Hydroxylamine derivative in the Purex Process

N,Ndiethylhydroxylamine (DEHAN) can rapidly reduce Pu(IV) and Np(VI) extractable with trinbutyl phosphate (TBP) to Pu(III) and Np(V) unextractable with TBP in nitric acid solution. In order to apply DEHAN in the purification cycle step of U (noted as contactor 2D) of the secondcycle of the Purex Process to separate Np and Pu from U, the reduction of Np(VI) and the stability of Np(V) with DEHAN and the singlestage reduction extraction and backextraction of Np(VI) have been studied according to the experimental conditions of contactor 2D. The results show that more than 99% of Np(VI) can entirely be reduced to Np(V) with DEHAN within a few minutes either in aqueous or in organic phase containing uranium and without containing uranium, and more than 99% of Np(VI) can be backextracted from the organic to the aqueous phase with DEHAN as a reductant. More than 99% of Np(V) exists in nitric acid solution at least for 8 hours in presence of 0.01 mol/l DEHAN. These results are of benefit to the cascade extractionseparation of U/Np in contactor 2D in order to decontaminate Np from U.     

An advanced partitioning process for key elements separation from high level liquid waste

To separate MA(Am,Cm) and some fission product elements(FPs) such as Tc,Pd,Cs and Sr from high level liquid waste(HLLW) systematically,we have been studying an advanced aqueous partitioning process,which uses selective adsorption as the separation method.For this process,we prepared several novel adsorbents which were immobilized in a porous silica/polymer composite support(SiO 2-P).Adsorption and separation behavior of various elements was studied experimentally in detail.Small scale separation tests using simulated HLLW solutions were carried out.Pd(II) was strongly adsorbed by the AR-01 anion exchanger and effectively eluted off by using thiourea.Successful separation of Pd(II) from simulated HLLW was achieved.Tc(VII) also exhibited strong adsorption on AR-01 and could be eluted off by using U(IV) as a reductive eluent.Am(III) presented significantly high adsorbability and selectivity onto R-BTP/SiO 2-P adsorbents over various FPs including Ln(III).The R-BTP adsorbents were fairly stable in 3 M HNO 3,but instable against-irradiation-3M HNO 3.An advanced partitioning process consisting of three separation columns for the target elements separation from HLLW was proposed and the obtained experiment results indicated that the proposed process is essentially feasible.     

Sequential determination of Am, Cm, Pu, Np and U by extraction chromatography

Environmental contamination by artificial radionuclides and the evaluation of their sources require precise isotopic analysis and accurate determination of actinide elements above all plutonium and americium. These can be achieved by alpha spectrometry or by inductively coupled plasma mass spectrometry (ICP-MS) after chemical separation. In the present work, a simple, rapid method has been developed for the sequential separation of actinide elements from aqueous solutions and their determination by alpha spectrometry. Extraction chromatography was applied to the separation of ²⁴¹Am, ²⁴⁴Cm, ^{239 + 240,238}Pu, ²³⁷Np and ^238,235,234U using microporous polyethylene supporting tri-n-octylamine as the stationary phase and hydrochloric acid with and without reducing agents as the mobile phase. Actinide in 9 M HCl solution is introduced into the anion exchange column; Pu (IV), Np (IV) and U(VI) are retained on the column while Am (III) and Cm passed through. Pu is eluted first, reductively, after which, Np and then U are eluted. The method can be applied to all aqueous solutions which do not contain strong complexing or precipitation agents for the elements considered.     

Some studies on the extraction of hexavalent actinide ions from aqueous carboxylic acid media by long-chain amines

The extraction of hexavalent actinides from aqueous carboxylic acid media by tertiary amines was studied. Both U(VI) and Pu(VI) are found to be extracted well whereas Np(VI) was practically inextractable except from acetic acid medium. The absorption spectral studies revealed that the inextractability of Np(VI) is due to its reduction to Np(V). Depending on the diluent used, both tetra and triacetato complexes of U(VI) were found to be present in the organic phase. The absorption spectral studies suggested that the formation of tetraacetato species occurs in the organic phase. An amine extraction method for the separation of U(VI) from a number of metallic impurities using malonic acid medium is suggested.     

