The skeleton is a target organ for most metals. This leads to their bioaccumulation, either as storage of useful oligoelements or as a protection against damage by toxic elements. The different events leading to their accumulation in this organ, under constant remodeling, are not fully understood, nor the full subsequent impact on bone metabolism. This lack of knowledge is particularly true for lanthanides and actinides, whose use has been increasing over recent decades. These metals, known as f-elements, present chemical similarities and differences. After a comparison of the biologically relevant physicochemical properties of lanthanides and actinides, and a brief reminder of the main events of bone metabolism, this review considers the results published over the past decade regarding the interaction between bones and f-elements. Emphasis will be given to the molecular events, which constitute the basis of the most recent toxicological studies in this domain but still need further investigation. Ionic exchanges with the inorganic matrix, interactions with bone proteins, and cellular mechanism disturbances are mainly considered in this review.
An efficient process for the recovery of palladium from waste printed circuits boards (PCBs) is detailed. Palladium is employed as an electrode material in multi-layer ceramic capacitors (MLCCs). These components can be easily removed from PCBs by desoldering. As palladium is alloyed with silver, its dissolution is readily achieved using dilute nitric acid. As a result, a solution containing palladium along with base metals, mostly copper and iron, is obtained. This solution is then processed through solvent extraction (SX) with a solvent based on N,N'-dimethyl,N,N'-dibutyltetradecylmalonamide (BDMA), a robust extracting molecule previously developed in the frame of the reprocessing of waste nuclear fuel. The volume of effluents generated during the SX sequence is limited: iron scrubbing is operated with a very low aqueous to organic phase volume ratio, no specific metal chelator is required for palladium stripping, and no shift from acidic to basic media is required. Finally, a ca 1 g/L Pd(II) aqueous solution with 99,4% purity is obtained, from which palladium is directly isolated as dichlorodiammine palladium(II) salt (Pd(NH 3 ) 2 Cl 2 ) after precipitation with ammonia. Overall, palladium is quantitatively recovered from the leaching solution, and no palladium was detected in the remaining solid residue. Purity is high, as no contaminating metal could be detected in the final palladium salt. The proposed approach is simple and complementary to existing hydrometallurgical processes dedicated to gold and copper recovery.
Tuning the affinity of a medium for a given metallic cation with the sole modification of weak interactions is a challenge for molecular recognition. Solvent extraction is a key technique employed in the recovery and purification of valuable metals, and it is facing an increased complexity of metal fluxes to deal with. The selectivity of such processes generally relies on the use of specific ligands, designed after their coordination chemistry. In the present study, we illustrate the possibility to employ the sole control of weak interactions to achieve the selective extraction of Pd(II) over Nd(III) : the control over selectivity is obtained by tuning the self-assembly of the organic phase. A model is proposed, after detailed experimental analysis of molecular (XRD, NMR) and supra-molecular (SAXS) features of the organic phases. We thus demonstrate that Pd(II) extraction is driven by metal coordination, whereas Nd(III) extraction requires aggregation of the extractant in addition to metal coordination. These results are of general interest for the applications which rely on the stabilization of metals in organic phases.
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