Chromatographic behavior of six lanthanides on a centrifugal mixer-settler extractor cascade.

This work furthers the development of counter-current chromatography as an industrial separation process method. It was demonstrated that the industrial counter-current chromatography methods, in particular, for the separation groups of rare earth metals, can be implemented in a modified cascade of centrifugal mixer-settler extractors. The retention behavior of rare earth elements (samarium, europium, gadolinium, terbium, dysprosium and yttrium) on the pilot chromatographic unit consisting of 70 serially connected centrifugal mixer-settler extractors was experimentally studied under isocratic elution conditions using the mixture of 30 vol.% CyanexⓇ572 + 10 vol.% tributylphosphate in a hydrocarbon diluent as the stationary phase and aqueous nitric acid as the mobile phase. Theoretical analysis of experimental studies showed an acceptable agreement between the assumptions of the theory and experimental results.

Comparison of Jordanian and standard diatomaceous earth as an adsorbent for removal of Sm(III) and Nd(III) from aqueous solution.

In this study, Jordanian diatomaceous earth (JDA) and commercial diatomaceous earth (standard diatomaceous earth, SDA) were used for adsorption of samarium (Sm)(III) and neodymium (Nd)(III) ions from aqueous solutions using batch technique as a function of initial concentration of metal ions, adsorbent dosage, ionic strength, initial pH solution, contact time, and temperature. Both adsorbents were characterized by Fourier transform infrared (FTIR), X-ray fluorescence (XRF), X-ray diffraction (XRD), scanning electron microscopy (SEM), Brunauer-Emmett-Teller surface area, and cation exchange capacity (CEC). Maximum metal ion uptake was observed after 100 min of agitation, and the uptake has decreased with increasing temperature and reached a maximum at pH ≈ 5. Different types of adsorption isotherms and kinetic models were used to describe the Nd(III) and Sm(III) ion adsorption. The experimental data fitted within the following isotherms in the order Langmuir > Dubinin-Radushkevich (DR) > Freundlich and the pseudo-second-order kinetic model based on their coefficient of determination (R2), chi-square (χ2), and error function (Ferror%) values. Maximum adsorption uptakes, according to the Langmuir model, were obtained as 188.679 mg/g and 185.185 mg/g for Sm(III) and 169.492 mg/g and 149.254 mg/g for Nd(III) by JDA and SDA, respectively. The results of thermodynamic parameters showed that the adsorption of Sm(III) and Nd(III) ions onto JDA and SDA is a feasible, spontaneous, exothermic, and entropy driven. The best recovery for Sm(III) and Nd(III) was obtained when the 0.05 M EDTA + 0.05 M H3PO4 mixture was used as an eluent.

Demand driven salt clean-up in a molten salt fast reactor - Defining a priority list.

The PUREX technology based on aqueous processes is currently the leading reprocessing technology in nuclear energy systems. It seems to be the most developed and established process for light water reactor fuel and the use of solid fuel. However, demand driven development of the nuclear system opens the way to liquid fuelled reactors, and disruptive technology development through the application of an integrated fuel cycle with a direct link to reactor operation. The possibilities of this new concept for innovative reprocessing technology development are analysed, the boundary conditions are discussed, and the economic as well as the neutron physical optimization parameters of the process are elucidated. Reactor physical knowledge of the influence of different elements on the neutron economy of the reactor is required. Using an innovative study approach, an element priority list for the salt clean-up is developed, which indicates that separation of Neodymium and Caesium is desirable, as they contribute almost 50% to the loss of criticality. Separating Zirconium and Samarium in addition from the fuel salt would remove nearly 80% of the loss of criticality due to fission products. The theoretical study is followed by a qualitative discussion of the different, demand driven optimization strategies which could satisfy the conflicting interests of sustainable reactor operation, efficient chemical processing for the salt clean-up, and the related economic as well as chemical engineering consequences. A new, innovative approach of balancing the throughput through salt processing based on a low number of separation process steps is developed. Next steps for the development of an economically viable salt clean-up process are identified.

Multi-objective optimization of chromatographic rare earth element separation.

