Potential use of tungstocerate matrices on the separation of <Superscript>113m</Superscript>In from <Superscript>110m</Superscript>Ag relevant to the separation of the cyclotron-produced <Superscript>111</Superscript>In from its silver target

A procedure for separation of no-carrier-added ^113mIn(III) radioisotope from a bulk of ^110mAg has been developed. The sorption behavior of ^113mIn(III) and ^110mAg(I) ions in HNO₃ acid solutions on different tungstocerate matrices showed high affinity of ^110mAg(I) ions towards tungstocerate(IV) gel matrices compared with ^113mIn(III) ions. No-carrier-added ^113mIn radionuclide was separated from ^110mAg on 12-tungstocerate(IV) column matrix. 11 mL 0.3M HNO₃ acid solution was enough for eluting the ^113mIn from the column bed. ^110mAg was recovered from the column by eluting the column bed with 12 mL 2M HNO₃ acid solution.     

Extraction chromatography for the separation of <Superscript>239</Superscript>Np from <Superscript>243</Superscript>Am

Summary An extraction chromatography method was developed for the separation of 239Np from ²⁴³Am in nitric acid solution. A sorbent based on aliphatic quaternary amine Aliquat-336 and hydrophobized silica gel was prepared. ²³⁹Np reduced to the oxidation state(IV) with ferrous sulfamate in 2M or 6M HNO₃ sorbs on the prepared silica gel column. After washing with 0.1M ferrous sulfamate in 2.5M HNO₃, ²³⁹Np is eluted with 0.1M HNO₃ containing 0.02M HF. The separation of ²⁴³Am from ²³⁹Np is very effective. The purity of ²³⁹Np was found to be better than 99.5%. The proposed ²³⁹Np milking procedure is suitable for the preparation of ²³⁹Np tracer that can be used for the determination of ²³⁷Np radiochemical yield.     

Separation of Zr in the rubble waste generated at the Fukushima Daiichi Nuclear Power Station

Separation method of Zr using trans uranium resin (TRU resin) and tetra valent actinide resin (TEVA resin) was developed for the analysis of ⁹³Zr contained in the rubble waste. Zr, Nb, and U were quantitatively extracted on the TRU resin from 3 M HNO₃ and striped with 0.01 M HF, in addition, some part of Mo, Hg, Bi, and Th were also included in the stripping solution. The stripping solution was evaporated to eliminate HNO₃ and the residue was dissolved in 0.1 M HF. Finally, Zr was separated from Nb and Mo with the TEVA resin.     

Determination of weight distribution ratios of Pa(V) and Np(V) with some extraction chromatography resins and the AG1-X8 resin

Literature data on distribution ratios (D_w) of Np(V) and Pa(V) for the AG1-X8 resin are scarce whereas those related on resin capacity factors (k′) values for TEVA, TRU and U/TEVA resins are absent. Therefore, batch extraction experiments for Pa(V) and Np(V) from HCl and HNO₃ media were realized, at tracer scale, with AG1-X8 and EIChroM resins (TEVA, TRU and U/TEVA). Based on the new D_w and k′ values obtained in this study, a new protocol for Pa/Np separation has been developed leading to a better separation factor of 10⁵ and a chemical yield of 97 ± 3% and 99 ± 1% for Pa and Np, respectively. A separation of ²³¹Pa from uranium matrix was successfully tested.     

Determination of uranium and thorium in complex samples using chromatographic separation, ICP-MS and spectrophotometric detection