Determination of 237Np and Pu isotopes in large soil samples by inductively coupled plasma mass spectrometry

A new method for the determination of (237)Np and Pu isotopes in large soil samples has been developed that provides enhanced uranium removal to facilitate assay by inductively coupled plasma mass spectrometry (ICP-MS). This method allows rapid preconcentration and separation of plutonium and neptunium in large soil samples for the measurement of (237)Np and Pu isotopes by ICP-MS. (238)U can interfere with (239)Pu measurement by ICP-MS as (238)UH(+) mass overlap and (237)Np via (238)U peak tailing. The method provides enhanced removal of uranium by separating Pu and Np initially on TEVA Resin, then transferring Pu to DGA resin for additional purification. The decontamination factor for removal of uranium from plutonium for this method is greater than 1×10(6). Alpha spectrometry can also be applied so that the shorter-lived (238)Pu isotope can be measured successfully. (239) Pu, (242)Pu and (237)Np were measured by ICP-MS, while (236)Pu and (238)Pu were measured by alpha spectrometry.     

Trennschema zur Isolierung von Pu-Np-Zr-Nb-Mo-Tc-Te und U aus Spaltproduktl?sungen

Zusammenfassung Für salzsaure Lösungen bereits bekannte Anionenaustauschertrennungen von Zr-Nb, Zr-Mo und Mo-Tc konnten zu einer Trennung von Zr-Nb-Mo-Tc zusammengefaßt werden, deren quantitativer Verlauf nachgewiesen wurde.Durch Zusatz von Alkohol zu den salzsauren Elutionslösungen konnte ein Trennungsgang zur Isolierung von Zr, Nb, Mo, Tc und U aufgestellt werden. Die Elemente werden aus hochmolarer Salzsäure adsorbiert und durch stufenweise Elution mit gemischten Lösungsmitteln sinkender Gesamtacidität getrennt. Tc, das mit Salzsäure oder Mischungen aus Salzsäure und Alkohol nicht desorbierbar ist, wird mit Salpetersäure eluiert.Es konnte gezeigt werden, daß Te in das Trennschema zur Auftrennung von Zr, Nb, Mo, Tc und U eingefügt werden kann. Eine Trennung von Np und Zr innerhalb des Trennschemas — also durch Adsorption aus hochmolarer Salzsäure und stufenweise Elution — war wegen der Ähnlichkeit der Verteilungskoeffizienten von Np und Zr nicht möglich. Es konnte jedoch eine Vortrennung in eine kleine Np-Fraktion und eine stark mit Np verunreinigte Zr-Fraktion erreicht werden. Für die Nachtrennung von Np und Zr wurde ein bei kleinen HCl-Molaritäten gefundenes Maximum des Verteilungskoeffizienten von Np^V ausgenützt, das eine Trennung beider Elemente durch Aufbringen aus 1,3 m Salzsäure auf den Anionenaustauscher ermöglicht. Zr wird nicht adsorbiert. Np bricht erst mit einer größeren Elutionsmenge 1,3 m Salzsäure durch. Da der ausgearbeitete Trennungsgang an die bereits bekannte Elution des Pu mit 12 m Salzsäure (unter Zusatz von NH₂OH · HCl und NH₄J) angeschlossen werden kann, war es möglich, ein Trennschema aufzustellen, das die Isolierung von Pu, Np, Zr, Nb, Mo, Tc, Te und U aus Spaltproduktlösungen gestattet.

