminated environment and enhanced its purification function by adjusting the synthesis of metabolites, such as carbohydrates, nucleotides, and amino acids. Chlorella demonstrated a remarkable self-flocculation phenomenon and a high-efficiency purification capability for Th4+, offering new possibilities for environmental remediation. Its purification mechanism involves environmental regulation, redox reactions, and complex metabolic adjustments. The results presented here provide theoretical support for environmental remediation using Chlorella.

Functionalization of MXene using iota-carrageenan, maleic anhydride, and N,N'-methylene bis-acrylamide for high-performance removal of thorium (IV), uranium (IV), sulfamethoxazole, and levofloxacin.

An increasing quantity of pollutants has been discharged into the aquatic media, posing a serious hazard to public health. To address this issue, a new sorbent material, MXene@i.Carr@MaMb, was developed through the functionalization of the MXene surface using iota-carrageenan (i.Carr), maleic anhydride, and N, N'-methylene bis-acrylamide. This sorbent material was designed to remove thorium (Th (IV)) effectively, uranium (U (IV)), sulfamethoxazole (SMX), and levofloxacin (LEV) from wastewater. The MXene@i.Carr@MaMb composite incorporated significant functional groups, including OH, F, and O from MXene, oxygen and ester sulfate groups from iota-carrageenan (i.Carr), and OH, NH, and CO groups from N, N'-methylene bis-acrylamide, and maleic anhydride, which interacted with the UV (IV), Th (IV), SMX, and LEV pollutants through electrostatic interaction, complexation, and hydrogen bonding. MXene@i.Carr@MaMb composite exhibited excellent sorption capacities for Th (IV) (3.6 ± 0.03 mmol g-1), U (IV) (3.7 ± 0.09 mmol g-1), SMX (5.8 ± 0.03 mmol g-1), and LEV (5.9 ± 0.05 mmol g-1) at 323.15 K. The sorption kinetics and isotherms of radioactive metals and antibiotics can be well-described using pseudo-first-order kinetic models and Langmuir and Sips isothermal equations. This study presented a novel sorbent material for efficiently removing radioactive metals and antibiotics from wastewater.

Ethyl thiosemicarbazide intercalated organophilic calcined hydrotalcite as a potential sorbent for the removal of uranium(VI) and thorium(IV) ions from aqueous solutions.

This work was conducted to determine the practicability of using a new adsorbent 4-ethyl thiosemicarbazide intercalated, organophilic calcined hydrotalcite (ETSC-OHTC) for the removal of uranium (U(VI)), and thorium (Th(IV)) from water and wastewater. The FTIR analysis helped in realizing the involvement of nitrogen and sulphur atoms of ETSC in binding the metal ions through complex formation. Parameters like adsorbent dosage, solution pH, initial metal ions concentration, contact time and ionic strength, that influence adsorption phenomenon, were studied. The optimum pH for maximum adsorption of U(VI) and Th(IV) was found to be in the range 4.0-6.0. The contact time required for reaching equilibrium was 4 hr. The pseudo second-order kinetic model was the best fit to represent the kinetic data. Analysis of the equilibrium adsorption data using Langmuir, Freundlich and Sips models showed that the Freundlich model was well suited to describe the metal ions adsorption. The K(F) values were 25.43 and 29.11 mg/g for U(VI) and Th(IV), respectively, at 30 degrees C. The adsorbent can be regenerated effectively from U(VI) and Th(IV) loaded ones using 0.01 mol/L HCl. The new adsorbent was quite stable for many cycles, without much reduction in its adsorption capacity towards the metals.

Selective uptake of thorium(IV) from nitric acid medium using two extraction chromatographic resins based on diglycolamide-calix[4]arenes: Application to thorium-uranyl separation in an actual sample.