The paper describes a research of possible application of UTEVA and TRU resins and anion exchanger AMBERLITE CG-400 in nitrate form for the isolation of uranium and thorium from natural samples. The results of determination of distribution coefficient have shown that uranium and thorium bind on TRU and UTEVA resins from the solutions of nitric and hydrochloric acids, and binding strength increases proportionally to increase the concentration of acids. Uranium and thorium bind rather strongly to TRU resin from the nitric acid in concentration ranging from 0.5 to 5 mol L⁻¹, while large quantities of other ions present in the sample do not influence on the binding strength. Due to the difference in binding strength in HCl and HNO₃ respectively, uranium and thorium can be easily separated from each other on the columns filled with TRU resin. Furthermore, thorium binds to anion exchanger in nitrate form from alcohol solutions of nitric acid very strongly, while uranium does not, so they can be easily separated. Based on these results, we have created the procedures of preconcentration and separation of uranium and thorium from the soil, drinking water and seawater samples by using TRU and UTEVA resins and strong base anion exchangers in nitrate form. In one of the procedures, uranium and thorium bind directly from the samples of drinking water and seawater on the column filled with TRU resin from 0.5 mol L⁻¹ HNO₃ in a water sample. After binding, thorium is separated from uranium with 0.5 mol L⁻¹ HCl, and uranium is eluted with deionised water. By applying the described procedure, it is possible to achieve the concentration factor of over 1000 for the column filled with 1 g of resin and splashed with 2 L of the sample. Spectrophotometric determination with Arsenazo III, with this concentration factor results in detection limits below 1 μg L⁻¹ for uranium and thorium. In the second procedure, uranium and thorium are isolated from the soil samples with TRU resin, while they are separated from each other on the column filled with anion exchanger in alcohol solutions. Anion exchanger combined with alcohol solutions enables isolation of thorium from soil samples and its separation from a wide range of elements, as well as spectrophotometric determination, ICP-MS determination, and other determination techniques.     

Systematic radiochemical separation for the determination of <Superscript>99</Superscript>Tc, <Superscript>90</Superscript>Sr, <Superscript>94</Superscript>Nb, <Superscript>55</Superscript>Fe and <Superscript>59,63</Superscript>Ni in low and intermediate radioactive waste samples

A simple and rapid separation procedure was systemized for the determination of ⁹⁹Tc, ⁹⁰Sr, ⁹⁴Nb, ⁵⁵Fe and ^59,63Ni in low and intermediate level radioactive wastes. The integrated procedure involves precipitation, anion exchange and extraction chromatography for the separation and purification of individual radionuclide from sample matrix elements and from other radionuclides. After separating Re (as a surrogate of ⁹⁹Tc) on an anion change resin column, Sr, Nb, Fe and Ni were sequentially separated as follows; Sr was separated as Sr (Ca-oxalate) co-precipitates from Nb, Fe and Ni followed by purification using Sr-Spec extraction chromatographic resin. Nb was separated from Fe and Ni by anion exchange chromatography. Fe was separated from Ni by anion exchange chromatography. Ni was separated as Ni-dimethylglyoxime precipitates after the removal of ^134,137Cs and ^110mAg by Cs-phosphotungstate and AgCl precipitation, respectively. Finally, the radionuclide sources were prepared by precipitation for their radioactivity measurements. The reliability of the procedure was evaluated by measuring the recovery of chemical carriers added to a synthetic radioactive waste solution.     

Separation of Sr in combination of ion exchange and Sr resin with alcohol-nitric acid solution and rapid determination of <Superscript>90</Superscript>Sr in wine and soil samples

This paper describes the procedures of isolating strontium from wine and soil samples which enable creating of procedure for rapid determination of ⁹⁰Sr. The method of determination of ⁹⁰Sr includes binding of Sr on the cationic exchanger IR-120 from the sample and simultaneous elution from the cation column and binding on the Sr column, separation of Sr on Sr resin with HNO₃ even in presence of alcohols and subsequent Cherenkov counting. Sr can be efficiently bind on Sr resin and separated from the other elements with lower acid concentrations in the presence of a low portion of alcohol, or even from a wine sample without the loss of Sr resin capacity. The binding strength of Sr on Sr resin decreases with the rising of HNO₃ concentration (1–5 M) in the presence of 13% of ethanol or methanol, and with the rising of the alcohol portion in constant concentration of HNO₃. Application of cation exchanger for Sr binding in phase of sample preparation decreases Sr column loading and improve Sr recovery. The method allows the determination of ⁹⁰Sr activities in wine and soil sample lower than 10 mBq in reasonable time.     

