Sequential separation of transuranic elements and fission products from uranium metal ingots in electrolytic reduction process of spent PWR fuels

A sequential separation procedure has been developed for the determination of transuranic elements and fission products in uranium metal ingot samples from an electrolytic reduction process for a metallization of uranium dioxide to uranium metal in a medium of LiCl-Li₂O molten salt at 650 °C. Pu, Np and U were separated using anion-exchange and tri-n-butylphosphate (TBP) extraction chromatography. Cs, Sr, Ba, Ce, Pr, Nd, Sm, Eu, Gd, Zr and Mo were separated in several groups from Am and Cm using TBP and di(2-ethylhexyl)phosphoric acid (HDEHP) extraction chromatography. Effect of Fe, Ni, Cr and Mg, which were corrosion products formed through the process, on the separation of the analytes was investigated in detail. The validity of the separation procedure was evaluated by measuring the recovery of the stable metals and ²³⁹Pu, ²³⁷Np, ²⁴¹Am and ²⁴⁴Cm added to a synthetic uranium metal ingot dissolved solution.     

Trennung von spaltprodukten durch Extraktionschromatographie

The separation of fission products which form anionic species in mineral acids and of uranium and neptunium from samples of neutron-irradiated uranium is described. The method used is extraction chromatography with tri-n-butylphosphate (TBP) and di-(2-ethylhexyl)-orthophosphoric acid (HDEHP) as extractants and polytrifluoromonochloroethylene powder as the solid support. In the first column Zr, U and Np are extracted with TBP from 8N HNO₃/NaClO₃. In the second column, HDEHP is applied as extractant and 9N HCl/NaClO₃ as the mobile phase for the isolation of Nb, Sb, and I, and in the third column (HDEHP), the rare earths and Mo are extracted from 0.1N HCl. Finally with the fourth column (TBP), Te and Tc are isolated from 6N HCl. These four groups of elements are further separated by elution from the columns. From the final effluent containing Ru, Rh, Cs, Sr, and Ba, Ru is distilled from HClO₄, and Rh is precipitated with NH₄OH. The determination of chemical yields with X-ray fluorescence techniques is described for Zr, Mo, Te, Cs, Ce and U.

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Aus einer Dissertation, Mainz 1967.     

Radiochemical measurement of <Superscript>237</Superscript>Np in a solution of mixed radionuclides: Experiences in chemical separation and alpha-spectrometry

A radiochemical procedure is described for the measurement of 0.1 Bq ²³⁷Np in a solution containing similar activity concentrations of Th, U, Pu and Am as well as activity concentrations of ⁶⁰Co, ⁹⁰Sr and ¹³⁷Cs one hundred times higher. A tracer of ²³⁹Np (milked from ²⁴³Am) was used as an isotopic spike for chemical yield determination. The relationship between gamma-counting geometries for ampoule (liquid) and NdF₃ (solid) ²³⁹Np sources was established so that Np chemical yields could be measured by a comparative method. Efficiencies of alpha-spectrometers for ²³⁷Np in NdF₃ sources were measured by a bootstrap technique. Two sets of experiments were designed and used to test out the procedure.     

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.     

Neutron activation analysis of pure uranium: Preconcentration of impurity elements

We have developed a radiochemical neutron activation analysis technique (RNAA) of pure uranium with using extraction chromatographic separation of ²³⁹Np from impurity elements in TBP-6M HNO₃ media. The estimation of influence of fission products of ²³⁵U on the results by radiochemical neutron activation analysis has been carried out. For it we have performed NAA with preconcentration of impurity elements. Experiments show that in this case the apparent concentration of Y, Zr, Mo, Cs, La, Ce, Pr, Nd exceeds the true concentration by 2500–3000 times. Therefore, determination of these elements is not possible by RNAA. This technique allowed to use the determination of 26 impurity elements with detection limit 10⁻⁵–10⁻⁹% by mass. This developed technique may be used for the determination of impurities in uranium and its compounds.     

