Chemical separation and ICP-AES determination of 22 metallic elements in U and Pu matrices using cyanex-923 extractant and studies on stripping of U and Pu

Comprehensive studies have been carried out on the extraction behavior of uranium and plutonium matrices using cyanex-923 extractant. The near total extraction of U/Pu and quantitative separation of 22 metallic elements at trace levels has been established using inductively coupled plasma-atomic emission spectrometry (ICP-AES). The studies carried out on back extraction of U/Pu from organic phase have established the near total recovery of these matrices into the aqueous phase using 1 M Na(2)CO(3) and saturated oxalic acid, respectively.     

Extraction of plutonium(IV) from oxalic acid-nitric acid solutions by Aliquat-336

The extraction of Pu(IV) from oxalic acid-nitric acid mixtures has been investigated using a liquid anion exchanger, Aliquat-336, in xylene. The presence of oxalic acid is known to have adverse effects on the extraction of Pu(IV) by Aliquat-336. The use of cations, Al(III), Fe(III) or Zr(IV) was explored to overcome the effect of oxalic acid on Pu(IV) extraction. The data obtained reveal that Pu(IV) is quantitatively extracted by Aliquat-336, even in the presence of oxalic acid, when Al(III), Fe(III) or Zr(IV) is added. The extracted Pu(IV) can be back-extracted using aqueous ammonium carbonate.     

Extraction of plutonium from acidic media using various phosphine oxides

Extraction, loading and stripping studies of Pu(IV) have been carried out using three phosphine oxides namely Cyanex^Ò-923 (cyn-923), Cyanex^Ò-925 (cyn-925) and TOPO in dodecane from nitric acid medium. All the three phosphine oxides have shown very high extraction of Pu. The order of extraction for Pu by these compounds is cyn-923 > TOPO - cyn-925. Loading of Pu (30.0 mg/l) in 3.0M HNO₃ was carried out using 5% solution of each of the phosphine oxides in dodecane. It was found that even at an organic to aqueous phase ratio of 1:10, the loading of Pu is >96%. From the loaded organic phase, Pu could be almost quantitatively stripped using 0.1 or 0.5M oxalic acid. The extraction of Pu(IV) with cyn-925 has also been carried out from HCl, HNO₃ or HClO₄ (0.5 to 9.1M). The species extracted into the cyn-925/dodecane phase from 3.0M HNO₃ or HCl media was found to be Pu(L)₄ ^.2 cyn-925 where L = NO₃ ^– or Cl^–. Similar species were observed to be formed when dodecane was replaced by xylene, chlorobenzene or o-dichlorobenzene.     

Studies on purification of plutonium from silver ions

Precipitation and solvent extraction methods have been investigated for the purification of plutonium from silver from the solution generated during oxidative dissolution of plutonium oxide using Ag(II) ions. Initial experiments have been carried out using thorium as representative of plutonium. Selecting the optimum conditions, the experiments were repeated with plutonium. The results revealed that Pu can be purified from silver ions either by precipitating silver as silver chloride or silver metal followed by Pu(IV) oxalate precipitation or by selective extraction of Pu(IV) into 20% Aliquat-336 or 30% TBP.     

Synergistic extraction of hexavalent actinides by HTTA and neutral donors-II

Synergistic extraction studies on Np(VI) and Pu(VI) have been carried out as a part of the programme on the synergistic extraction of hexavalent actinides. Extraction of Np(VI) and Pu(VI) were carried out by mixtures of HTTA and TBP in benzene from aqueous perchlorate and nitrate media. Equilibrium constant values for the various reaction equilibria involved were calculated from the data obtained by using slope-ratio as well as Job’s method. The extraction of Np(VI) by the synergistic mixture from 1M nitric acid indicated that the species NpO₂ (TTA) (NO₃). TBP was not involved in the extraction. The log values of K_A, K_AB and β_AB were −1.5, 2.92 and 4.43, respectively for Np(VI) and −1.63, 2.50 and 4.13 respectively for Pu(VI).     