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Summary A procedure has been worked out for the total separation of Zr-Nb-Mo, and Tc by anion-exchange in hydrochloric acid solutions using known single separations of Zr-Nb, Zr-Mo, and Mo-Tc, and proved to be quantitative.Utilizing hydrochloric acid solutions containing alcohol as eluents, a method for the separation of Zr-Nb-Mo-Tc, and U has been developed. Highly concentrated hydrochloric acid solutions of these elements are added to the resin column and eluted sequentially with mixed solvents of decreasing over-all acidity. Tc is not desorbed with hydrochloric acid or mixtures of hydrochloric acid and alcohol; it is removed from the column with nitric acid. Investigations indicated that the separation of Zr-Nb-Mo-Tc-U, and Te is possible. Experiments to include Np in the sequential separation scheme developed, did not yield satisfying results because of the similarity of the elution curves of Zr^IV and Np^V. The eluted Zr was contaminated with Np and required further purification. Based on the measurement of the distribution coefficients of Np^V in hydrochloric acid solutions, showing a maximum of adsorption at low concentrations of hydrochloric acid, a method for the separation of Zr from Np has been developed. The elements in 1.3 M HCl solution are added to the resin column; Zr is not absorbed. The elution is continued with 1.3 M HCl solution to remove Np, which is eluted only with larger volumes of this acid.Since Pu can be removed from the resin column with highly concentrated hydrochloric acid solutions prior to the other elements, the sequential separation scheme makes possible the isolation of Pu-Np-Zr-Nb-Mo-Tc-Te, and U from fission product mixtures.

     

The application of <Emphasis Type="Italic">N</Emphasis>,<Emphasis Type="Italic">N</Emphasis>-dimethylhydroxylamine as reductant for the separation of plutonium from uranium

Both single stage and multi-stages experiments on stripping plutonium with N,N-dimethylhydroxylamine (DMHAN) as reductant with methylhydrozine (MMH) as supporting reductant were carried out. The effect of contact time, temperature, acidity, concentration of DMHAN on back-extraction rate of plutonium was investigated in the single stage experiment. The results demonstrated that the reaction of stripping Pu(IV) in the organic phase (30% TBP–kerosene) 1BF solutions by DMHAN exhibits excellent stripping efficiency. Under the given conditions, the back-extraction rate of plutonium reaches 90% within 2 min. Higher temperature, lower acidity and the increased concentration of DMHAN benifit the stripping reaction. The concentration profile of HNO₃, uranium and plutonium were determined in a multi-stages mixer-settler after the steady state of the back-extraction, and the multi-stages results show that the plutonium can be separated effectively from uranium. The recovery of plutonium and uranium reach 99.995% or over 99.99% respectively. The separation factor of U from Pu (SF_Pu/U) is about 2 × 10⁴.     

Reduction and removal of neptunium from synthetic high level liquid waste by TRPO process

Valency control of neptunium is an important issue in the partitioning of high level liquid waste (HLLW) from power-reactor spent fuel treatment. The redox behavior of neptunium in HLLW is quite different from that in nitric acid because of the effect of the large amount of ions in HLLW. In order to remove neptunium from HLLW, we studied the reduction of neptunium in synthetic HLLW (SHLLW) to maintain its valency at IV so that it can be extracted by TRPO extractant in the well developed Chinese TRPO process. Five different reductants were tested and the reduction behavior was investigated. The influence of some active elements in SHLLW was studied. The mechanism that the reductants react with neptunium through Fe element was supposed and proved by experiments. The reduction rate of Np(V) was highly enhanced by Fe element. Finally, a hybrid reductant was suggested and good reduction efficiency was obtained.     