The importance of rare earth elements in modern technological industry grows, and as a result the interest for developing separation processes increases. This work is a part of developing chromatography as a rare earth element processing method. Process optimization is an important step in process development, and there are several competing objectives that need to be considered in a chromatographic separation process. Most studies are limited to evaluating the two competing objectives productivity and yield, and studies of scenarios with tri-objective optimizations are scarce. Tri-objective optimizations are much needed when evaluating the chromatographic separation of rare earth elements due to the importance of product pool concentration along with productivity and yield as process objectives. In this work, a multi-objective optimization strategy considering productivity, yield and pool concentration is proposed. This was carried out in the frame of a model based optimization study on a batch chromatography separation of the rare earth elements samarium, europium and gadolinium. The findings from the multi-objective optimization were used to provide with a general strategy for achieving desirable operation points, resulting in a productivity ranging between 0.61 and 0.75 kgEu/mcolumn(3), h(-1) and a pool concentration between 0.52 and 0.79 kgEu/m(3), while maintaining a purity above 99% and never falling below an 80% yield for the main target component europium.

Experimental productivity rate optimization of rare earth element separation through preparative solid phase extraction chromatography.

Separating individual rare earth elements from a complex mixture with several elements is difficult and this is emphasized for the middle elements: Samarium, Europium and Gadolinium. In this study we have accomplished an overloaded one-step separation of these rare earth elements through preparative ion-exchange high-performance liquid chromatography with an bis (2-ethylhexyl) phosphoric acid impregnated column and nitric acid as eluent. An inductively coupled plasma mass spectrometry unit was used for post column element detection. The main focus was to optimize the productivity rate, subject to a yield requirement of 80% and a purity requirement of 99% for each element, by varying the flow rate and batch load size. The optimal productivity rate in this study was 1.32kgSamarium/(hmcolumn(3)), 0.38kgEuropium/(hmcolumn(3)) and 0.81kgGadolinium/(hmcolumn(3)).

Isolation of three isomers of Sm@C84 and X-ray crystallographic characterization of Sm@D(3d)(19)-C84 and Sm@C2(13)-C84.

Three isomers with the composition Sm@C(84) were isolated from carbon soot obtained by electric arc vaporization of carbon rods doped with Sm(2)O(3). These isomers were labeled Sm@C(84)(I), Sm@C(84)(II), and Sm@C(84)(III) in order of their elution times during chromatography on a Buckyprep column with toluene as the eluent. Analysis of the structures by single-crystal X-ray diffraction on cocrystals formed with Ni(II)(octaethylporphyrin) reveals the identities of two of the isomers: Sm@C(84)(I) is Sm@C(2)(13)-C(84), and Sm@C(84)(III) is Sm@ D(3d)(19)-C(84). Sm@C(84)(II) can be identified as Sm@C(2)(11)-C(84) on the basis of the similarity of its UV/vis/NIR spectrum with that of Yb@C(2)(11)-C(84), whose carbon cage has been characterized by (13)C NMR spectroscopy. Comparison of the three Sm@C(84) isomers identified in this project with two prior reports of the preparation and isolation of isomers of Sm@C(84) indicate that five different Sm@C(84) isomers have been found and that the source of samarium used for the generation of fullerene soot is important in determining which of these isomers form.

Selective separation of samarium(III) by synergistic extraction with ß-diketone and methylphenylphenanthroline carboxamide.

Synergistic extraction of trivalent lanthanides (Lns(III)) with pivaloyltrifluoroacetone (HA) and N-methyl-N-phenyl-1,10-phenanthroline-2-carboxamide (MePhPTA) was evaluated across the Ln series. The distribution ratio (D) of Sm(III) under an identical condition was the largest among all Lns(III). The separation factor (SF) between Sm(III) and Nd(III) (SF=D(Sm)/D(Nd)) was 2.0 and SF between Sm(III) and Eu(III), (D(Sm)/D(Eu)) was 1.4. Upon analyzing the extraction data in detail on the basis of mass balance, it was found that the dominant extracted species of light Lns(III) was a stable ternary complex consisting of Ln(III), HA, and MePhPTA (B), namely, LnA(3)B, while the dominant extracted species of heavy Lns(III) was the ion pair, [LnA(2)B](+)ClO(4)(-). The complex for Pr(III) was very stable (the stability constant, ߯, denoted as [LnA(3)B](o)[LnA(3)](o)(-1)[B](o)(-1), was 10(8.3)). It suggests that LnA(3) can form two 5-membered rings with MePhPTA, and the size of Pr(III) matches to the distance between the donor atoms in MePhPTA. Although the stability constant decreased with increasing Ln atomic number, the synergistic extraction constant (K(ex31)=[LnA(3)B](o)[H(+)](3)[Ln(3+)](-1)[HA](o)(-3)[B](o)(-1)) was the largest for Sm(III). Since the constant, K(ex31,) is given by K(ex31)=K(ex30)×߯ where K(ex30)=[LnA(3)](o)[H(+)](3)[Ln(3+)](-1)[HA](o)(-3), the largest K(ex31) of Sm(III) is attributable to the difference of the degree of the variation of K(ex30) between the light and the heavy Lns(III); the increment of extraction constant of LnA(3) (logK(ex30)) for light Lns is larger than the decrement of the stability constant of LnA(3)B (log߯), while the increment of logK(ex30) of post-Sm lessens than the decrement of log߯. From these results, it is concluded that selective separation of a particular Ln(III) among all Lns(III) is possible using synergistic extraction with a suitable combination of a multidentate ß-diketone and a Lewis base.