Separation of radioarsenic from irradiated germanium oxide targets for the production of <Superscript>71</Superscript>As and <Superscript>72</Superscript>As

A method for the separation of no-carrier-added arsenic radionuclides from the bulk amount of proton-irradiated GeO₂ targets as well as from coproduced radiogallium was developed. The radionuclides ⁶⁹Ge and ⁶⁷Ga produced during irradiation of GeO₂ were used as tracers for Ge and Ga in the experiments. After dissolution of the target the ratio of As(III) to As(V) was determined via thin layer chromatography (TLC). The extraction of radioarsenic by different organic solvents from acid solutions containing alkali iodide was studied and optimized. The influence of the concentration of various acids (HCl, HClO₄, HNO₃, HBr, H₂SO₄) as well as of KI was studied using cyclohexane. The optimum separation of radioarsenic was achieved using cyclohexane with 4.75 M HCl and 0.5 M KI and its back-extraction with a 0.1% H₂O₂ solution. The separation leads to high purity radioarsenic containing no radiogallium and <0.001% [⁶⁹Ge]Ge. The overall radiochemical yield is 93 ± 3%. The practical application of the optimized procedure in the production of ⁷¹As and ⁷²As is demonstrated and batch yields achieved were in the range of 75–84% of the theoretical values.     

Measurement of <Superscript>99</Superscript>Tc in Savannah River Site high activity waste

Summary Waste cleanup efforts currently underway at the Savannah River Site have created a need to characterize ⁹⁹Tc in the various high activity waste matrices currently in Site inventories. The traditional method our laboratory used for analyzing ⁹⁹Tc in higher activity matrices was a solvent-solvent extraction method using Aliquat-336 in xylene. In an effort to eliminate the resulting generation of mixed wastes, a variety of different separation methodologies have been studied. Eichrom TEVA solid phase extractions using column technology have been employed in a case by case basis over the last several years. More recently, applications using Eichrom TEVA extraction discs and 3M Empore Tc extraction discs have also been explored.     

Atmospheric depositional fluxes of cosmogenic <Superscript>32</Superscript>P, <Superscript>33</Superscript>P and <Superscript>7</Superscript>Be in the Sevastopol region

⁹⁰Y was separated from ⁹⁰Sr using an extraction chromatographic resin consisting of 4, 4′(5′)-bis-t-butylcyclohexano-18-crown-6 (DtBuCH₁₈C₆), 1-ethyl-3-methylimidazolium bis(trifluoromethanesulfonyl) amide (C₂mimNTf₂), and a polymer (Amberlite XAD-7). Ionic liquid was introduced into the column to improve the separation efficiency. The column showed an excellent performance for the separation of Y from Sr. After the separation, the ratio of ⁹⁰Sr/⁹⁰Y was <2.0 × 10^?5; the column was recycled for >18 times. This study provides preliminary results on columns to produce ⁹⁰Y with a high purity in radiopharmaceuticals.     

Radiochemical separation of Pu, U, Am and Sr isotopes in environmental samples using extraction chromatographic resins

This study presents a rapid and quantitative sequential radiochemical separation method for Pu, U, Am and Sr isotopes in environmental samples with extraction chromatographic resins. After radionuclides were leached from the samples with 6 M HNO₃, Pu and U isotopes were adsorbed onto the UTEVA column and Am isotopes were adsorbed onto the TRU column connected with the UTEVA column. Also, ⁹⁰Sr was adsorbed onto the Sr column connected with the TRU column. Pu and U isotopes were purified from other nuclides through the UTEVA column. In addition, Am isotopes were separated from other nuclides with the TRU column. Finally, ⁹⁰Sr was purified with the Sr resin. After α source preparation for the purified Pu, U and Am isotopes with micro-coprecipitation method, Pu, U and Am isotopes were measured using alpha spectrometry. On the other hand, ⁹⁰Sr was measured using a low level liquid scintillation counter. The radiochemical procedure for Pu, U, Am and Sr nuclides investigated in this study has been applied to environmental samples after validating the simulated samples.     