Two novel extraction chromatography resins (ECRs) containing two diglycolamide (DGA) -functionalized calix[4]arenes with n-propyl and isopentyl substituents at the amide nitrogen atom, termed as ECR-1 and ECR-2, respectively, were evaluated for the uptake of Th(IV) from nitric acid feed solutions. While both the resins were having a quite high Th(IV) uptake ability (Kd >3000 at 3 M HNO3), the uptake was relatively lower with the resin containing the isopentyl DGA, which appeared magnified at lower nitric acid concentrations. Kinetic modeling of the sorption data suggested fitting to the pseudo-second order model pointing to a chemical reaction during the uptake of the metal ion. Sorption isotherm studies were carried out showing a good fitting to the Langmuir and D-R isotherm models, suggesting the uptake conforming to monolayer sorption and a chemisorption model. Glass columns with a bed volume of ca. 2.5 mL containing ca. 0.5 g lots of the ECRs were used for studies to assess the possibility of actual applications of the ECRs. Breakthrough profiles obtained with feed containing 0.7 g/L Th(NO3)3 solution resulted in breakthrough volumes of 8 and 5 mL, respectively, for the ECR-1 and ECR-2 resins. Near quantitative elution of the loaded metal ion was possible using a solution of oxalic acid and nitric acid. A method for the separation of Th-234 from natural uranium was demonstrated for the possible application of ECR-1.

Radiochemical separation of 224Ra from 232U and 228Th sources for 224Ra/212Pb/212Bi generator.

The application of diagnostic and therapeutic radionuclides in nuclear medicine has grown significantly and has translated into the increased interest in radionuclide generators and their development. 224Ra and its shorter-lived daughters, 212Pb and 212Bi, are very interesting radionuclides from Targeted Alpha Therapy point of view for treatment of small cancers or metastatic forms. The purpose of the present work was to develop a simple generator for rapid elution of carrier-free 224Ra from 232U or 228Th sources by radiochemical separation based on extraction chromatography with the utilization of a home-made material. The bis(2-ethylhexyl) hydrogen phosphate (HDEHP) extractant was immobilized on polytetrafluroethylene (PTFE) grains and its ability to selectively adsorb 232U and 228Th, with simultaneous high elution recovery of 224Ra, was checked over few years. The 224Ra was quantitatively eluted with small volume (3-5 mL) of 0.1 M HNO3 with low breakthrough (<0.005%) and was used for further milking of 212Bi and 212Pb from DOWEX 50WX12 by 0.75 M and 2.0 M HCl, respectively. The elaborated here methods allowed high recovery of 224Ra, 212Pb and 212Bi radionuclides and their application in radiolabeling of various biomolecules.

Quantification of U, Th and specific radionuclides in coal from selected coal fired power plants in South Africa.

Most of South Africa's energy is derived from the combustion of coal in pulverized coal-fired power plants (CFPP). However, when compared with the rest of the world, limited information regarding the main radioactive elements (U and Th) and specific radionuclides of interest (K40, Ra226 and Th232) from South African CFPP is available in the public domain. This paper aims to quantify the U, Th and specific radionuclides found in the coal used in selected South African CFPP in comparison to world averages found in literature. The U and Th concentrations were obtained by ICP-MS. The main radionuclides, K40, Ra226 and Th238, were quantified using gamma spectrometry. The U concentration and Th concentrations for the coal used in all the power plants was above the world average of 1.9 mg/kg and 3.2 mg/kg respectively. The coals with the highest Th content originated from the Mpumalanga power plant, while the U content in the Freestate power plant samples was the highest of the three. The concentrations of the K40 were between 88.43±10.75-110.76±8.92 Bq/kg, which are in-line with world averages of 4-785 Bq/kg. Similarly, the Ra226 and Th232 values were between 21.69±2.83-52.63±4.04 Bq/kg and 19.91±1.24-22.97±1.75 Bq/kg respectively, which are also in line with the world averages of 1-206 Bq/kg and 1-170 Bq/kg respectively. Radiological hazard indices such as radium equivalent (Raeq); external hazard index (Hex) and internal hazard index (Hin), that were estimated from these average radionuclide concentrations were less than the prescribed values found in literature. This indicated that no significant health risk was posed by the coal being used from these coal fields.

Separation techniques for quantification of radionuclides in environmental samples.

