Search

We have developed an extraction method for the retrieval of Cs+ from chloridecontaining salt brine solutions. We employ the calixarene crown ether known as MAXCalix as the extractant, which exhibits a remarkable selectivity for Cs+ over Na+, K+, Mg2+ and Ca2+, with separation factors ranging from 100 to 104. The efficiency of the extraction strongly depends on the chloride concentration in the aqueous phase. Notably, when the chloride concentration reaches 4 mol L−1, we achieve a Cs+ distribution ratio of 7.9. Accordingly, the retrieval of Cs+ from the organic phase is achieved when the HCl concentration is maintained at a low level. In multicomponent chloride brine solutions, the distribution ratios for Cs+ are somewhat lower, yet still fall within the range of 4–6. Nevertheless, these ratios remain favorable for separation purposes. Additionally, the distribution ratios of Na+, K+, Mg2+, and Ca2+ offer insights into the coordination chemistry of MAXCalix. Our experimental data indicate a correlation between ionic size and distribution ratio. Cs+ forms the strongest complex, followed by K+ and Na+, while Mg2+ and Ca2+ exhibit minimal extraction, potentially due to interactions with the diluent. These findings may open new approaches for the development of a decontamination strategy tailored to address salts and brine solutions contaminated with Cs-137. [ABSTRACT FROM AUTHOR]

The diglycolamide 2,2’-oxybis(N,N-di-n-decylpropanamide) (mTDDGA) is being studied as an extractant for actinides and lanthanides in the European Grouped Actinide Extraction (EUROGANEX) process. The aim is the development of a more simplified process using a single extractant instead of a mixture of extractants used in the current EURO-GANEX process. This work presents solvent optimization studies of mTDDGA, with regards to the extraction characteristics of the different diastereomers of mTDGA and of mixed diastereomer solutions. Also radiolysis behavior has been studied by irradiation of solvent extraction systems in a gamma irradiation facility using 60Co. The availability of irradiated organic solutions made it possible to gain valuable insights into the plutonium loading capacity after gammairradiation of the solvent up to 445 kGy and to quantify degradation compounds. Solvent extraction characteristic of the major degradation compounds themselves were determined. Like other methylated diglycolamides, we found a remarkable difference in extraction of up to two orders of magnitude between the two diastereomers. High plutonium loading (36 g L−1) is feasible using this single extractant, even after absorbing a dose of 445 kGy. This remarkable observation is possibly promoted by the presence of the main degradation compound which extracts plutonium verywell. [ABSTRACT FROM AUTHOR]

In comparison, the log I i ' SB 3 sb values for the complexation with I cis i -mTDDGA are 1.1 (for Cm(III)) and 1.8 (for Eu(III)) orders of magnitude higher than for the complexation with I trans i -mTDDGA, confirming I cis i -mTDDGA to be the stronger ligand. In contrast to the complexation of Cm(III) with I cis i - and I trans i -mTDDGA no spectroscopic evidence for a 1:2 complex with I cis i - or I trans i -mTDDGA with Eu(III) could be found. 2.2 Preparation of monophasic samples For monophasic experiments in dependence of the ligand concentration 4.5 mg I cis i -mTDDGA or 118.2 mg I trans i -mTDDGA were dissolved in 2 mL ( I cis i -mTDDGA) or 1 mL ( I trans i -mTDDGA) of 2-propanol with 5 vol% H SB 2 sb O and 1 × 10 SP -2 sp mol L SP -1 sp HClO SB 4 sb . 3 Results and discussion 3.1 Complexation of Cm(III) with cis - and trans -mTDDGA 3.1.1 cis -mTDDGA The complexation of Cm(III) with I cis i -mTDDGA was studied in 2-propanol with 5 vol% H SB 2 sb O and 1 × 10 SP -2 sp mol L SP -1 sp HClO SB 4 sb . [Extracted from the article]

