Reversed-phase partition chromatographic separation of minor actinides with bis(2-ethylhexyl) sulfoxide from acidic nitrate PUREX waste solutions

The uptake behavior of U(VI), Pu(IV), Am(III) and a few long-lived fission products from nitric acid media by bis(2-ethylhexyl) sulfoxide (BESO) adsorbed on Chromosorb has been studied U(VI), Pu(IV) and Zr(IV) are taken up appreciably as compared to trivalent actinides/lanthanides including some coexisting fission product contaminants which are weakly sorbed on the column. Chromosorb could be loaded with (1.12±0.03) g of BESO per g of the support. Maximum sorption is observed around 4–5 mol·dm^–3 HNO₃ for both U(VI) and Pu(IV), which are sorbed as their disolvates. The elution of (U(VI) and Pu(IV) from the metal loaded sorbent has also been optimized. Desorption of U(VI) is easily accomplished with dilute nitric acid (ca. 0.01 mol·dm^–3)while Pu(IV) is reductively stripped with 0.1 mol·dm^–3 NH₂OH·HCl. Effective sequential separation of U(VI), Pu(IV) and Am(III) from their several admixtures could be readily achieved from real medium and low level active acidic process raffinates.     

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.     

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.     

Radiochemical separation of Pu, U, Am and Sr isotopes in environmental samples using extraction chromatographic resins

This study presents a rapid and quantitative sequential radiochemical separation method for Pu, U, Am and Sr isotopes in environmental samples with extraction chromatographic resins. After radionuclides were leached from the samples with 6 M HNO₃, Pu and U isotopes were adsorbed onto the UTEVA column and Am isotopes were adsorbed onto the TRU column connected with the UTEVA column. Also, ⁹⁰Sr was adsorbed onto the Sr column connected with the TRU column. Pu and U isotopes were purified from other nuclides through the UTEVA column. In addition, Am isotopes were separated from other nuclides with the TRU column. Finally, ⁹⁰Sr was purified with the Sr resin. After α source preparation for the purified Pu, U and Am isotopes with micro-coprecipitation method, Pu, U and Am isotopes were measured using alpha spectrometry. On the other hand, ⁹⁰Sr was measured using a low level liquid scintillation counter. The radiochemical procedure for Pu, U, Am and Sr nuclides investigated in this study has been applied to environmental samples after validating the simulated samples.     

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.     

Determination of fission-products and actinides in the Black Sea following the Cherynobyl accident

Radiochemical procedures are discussed for the isolation and determination of a suite of radionuclides in samples from the Black Sea following their input from the Chernobyl reactor accident. The samples analyzed include discrete water samples and both suspended and dissolved phases collected by in-situ chemisorption techniques. The radiochemical scheme permits the separation and analysis of¹³⁴Cs,¹³⁷Cs,⁹⁰Sr,¹⁴⁴Ce,¹⁴⁷Pm,¹⁰⁶Ru,²³⁹Pu,²⁴⁰Pu, and in some instances²⁴²Cm,²³⁸Pu, and²⁴¹Am. The detection techniques employed include various instrumental gamma spectrometric methods, low-level beta counting, alpha spectrometry, and mass spectrometry.The method's developments are described and data are presented on some representative samples from the Black Sea. The sensitivity of the analysis for the various nuclides and sample types is summarized and questions of radiochemical interferences are addressed.     

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.     

Determination of uranium,plutonium and selected fission products in the coolant of the KS-150 reactor

The method of monitoring of U, Pu and some fission products (^103,106Ru,^134,137Cs and^141,144Ce) in gaseous CO₂ coolant is described. The method is based on the retention of the radionuclides studied by membrane filters built in by-pass of the burst-cartridge detection (BCD) system. The purpose of the present study was the determination of U, Pu in CO₂ and the verification of the possibility of the indirect monitoring of U and Pu contents in the coolant, using the gamma-spectrometric determination of selected fission products retained by the filter. For calibration of the proposed method after decomposition of the filters, uranium was determined spectrophotometrically using Arsenazo III, plutonium was determined radiometrically after its separation by extraction with 2-thenoyltrifluoracetone and the fission products were determined by gamma-spectrometry. From the results obtained it follows that a correlation exists between the U and Pu content in the coolant and the activity of certain fission products retained on the filter.     

