Electrodeposition of actinides for alpha-spectrometry

The electrodeposition of the actinides U, Th, Pu, Am, and Cm on stainless steel disks was studied. A sodium hydrogen sulphate — sodium sulphate buffer 0.63M in total sulphate and a ratio sodium hydrogen sulphate to total sulphate ranging from 0.16 (pH 1.8) to 0.48 (pH 1.3) allows the quantitative electrodeposition of the given actinides. No actual pH measurement is needed. Moreover, sodium hydrogen sulphate is an excellent substrate for the wet ashing of organic matter prior to electrodeposition. The method is very robust.     

Sequential separation of actinides by ion chromatography coupled with on-line scintillation detection

The separation and measurement of actinides by ion chromatography (IC) coupled with on-line scintillation detection was investigated. Separation of (237)Np, (239)Pu, (241)Am, (244)Cm, (230)Th, and (233)U was accomplished using a Dionex CG5 guard column, CS5 separation column, and an elution program utilizing oxalic, diglycolic, and nitric acid eluents. Np(V) was eluted as a weak anionic oxalate complex or as free NpO(2)(+) cation, Am(III) and Cm(III) as anionic oxalate complexes, Pu(IV) and Th(IV) as nonionic diglycolate complexes, and U(VI) as a free uranyl cation. Response of the flow-cell detector was linear over the full range of activities tested (4-1500 Bq). The minimum detectable activities for the investigated analytes ranged from 3.6 Bq for (244)Cm to 5.4 Bq for (230)Th and (239)Pu. The corresponding minimum detectable concentrations based on a 1-L sample ranged from 3.6 to 5.4 KBq m(-3) (96 to 150 pCi L(-1)).     

Optimization of extraction chromatography separations of trace levels of actinides with ICP-MS detection

The separation of trace level actinides has been evaluated on extraction chromatography columns. Detection of the actinides was achieved through the use of an inductively coupled plasma MS (ICP-MS). The columns that we tested were prepared from a commercial TRU resin. The separation of the actinides was optimized for several parameters including particle size, column length, packing pressure, and eluent flow rate. We also examined the possibility of reducing or eliminating oxalic acid in the eluents in order to improve the performance of the mass spectrometer. We were able to separate a mixture of five actinides ((232)Th,( 238)U,( 237)Np, (239)Pu,( 243)Am) in less than 4 min. This work has application to rapid bioassay as well as for automated separations of actinide materials.     

Development of automated separations for actinides analysis

Journal of Radioanalytical and Nuclear Chemistry - Novel methods for sample preparation by adapting an automated chromatography system to radiochemical analysis for analysis of trace impurities is...     

Synthesis of carbamoylphosphonate silanes for the selective sequestration of actinides

The synthesis of carbamoylphosphonate silanes (CMPO analogs) designed for sequestering actinide cations in self-assembled monolayers on mesoporous supports (SAMMS) is described.     

A robust,field-deployable method for the electrodeposition of actinides

Several methods for the electrodeposition of actinides for alpha-spectrometry analysis have been developed over the past few decades, but none have been specifically designed to facilitate rapid analysis in a field situation. This paper describes the development of an electrodeposition procedure that is specifically adapted for use in a mobile lab. Using these techniques one would be able to obtain preliminary results in the event of a radiological incident. Quantitative yields with associated uncertainties have been determined for the procedure. It has also been shown that short deposition times can provide quantitative results.     

Atomic interaction parameters for lanthanides and actinides

A correlation between the Mie-Lennard-Jones interatomic potential and the position of the element in the Periodic Table is used to correct the parameters for lanthanides and to estimate the parameters of the interatomic potential of promethium (Pm-61) for two structures. From the similarity in the double periodicity for the lanthanides and actinides, the minimum coordinates of the interatomic potential r _o are estimated for the elements from curium (Cm-96) through dubnium (Db-105). From the fact that, for Z _a > 60, r _o decreases with increasing atomic number Z _a for the elements of one column, r _o for roentgenium (Rg-111) is estimated. The corrected parameters of the potential are predicted for the elements from francium (Fr-87) through dubnium (Db-105). From the derived parameters of the interatomic potential, the Debye temperatures and the Grüneisen parameters are calculated for neptunium (Np-93) and americium (Am-95).     

Simultaneous electrodeposition of actinides

A new system for simultaneous electrodeposition of U, Np, Pu, Am and Cm has been developed. The system consists of (NH₄)₂C₂O₄–H₂SO₄–HCl. The effects on recovery of pH, current density, interfering ions and the amount of added HCl have been studied. The optimum condition for simultaneous electrodeposition of actinides has been recommended. Under the recommended condition recoveries of U, Np, Pu, Am and Cm have been obtained by using²³²U,²³⁷Np,²⁴¹Am,²⁴²Pu and²⁴⁴Cm. The counting sources prepared are uniform, adherent and suitable for -spectrometry.     

Radiation chemistry of actinides

The paper presents data on the development of a mathematical model describing the radiation-chemical behaviour of plutonium in 3–6 mol/l HNO₃ with uranium present and absent. Using experimental data on the kinetics of Pu(VI) reduction and Pu(IV) oxidation, and comparing them with the calculated values, we succeeded in finding the previously unknown rate constants of many reactions between plutonium ions and HNO₃ radiolysis products, between plutonium ions and between plutonium ions and uranium ions. The mechanism of the radiation-chemical processes has been established.     