Biphasic kinetic investigations on the evaluation of non-salt forming reductants for Pu(IV) stripping from tributyl phosphate and N,N-dihexyl octanamide solutions in n-dodecane

The relative stability of different oxidation states of actinide elements is influenced by the nature of complexes formed and redox equilibria in aqueous/non-aqueous solutions. The reduction/stripping studies on Pu(IV) ions from loaded organic phases of 1.1 M tributyl phosphate and of 1.1 M N,N-dihexyl octanamide in n-dodecane were studied using organic soluble tert-butyl hydroquinone (TBH) and aqueous soluble reductants like acetaldoxime (AX) and hydroxyurea (HU). These studies were carried out as a function of reductant and nitric acid concentration (0.5–4 M HNO₃) and of time. The changes in Pu oxidation states were followed by spectrophotometry for TBH and by distribution ratio values for AX and HU as reductants. Spectrophotometric investigations using TBH as reductant showed that it was desirable to strip Pu(III) formed after reduction of Pu(IV) in the organic phase, which may otherwise be reconverted to extractable Pu(IV) by in situ generated HNO₂ from oxidative degradation of TBH to tert-butyl quinone. Similarly, the biphasic reduction/stripping of Pu(IV) using AX and HU as reductant rate was affected adversely with increased aqueous phase acidity. This data will help in the accurate simulation of Pu separation processes using these reductants in mixer-settlers/pulsed columns or centrifugal contactors.     

The studies on absorption behavior of calix[4]-bis-crown-6 chromatographic resin and its application to the separation of HLW

In this paper, to separation Cs(I) effectively from HLW, a kind of chromatographic rein was synthesized through immobiling calix[4]-bis-crown-6 on the macroporous polystyrene -divinylbenzene polymeric material. The synthesized chromatographic resin showed high ability to absorb Cs(I). While the radioactive elements Pu(III), Np(V), U(VI), Th(IV), as well as all of the fission and non-fission products showed almost no sorption towards chromatographic rein. The separation of Cs from HLW can be realized through adjusting the valence of Np and Pu or adding H₂C₂O₄. All the results showed that the application of the new chromatographic rein to the analysis of HLW is possible.     

Partitioning of plutonium and uranium in aqueous medium using hydroxyurea as reducing agent

A new process for the partitioning of plutonium and uranium during the reprocessing of spent fuel discharged from fast reactor was optimised using hydroxyurea (HU) as a reductant. Stoichiometric ratio of HU required for the reduction of Pu(IV) was studied. The effect of concentration of uranium, plutonium and acidity on the distribution ratio (Kd) of Pu in the presence of HU was studied. The effect of HU in further purification of Pu such as solvent extraction and precipitation of plutonium as oxalate was also studied. The results of the study indicate that Pu and U can be separated from each other using HU as reductant.     

Distribution and behaviour of99Tc,237Np,239,240Pu,and241Am in the coastal and estuarine sediments of the Irish Sea

Intertidal coastal and estuarine sediments from 24 sites in the Irish Sea have been analyzed for⁹⁹Tc,²³⁷Np,²³⁸Pu,^239,240Pu and²⁴¹Am. The²³⁷Np activity and²³⁹Pu/²⁴⁰Pu ratio were measured simultaneously by ICP-MS, and⁹⁹Tc was determined by HR-ICP-MS which is ten times more sensitive than Q-ICP-MS.The activities of⁹⁹Tc,²³⁷Np,^239,240Pu and²⁴¹Am were distributed over a wide range of 1.5–70.5, 0.01–13.3, 2.3–1589, 2.6–1894 Bq/kg, respectively. Activities of these radionuclides decreased exponentially with distance from the Sellafield source. The²⁴¹Am/^239,240Pu and²³⁷Np/^239,240Pu ratios were almost constant with distance from the Sellafield. This result suggests that the distribution and behavior of Np and Pu are controlled by complicated factors such as the influence of transport, the variation with time of Np/Pu ratio in the Sellafield discharges and sedimentary mixing processes in the Irish Sea.     