The reliable and quantitative measurement of radionuclides is important in order to determine environmental quality and radiation safety, and to monitor regulatory compliance. We examined soil samples from Podunajske Biskupice, near the city of Bratislava in the Slovak Republic, for the presence of several natural ((238)U, (232)Th, (40)K) and anthropogenic ((137)Cs, (90)Sr, (239)Pu, (240)Pu, (241)Am) radionuclides. The area is adjacent to a refinery and hazardous waste processing center, as well as the municipal incinerator plant, and so might possess an unusually high level of ecotoxic metals. We found that the levels of both naturally occurring and anthropogenic radionuclides fell within the expected ranges, indicating that these facilities pose no radiological threat to the local environment. During the course of our analysis, we modified existing techniques in order to allow us to handle the unusually large and complex samples that were needed to determine the levels of (239)Pu, (240)Pu, and (241)Am activity. We also rated three commercial techniques for the separation of 90Sr from aqueous solutions and found that two of them, AnaLig Sr-01 and Empore Extraction Disks, were suitable for the quantitative and reliable separation of (90)Sr, while the third, Sr-Spec Resin, was less so. The main criterion in evaluating these methods was the chemical recovery of (90)Sr, which was less than we had expected. We also considered speed of separation and additional steps needed to prepare the sample for separation.

Separation of Uranium and Thorium for 230Th-U Dating of Submarine Hydrothermal Sulfides.

The age of a submarine hydrothermal sulfide is a significant index for estimating the size of hydrothermal ore deposits. Uranium and thorium isotopes in the samples can be separated for 230Th-U dating. This article presents a method to purify and separate U and Th isotopes in submarine hydrothermal sulfide samples. Following this technique, the separated U and Th fractions can meet measuring requirements by multi-collector inductively coupled plasma mass spectrometry (MC-ICPMS). The age of the hydrothermal sulfide sample can be calculated by measuring the present-day activity ratios of 230Th/238U and 234U/238U. A super clean room is necessary for this experiment. Cleaned regents and supplies are used to reduce the contamination during the sample processes. Balance, hotplate, and centrifuge are also used. The sulfide sample is powdered for analysis and less than 0.2 g sample is used. Briefly, the sample is weighed, dissolved, added to 229Th-233U-236U double spike solution, Fe co-precipitated, and separated on an anion-exchange resin extraction column. Approximately 50 ng U is consumed for 230Th-U dating of sulfides sample by MC-ICPMS.

Use of o-phenylene dioxydiacetic acid impregnated in Amberlite XAD resin for separation and preconcentration of uranium(VI) and thorium(IV).

The impregnation of o-phenylene dioxydiacetic acid (OPDA) into a polymeric matrix, Amberlite XAD-2000, is reported and was characterized by infrared spectroscopy. The amount of attached OPDA to the polymer resin was found to be 1.77mmolg(-1) resin. The resin was used for the sorption of U(VI) and Th(IV) from aqueous solution. This sorbent was capable of preconcentrating U(VI) and Th(IV) from weakly acidic or neutral solution. The retained metals were eluted sequentially using 0.25molL(-1) HCl for U(VI) and 1molL(-1) HCl for Th(IV) and determined spectrophotometrically using arsenazo-(III). The capacity of the resin for U(VI) and Th(IV) was found to be 0.121 and 0.113mmolg(-1), respectively. The impregnated resin exhibits a high chemical stability, reusability and fast equilibration. The method was used for the determination of U(VI) and Th(IV) in synthetic samples and rock samples.

Micro-column solid phase extraction to determine uranium and thorium in environmental samples.

Extraction chromatographic separation techniques based on U/TEVA and TEVA resins were utilized to separate uranium and thorium isotopes in complex matrices from environmental samples. This approach has the advantages of ease of quantitative analysis, small sample size, an absence of mixed waste solvents, complete separation of U/Th isotopes, acceptable chemical yields and good energy resolution in the alpha spectrum. The procedure for analyzing alpha-emitting isotopes of uranium and thorium in geothermal water from Peito, Taiwan, is illustrated in detail. It involves sample pre-concentration, filtration and separation by highly selective extraction chromatographic resins, followed by electroplating and alpha-spectroscopy. The analytical results show a chemical recovery exceeding 55% for U and 65% for Th, respectively, under optimized conditions. The efficient and cost-effective use of recyclable columns makes the analytical methods simple, accurate, rapid, reliable and robust.

Ion-imprinted electrospun nanofibers of chitosan/1-butyl-3-methylimidazolium tetrafluoroborate for the dynamic expulsion of thorium (IV) ions from mimicked effluents.