Characteristics of Dicesium Plutonium(IV) Nitrate Formation in Separation System of Uranyl Nitrate Hexahydrate Crystal

There is a concerned that Cs and Pu double salt Cs2Pu(NO3)6 is formed under certain conditions in the course of U crystallization. The influence of the Cs concentration in a feed solution on Cs2Pu(NO3)6 formation was thus examined in the U crystallization process. Cesium and Pu were decontaminated after crystal washing with a decreasing Cs concentration in the feed solution. Although Cs remained in the mother liquor at a Cs concentration of 1.0 g/dm³ in the feed solution, Cs2Pu(NO3)6 precipitated at a Cs concentration of 2.2 g/dm³. There is, therefore, a lower limit for the Cs concentration in the feed solution at which Cs2Pu(NO3)6 precipitates, and this limit falls in the range from 1.0 to 2.2 g/dm³ Cs.     

Extractive—spectrophotometric determination of americium at trace levels with arsenazo-III

Americium(III) can be quantitatively extracted with 1 M diisoamylsulphoxide in Solvesso-100 from aqueous 0.02 M HNO₃—2.5 Al(NO₃)₃ solutions and, after dilution of the extract with ethanol and nitric acid, determined in the organic phase with arsenazo-III. The apparent molar absorptivity is 1.58 × 10⁵ l mol^-1 cm^-1 at 652 nm. The system obeys Beer's law within the range 0.1–1.6 μg Am ml^-1; 0.11 μg Am ml^-1 is determined with a reproducibility better than ±2%. Relatively large amounts of Ca(II), Cr(III), Fe (III), U(VI), Cl^-, NO₂^-, NO₃^- and F^- are tolerated. Interferences of Ce(IV), Pu(IV) and Th(IV) are eliminated by prior extraction with 2-thenoyltrifluoroacetone; only europium(III) interferes appreciably. Colour development is almost instantaneous and absorbances are virtually constant for 12 h.     

Application of inorganic sorbents for removal of Cs, Sr, Pu and Am from contaminated solutions

A sorption ability of titanium silicates (TiSi) and iron oxides towards Cs, Sr, Pu and Am was tested using the laboratory batch method. The obtained results are expressed as distribution coefficients (K_d). TiSi synthesised using TiOSO₄ revealed better sorption ability towards all studied radionuclides in comparison with TiSi produced on the basis of TiCl₄. The K_d values ranged from 3.9 × 10² to 1.6 × 10⁵ mL g⁻¹ for Sr, from 6 to 4.1 × 10⁴ mL g⁻¹ for Cs, from 2.2 × 10² to 2.6 × 10⁵ mL g⁻¹ for Pu and from 50 to 1.6 × 10⁴ mL g⁻¹ for Am. The highest Pu K_d values (9 × 10³–6.2 × 10⁴ mL g⁻¹) and better kinetics were found for iron oxides.     

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.     

Sorption characteristics of Am(III), Sr(II) and Cs(I) on bentonite and granite

The ability of the back-fill and the host rock materials to take up radioisotopes like ²⁴¹Am, ^85,89Sr and ¹³⁷Cs has been examined as a function of contact time, pH, amount of sorbent, sorbate concentration, and the presence of complementary cations. A batch technique using actual borehole water from the granite formation has been utilized. In general, the uptake of nuclides by bentonite is much higher than that with granite. The sorption order of nuclides on bentonite is Am>Cs>Sr. The presence of complementary cations, Na⁺, K⁺, Ca²⁺ and Mg²⁺ depresses the sorption of Cs and Sr on bentonite. The sorption data have been interpreted in terms of Freundlich and Langmuir isotherm equations. Utilizing the Langmuir isotherm equation, the monolayer capacity, V _m ,and the binding constant, K, have been evaluated. The change in free energy for the sorption of nuclides on bentonite has also been calculated.     

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.

---

---

Aus einer Dissertation, Mainz 1967.     

Sorption and diffusion processes with134Cs and85Sr in natural sorbents

Sorption and diffusion processes with¹³⁴Cs and⁸⁵Sr in natural bentonites have been investigated. The distribution coefficients (K _d ) have been determined by a batch method. Various factors affecting theK _d value as water-to-bentonite ratio, concentration of the competitive cations in the aqueous phase or bentonite-to-sand ratio in the mixed sorbents have been evaluated. A comparison of the sorption and diffusion data has been made.     

