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.

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).

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 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.

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.

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.

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.

Separation of 103Ru from a proton irradiated thorium matrix: A potential source of Auger therapy radionuclide 103mRh.

Ruthenium-103 is the parent isotope of 103mRh (t1/2 56.1 min), an isotope of interest for Auger electron therapy. During the proton irradiation of thorium targets, large amounts of 103Ru are generated through proton induced fission. The development of a two part chemical separation process to isolate 103Ru in high yield and purity from a proton irradiated thorium matrix on an analytical scale is described herein. The first part employed an anion exchange column to remove cationic actinide/lanthanide impurities along with the majority of the transition metal fission products. Secondly, an extraction chromatographic column utilizing diglycolamide functional groups was used to decontaminate 103Ru from the remaining impurities. This method resulted in a final radiochemical yield of 83 ± 5% of 103Ru with a purity of 99.9%. Additionally, measured nuclear reaction cross sections for the formation of 103Ru and 106Ru via the 232Th(p,f)103,106Ru reactions are reported within.

An initial demonstration of hierarchically porous niobium alkylphosphonates coordination polymers as potent radioanalytical separation materials.

Combining the merits of soft-templating and perchlorate oxidation methods, the first-case investigation of niobium alkylphosphonates has uncovered their unique morphology, backbone composition, thermal behavior and huge potentiality as radioanalytical separation materials. These hierarchically porous solids are random aggregates of densely stacked nanolayers perforated with worm-like holes or vesicular voids, manifesting the massif-, tower-like "polymer brush" elevated up to ∼150nm driven by the minimal surface free energy principle. These coordination polymers consist of distorted niobium (V) ions strongly linked with tetrahedral alkylphosphonate building units, exposing uncoordinated phosphonate moieties and defective metal sites. Despite the amorphous features, they demonstrate multimodal porosity covering continuous micropores, segregated mesopores and fractional macropores, beneficial for the sequestration by active Lewis acid-base center. Evidenced by the maximum distribution coefficients of thorium, lanthanides reaching 9.0×104, 9.5×104mLg-1 and large separation factor at pH≤1 20-element cocktail, this category of niobium alkylphosphonates are capable of harvesting thorium, lanthanides directly from the radionuclide surrogate, comparable to or even surpass the performance of the metal (IV) arylphosphonates counterparts. They also display appreciable SFEu/Sm ∼20 in 1molL-1 HNO3, shedding light on dual approaches to achieve the isolation of americium from curium. A combinatorial radioanalytical separation protocol has been proposed to enrich thorium and europium, revealing facile utilization of these highly stable, phosphonated hybrids in sustainable development of radioanalytical separation.

Assessment of the bioavailability and depuration of uranium, cesium and thorium in snails (Cantareus aspersus) using kinetics models.

Uranium ore waste has led to soil contamination that may affect both environmental and soil health. To analyze the risk of metal transfer, metal bioavailability must be estimated by measuring biological parameters. Kinetic studies allow taking into account the dynamic mechanisms of bioavailability, as well as the steady state concentration in organisms necessary to take into account for relevant risk assessment. In this way, this work aims to model the snail accumulation and excretion kinetics of uranium (U), cesium (Cs) and thorium (Th). Results indicate an absence of Cs and Th accumulation showing the low bioavailability of these two elements and a strong uranium accumulation in snails related to the levels of soil contamination. During the depuration phase, most of the uranium ingested was excreted by the snails. After removing the source of uranium by soil remediation, continued snails excretion of accumulated uranium would lead to the return of their initial internal concentration, thus the potential trophic transfer of this hazardous element would stop.

Evaluation of the separation and purification of 227Th from its decay progeny by anion exchange and extraction chromatography.

Thorium-227 is currently undergoing evaluation as a potential radionuclide for targeted cancer therapy, and as such a high chemical purity of the material is required. To establish a reliable procedure for radiochemical isolation of 227Th from the parent 227Ac and decay progeny, which includes the radiotherapeutic 223Ra, the performance of three different separation schemes based on ion-exchange and extraction chromatography have been evaluated. The results suggest that both ion exchange and extraction chromatographic techniques can be successfully used for the separation of 227Th from its decay progeny, however extraction chromatographic resins demonstrate favourable performance in terms of Th recovery and purification from radionuclide impurities.

Separation of thorium and uranium in nitric acid solution using silica based anion exchange resin.

To separate thorium and uranium in nitric acid solution using anion exchange process, a strong base silica-based anion exchange resin (SiPyR-N4) was synthesized. Batch experiments were conducted and the separation factor of thorium and uranium in 9M nitric acid was about 10. Ion exchange chromatography was applied to separate thorium and uranium in different ratios. Uranium could be eluted by 9M nitric acid and thorium was eluted by 0.1M nitric acid. It was proved that thorium and uranium can be separated and recovered successfully by this method.

Solid phase extraction, separation and preconcentration of rare elements thorium(IV), uranium(VI), zirconium(IV), cerium(IV) and chromium(III) amid several other foreign ions with eriochrome black T anchored to 3-D networking silica gel.