The present study explores the innocuous, biocompatible, and extremely competent molecularly imprinted chitosan/RTIL electrospun nanofibers having average diameter of 30 nm for the expulsion of thorium (IV) ions from the mimicked effluent waste. The extended Flory-Huggins theory and three-dimensional molecular modeling have been effectively premeditated via Materials Studio software for enumerating the inter-miscibility and compatibility (Chi parameter (χ) = 1.019, mixing energy (Emix) = 0.603 kcal/mol) of the chitosan/RTIL (1-butyl-3-methylimidazolium tetrafluoroborate). The maximum adsorption efficiency is found to be 90% at a neutral pH of 7, and a temperature of 298 K within 120 min. The adsorption process was extensively studied by two-parameter adsorption isotherms like Langmuir, Freundlich, Temkin, and Dubinin-Radushkevich (D-R) and three-parameter models like Redlich-Paterson and Sips isotherm. Pseudo-second-order kinetics model (R2 = 0.982) and Langmuir isotherm (R2 = 0.994) bestowed the best fitting on chitosan/RTIL nanofibers for the adsorption of Th (IV) ions. The thermodynamic study reveals the spontaneity and exothermic nature of the reaction. The experimental analysis conjoint with isotherm and kinetic models, and simulation study establish the applicability of chitosan/RTIL nanofibers for the expulsion of Th (IV) and other toxic metal ions from the effluents. Graphical abstract Ion-imprinted electrospun nanofiber for expulsion of thorium (IV) ion.

On the sequential separation and quantification of 237Np, 241Am, thorium, plutonium, and uranium isotopes in environmental and urine samples.

The implementation of the one-pass-through separation technique using two stacked chromatography columns of TEVA - TRU resins for the separation of 237Np, 241Am, thorium, plutonium and uranium from environmental and urine samples was investigated. The sequential separation technique proved to be successful and gave similar results to those obtained when using individual separations. The analysis time was considerably improved. The amount of chemical waste was also reduced by 50% and the use of HClO4 was avoided. The technique of ICP-MS was also investigated as a complementary technique to alpha-spectrometry.

Selective biosorption of thorium (IV) from aqueous solutions by ginkgo leaf.

Low-cost biosorbents (ginkgo leaf, osmanthus leaf, banyan leaf, magnolia leaf, holly leaf, walnut shell, and grapefruit peel) were evaluated in the simultaneous removal of La3+, Ce3+, Pr3+, Nd3+, Sm3+, Eu3+, Gd3+, Yb3+, Lu3+, UO22+, Th4+, Y3+, Co2+, Zn2+, Ni2+, and Sr2+ from aqueous solutions. In single metal systems, all adsorbents exhibited good to excellent adsorption capacities toward lanthanides and actinides. In a simulated multicomponent mixed solution study, higher selectivity and efficiency were observed for Th4+ over other metal cations, with ginkgo leaves providing the highest adsorptivity (81.2%) among the seven biosorbents. Through optimization studies, the selectivity of Th4+ biosorption on ginkgo leaf was found to be highly pH-dependent, with optimum Th4+ removal observed at pH 4. Th4+ adsorption was found to proceed rapidly with an equilibrium time of 120 min and conform to pseudo-second-order kinetics. The Langmuir isotherm model best described Th4+ biosorption, with a maximum monolayer adsorption capacity of 103.8 mg g-1. Thermodynamic calculations indicated that Th4+ biosorption was spontaneous and endothermic. Furthermore, the physical and chemical properties of the adsorbent were determined by scanning electron microscopy, Brunauer-Emmett-Teller, X-ray powder diffraction, and Fourier transform infrared analysis. The biosorption of Th from a real sample (monazite mineral) was studied and an efficiency of 90.4% was achieved from nitric acid at pH 4 using ginkgo leaves.

Application of extraction chromatography to the separation of thorium and uranium dissolved in a solution of high salt concentration.