Sorption of Chromium(VI) from Aqueous Solutions on AM-2b Anion Exchanger

Sorption of chromium(VI) from a solution with the initial concentration of CrO₃ of up to 30 mg dm^{- 3} on a commercial macroporous AM-2b anion exchanger pretreated by various methods was studied. The optimal conditions for efficient sorption were found.     

Americium(III) sorption from multicomponent solutions by macrocyclic polyester-based sorbents

Americium sorption by crown-ether-impregnated polymeric sorbents from nitric acid solutions and multicomponent nitrate solutions that model process solutions was studied. Sorption of ballast elements by the unimpregnated Porolas-T support was studied. The sorption coefficients K _d of these elements on Porolas-T do not exceed 0.01. Sorption of the same elements by crown-ether-impregnated sorbents was also studied. Dicyclohexano-18-crown-6 (DCH18C6) and its alkyl derivatives were used. Sorption coefficients were determined for all ballast elements. At the final stage of the study, ²⁴¹Am sorption coefficients of from multi-component solutions were determined. The data obtained signify the utility of crown-ether-impregnated sorbents for recovering ²⁴¹Am from multicomponent technological solutions.     

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.     

137Cs, 40K, 90Sr, 238, 239+240Pu, 241Am and 243+244Cm in forest litter and their transfer to some species of insects and plants in boreal forests: Three case studies

Results for ¹³⁷Cs, ⁴⁰K, ⁹⁰Sr, ^238,239+240Pu, ²⁴¹Am and ^243+244Cm measurements in plant, insects and forest litter samples collected at three sites in Poland are presented. New results are compared with some existing data for locations examined during previous studies. Insect samples were introduced now for the first time. Relatively high activities of ⁹⁰Sr were noticed for spruce bark beetle (Ips typographus) and those for ¹³⁷Cs, plutonium and ²⁴¹Am for forest dung beetle (Anoplotrupes stercorosus). Faster than caused by physical decay decrease of radiocesium activity was noticed for the majority of plant and litter samples. The results for ^239+240Pu for litter were similar to previous results, but the activities of ²³⁸Pu were smaller. The activity ratio between ²⁴¹Am and ^239+240Pu was found lower than expected for known proportions between global and Chernobyl fallout. Thus a kind of dynamic behavior of Pu and Am in the forest ecosystem is concluded. Transfer factors and aggregation coefficients were estimated and discussed for both plants and insects as well as between insects and the part of plants (or litter) they feed on. Many of them were never presented before.The authors are thankful to the Polish State Committee for Scientific Research for financial support of this investigation, Grant No. PG04 07520.     

137Cs, 40K, 90Sr, 238, 239+240Pu, 241Am and 243+244Cm in forest litter and their transfer to some species of insects and plants in boreal forests: Three case studies

Results for ¹³⁷Cs, ⁴⁰K, ⁹⁰Sr, ^238,239+240Pu, ²⁴¹Am and ^243+244Cm measurements in plant, insects and forest litter samples collected at three sites in Poland are presented. New results are compared with some existing data for locations examined during previous studies. Insect samples were introduced now for the first time. Relatively high activities of ⁹⁰Sr were noticed for spruce bark beetle (Ips typographus) and those for ¹³⁷Cs, plutonium and ²⁴¹Am for forest dung beetle (Anoplotrupes stercorosus). Faster than caused by physical decay decrease of radiocesium activity was noticed for the majority of plant and litter samples. The results for ^239+240Pu for litter were similar to previous results, but the activities of ²³⁸Pu were smaller. The activity ratio between ²⁴¹Am and ^239+240Pu was found lower than expected for known proportions between global and Chernobyl fallout. Thus a kind of dynamic behavior of Pu and Am in the forest ecosystem is concluded. Transfer factors and aggregation coefficients were estimated and discussed for both plants and insects as well as between insects and the part of plants (or litter) they feed on. Many of them were never presented before.The authors are thankful to the Polish State Committee for Scientific Research for financial support of this investigation, Grant No. PG04 07520.