Metal ion separations are critical to numerous fields, including nuclear medicine, waste recycling, space exploration, and fundamental research. Nonetheless, operational conditions and performance are limited, imposing compromises between recovery, purity, and cost. Siderophore-inspired ligands show unprecedented charge-based selectivity and compatibility with harsh industry conditions, affording excellent separation efficiency, robustness and process control. Here, we successfully demonstrate a general separation strategy on three distinct systems, for Ac, Pu, and Bk purification. Separation factors (SF) obtained with model compound 3,4,3-LI(1,2-HOPO) are orders of magnitude higher than with any other ligand currently employed: 10⁶ between Ac and relevant metal impurities, and over 10⁸ for redox-free Pu purification against uranyl ions and trivalent actinides or fission products. Finally, a one-step separation method (SF > 3 × 10⁶ and radiopurity > 99.999%) enables the isolation of Bk from adjacent actinides and fission products. The proposed approach offers a paradigm change for the production of strategic elements.

The recovery of Nb(V) and Ta(V) from alkaline solutions was investigated using calcium-bearing reagents (CaCl2(aq), Ca(CH3COO)+(aq), Ca(NTA)−(aq), Ca(EDTA)2 −(aq), CaCO3(s) and Ca(OH)2(s)) at 25 °C. It was found that hexaniobate and hexatantalate ions (HxNb6O19x − 8 and HxTa6O19x − 8; 0 ≤ x ≤ 3) can be quantitatively precipitated with calcium chloride, calcium acetate or calcium hydroxide when the ratio (Ca/M)initial is at least 0.4 mol/mol (M = Nb, Ta). Precipitation yields higher than 95% are obtained for solutions that contain, as low as, 3 ∗ 10− 4 mol/L of Nb and 1 ∗ 10− 4 mol/L of Ta. Moreover, the proposed precipitation method can be operated in a wide pH range and consumes two times less reactant than the classical way for recovering Nb and Ta which consists of neutralizing their alkaline solutions with a mineral acid. The amorphous calcium niobate concentrate was characterized by elemental analysis (ICP-OES), thermogravimetric analysis (TGA-MS) and Raman spectroscopy and the solid phase K3Ca2.2(H0.6Nb6O19)·nH2O was identified under specific conditions.

Separation of lanthanides (Ln) from actinides (An) is unanimously challenging in reprocessing used nuclear fuel despite of much dedicated efforts over the past several decades. The TALSPEAK process is the current reference method in the United States for Ln³⁺/An³⁺ separation but suffers from several limitations, such as a narrow working pH window (3.5-4.0), costly pH buffers, and slow extraction kinetics. Studies aiming at improving TALSPEAK have so far focused on polyaminocarboxylates hold-back reagents. Here, a new class of water-soluble ligands comprising hydroxypyridinone metal-binding units are evaluated for Ln³⁺/An³⁺ separation. The model octadentate chelator 3,4,3-LI(1,2-HOPO) (abbreviated as HOPO) was used in combination with several industry-relevant organic extractants to separate Gd from four transplutonium elements (Am, Cm, Bk, and Cf). Cyanex 301 GN and HDEHP worked best in combination with HOPO, whereas HEH[EHP], Cyanex 572, and ACORGA M5640 did not yield practical Ln³⁺/An³⁺ separation. Separation factors between Gd³⁺ and Am³⁺ reach about 50 with the HOPO/Cyanex 301 GN system and 30 with the HOPO/HDEHP system. The results using HDEHP (SF_Gd/Am = 30, SF_Gd/Cm = 8.5, and SF_Gd/Cf = 773) are high enough for industrial applications, and the proposed system works at pH values as low as 1.5, which simplifies the process by eliminating the need for pH buffers. In contrast to previously proposed methods, the HOPO-based process is also highly selective at separating Bk from Ln³⁺ (SF_Gd/Bk = 273) owing to in situ, spontaneous oxidation of Bk(III) to Bk(IV) by HOPO. The optimal pH in the case of HOPO/Cyanex 301 GN is 3.6 (SF_Am/Gd = 50, SF_Cm/Gd = 23, SF_Bk/Gd = 1.4, and SF_Cf/Gd = 3.2), but this system has the advantage of extracting An ions into the organic phase while keeping Ln ions in the aqueous phase, which is opposite to the conventional TALSPEAK process. This study represents the first optimization of a TALSPEAK-like Ln/An separation method using a HOPO chelator and paves the avenue for further developments of analytical science and reprocessing of used nuclear fuel.