Extraction chromatography with commercially available UTEVA resin (for uranium and tetravalent actinide) was applied for the separation of Th and U from control solutions prepared from a multi-element control solution and from sample solutions of solidified simulated waste. Thorium and U in control solutions with 1-5mol/dm(3) HNO(3) were extracted with UTEVA resin and recovered with a solution containing 0.1mol/dm(3) HNO(3) and 0.05mol/dm(3) oxalic acid to be separated from the other metallic elements. Extraction behavior of U in the sample solutions was similar to that in the control solutions, but extraction of Th was dependent on the concentration of HNO(3). Thorium was extracted from 5mol/dm(3) HNO(3) sample solutions but not from 1mol/dm(3) HNO(3) sample solutions. We conjecture that thorium fluoride formation interferes with extraction of Th. Addition of Al(NO(3))(3) and Fe(NO(3))(3), which have higher stability constant with fluoride ion than Th, does improve extractability of Th from 1mol/dm(3) HNO(3) sample solution.

Retention studies on uranium, thorium and lanthanides with amide modified reverse phase support and its applications.

The retention behaviour of uranium and thorium was investigated on modified reverse phase supports using 3-oxo-pentanedioicacid bis-[bis-(2-ethyl-hexyl)-amide (OPAEHA), 3-oxo-pentanedioicacid bis diisobutyl amide (OPAIBA) and bis-2-ethylhexyl succinamic acid (BEHSA). alpha-Hydroxy isobutyric acid (alpha-HIBA) was employed as the complexing reagent for elution. Elution profiles of uranium and thorium were studied as a function of the modifier concentration, mobile phase composition and its pH. Based on these investigations, a novel high performance liquid chromatography (HPLC) based separation technique was developed using BEHSA modified support for the isolation and quantitative determination of lanthanides as a group in uranium matrix. Hundreds of samples obtained from pyrochemical reprocessing of molten salts containing lanthanides in uranium matrix (e.g. 1:20,000) were separated and determined within 7 min using the coated support. The advantage of the present HPLC technique lies in the simultaneous separation and assay of total lanthanides and uranium whereas other analytical methods necessitate the separation of uranium matrix prior to lanthanide assay.

Study of the behaviour of thorium adsorption on PAN/zeolite composite adsorbent.

The adsorption behaviour of thorium from aqueous solutions by a composite adsorbent has been investigated by a batch technique. The thorium adsorption on composite adsorbent was studied as a function of initial concentration, pH, shaking time and temperature. The sorption of thorium at the determined optimum conditions follows Langmuir, Freundlich and D-R type isotherms. Langmuir constants Q=0.04 mmol g(-1) and b=64.94 L mol(-1) and of D-R parameter Xm = 0.04, beta=0.79 and of sorption energy E=0.80 and Freundlich constants 1/n=3.12 and cm = 0.012 mmol g(-1) were evaluated. Thermodynamic parameters such as DeltaH and DeltaS were found to be 37.32 kJ mol(-1) and 206.17 J mol(-1)K(-1), respectively.

Sequential separation of lanthanides, thorium and uranium using novel solid phase extraction method from high acidic nuclear wastes.

A novel grafted polymer for selective extraction and sequential separation of lanthanides, thorium and uranium from high acidic wastes has been developed by grafting Merrifield chloromethylated (MCM) resin with octyl(phenyl)-N,N-diisobutylcarbamoyl-methylphosphine oxide (CMPO) (MCM-CMPO). The grafting process is well characterized using FT-IR spectroscopy, (31)P and (13)C CPMAS (cross-polarized magic angle spin) NMR spectroscopy and CHNPS elemental analysis. The influence of various physico-chemical parameters during metal ion extraction by the resin phase are studied and optimized by both static and dynamic methods. The resin shows very high sorption capacity values of 0.960mmolg(-1) for U(VI), 0.984mmolg(-1) for Th(IV), 0.488mmolg(-1) for La(III) and 0.502mmolg(-1) for Nd(III) under optimum HNO(3) medium, respectively. The grafted polymer shows faster rate exchange kinetics (<5min is sufficient for 50% extraction) and greater preconcentration ability, with reusability exceeding 20 cycles. During desorption process, sequential separation of the analytes is possible with varying eluting agents. The developed grafted resin has been successfully applied in extracting Th(IV) from high matrix monazite sand, U(VI) and Th(IV) from simulated nuclear spent fuel mixtures. All the analytical data is based on triplicate analysis and measurements are within 3.5% rsd reflecting the reproducibility and reliability of the developed method.