The solubility of Nd(III), Th(IV) and U(VI) was studied from undersaturation conditions in the presence of selected organic cement additives and model compounds: adipic acid, methyl acrylate, citric acid, melamine, ethylene glycol, phthalic acid and gluconic acid. Experiments were performed under Ar atmosphere in NaCl (2.5 and 5.0 M), MgCl2 (1.0 and 3.5 M) and CaCl2 (1.0 and 3.5 M) solutions with 9 ≤ pHm ≤ 13 (pHm = −log[H+]). Initial concentrations of organic ligands in solution were set constant in all systems to [L]0 = 0.025 M, except in specific cases (e.g. adipic acid, melamine and phthalic acid) where the ligand concentration in the matrix solutions was lower and controlled by solubility. Adipic acid, methyl acrylate, melamine, ethylene glycol and phthalic acid do not impact the solubility of Nd(III), Th(IV) and U(VI) in the investigated NaCl, MgCl2 and CaCl2 systems. Citrate significantly enhances the solubility of Nd(III), Th(IV) and U(VI) in NaCl systems. A similar effect was observed for Th(IV) and U(VI) in the presence of gluconate in NaCl systems. The impact of pH on the stability of the complexes is different for both ligands. Because of the larger number of alcohol groups in the gluconate molecule, this ligand is prone to form more stable complexes under hyperalkaline conditions that likely involve the deprotonation of several alcohol groups. The complexation of gluconate with U(VI) at pHm ≈ 13 is however weaker than at pHm ≈ 9 due to the competition with the highly hydrolysed moiety prevailing at pHm ≈ 13, i.e. UO2(OH)42−. The impact of citrate and gluconate in MgCl2 and CaCl2 systems is generally weaker than in NaCl systems, expectedly due to the competition with binary Mg-L and Ca-L complexes. However, the possible formation of ternary complexes further enhancing the solubility is hinted for the systems Mg/Ca-Th(IV)-GLU and Ca-U(VI)-GLU. These observations reflect again the differences in the complexation properties of citrate and gluconate, the key role of the alcohol groups present in the latter ligand, and the importances of interacting matrix cations. The screening experiments conducted within this study contribute to the identification of organic cement additives and model compounds potentially impacting the solution chemistry of An(III)/Ln(III), An(IV) and An(VI) under intermediate to high ionic strength conditions (2.5 ≤ I ≤ 10.5 M). This shows evident differences with respect to investigations conducted in dilute systems, and thus represents a very relevant input in the safety assessment of repositories for radioactive waste disposal where such elevated ionic strength conditions are expected. [ABSTRACT FROM AUTHOR]

The synthesis and evaluation of three novel bis‐1,2,4‐triazine ligands containing five‐membered aliphatic rings are reported. Compared to the more hydrophobic ligands 1–3 containing six‐membered aliphatic rings, the distribution ratios for relevant f‐block metal ions were approximately one order of magnitude lower in each case. Ligand 10 showed an efficient, selective and rapid separation of AmIII and CmIII from nitric acid. The speciation of the ligands with trivalent f‐block metal ions was probed using NMR titrations and competition experiments, time‐resolved laser fluorescence spectroscopy and X‐ray crystallography. While the tetradentate ligands 8 and 10 formed LnIII complexes of the same stoichiometry as their more hydrophobic analogues 2 and 3, significant differences in speciation were observed between the two classes of ligand, with a lower percentage of the extracted 1:2 complexes being formed for ligands 8 and 10. The structures of the solid state 1:1 and 1:2 complexes formed by 8 and 10 with YIII, LuIII and PrIII are very similar to those formed by 2 and 3 with LnIII. Ligand 10 forms CmIII and EuIII 1:2 complexes that are thermodynamically less stable than those formed by ligand 3, suggesting that less hydrophobic ligands form less stable AnIII complexes. Thus, it has been shown for the first time how tuning the cyclic aliphatic part of these ligands leads to subtle changes in their metal ion speciation, complex stability and metal extraction affinity. [ABSTRACT FROM AUTHOR]