To overcome the low recovery, generally obtained for the heavy and middle rare earth elements (HREE and MREE) by sodium double sulfate precipitation, the recovery of the MREE and HREE as phosphate salts was investigated. High recovery yields (≥ 95%) were obtained even for sulfate solutions containing low concentrations of REE and a high concentration of iron(II). The influence of many industry-relevant parameters (temperature, pH, stoichiometric excess of phosphate, aluminum contamination, residence time) is discussed in order to optimize the REE recovery and to minimize the precipitation of iron. The developed process was also validated in continuous operation at a pilot scale. Finally, the REE phosphate concentrate could be converted into REE hydroxides which allows its dissolution into diluted HCl. Taking into account the phosphate precipitation, the conversion into hydroxides and the dissolution in HCl(aq), high recovery yields were obtained for Y, Gd and La (68%, 77% and 86% respectively). The results show that it is possible to economically obtain purified REE solutions starting from industrial solutions which are usually discarded.

Tantalum (Ta) and niobium (Nb) are two strategic metals essential to several key sectors, like the aerospace, gas and oil, nuclear and electronic industries, but their separation is really difficult due to their almost identical chemical properties. Whereas they are currently produced by hydrometallurgical processes using fluoride-based solutions, efforts are being made to develop cleaner processes by replacing the fluoride media by alkaline ones. However, methods to analyze Nb and Ta simultaneously in alkaline samples are lacking. In this work, we developed a capillary zone electrophoresis (CE) method able to separate and quantify Nb and Ta directly in alkaline media. This method takes advantage of the hexaniobate and hexatantalate ions which are naturally formed at pH>9 and absorb in the UV domain. First, the detection conditions, the background electrolyte (BGE) pH, the nature of the BGE co-ion and the internal standard (IS) were optimized by a systematic approach. As the BGE counter-ion nature modified the speciation of both ions, sodium- and lithium-based BGE were tested. For each alkaline cation, the BGE ionic strength and separation temperature were optimized using experimental designs. Since changes in the migration order of IS, Nb and Ta were observed within the experimental domain, the resolution was not a monotonic function of ionic strength and separation temperature. This forced us to develop an original data treatment for the prediction of the optimum separation conditions. Depending on the consideration of either peak widths or peak symmetries, with or without additional robustness constraints, four optima were predicted for each tested alkaline cation. The eight predicted optima were tested experimentally and the best experimental optimum was selected considering analysis time, resolution and robustness. The best separation was obtained at 31.0°C and in a BGE containing 10mM LiOH and 35mM LiCH3COO.The separation voltage was finally optimized, resulting in the separation of Nb, Ta, and IS in less than 2.5min, which is three times faster than any CE method ever reported for the separation of Nb and Ta (acidic media included). Some figures of merit of the method were determined such as linearity ranges and limits of quantitation. Finally, the method was successfully applied to the analysis of a real industrial sample.

The toxicity of heavy metals such as lead (Pb), cadmium (Cd) and tin (Sn) has long been known but accidental exposures of large populations to these elements remain unfortunately a topical issue. Chelating agents against Pb, Cd, or Sn poisoning are still limited to classical ligands such as ethylenediamine tetraacetic acid (EDTA). Here, we evaluate the ability of 3,4,3-LI(1,2-HOPO) (L4-), an octadentate ligand currently under evaluation for actinide decorporation, to bind Pb, Cd and Sn metal ions in aqueous solutions. This ligand forms 1:1 complexes with Pb(ii), Cd(ii) and Sn(iv) as well as bimetallic 2:1 species with Pb(ii) and Cd(ii), all of which were characterized by high resolution mass spectrometry and spectrophotometric titrations. The 3,4,3-LI(1,2-HOPO) ligand exhibits an extreme affinity for Sn(iv) ions (logβ110 > 40), with the complex remaining stable from highly acidic conditions to alkaline media (from 3 M HCl to pH 8). Single crystals of the neutral complex [SnIV3,4,3-LI(1,2-HOPO)·3H2O] were obtained and its structure determined, revealing a chiral conformation. Although not initially designed for hexacoordinated metals such as Pb(ii) and Cd(ii), the octadentate ligand shows promise for the in vitro or in vivo sequestration of toxic heavy metals, as evidenced by decorporation experiments performed in mice contaminated with 210Pb(ii) and treated with either EDTA or 3,4,3-LI(1,2-HOPO).