Pu and Am sorption to the Baltic Sea bottom sediments

Sorption of Am and Pu isotopes to bottom sediments of the Baltic Sea has been studied under natural and laboratory conditions. Data obtained from sequential extraction, sorption of Am(III), Pu(IV) and Pu(V) as well as oxidation state distribution experiments have shown that Pu(V) sorption mechanism includes a very fast Pu(V) reduction (reaction rate ≤ 2.33 × 10^?3 s^?1) to Pu(IV) by humic substances and/or by Fe(II) to Pu(IV) and partly to Pu(III). Following reduction Pu isotopes were bound to various components of bottom sediments via ion exchange and surface complexation reactions and a slow incorporation into the crystalline structure of Fe minerals. Kinetics experiments showed that the sorption of Pu(V), Pu(IV) and Am(III) to bottom sediments from natural seawater was controlled by the inert layer diffusion process.     

Extraction of uranium(VI) and plutonium(IV) with some high molecular weight aliphatic monoamides from nitric acid medium

The extraction behavior of U(VI) and Pu(IV) with dioctyloctanamide (DOOA), dioctylethylhexanamide (DOEHA) and diisobutylethylhexanamide (DIBEHA) was investigated from nitric acid medium. With DOOA, U(VI) extraction is higher than that for Pu(IV) upto 5M HNO₃ and the trend is reversed at higher acid concentrations. Extraction yield of U(VI) is higher than that for Pu(IV) in the case of DOEHA and DIBEHA. DIBEHA extraction of Pu(IV) is found to be very small. The lower value of the distribution ratio for Pu(IV) with branched amides was attributed to steric reasons. The possibility of using these amides for separation of U(VI) and Pu(IV) without valency adjustment was explored. Both U(VI) and Pu(IV) are extracted as their disolvates by DOOA and DOEHA.     

Recovery of plutonium from oxalate supernatant using 1-phenyl-3-methyl-4-benzoyl-5-pyrazolone

Summary Extraction of Pu(IV) from oxalate supernatant was carried out employing 1-phenyl-3-methyl-4-benzoyl-5-pyrazolone (PMBP) in xylene as extractant. The conditions for quantitative extraction were determined by the variation of ligand, oxalic acid and nitric acid concentration. Quantitative stripping was achieved using a mixture of 0.4M oxalic acid and 0.4M ammonium oxalate. Extraction of Pu(IV) from synthetic oxalate supernatant solution containing 3M nitric acid and 0.2M oxalic acid was investigated under various loading conditions employing 1-phenyl-3-methyl-4-benzoyl-5-pyrazolone in xylene as extractant. Under uranium loading conditions the Pu extraction decreased significantly while with increased Pu loading whereas the D_Pu value was influenced marginally. The effect of a redox reagent on Pu extraction was also investigated.     

Purification and recovery of plutonium from uranium oxide obtained in the fast reactor fuel reprocessing plant using hydroxyurea as reductant

Spent fuel discharged from Fast Breeder Test Reactor (FBTR) in Kalpakkam is being reprocessed by modified plutonium uranium reduction extraction (PUREX) process using 30% TBP (tributylphosphate) as extractant in the presence of heavy normal paraffin (HNP) as diluent. Partitioning of uranium (U) and plutonium (Pu) is carried out using oxalate precipitation method. Uranium oxide product obtained by this method contains appreciable amount of plutonium which has to be recovered. Recovery of plutonium from this uranium oxide product is carried out by reducing Pu to inextractable Pu(III) using hydroxyurea (HU) and then uranium is extracted into 30% TBP. A small amount of Pu which is extracted in the organic phase is stripped back to aqueous phase by scrubbing with scrubbing agent containing 0.1 M HU in 4 M nitric acid. Similarly U and Pu are co-extracted into 30% TBP and then Pu is removed by scrubbing with 0.1 M HU in 4 M nitric acid. Further decontamination from Pu is obtained in the stripping stages. By this method Pu contamination in the uranium oxide is brought from 7300 ppm to 0.4–3 ppm (wt/wt). This uranium product obtained can be handled on table top.     

Di(2-ethyl hexyl) butyramide and di(2-ethyl hexyl)isobutyramide as extractants for uranium(VI) and plutonium(IV)

The extraction of uranium(VI) and plutonium(IV) from nitric acid into n-dodecane was studied using two isomeric branched alkyl amides, di(2-ethyl hexyl) butyramide (DEHBA) and di(2-ethyl hexyl) isobutyramide (DEHIBA). The extraction ratios of Pu(IV) at relatively high acidities were higher than the corresponding values for U(VI) in the case of DEHBA. However, with DEHIBA the values for Pu(IV) were negligibly small. Pu(IV) was found to be extracted as trisolvate by DEHBA and as disolvate by DEHIBA. U(VI) was extracted by both the amides. From the study of the extraction reactions at different temperatures, it was shown that all the reactions in the present investigation were enthalpy favoured and entropy disfavoured. Separation of Pu(IV) from bulk of U(VI) was feasible. However, the purity of the separated plutonium was not satisfactory in batch extraction studies.     