Analysis of Th, U, Pu, and Am in radioactive metal waste using extraction chromatography

In order to analyze actinide elements in radioactive metal waste, the dissolution and chemical separation conditions were optimized. The surfaces of a type 304 stainless steel plate and of pipe waste sampled from the prototype advanced thermal reactor (Fugen) were dissolved in mixed acid solution (HNO₃:HCl:H₂O = 1:1:4). The resulting solution was evaporated to dryness and dissolved with 2 mol/dm³ of HNO₃ to prepare sample solutions. In order to analyze trivalent actinide elements in the sample solution containing a large amount of Fe(III) (>0.1 g) using TRU resin, the effect of Fe(III) concentration on the recovery of Am(III) and reduction effect of Fe(III) to Fe(II) with ascorbic acid were studied. On the basis of results of this study, chemical separation scheme was constructed and Pu and Am in the sample solutions were separated. Thorium and U in the sample solutions were separated with UTEVA resin. High recoveries for all experimented elements were obtained from the analysis of spiked sample solutions, the effectiveness of the method was confirmed.     

Large volume preconcentration and purification for determining the240Pu/<Superscript>239</Superscript>Pu isotopic ratio and <Superscript>238</Superscript>Pu/<Superscript>239+240</Superscript>Pu alpha-activity ratio in seawater

Summary The present paper describes a new analytical method for determining the ²⁴⁰Pu/²³⁹Pu isotopic ratio and ²³⁸Pu/^239+240Pu α -activity ratio in seawater, both of which are important parameters for determining Pu sources in the ocean. Plutonium isotopes were preconcentrated from a large volume of seawater (4700-10800 liter) by solid phase extraction using MnO₂-impregnated fibers and eluted into 3M HCl. After the elution, the Pu species of all oxidation states were converted to Pu(IV) using NaNO₂, purified by solvent extraction using thenoyltrifluoroacetone (TTA)-benzene, and concentrated in 5 ml of 0.2M HNO₂. The ²⁴⁰Pu/²³⁹Pu and ²³⁸Pu/^239+240Pu ratios in the 5-ml final solution were determined by inductively coupled plasma-mass spectrometry (ICP-MS) and α-spectrometry, respectively. A pg level of Pu, which was a sufficiently large amount for the determination, was obtained by the solid phase extraction. Through the redox conversion and solvent extraction, the Pu species, such as Pu(III), Pu(IV) and Pu(VI), were collected at a high recovery of 96±2% (n=3) despite the presence of large amounts of Mn, and interfering ²³⁸U (3.3 μg^. l^-1in seawater) was effectively removed with a decontamination factor of 1.7·10⁷. The accuracy of the method for the ²⁴⁰Pu/²³⁹Pu ratio was verified using reference materials of seawater and a terrestrial soil sample. The present technique was applied to the determination of the ²⁴⁰Pu/²³⁹Pu and ²³⁸Pu/^239+240Pu ratios in coastal and oceanic water.     

Isolation of iron and strontium from liquid samples and determination of Fe and Sr in liquid radioactive waste