Separation of zirconium,niobium, cerium and ruthenium on chitin and chitosan columns for the determination of cesium in nuclear fuel solutions

Nuclear fuel solutions atpH=2.5 can be passed through 7×1 cm chitin or chitosan columns to fix the Zr, Nb, Ce and Ru radioisotopes. This rapid and quantitative separation clears the γ-ray spectrum of the solution from the main activity contribution and leaves the¹³⁷Cs spectrum alone for accurate Cs determination. The process can be extended to radioactive waste waters.     

The preparation of the 239Np tracer from 243Am and the purification of the stock solution

The present work describes preparation of ²³⁹Np tracer from ²⁴³Am stock solution and the purification of this solution from ferric cation. The method of the preparation of tracer involves stabilization of Np(IV) by ascorbic acid and ferric nitrate, separation of ²³⁹Np from ²⁴³Am by extraction chromatography and determination of recoveries of ²³⁹Np by means of gamma spectroscopy. We used the commercially available sorbents TEVA^®Resin for the ²³⁹Np preparation and DGA Resin for ²⁴³Am purification. All sorbents were purchased from Eichrom Industries, Inc. The first eluate from the column can be stored for a future preparation of the tracer and fraction with ²³⁹Np will be used to monitor radiochemical yield of ²³⁷Np.     

Neptunium distribution in a high acid first cycle Purex Process

This work deals with the extraction behavior of neptunium in a high acid Purex Process. The composition of PWR fuel type with 3.2% enrichment, 500 MWd/t burn-up and 100 d cooling time was considered. Two consecutive cold runs were performed in a mock-up facility at IPEN-CNEN/SP with simulated feed solutions containing: 3M HNO₃; 1M U; 455 g²³⁷Np labeled with²³⁹Np; 15 mg Zr l^–1, 12 mg Ce l^–1, 7 mg Ru l^–1 and 13 mg Mo l^–1 traced with active isotopes⁹⁵Zr,¹⁴¹Ce,¹⁰³Ru and⁹⁹Mo as FP. A 30 vol% TBP/n-dodecane was used as solvent. Countercurrent experiments were carried out using two 16 stages plexiglass mixer-settlers, at 25°C, during 21 h continuous operation, with O/A ratio of 2 in the extraction section and 9 and 13 in the 1st and 2nd scrubbing sections, respectively. For a 65% organic loading, ca. 77% of neptunium remains in the waste stream, without any Np valence adjustment.     

Milking process for the preparation of 239Np

A milking process is described for preparing ²³⁹Np from ²⁴³Am. The process includes the stabilization of Np(IV) with ascorbic acid, isolation of Np(IV) by extraction with TOPO/dodecane and stripping of Np with (NH₄)₂CO₃. The yield amounts to 60%. During milking, about 2% of the ²⁴³Am ends up in the scrub which is collected and reprocessed together with the remaining feed after 25 operations using extraction chromatography.     

Extraction of137Cs by cobalt dicarbolide

The possibility of the use of chlorinated cobalt dicarbolide, H⁺C₄B₁₈H₁₅Cl₇Co⁻, it nitrobenzene for the selective extraction of¹³⁷Cs from mixtures of⁹⁵Zr−⁹⁵Nb,¹⁰⁶Ru-¹⁰⁶Rh and¹⁴⁴Ce was studied. The effect of aqueous phase acidity on the distribution ratio of Cs, Ru and Zr as well as the effect of the amount of isotopic and non-isotopic carriers of alkali metals on the distribution ratio were determined. Separation factors for cesium from ruthenium, zirconium and cerium were calculated, all being extracted from nitric acid solutions. The efficiency of cesium separation was verified by gamma-spectrometry.     