The present work reports the systematic studies on extraction, separation and preconcentration of Th(IV), U(VI), Zr(IV), Ce(IV) and Cr(III) amid several other foreign ions using EBT anchored {SiO2}n3-D microarray. The effect of various sorption parameters, such as pH, concentration, temperature, sample volume, flow-rate and co-existing foreign ions were investigated. Quantitative sorption was ensured at solution pH: 6.0-6.5 for Th(IV), Ce(IV), Cr(III) and pH: 2.75-3.0 for Zr(IV), U(VI) couple. Analysis on extracted species and extraction sites reveals that [Th4(µ(2)-OH)8(H2O)4](8+), [Ce6(µ(2)-OH)12(H2O)5](12+), [Cr3(µ(2)-OH)4(H2O)](5+), [(UO2)3(µ(2)-OH)5(H2O)3](+) and [Zr4(µ(2)-OH)8(H2O)0.5](8+) for the respective metal ions gets extracted at HOMO of the extractor. HOMO-{metal ion species} was found to be 1:1 complexation. Sorption was endothermic, entropy-gaining, instantaneous and spontaneous in nature. A density functional theory (DFT) calculation has been performed to analyze the 3-D structure and electronic distribution of the synthesized extractor.

Application of ion exchange and extraction chromatography to the separation of actinium from proton-irradiated thorium metal for analytical purposes.

Actinium-225 (t1/2=9.92d) is an α-emitting radionuclide with nuclear properties well-suited for use in targeted alpha therapy (TAT), a powerful treatment method for malignant tumors. Actinium-225 can also be utilized as a generator for (213)Bi (t1/2 45.6 min), which is another valuable candidate for TAT. Actinium-225 can be produced via proton irradiation of thorium metal; however, long-lived (227)Ac (t1/2=21.8a, 99% ß(-), 1% α) is co-produced during this process and will impact the quality of the final product. Thus, accurate assays are needed to determine the (225)Ac/(227)Ac ratio, which is dependent on beam energy, irradiation time and target design. Accurate actinium assays, in turn, require efficient separation of actinium isotopes from both the Th matrix and highly radioactive activation by-products, especially radiolanthanides formed from proton-induced fission. In this study, we introduce a novel, selective chromatographic technique for the recovery and purification of actinium isotopes from irradiated Th matrices. A two-step sequence of cation exchange and extraction chromatography was implemented. Radiolanthanides were quantitatively removed from Ac, and no non-Ac radionuclidic impurities were detected in the final Ac fraction. An (225)Ac spike added prior to separation was recovered at ≥ 98%, and Ac decontamination from Th was found to be ≥ 10(6). The purified actinium fraction allowed for highly accurate (227)Ac determination at analytical scales, i.e., at (227)Ac activities of 1-100 kBq (27 nCi to 2.7 µCi).

Application of hollow cylindrical wheat stem for electromembrane extraction of thorium in water samples.

In this study, wheat stem was used for electromembrane extraction (EME) for the first time. The EME technique involved the use of a wheat stem whose channel was filled with 3 M HCl, immersed in 10 mL of an aqueous sample solution. Thorium migrated from aqueous samples, through a thin layer of 1-octanol and 5%v/v Di-(2-ethylhexyl) phosphate (DEHP) immobilized in the pores of a porous stem, and into an acceptor phase solution present inside the lumen of the stem. The pH of donor and acceptor phases, extraction time, voltage, and stirring speed were optimized. At the optimum conditions, an enrichment factor of 50 and a limit of detection of 0.29 ng mL(-1) was obtained for thorium. The developed procedure was then applied to the extraction and determination of thorium in water samples and in reference material.

N-benzoyl-n-phenylhydroxylamine impregnated Amberlite XAD-4 beads for selective removal of thorium.

n-Benzoyl-n-phenylhydroxylamine impregnated Amberlite XAD-4 beads were used for the removal of Th(IV) from a mixture of ions. The impregnated XAD was characterized using different techniques like weight and colour change, IR spectra, surface area and pore size measurements to confirm the presence of n-BPHA within the macroreticular resin structure. The experimental conditions were optimized to make the separation fast and selective. It was seen that the maximum sorption was achieved in the pH range of 3-7.5 and uptake was nearly complete within half an hour. The results obtained in the present study were subjected to extensive modelling in order to get a complete understanding of the sorption process. It is seen that the maximum uptake was calculated to be 500 mg/g and has very fast kinetics it was seen that the process is chemisorption. It was further deduced from the modelling that the overall sorption process was controlled dominantly by external mass transfer. Considering the simplicity this procedure, the present study has a possible application for the removal of thorium from different mixtures.

Uranium and thorium sequential separation from norm samples by using a SIA system.

This study presents a sequential radiochemical separation method for uranium and thorium isotopes using a novel Sequential Injection Analysis (SIA) system with an extraction chromatographic resin (UTEVA). After the separation, uranium and thorium isotopes have been quantified by using alpha-particle spectrometry. The developed method has been tested by analyzing an intercomparison sample (phosphogypsum sample) from International Atomic Energy Agency (IAEA) with better recoveries for uranium and thorium than the obtained by using a classical method (93% for uranium using the new methodology and 82% with the classical method, and in the case of thorium the recoveries were 70% for the semi-automated method and 60% for the classical strategy). Afterwards, the method was successfully applied to different Naturally Occurring Radioactive Material (NORM) samples, in particular sludge samples taken from a drinking water treatment plant (DWTP) and also sediment samples taken from an area of influence of the dicalcium phosphate (DCP) factory located close to the Ebro river reservoir in Flix (Catalonia). The obtained results have also been compared with the obtained by the classical method and from that comparison it has been demonstrated that the presented strategy is a good alternative to existing methods offering some advantages as minimization of sample handling, reduction of solvents volume and also an important reduction of the time per analysis.

[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.