Seperation of neptunium from irradiated uranium targets

A new chemical method based in two separation steps was developed to isolate²³⁵Np from uranium targets irradiated with charged particles. Neptunium and plutonium are separated from uranium and most of the fission products by ion exchange. Then, neptunium is isolated from plutonium and remaining contaminants by extraction chromatography with tributyl phosphate in hydrochloric acid solution. High decontamination was achieved.     

A study of separation methods of 178m2Hf from irradiated ytterbium targets

The source material for the study of X-ray induced γ emission,^178m2Hf was obtained as Hf(OH)₄ by a variety of separation methods, such as precipitation, solvent extraction and ion exchange chromatography to isolate ^178m2Hf from an ytterbium target with a copper substrate, after irradiation in a cyclotron with α particles. The target was prepared by vacuum filtration technology. The overall chemical yield and decontamination factors of this separation process were measured with radioactive tracers. The results show that the chemical yield of the whole process is about 69 % for hafnium and the decontamination factor is very good for ⁶⁵Zn (~10⁵) and good for ¹⁷³Lu (~10³).     

Uranium/plutonium and uranium/neptunium separation by the Purex process using hydroxyurea

Hydroxyurea dissolved in nitric acid can strip plutonium and neptunium from tri-butyl phosphate efficiently and has little influence on the uranium distribution between the two phases. Simulating the 1B contactor of the Purex process by hydroxyurea with nitric acid solution as a stripping agent, the separation factors of uranium/plutonium and uranium/neptunium can reach values as high as 4.7·10⁴ and 260, respectively. This indicates that hydroxyurea is a promising salt free agent for uranium/plutonium and uranium/neptunium separations.     

Uranium/plutonium and uranium/neptunium separation by the Purex process using hydroxyurea

Hydroxyurea dissolved in nitric acid can strip plutonium and neptunium from tri-butyl phosphate efficiently and has little influence on the uranium distribution between the two phases. Simulating the 1B contactor of the Purex process by hydroxyurea with nitric acid solution as a stripping agent, the separation factors of uranium/plutonium and uranium/neptunium can reach values as high as 4.7·10⁴ and 260, respectively. This indicates that hydroxyurea is a promising salt free agent for uranium/plutonium and uranium/neptunium separations.     

Evaluation of methods for the assay of neptunium and other long-lived actinides in environmental matrices

Inductively coupled plasma mass spectrometry (ICP-MS) and neutron activation analysis (NAA) have been investigated as alternatives to alpha-spectrometry for the low-level determination of²³⁷Np and other actinides in environmental matrices. ICP-MS in particular, has been shown here to offer suitable sensitivity, precision and accuracy compared to the other techniques, with considerably faster sample throughput relative to radiometric and activation approaches. Added advantages of ICP-MS are found to include the abilities to determine other long-lived actinides simultaneously and to quantify²³⁹Pu:²⁴⁰Pu ratios. The neutron activation analysis approach was found to be particularly prone to interference especially from uranium nuclides.     

One step ion exchange process for the radiochemical separation of americium, plutonium and neptunium in sediments

A radiochemical separation is presented for americium, plutonium and neptunium from sediment samples by using an unique anionic exchange process. An oxidation-reduction step was introduced in the classical procedure of the radiochemical determination of transuranic elements in order to control the valence of the separated elements.     

Nano-crystalline zirconia: a viable adsorbent for the column chromatographic separation of 58Co from neutron irradiated nickel targets

Owing to the high chemical reactivity of molten uranium alloys, the use of traditional graphite crucibles for casting fuel slugs for a sodium-cooled fast reactor (SFR) is problematic. Moreover, rare earth (RE) elements retained in the fuel slugs for an SFR, which are extracted from the spent fuel by pyro-processing, are more reactive than uranium melt. Therefore, in this study, Y₂O₃ single-layer coatings with thicknesses of approximately 50, 70, and 120 μm and double-layer coatings of TaC/Y₂O₃ and Y₂O₃/TaC were plasma-sprayed onto niobium substrates and tested for thermal shock resistance and compatibility against U–10 wt% Zr and U–10 wt% Zr–5 wt% RE melt. The Y₂O₃ single-layer coating, regardless of coating thickness, and the TaC/Y₂O₃ double-layer coating showed good contact at the interface between the coating and the niobium substrate, with no deterioration after the thermal cycling test. In the interaction studies, the single- and double-layer coatings showed good compatibility with the U–Zr melt. However, the Y₂O₃ coatings with thicknesses of approximately 50 and 70 μm showed severe penetration of the U–Zr–RE melt and reacted with the niobium substrate. The single-layer Y₂O₃ coating with a thickness of 120 μm and the double-layer TaC/Y₂O₃ coating exhibited the most promising performance among the candidate coatings.     

Rapid separation of actinides and radiostrontium in vegetation samples

A new rapid method for the determination of actinides and radiostrontium in vegetation samples has been developed at the Savannah River Site Environmental Lab (Aiken, SC, USA) that can be used in emergency response situations or for routine analysis. The actinides in vegetation method utilizes a rapid sodium hydroxide fusion method, a lanthanum fluoride matrix removal step, and a streamlined column separation process with stacked TEVA, TRU and DGA Resin cartridges. Lanthanum was separated rapidly and effectively from Am and Cm on DGA Resin. Alpha emitters are prepared using rare earth microprecipitation for counting by alpha spectrometry. The purified ⁹⁰Sr fractions are mounted directly on planchets and counted by gas flow proportional counting. The method showed high chemical recoveries and effective removal of interferences. The actinide and ⁹⁰Sr in vegetation sample analysis can be performed in less than 8 h with excellent quality for emergency samples. The rapid fusion technique is a rugged sample digestion method that ensures that any refractory actinide particles or vegetation residue after furnace heating is effectively digested.     