Rapid determination of 237Np and Pu isotopes in water by inductively-coupled plasma mass spectrometry and alpha spectrometry

A new method that allows rapid preconcentration and separation of plutonium and neptunium in water samples was developed for the measurement of ²³⁷Np and Pu isotopes by inductively-coupled plasma mass spectrometry (ICP-MS) and alpha spectrometry. ²³⁸U can interfere with ²³⁹Pu measurement by ICP-MS as ²³⁸UH⁺ mass overlap and ²³⁷Np via peak tailing. The method provide enhanced removal of uranium by separating Pu and Np initially on TEVA Resin, then moving Pu to DGA resin for additional removal of uranium. The decontamination factor for uranium from Pu is almost 100,000 and the decontamination factor for U from Np is greater than 10,000. This method uses stacked extraction chromatography cartridges and vacuum box technology to facilitate rapid separations. Preconcentration is performed using a streamlined calcium phosphate precipitation method. Purified solutions are split between ICP-MS and alpha spectrometry so that long and short-lived Pu isotopes can be measured successfully. The method allows for simultaneous extraction of 20 samples (including QC samples) in 4?C6 h, and can also be used for emergency response. ²³⁹Pu, ²⁴²Pu and ²³⁷Np were measured by ICP-MS, while ²³⁶Pu, ²³⁸Pu, and ²³⁹Pu were measured by alpha spectrometry.     

Hot Test in Mixer Settlers of Alpha Barrier with AHA in PUREX Process

In the PUREX process, the first U-Pu purification cycle (1CUPu) is not efficient enough for the decontamination of uranium flow out of neptunium. In this context, molecules known for their strong complexing power for actinides(IV) in aqueous phase, such as acetohydroxamic acid (AHA) have been tested in batch experiments to strip Np and Pu from TBP solvent loaded with U. A phenomenological model was developed and with the help of this model, a flowsheet of a counter-current alpha barrier process was designed and tested in C17 glove boxes in ATALANTE facility. A decontamination factor DFU/Np of 480 was obtained, higher than DFU/Np required by UNIREP standards.     

Determination of actinide nuclides in water samples from the primary circuit of a research reactor

Primary coolant samples from a research have been analyzed for^239,240Pu,²³⁸Pu,²³⁸U,²³⁷Np and²³⁹Np. The determination of²³⁷Np and²³⁸U was carried out with the help of isotope dilution neutron activation analysis with²³⁹Np or²³⁸Np as tracer. For determination of^239,240Pu and²³⁸Pu alpha spectroscopic isotope dilution analysis with²³⁸Pu as tracer was used.²³⁹Np was determined with the help of isotope dilution analysis using²³⁸Np as tracer. Nuclides were isolated by chemical separation on anionite resin. Before measurement, Pu isotopes were electrolytically deposited on stainless steel plates. Activity ratios referred to²³⁸U were reported. They are helpful for identification of the sources of actinide activity in reactor effluents.     

Gas-phase uranyl, neptunyl, and plutonyl: hydration and oxidation studied by experiment and theory

The following monopositive actinyl ions were produced by electrospray ionization of aqueous solutions of An(VI)O(2)(ClO(4))(2) (An = U, Np, Pu): U(V)O(2)(+), Np(V)O(2)(+), Pu(V)O(2)(+), U(VI)O(2)(OH)(+), and Pu(VI)O(2)(OH)(+); abundances of the actinyl ions reflect the relative stabilities of the An(VI) and An(V) oxidation states. Gas-phase reactions with water in an ion trap revealed that water addition terminates at AnO(2)(+)·(H(2)O)(4) (An = U, Np, Pu) and AnO(2)(OH)(+)·(H(2)O)(3) (An = U, Pu), each with four equatorial ligands. These terminal hydrates evidently correspond to the maximum inner-sphere water coordination in the gas phase, as substantiated by density functional theory (DFT) computations of the hydrate structures and energetics. Measured hydration rates for the AnO(2)(OH)(+) were substantially faster than for the AnO(2)(+), reflecting additional vibrational degrees of freedom in the hydroxide ions for stabilization of hot adducts. Dioxygen addition resulted in UO(2)(+)(O(2))(H(2)O)(n) (n = 2, 3), whereas O(2) addition was not observed for NpO(2)(+) or PuO(2)(+) hydrates. DFT suggests that two-electron three-centered bonds form between UO(2)(+) and O(2), but not between NpO(2)(+) and O(2). As formation of the UO(2)(+)-O(2) bonds formally corresponds to the oxidation of U(V) to U(VI), the absence of this bonding with NpO(2)(+) can be considered a manifestation of the lower relative stability of Np(VI).     