This paper describes the method of isolating iron and strontium from liquid samples with a low concentration of ions that enables simple and rapid determination of and . The method consists of binding (concentrating) Fe and Sr at the cation exchanger Amberlite IR-120, their elution from cation exchanger with 4 M HCl or 8 M HNO₃, isolating Fe on the TRU extraction chromatographic column with 4 M HCl or 8 M HNO₃, and isolating Sr on the Sr.spec column with the mixture of 8 M HNO₃+2 M HCl or 5 M HNO₃. After the isolation, is determined by liquid scintillation counting with scintillation solution, while activity of is obtained by Cherenkov counting in 5 M HNO₃. It was shown that successive counting can be used for simultaneous determination of activity. The activity ratio of (up to 20:1) and vice versa does not impact the determination. is also determined immediately after isolation. The measurements in α,β mode can be used to verify any presence of α-emitter (americium) in the fraction of iron and to correct the result. The method was tested by determining and in model samples and radioactive waste samples. The paper also shows that Fe and Zn can be bound to the TEVA and TRU resins from the solutions of HCl, HNO₃, and mixture of HCl+HNO₃. The binding strength depends on the type of resin and the concentration of the acid or the concentration of acids in the mixture. These resin and acids can be used for mutual separation of Fe and Zn and their separation from other elements.     

Radiochemical separation of <Superscript>67</Superscript>Ga from Zn and Cu using the adsorbent resin Amberlite XAD-7

Summary A column chromatography was developed using a nonionic, polar adsorbent resin Amberlite XAD-7 for routine radiochemical separation of ⁶⁷Ga from Zn and Cu. 7M HCl was found to be the optimum concentration for adsorption of ⁶⁷Ga and elution of both Zn and Cu. Distilled water was used for elution of ⁶⁷Ga from the column. The optimum flow rate of the solutions on to the column was 5 ml/min. The concentrations of Zn and Cu in the final product (30 ml), measured by a polarography method, were 2.0 and 0.5 ppm, respectively. A solvent extraction method, using diisopropyl ether/7M HCl system was also tested to perform the same separation and a comparison between the two methods was made. The radiochemical chromatographic separation system is simple in design and easy to operate for separations in a hot cell.     

<Superscript>47</Superscript>Sc production development by cyclotron irradiation of <Superscript>48</Superscript>Ca

The therapeutic radionuclide ⁴⁷Sc was produced through the ⁴⁸Ca(p,2n) channel on a proton beam accelerator. The obtained results show that the optimum proton energies are in the range of 24–17 MeV, giving the possibility to produce ⁴⁷Sc radionuclide containing 7.4% of ⁴⁸Sc. After activation, the powdery CaCO₃ target material was dissolved in HCl and scandium isotopes were isolated from the targets. The performed separation experiments indicate that, due to the simplicity of the operations and the chemical purity of the obtained ⁴⁷Sc the best separation process is when scandium radioisotopes are separated on the 0.2 µm filter.     

Determination of radioactive strontium in seawater

This paper describes the procedures of isolating strontium and yttrium from seawater that enable the determination of ^89,90Sr. In one procedure, strontium is directly isolated from seawater on the column filled with Sr resin by binding of strontium to the resin from 3 M HNO₃ in a seawater, and successive elution with HNO₃. In others, strontium is precipitated from seawater with (NH₄)₂CO₃, followed by isolation on a Sr column or an anion exchange column. It is shown that strontium precipitation is optimal with concentration of 0.3 M (NH₄)₂CO₃ at pH = 11. In these conditions, 100% Y, 78% Sr, 80% Ca and 50% Mg are precipitated. Strontium is bound on to Sr column from 5 to 8 M HNO₃, separated from other elements by elution with 3 M HNO₃ and 0.05 M HNO₃. Strontium and yttrium are bound on to anion exchange column from alcoholic solutions of nitric acid. The optimum mixture of alcohols for sample binding is a mixture of ethanol and methanol with the volume ratio 1:3. Strontium and yttrium are separated from Mg, Ca, K, and other elements by elution with 0.25 M HNO₃ in the mixture of ethanol and methanol. After the separation, yttrium and strontium are eluted from the column with water or methanol.In the procedure of direct isolation from 1 l of the sample, the average recovery of 50% was obtained. In the remaining two procedures, the strontium recovery was about 60% for the Sr column and 65% for anion exchange column. Recovery of yttrium is about 70% for the anion exchange column. It turned out that the procedure with the Sr resin (direct isolation and isolation after precipitation) is simpler and faster in the phase of the isolation on the column in comparison with the procedure with the anion exchanger. The procedure with the anion exchanger, however, enables the simultaneous isolation of yttrium and strontium and rapid determination of ^89,90Sr. These procedures were tested by determination of ^89,90Sr on liquid scintillation counter and Cherenkov counting in 5 M HNO₃. Obtained results showed that activity of 50 mBq l⁻¹ of ^89,90Sr and higher can be simultaneously determined.     