Stereo- and Regiochemical Effect of N,N-Dialkylamide Extractants on the Speciation of Pu Complexes

The relationship between extractant stereochemistry and their extraction performance has only poorly been established. In order to address a part of this concern, we investigated the Pu(IV) liquid-liquid extraction (LLE) by using the N,N-di-(2-ethylhexyl)butyramide (DEHBA), as well as those of its position isomers. DEHBA (ββ-isomer) and N-(2-ethylhexyl)-N-(oct-3-yl)butyramide (EHOBA or αβ-isomer) were synthesized as a mixture of stereoisomer or stereoenriched (R,S)- and (S,S)-diastereoisomers, and were all assessed for Pu^IV LLE. The results showed that both the position and the stereoisomerism of the aliphatic substituents affect Pu^IV complexation and extraction. We found that Pu extraction is lowered by factor 2 to 4 when the ethyl branching group is closer to the complexing site. UV-vis spectroscopy showed that this extraction decrease was affected by steric hindrance inducing a deprivation of Pu inner sphere complex. Effect of stereoisomerism is highlighted for branching closer to the complexing site (α-position). Enantiopure DEHBA stereoisomers provided similar Pu extraction, whereas a slight decrease could be noticed for the more cluttered stereoenriched (αβ)-isomers, which was also concomitant with a smaller population of inner sphere complex. In contrast, the stereoisomers mixture led to a strong decrease of Pu extraction because of an antagonistic association in the mixed complexes.     

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.     

Preconcentration of plutonium and americium using the Actinide-CUTM Resin for human tissue analysis

A method for the preconcentration of Am and Pu from human tissue solutions (liver, lung, bone etc) using the Actinide-CU Resin (ElChroM Industries) has been developed for their alpha-spectrometric determination. With near 100% recoveries were obtained by preconcentration, subsequent decomposition methods for eluent were developed. Good agreement for Pu and Am determination with the USTUR anion-exchange/solvent extraction method was demonstrated using previously analyzed human tissue solutions and NIST SRMs. The advantages of the preconcentration method applied to human tissue analysis are simplicity of operation, shorter analysis time compared to anion exchange/solvent extraction methods, and capacity to analyze large tissue samples (up to 15 g bone ash per analysis and 500 g soft tissue).     

Evaluation of plutonium(IV) extraction rate between nitric acid and tri‐n‐butylphosphate solution using a glass chip microchannel

Extraction of Pu(IV) with tri‐n‐butylphosphate is performed using a glass chip microchannel to evaluate the extraction rate. Two‐phase flow forms in the microchannel by introducing a solution of Pu(IV) and tri‐n‐butylphosphate with flow rates above 5 μL/min. The Pu(IV) extraction reaction proceeds at the interface between the two phases. To evaluate the extraction rate, the contact time between the two phases is varied from 0.48 to 4.8 s by changing the confluent length of the microchannel and the flow rate. The Pu concentration of each phase collected from the microchannel is measured with an alpha liquid scintillation counter, and the contact time dependence of Pu(IV) extraction is obtained. An extraction model based on diffusion in the microchannel and the reaction at the interface is proposed and applied to determine the extraction rate. The extraction process is assumed to follow pseudo‐first‐order kinetics, and the extraction rate constant of Pu(IV) is determined to be 1.5 × 10^?2 cm/s. The investigation demonstrates that a microfluidic device can be a new tool to determine Pu(IV) extraction rates.     

Studies on the extraction behaviour of plutonium(IV) from mixed aqueous-organic media with sulphoxides

Extraction behaviour of plutonium (IV) from nitric acid media by two long-chain aliphatic sulphoxides, namely, di-n-hexylsulphoxide and di-n-octylsulphoxide has been investigated in the presence of several water-miscible organic solvents to study their possible synergistic effect on metal ion extraction. Methanol, ethanol, n-and iso-propanol, dioxane, acetone as well as as acetonitrile were used as the organic component of the mixed (polar) phase. These additives affected the extraction to varying degrees. Thus, extractability of Pu increases 2–3 fold with increasing concentration (upto 20%) of acetonitrile, acetone, methanol and ethanol while it decreases with increasing concentration of n-and isopropanol. At high concentration of the former, synergism changes into antagonism. Possible reasons for such behaviour are briefly discussed. Among these organic additives, maximum enhancement in the extraction of Pu(IV) was observed in the presence of acetonitrile. The relative increase in extraction was found to be more at lower sulphoxide concentrations.     