Carbamoylmethyl sulfoxides as novel extractants for actinides

The present paper describes a novel type of extractant for actinides called bis (dioctylcarbamoylmethyl) sulfoxide which neither contains phosphorus nor entails the addition of tributyl phosphate as phase modifier for extraction. This extractant, abbreviated as CMSO, has been found to be freely soluble in dodecane and to form no third phase even with concentrations of nitric acid as high as 10M. The distribution ratios for the extraction of Am(III), Pu(IV) and U(VI) at trace levels have been found to be 13, 220 and 11, respectively, from 5M nitric acid using 0.2M CMSO in dodecane and those for back-extraction have been found to be 2×10^–4, 8×10^–3 and 5×10^–2 using 0.01M nitric acid, 0.1M oxalic acid and 0.35M sodium carbonate, respectively. Similar distribution ratios were obtained with the recycled extractant. Extraction was found to be very rapid. Eu(III) and Sr(II) were found to be moderately extracted with distribution ratios of 2 and 0.77, respectively, while the extraction of Cs(I) was negligible (K_D=0.005).     

Lanthanum fluoride coprecipitation technique for the preparation of actinides for alpha-particle spectrometry

A simple and rapid procedure is described by which actinides can be mounted in a form suitable for alpha-particle spectrometry without recourse to electrodeposition. The actinides are coprecipitated as fluorides with 100 g of lanthanum carrier from an acidic solution. The precipitate is mounted on a 0.1 -pore membrane filter containing LaF₃ substrate, also prepared from 100 g of lanthanum. The resolution obtained using samples of pure radiotracers and of frations isolated from lake sediments is generally comparable to that afforded by the conventional electrodeposition technique. The coprecipitation yield is generally quantitative. The entire procedure can be completed in about 90 min.     

An improved rapid method for the determination of actinides in water

A new rapid method has been developed for the determination of Th, Pu, Np, U, Am and Cm isotopes in water samples of about 1 L. Actinides are pre-concentrated by co-precipitation with Ca phosphate, sequentially separated on stacked TEVA and TK221 cartridges and measured by alpha spectrometry. The TK221 extraction chromatographic resin contains i.e. CMPO and DGA extractants. It has been characterized by measuring the weight distribution ratios (D_w) of actinides which are higher than 1000 for all actinides in 3 M HNO₃. The method has been optimized, applied for the analysis of tap and seawater samples and validated by participating in an IAEA proficiency test. Chemical recoveries for all actinides are better than 50%. The method can be performed within one day.

     

New conceptual process for the extraction of actinides based on oxapentane-diamides

Several diamide derivates were synthesized in our laboratory. The extraction of actinides and some fission products by these compounds were studied. N,N,N’,N’-tetra-(2-ethylhexyl)-3-oxa pentanediamide [TEHOPDA) was proven to be a suitable extractant for the removal of actinides from nitric acid solution. The actinides can be stripped from the loaded solvent by the dilute nitric acid. TEHOPDA showed a high loading capacity to actinides and lanthanides with a mixture of n-octanol and kerosene as the diluent. Considering the effective-extraction and easy-stripping of actinides, 0.25 mol/l TEHOPDA — 30% n-octanol + 70% kerosene was selected as the solvent. A cascade extraction experiment was carried out with the simulated dissolver solution of spend fuel as feed. 99.99% U and 99.999% Am, Pu, and Np were extracted in a 4-stage test. Based on the experimental results, a conceptual reprocessing process was proposed.     

Cyclotriphosphazotriene complexing with actinides

The dependence of uranium, plutonium and americium extraction by substituted cyclotriphosphazotriene is discussed.     

Extraction of actinides with tropolone

The partition coefficient of tropolone in xylene, dichloroethane and chloroform was determined from 0.05M HCl medium. The values obtained were 5.6, 25.5 and 43, respectively. In the extraction of UO ₂ ²⁺ using tropolone (HT) in xylene from an aqueous medium of ionic strength 0.05, the species UO₂T₂·HT was established. The species extracted in presence of a neutral donor was found to be UO₂T₂·S[S+dioctyl sulfide (DOS), dibutylhexanamide (DBHA), tri-n-butyl phosphate (TBP), dioctyl sulfoxide (DOSO), and tri-n-octylphosphine oxide (TOPO)]. The equilibrium constant of complex formation between the self-adduct and the neutral donor was calculated and was found to follow the basicity order (DOS«DBHA<TBP<DOSO»TOPO). The thermodynamic parameters of the adduct UO₂T₂·DOSO were also calculated by the temperature coefficient method. The values of free energy, enthalpy and entropy changes obtained were ?1.26 kJ·mol^?1, ?1.98 kJ/mol and ?2.5 J·mol^?1·deg^?1, respectively.     

Electrodeposition of actinides from saline groundwaters for alpha-spectrometric determination

An establishéd electrodeposition method for separating americium and plutonium from highly saline used-fuel-leaching solutions has been extended to the determination of Np and U in saline groundwaters. The interference of major ionic species in groundwater on the yield was investigated using three groundwaters of varying salinity (ionic strength I=1.37, 0.0748 and 0.0253 mol/l). High average yields (>92%), and good reproducibility were obtained for Np and U electroplated from solutions with ionic strength less than 0.1. The greatest interferences from individual ions were caused by Mg²⁺ and HCO ₃ ^– .     

Oxalate complexing of tetravalent actinides

The oxalate complexing of the tetravalent actinides Th(IV), Np(IV) and Pu(IV) in aqueous solutions was studied by the thenoyltrifluoroacetone extraction method, at unit ionic strength at 25°C and the stability constant values obtained are reported. The oxalate complexing of these ions follows the order Th(IV) < Np(IV) < Pu(IV).