Separation of no-carrier-added <Superscript>149</Superscript>Gd from <Superscript>12</Superscript>C activated natural praseodymium matrix

¹⁴⁹Gd was produced from the ¹²C induced reaction on natural praseodymium target. No-carrier-added (nca) ¹⁴⁹Gd was separated from the bulk target matrix by liquid–liquid extraction (LLX) using cation exchanger di-(2-ethylhexyl)phosphoric acid (HDEHP) dissolved in cyclohexane. High separation factor of 2,450 was achieved at the optimal experimental condition when 1% HDEHP and 0.1 M HCl were used as organic and aqueous phases respectively. The result was also compared with the previous reports.     

Continuous separation of Sr, Y and some actinides by mixed solvent anion exchange and determination of 89,90Sr, 238,239Pu and 241Am in soil and vegetation samples

Methodology for the determination of ^89,90Sr, Am and Pu isotopes in complex samples is given. Methodology is based on simultaneous isolation of Sr, Y and actinides from samples by mixed solvent anion exchange chromatography, mutual separation of ^89,90Sr and ⁹⁰Y from actinides, mutual separation of Th, Pu and Am by extraction chromatography, quantitative determination of ^89,90Sr by Cherenkov counting and quantitative determination of Pu and Am isotopes in soil and vegetation samples by alpha spectrometry. It is shown that Y and Sr can be efficiently separated from alkaline, alkaline earth and transition elements as well as from lanthanides and actinides on the column filed by strong base anion exchanger in nitrate form and 0.25?M HNO₃ in mixture of ethanol and methanol as eluent. It is also shown that Pu, Am and Th strongly binds on the mentioned column, can be separated from number of elements and easily be eluted from column by water. After elution actinides were mutually separated on TRU column and electrodeposited on stainless steel disc. Examination of conditions of electrodeposition was shown that chloride-oxalate electrolyte with addition of DTPA in presence of sodium hydrogen sulphate in cell with cooling and rotating platinum anode enables deposition of actinides within 1?h by 0.8?A?cm^?2 current density. Obtained peaks FWHM for Pu, Am and Th isotopes are between 27 and 40?keV. Scanning electron microscopy picture and ED XRF analysis of electroplated discs showed that actinide deposition is followed by iron oxide formation on disc surface. The methodology was tested by determination of ^89,90Sr, Am and Pu isotopes in ERA proficiency testing samples (low level activity samples). Obtained results shows that ^89,90Sr, ²⁴¹Am and ^238,239Pu can be simultaneously separated on anion exchange column, ^89,90Sr can be determined by Cherenkov counting with a satisfactory accuracy and limit of determination within 1?C3?days after separation. ²⁴¹Am and ^238,239Pu can easily be separated on TRU column and determined after electrodeposition with acceptable accuracy within 1?day.     

<Superscript>239</Superscript>Np as a tracer of <Superscript>237</Superscript>Np in effluent samples and low level nuclear waste

In this paper a technique to separate and measure both isotopes (²³⁷Np and ²³⁹Np) together is presented. A combined shape pulse discrimination liquid scintillation measurement with gamma-spectrometry, permits a precise measurement after the radiochemical separation. This technique was carried out by using an Eichrom chromatographic column (TEVA) as the first step of a more complete method, applied in the Nuclear Regulatory Authority, to separate actinides in nuclear waste and liquid effluents. The MCA is 0.08 Bq/l by alpha-spectrometry and 0.22 Bq/l (2σ) by liquid scintillation counting (LSC) for 93.7% of measurement efficiency and 98.4% of chemical recovery.