Use of organophosphorus extractants impregnated on silica gel for the extraction chromatographic separation of minor actinides from high level waste solutions

Silica-gel has been used as an inert support for the extraction chromatographic separation of actinides and lanthanides from HNO₃ and synthetic high level waste (HLW) solutions. Silica-gel was impregnated with tri-butyl phosphate (TBP), to yield STBP; 2-ethylhexyl phosphonic acid, mono 2-ethylhexyl ester (KSM-17, equivalent to PC-88A), SKSM; octyl(phenyl)-N,N-diisobutyl carbamoylmethylphosphine oxide (CMPO), SCMPO; and trialkylphosphine oxide (Cyanex-923), SCYN and sorption of Pu(IV), Am(III) and Eu(III) from HNO₃ solutions was studied batchwise. Several parameters, like time of equilibration, HNO₃ and Pu(IV) concentrations were varied. The uptake of Pu(IV) from 3.0M HNO₃ followed the order SCMPO>SCYN>SKSM>STBP. With increasing HNO₃ concentration, D _Pu increased up to 3.0M of HNO₃ for STBP, SKSM and SCMPO and then decreased. In the case of Am and Eu with SCMPO, the D values initially increased between 0.5 to 1.0M of HNO₃, remained constant up to 5.0M and then slightly decreased at 7.5M. Also, the effects of NaNO₃, Nd(III) and U(VI) concentrations on the uptake of Am(III) from HNO₃ solutions were evaluated. With increasing NaNO₃ concentration up to 3.0M, D _Am remained almost constant while it was observed that it decreases drastically by adding Nd(III) or U(VI). The uptake of Pu and Am from synthetic pressurized heavy water reactor high level waste (PHWR-HLW) in presence of high concentrations of uranium and after depleting the uranium content, and finally extraction chromatographic column separation of Pu and Am from U-depleted synthetic PHWR-HLW have been carried out. Using SCMPO, high sorption of Pu, Am and U was obtained from the U-depleted HLW solution. These metal ions were subsequently eluted using various reagents. The sorption results of the metal ions on silica-gel impregnated with several phosphorus based extractants have been compared. The uptake of Am, Pu and rare earths by SCMPO has been compared with those where CMPO was sorbed on Chromosorb-102, Amberchrom CG-71 and styrene divinylbenzene copolymer immobilized in porous silica particles.     

Dissolution and extraction of actinide oxides in supercritical carbon dioxide containing the complex of tri-n-butylphosphate with nitric acid

Dissolution of individual actinide oxides (Th, U, Pu, Np), or their mechanical mixtures, as well as of solid solutions U–Pu, U–Np, U–Am and U-Pu-Eu oxides in supercritical fluid carbon dioxide (SF-CO₂) containing the complex of tri-n-butyl phosphate (TBP) with nitric acid (TBP–HNO₃) has been investigated. The effect of the calcination temperature of solid solutions of dioxides on the separation of actinides during supercritical fluid extraction (SFE) has been studied as well. It was shown for the first time that milligram amounts of uranium dioxide could be quantitatively dissolved in (SF-CO₂) containing the TBP–HNO₃ complex and efficiently separated from Pu, Np, and Th during SFE of mechanical mixture of these oxides. On the contrary, both U and Pu are quantitatively dissolved in SF-CO₂–TBP–HNO₃ during SFE from solid solutions of U–Pu dioxide. An increase of the calcination temperature of the mixed U(IV)–Pu(IV) dioxide from 850 to 1200 °C has no influence on the relative extraction yield of these actinides during SFE. To cite this article: T. Trofimov et al., C. R. Chimie 7 (2004).