Improved separation method for determining actinides in soil samples

Radionuclides have been identified as a significant source of contamination at many United States Department of Energy (DOE) sites. As a result, reliable and accurate methods to determine actinide content in environmental samples have become increasingly important. Therefore, an improved analytical scheme using a series of actinide-selective extraction chromatography (Tru-Spec, Teva-Spec) and ion-exchange (Diphonix) resins was designed to satisfy the requirements of both alpha spectrometry and inductively coupled plasma mass spectrometry (ICP-MS). Alpha spectrometry required the sequential isolation of the actinides, whereas ICP-MS required only a group separation of the actinides. The separation schemes were designed to allow analysis of the actinides in soil, whether the soils were acid leached or totally dissolved through fusion. For those analytes present as contaminants (^239/240Pu,²⁴¹Am), the laboratory results agreed favorably with the accepted values for several reference soils. However, for the acid digestion procedure, the results for matrix constitutents (²³⁸U,²³⁴U,²³²Th) were quite low because the silicate matrix was not decomposed. The sodium hydroxide fusion technique described allowed accurate analysis of both matrix constituents and contaminants because a total dissolution was achieved.     

用于三价锕镧分离的萃取剂的合成与表征

以6,6'-二氰-2,2'-联吡啶为原料,经两步反应,合成了6,6'二(5,6二乙基-1,2,4-三嗪-3-基)-2,2'-联吡啶.第一步改变条件使反应时间由17d缩短到3d,得到的中间体和目标产物经元素分析、IR,1 HNMR和MS等表征确认.此外,对反应机理进行了初步探讨.     

Concentration and separation of actinides from urine using a supported bifunctional organophosphorus extractant

A method has been developed to isolate quantitatively the actinide elements (as a group) from urine samples and to produce near massless electrodeposits suitable for high-resolution α-spectrometry. The actinides are concentrated from the bulk urine sample by coprecipitation with calcium phosphate. The precipitate is then ashed, dissolved in dilute nitric acid and passed through a column of octyl(phenyl)-N,N-diisobutylcarbamoylmethylphosphine oxide (CMPO) dissolved in tributyl phosphate (TBP) supported on an inert substrate (Amberlite XAD-7) which absorbs the actinides. The actinides are stripped from the column with dilute ammonium hydrogenoxalate, electrodeposited on a stainless-steel disk and counted on an α-spectrometer. Recoveries of added tracers are uniformly high (? 90%) so that samples can be routinely run without yield monitors, permitting an α peak anywhere in the spectrum to be detected with few interferences. Detection limits are influenced only by the available sample size, counting time and counter backgrounds.     

Separation of heavier rare earths from neutron irradiated uranium targets

A radiochemical method is described for the separation of heavier rare earths from the fission of uranium. The method is particularly suitable for the separation of low yield (10⁻⁵%–10⁻⁷%), highly asymmetric rare earth fission products viz.^179,177Lu,¹⁷⁵Yb,¹⁷³Tm,^172,171Er,¹⁶⁷Ho and^161,160Tb in the neutron induced fission of natural and depleted uranium targets. Additional separation steps have been incorporated for decontamination from²³⁹Np (an activation product) and^93-90Y (a high fission-yield product) which show similar chemical behaviour to rare earths. Separation of individual rare earths is achieved by a cation exchange method performed at 80°C by elution with α-hydroxyisobutyric acid (α-HIBA).     

Behavior of Na and K in the extraction process of lithium isotope separation

Russian Chemical Bulletin - The extraction behavior of Na and K during lithium isotope separation using benzo-15-crown-5 (B15C5) in chloroform as the extractant was investigated. It was found that...     

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.     

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.     

Rapid sequential separation of actinides using Eichrom's extraction chromatographic material

The presence of ²²⁶ Ra in an estuary formerly affected by direct discharges of waste from a phosphate fertilizer complex has been investigated. Specific activities ranging from 3.6 to 45.2 mBq/l have been detected. In general, activity levels are lower than those detected when direct discharges were carried out. However, there is still a clear contamination due to the disposal of phosphogypsum in open air piles by the river. Moreover, it seems that ²²⁶ Ra is being redissolved from the contaminated bed sediments, which also contributes to an enhancement in the activity levels of the estuary waters.     

Automated pressurized injection system for the separation of actinides by extraction chromatography

This article describes a novel separation scheme developed for an automated system to efficiently separate actinides in individual fractions. The automated pressurized injection (PI) system developed allows precise collection of high-purity actinide fractions (≥99 %) at elevated flow rates (15–30 mL min^?1) using two extraction chromatographic TEVA and DGA resins. This system is sufficiently robust to enable the use of highly viscous acid media, limit acid corrosion, and tolerate large amount of gases generated by redox reactions by some of the reagents. The PI system was successfully applied to the separation of actinides in individual fractions (recovery yield ≥97 % for Th, U, Np, Pu, and Am) and shows the absence of cross contamination even with highly concentrated actinide solutions. The methodology was also applied to the measurement of actinides in large spiked soil samples.