A simple and effective method for the purification of californium from other elements

The distribution coefficients of californium and other elements between an anion exchange resin and alcohol solutions of nitric acid of different concentrations have been determined. An effective method is suggested for the purification of californium from other elements which are slightly adsorbed when Cf is concentrated on an anion exchanger from 0.5–1.0N solutions of nitric acid containing 95–90% alcohol; Cf is subsequently eluted with a 0.5N HNO₃ solution in 85% CH₃OH and simultaneously separated from the elements which are strongly adsorbed on the anion exchange resin. Under the chosen conditions the coefficients of californium purification were determined for a number of elements; the values are 5.4·10²–1.8·10³ for Al, Ca, Fe and ∼10³–10⁵ for Am, Pm, Nd, Ce, Pb, Bi and Na, for one cycle.     

Redox Behavior of Neptunium(V) in Tributyl Phosphate and <Emphasis Type="Italic">N</Emphasis>,<Emphasis Type="Italic">N</Emphasis>-Dihexyl Octanamide Extractants Dissolved in <Emphasis Type="Italic">n</Emphasis>-Dodecane

Spectrophotometric investigations have been carried out on the disproportionation of Np(V) to form Np(IV) and Np(VI) in 1.1 mol⋅L⁻¹ solutions of tributyl phosphate (TBP) and in N,N-dihexyl octanamide (DHOA) in n-dodecane medium. The Np(V) was found to coordinate with Np(IV) in 1.1 mol⋅L⁻¹ TBP solution in n-dodecane to form a mixed valence “cation–cation” complex by bonding through an axial oxo group on Np(V). By contrast, this interaction was less prominent in the case of 1.1 mol⋅L⁻¹ DHOA solutions. The effect of 1-octanol, added as phase modifier, on the disproportionation behavior of Np(V) was also investigated. An attempt was made to calculate the disproportionation/reduction rate constants for Np(V) under the conditions of these studies. Absorbance measurements on the Np stripped from organic phases revealed the occurrence of Np(V) in the aqueous phase.     

Inherent isotope dilution analysis of237Np in spent nuclear fuels

A combined -spectrometric and mass-spectrometric determination of²³⁷Np in spent nuclear fuels using²³⁹Np as an inherent spike has been developed. In spent fuel²³⁹Np is in radiochemical equilibrium with²⁴³Am. Neptunium in the tetravalent state is separated by TTA solvent extraction from the other actinides and most of the fission products and the -activity ratio of²³⁷Np to²³⁹Np is measured. The²³⁷Np activity is via²³⁹Np directly linked to the²⁴³Am mass in a sample, which is determined by mass-spectrometric isotope dilution analysis.     

Rapid determination of low 237Np activities in uranyl nitrate solutions using extraction chromatography and gamma-ray spectrometry

A fast and simple separation method for the determination of low activities of ²³⁷Np in enriched uranyl nitrate solutions (U » 10 mg^.ml^-1) is presented. The extraction chromatographic isolation of neptunium by means of an Ln resin^Ò resulted in high separation factors of neptunium from uranium and a nearly complete removal of other interfering nuclides. The chemical yield was determined through a ²³⁹Np tracer, which was isolated from a ²⁴³Am standard solution during the same separation. The detection limits of 50 mBq^.ml^-1 were obtained by g-ray spectrometry, sufficiently low to meet the requirements of waste management.     

Use of actinides in uncommon oxidation states for their extraction and separation from alkaline solutions

The extraction behavior of Am(IV–VI) from high pH solutions in the presence of carbonates, pyrophosphates or polyphosphates of alkali metals and of Np(VI–VII) from alkaline solutions with acylpyrazolones (1-phenyl-3-methyl-4-benzoylpyrazolone-5, PMBP) and extractants of the phenol type [bis(2-oxy-4-alkyl-benzoil)amin, CAAF] has been studied. The extraction ability of phenolic extractants with respects to Np(VII) is determined generally by its state in the alkaline solution. Maximum extraction is observed when Np(VII) is present as hydroxo complex and minimum extraction, when the solution contains oxo-ions. During the extraction the reduction of Np(VII) to Np(VI) is possible. Hexavalent neptunium can be extracted by phenol extractants too, but more slowly and with smaller distribution coefficients in comparison with Np(VII). The stabilization of transplutonium elements (TPE) in the highest oxidation states in alkaline solutions contaning carbonate and pyrophosphate ions, in combination with extraction by PMBP and CAAF, allows to realize the separation of transplutonium elements which are very similar in their properties. Methods of separation for americium and curium have been developed. They are based on the ability of trivalent curium to be extracted quantitatively from 0.1M sodium pyrophosphate solution (pH 10) and 1.0M potassium carbonate solution (ph 13.4) by PMBP in chloroform and by CAAF in carbon tetrachloride, respectively, with high distribution coefficients, whereas americium which is electrochemically oxidized to Am(VI) in these media, remains in the aqueous phase, since it reduces only to Am(V) when contacting the extractant. The separation factor of the couple Cm(III) Am(VI) is about 10³.     