Labeling of monoclonal antibodies with 153Sm for potential use in radioimmunotherapy.

The labeling of a monoclonal (anti-CEA) and a polyclonal (IgG) antibody with 153Sm has been investigated, using the bicyclic anhydride of DTPA (cDTPAa) as the chelating agent. The radiochemical study was performed using a combination of radioanalytical techniques (gel filtration, HPLC, ITLC-SG and SDS-PAGE). Optimization of factors affecting labeling (pH, Ab, Ab-DTPA concentration, etc.) leads to a labeling yield higher than 90%. Biodistribution studies in normal mice showed slow blood clearance and high uptake into the liver, kidney and lungs.

Production logistics and radionuclidic purity aspects of 153Sm for radionuclide therapy.

153Sm, an attractive therapeutic radionuclide, was produced by neutron activation of both natural Sm2O3 and 98% enriched 152Sm2O3 targets. The production logistics and radionuclidic purity aspects of 153Sm obtained using both these targets are discussed with respect to the intended end use for metastatic bone pain palliation (MBPP) in terminal cancer patients and radiation synovectomy (RS) of medium size joints. The specific activity of 153Sm obtained was around 11 GBq x mg(-1) (approximately 300 mCi x mg(-1)) and 44 GBq x mg(-1) (approx. 1200 mCi x mg(-1)) from natural and enriched targets, respectively. The level of the long-lived radionuclidic impurity burden in 153Sm obtained from the natural Sm2O3 targets, namely, due to 154Eu (5 Bq x MBq(-1) 153Sm (5 nCi x mCi(-1) 153Sm)) and 155Eu (75 Bq x MBq(-1) 153Sm (75 nCi x mCi(-1) 153Sm)), appears low enough not to pose a problem, both in the palliative treatment of terminal cancer patients (at 1.85-2.22 GBq (50-60 mCi) dose) as well as in RS (at 74 MBq (2 mCi) dose). The 154Eu content in 153Sm from the enriched target was comparable, while, as expected, the level of 155Eu was nearly two orders of magnitude lower. There is a notable overall advantage of 153Sm over the use of 186Re, the other radionuclide of interest for the same purposes.

Studies on the preparation and stability of samarium-153 propylene diamine tetramethylene phosphonate (PDTMP) complex as a bone seeker.

Propylene diamine tetra methylene phosphonate (PDTMP) was synthesised by modifying a method reported for the synthesis of EDTMP. Complexation of the synthesised phosphonate ligand with 153Sm was carried out by varying the experimental parameters and the complex was radiochemically characterized. Biodistribution studies showed that the uptake by bone in rats was 2% per g of bone, which was retained upto 48 h. The uptake by other organs was insignificant, except by the liver which showed a slightly higher absorption.

Preparation and evaluation of samarium (III) phosphate [(153)Sm] colloid (SMPC) for possible therapeutic use.

A simple method of preparation of a new therapeutic colloid, samarium(III) phosphate-(153)Sm (SMPC), is reported involving the reaction of carrier-added (153)SmCl(3) with phosphoric acid. Recovery of the colloid was accomplished by dialysis leading to purification and a radiochemical (RC) yield of more than 90%. The RC purity of purified colloid formulated in isotonic phosphate buffer was more than 99% as assessed by paper chromatography. The product retained its RC purity throughout the period of stability study of 7 days. Complete retention of radioactivity instilled in the rabbit knee joint was observed over the study period of 6 days, with radioactivity in the blood being indistinguishable from the natural background activity. Ninety-six percent of colloidal particles were in the size range of 0.3-2 microm. The promising results demonstrated warrant further studies on SMPC for assessing the suitability for therapy.