Résumé

Dissolution d’oxides d'actinides et extraction d’éléments dans le dioxide de carbone supercritique contenant le complexe tri-n-butylphosphate–acide nitrique. La dissolution d’oxydes de Th, U, Pu et Np, de leurs mélanges et de solutions solides U–Pu, U–Np, U–Am et U–Pu–Eu dans le dioxyde de carbone supercritique (CO₂-SC) contenant le complexe tri-n-butyl phosphate–acide nitrique (TBP–HNO₃) a été étudiée, et notamment l’effet de la température de calcination des solutions solides. On montre que quelques milligrammes de UO₂ peuvent être dissous dans le système CO₂-SC–TBP–HNO₃ et être séparés de Pu, Np et Th en traitant un mélange d’oxydes. En revanche, U et Pu sont dissous dans la phase CO₂-SC–TBP–HNO₃ durant le traitement des solutions solides U(IV)–Pu(IV). Une augmentation de la température de calcination de 850 à 1200 °C de ces solutions solides n’a pas d’effet sur le rendement d’extraction des actinides. Pour citer cet article : T. Trofimov et al., C. R. Chimie 7 (2004).     

Solvent extraction studies of plutonium(IV) and americium(III) in room temperature ionic liquid (RTIL) by di-2-ethyl hexyl phosphoric acid (HDEHP) as extractant

Solvent extraction of Pu(IV) and Am(III) from aqueous nitric acid into room temperature ionic liquid (RTIL) by an acidic extractant HDEHP (di-2-ethyl hexyl phosphoric acid) was carried out. The D values indicated substantial extraction for Pu(IV) and poor extraction for Am(III) at 1M aqueous nitric acid concentration. However at lower aqueous nitric acid concentrations (pH 3), the Am(III) extraction was found to be quantitative. The least squares analysis of the extraction data for both the actinides ascertained the stoichiometry of the extracted species in the RTIL phase for Pu(IV) and Am(III) as [PuH(DEHP)₂]³⁺, AmH(DEHP)²⁺. From the D values at two temperatures, the thermodynamic parameters of the extraction reaction for Pu(IV) was calculated.     

Modified TTA method for the determination of plutonium

The spent fuel from Fast Breeder Test Reactor of various burnups from 25 to 155?GWd/te is being reprocessed in CORAL (COmpact Reprocessing of Advanced fuels in Lead shielded cell) using a modified PUREX (Plutonium Uranium Recovery by EXtraction) process. Total plutonium (Pu^{238, 239, 240, 241 & 242}) concentration in the sample is analysed by HTTA (Thenoyl Trifluoro Acetone) extraction method wherever interference from other alpha emitting nuclides (Raffinate) and bulk natural uranium (uranium products) are present "as reported by Milyukov et al. (Analytical chemistry of plutonium, 1967) and Natarajan and Subba Rao (BARC, pp. 38?C43, 2007)". This method requires the addition of corrosive reagents such as NH₂OH.HCl which is a problem in waste disposal for reduction. A salt-free reagent such as Hydroxyurea is studied as a reducing agent which has the ability to reduce both Pu(VI) and Pu(IV) to Pu(III) "as reported by Zhaowu (260(3):601?C606, 2004) and Zhaowu (262(3):707?C711, 2004)". Pu(III) thus formed can be easily oxidised to Pu(IV) by NaNO₂ for the extraction of Pu by HTTA.     

Extraction of uranium (VI), plutonium (IV) and some fission products by tri-iso-amyl phosphate

The extractive properties of tri-isoamyl-phosphate (TAP), an indigenously prepared extractant, and the loading capacity of extraction solvent containing TAP for U(VI) and Pu(IV) ions in nitric solution have been investigated. The dependence of the distribution ratio on the concentration of nitric acid showed that TAP has an ability to extract these actinides, while the fission product contaminants are poorly extracted. The distribution data revealed a quantitative extraction of both U(VI) and Pu(IV) from moderate nitric acidities in the range 2–7 mol · dm^–3. Slope analysis proved predominant formation of the disolvated organic phase complex of the type UO₂(NO₃). 2TAP and Pu(NO₃)₄·2TAP with U(VI) and PU(IV), respectively. On the contrary, the extraction of fission product contaminants such as¹⁴⁴Ce,¹³⁷Cs,⁹Nb.,¹⁴⁷Pr,¹⁰⁶Ru,⁹⁵Zr was almost negligible even at very high nitric acid concentrations in the aqueous phase indicating its potential application in actinide partitioning. The recovery of TAP from the loaded actinides could be easily accomplished by using a dilute sodium carbonate solution or acidified distiled water (0.01 mol · dm^–3 HNO₃) as the strippant for U(VI) and using uranous nitrate or ferrous sulphamate as that for Pu(IV). Radiation stability of TAP was adequate for most of the process applications.