Recovery of uranium from U3O8 irradiated with thermal neutrons

The extraction of uranium with different concentrations of HDEHP in n-hexane from varying concentrations of nitric acid solutions was investigated. Uranium in the organic phase was quantitatively stripped with a solution containing 8M H₂SO₄ and 6M HCl, the partition coefficient was determined by X-ray fluorescence and U. V. spectrophotometry. The assay of⁹⁵Zr,⁹⁵Nb,²³⁹Np and other gamma-emitters was made with a Ge(Li) detector coupled to a 4096 multichannel analyzer.     

Recent developments in the analysis of transuranics (Np,Pu, Am) in seawater

Summary A procedure is described to extend the current radiochemical method of seawater analysis for Pu and Am including Np. Short-lived ²³⁹Np tracer was prepared by separation from its ²⁴³Am parent. Irish Sea Water reference material (IAEA-381) containing known concentrations of ²³⁷Np, Pu isotopes and ²⁴¹Am was used to test the procedure for small water volumes. Inductively-coupled plasma mass spectrometry (ICP-MS) was used in addition to alpha spectrometry for measurement of ²³⁷Np in the purified final Np fractions.     

Thermochromatographic separation of americium and neptunium hexafluoroacetylacetonates in the flow of a carrier gas saturated with hexafluoroacetylacetone vapour

Separation of²³⁹Np from²⁴³Am including extraction of Np/IV/ and Am/III/ by thenoyltrifluoroacetone solution in benzene, transformation of thenoyltrifluoroacetonates into volatile hexafluoroacetylacetones in the flow of a carrier gas saturated with hexafluoroacetylacetone vapours are described.     

The adsorption behaviour of99Mo(VI),238U(VI),95Zr(IV) and95Nb(V) on alumina

The distribution of Mo(VI) and the interfering radiocontaminants U(VI), Zr(IV) and Nb(V) have been investigated between chromatographic alumina and aqueous hydrochloric acid solutions of concentrations ranging from 0.5M to 11M. At low acidities (less than 1M HCl) the distribution coefficients increase with the decrease of acid concentration, while in the region of 2–4M they increase with the increase of the acid concentration. Above 4M HCl, the increase inK _D continues with the acid concentration for both Zr(IV) and Nb(V), but constant values are reached for U(VI) and Mo(VI).     

Rapid determination of 237Np in soil samples by multi-collector inductively-coupled plasma mass spectrometry and gamma spectrometry

A radiochemical procedure is developed for the determination of ²³⁷Np in soil with multi-collector inductively-coupled plasma mass spectrometry (MC-ICP-MS) and gamma-spectrometry. ²³⁹Np (milked from ²⁴³Am) was used as an isotopic tracer for chemical yield determination. The neptunium in the soil is separated by thenoyl-trifluoracetone extraction from 1 M HNO₃ solution after reducing Np to Np(IV) with ferrous sulfamate, and then purified with Dowex 1 × 2 anion exchange resin. ²³⁹Np in the resulting solution is measured with gamma-spectrometry for chemical yield determination while the ²³⁷Np is measured with MC-ICP-MS. Measurement results for soil samples are presented together with those for two reference samples. By comparing the determined value with the reference value of the ²³⁷Np activity concentration, the feasibility of the procedure was validated.