The current hydrometallurgical processes used for niobium and tantalum recovery are operated in strongly acidic and fluoride-containing solutions. To avoid the use of these highly toxic media, a fluoride-free process was developed to recover Nb and Ta from low-grade industrial concentrates. The process is based on the caustic conversion of the raw material with NaOH(aq) at atmospheric pressure and at relatively low temperature which then allows the selective dissolution of sodium hexaniobates. Finally, Nb is recovered as purified hydrous oxide by acidification of the hexaniobate solution. The influence of many industry-relevant parameters (temperature, initial NaOH concentration, residence time, impurity content in the initial concentrate, pH of precipitation) was studied in order to optimize the recovery and purification of the valuable metals. Finally, the process was validated in continuous operation at a pilot scale. High recovery yields for Nb and Ta (65%) were obtained as well as high separation factors toward Ti, Fe, P, S, Th and U. The results demonstrate that it is possible to recover and purify Nb and Ta from industrial concentrates without using fluoride solutions.

In order to reveal subtle differences between the solution chemistries of trivalent 4f and 5f elements, the physicochemical and photophysical properties of europium(iii), terbium(iii) and curium(iii) complexes formed with a 7-methoxy-coumarin appended 1,4,7,10-tetraazadodecane-1,4,7-triacid (DO3A) ligand were studied. All three complexes were found to be kinetically inert and exhibit stability constants similar to their 1,4,7,10-tetraazacyclododecane-1,4,7,10-tetraacetic acid (DOTA) equivalents. The Cm(iii) and Eu(iii) complexes feature strong sensitised emission, while the triplet energy of the coumarin prohibits efficient sensitisation of the Tb(iii) analogue. The data presented here indicate significant differences in perturbation of the sensitising chromophore photophysics between the 4f and 5f elements. In contrast, the size of the metal center appears to not be a determining factor for the physicochemical properties of these kinetically inert Eu(iii), Tb(iii), and Cm(iii) complexes.

Several MRI contrast agent clinical formulations are now known to leave deposits of the heavy metal gadolinium in the brain, bones, and other organs of patients. This persistent biological accumulation of gadolinium has been recently recognized as a deleterious outcome in patients administered Gd-based contrast agents (GBCAs) for MRI, prompting the European Medicines Agency to recommend discontinuing the use of over half of the GBCAs currently approved for clinical applications. To address this problem, we find that the orally-available metal decorporation agent 3,4,3-LI(1,2-HOPO) demonstrates superior efficacy at chelating and removing Gd from the body compared to diethylenetriaminepentaacetic acid, a ligand commonly used in the United States in the GBCA Gadopentetate (Magnevist). Using the radiotracer ¹⁵³Gd to obtain precise biodistribution data, the results herein, supported by speciation simulations, suggest that the prophylactic or post-hoc therapeutic use of 3,4,3-LI(1,2-HOPO) may provide a means to mitigate Gd retention in patients requiring contrast-enhanced MRI.

Solvent extraction of Nb(v) from alkaline aqueous media using quaternary ammonium solutions, especially Aliquat® 336 diluted in an aliphatic diluent, was investigated. The hexaniobate ions (H_xNb₆O₁₉^x-8) were extracted into the organic phase with very high yields at room temperature and within a few minutes, affording easy access to organic solutions of hexaniobates. Several parameters were found to influence the extraction of H_xNb₆O₁₉^x-8 including the nature and concentration of alkali cations, confirming subtle effects previously described for polyoxoniobates such as ion-pairing with alkali ions. The extraction of H_xNb₆O₁₉^x-8 with Aliquat® 336 is also influenced if competing anions are present in the aqueous phase (NO₃^-, Cl^-, C₂O₄^2-, SO₄^2- and CO₃^2-) and varies with the pH mainly due to the competitive extraction of hydroxide ions at high pH. The co-extraction of sodium ions with H_xNb₆O₁₉^x-8 was observed as well as the co-extraction of water molecules, suggesting a self-association of the extractant. The proposed liquid-liquid extraction generic system paves the way for innovative niobium (and potentially tantalum) hydrometallurgical processes and it may also afford more direct routes for exploring the chemistry of hexaniobates in organic solvents.