New approaches to reprocessing of oxide nuclear fuel

Dissolution of UO₂, U₃O₈, and solid solutions of actinides in UO₂ in subacid aqueous solutions (pH 0.9–1.4) of Fe(III) nitrate was studied. Complete dissolution of the oxides is attained at a molar ratio of ferric nitrate to uranium of 1.6. During this process actinides pass into the solution in the form of U(VI), Np(V), Pu(III), and Am(III). In the solutions obtained U(VI) is stable both at room temperature and at elevated temperatures (60 °C), and at high U concentrations (up to 300 mg mL^?1). Behavior of fission products corresponding to spent nuclear fuel of a WWER-1000 reactor in the process of dissolution the simulated spent nuclear fuel in ferric nitrate solutions was studied. Cs, Sr, Ba, Y, La, and Ce together with U pass quantitatively from the fuel into the solution, whereas Mo, Tc, and Ru remain in the resulting insoluble precipitate of basic Fe salt and do not pass into the solution. Nd, Zr, and Pd pass into the solution by approximately 50 %. The recovery of U or jointly U + Pu from the dissolution solution of the oxide nuclear fuel is performed by precipitation of their peroxides, which allows efficient separation of actinides from residues of fission products and iron.     

Extraction and stripping behavior of U–Np–Tc ternary system to TBP

Stripping of the nuclides U, Np, Pu, Am, Eu, Zr, Ru and Fe from the loaded TRUEX solvent (0.2M CMPO+1.2M TBP in dodecane) has been carried out with a potassium ferrocyanide solution. In four contacts, 98% or more of U, Pu, Am and Eu could be stripped whereas Zr and Ru recoveries were 94% and 92%, respectively. Further, the co-precipitation of Am, Pu, U and Eu on ferric ferrocyanide precipitate from the CMPO phase has shown high recovery of Am, Pu and Eu but lower for U.     

Wide-area aquatic sampling and analysis for the detection of nuclear proliferation

Nuclear proliferation signature radionuclides can be delivered to the aquatic environs via direct liquid discharges or atmospheric routes. The candidate radionuclides for detection are ³H, ⁹⁰Sr, ⁹⁵Nb, ⁹⁵Zr, ⁹⁹Tc, ¹⁰⁶Ru, ¹²⁵Sb, ¹²⁹I, ¹³⁴Cs, ¹³⁷Cs, ¹⁴⁴Ce, ¹⁴⁷Pm, ^NatU, ²³⁸U, ²³⁵U, ²³⁷Np, ²³⁹Pu, ²⁴⁰Pu, and ²⁴¹Pu. The criteria for detection are the limits of radionuclide analysis, the nature and variability of background oncentrations, and the transport characteristics between the source and sample site. The type of sample to be taken is determined by the signature radionuclides sorption on/in the media sampled. Non-sorbing radionuclides such as ³H, ⁹⁹Tc, and ¹²⁹I are in the water, whereas the Pu radionuclides are in the transported sediments. Results are discussed for monthly releases of radionuclides such as ⁹⁰Sr, ¹³⁷Cs, and ²³⁹Pu for variable flow-rate conditions with typical backgrounds and typical detection limits.     

Dosage du237Np en trances dans l'uranium et le plutonium

The²³⁷Np content of²³⁸Pu or²³⁹Pu samples were determined by the gammaspectrometry of²³⁸Np formed by thermal neutron activation. The measurements were carried out on irradiated²³⁸Pu samples directly, and after the chemical separation of²³⁹Pu samples. The²³⁷Np content of natural uranium was determined from the ratio of the alpha-activities of²³⁸Pu and²³⁹Pu isotopes formed from the decay of neptunium isotopes produced by the activation of²³⁷Np and²³⁸U isotopes, respectively.