NMR and TRLFS studies of Ln(III) and An(III) C5-BPP complexes

C5-BPP is a highly efficient N-donor ligand for the separation of trivalent actinides, An(III), from trivalent lanthanides, Ln(III). The molecular origin of the selectivity of C5-BPP and many other N-donor ligands of the BTP-type is still not entirely understood. We present here the first NMR studies on C5-BPP Ln(III) and An(III) complexes. C5-BPP is synthesized with 10% 15N labeling and characterized by NMR and LIFDI-MS methods. 15N NMR spectroscopy gives a detailed insight into the bonding of C5-BPP with lanthanides and Am(III) as a representative for trivalent actinide cations, revealing significant differences in 15N chemical shift for coordinating nitrogen atoms compared to Ln(III) complexes. The temperature dependence of NMR chemical shifts observed for the Am(III) complex indicates a weak paramagnetism. This as well as the observed large chemical shift for coordinating nitrogen atoms show that metal–ligand bonding in Am(C5-BPP)3 has a larger share of covalence than in lanthanide complexes, confirming earlier studies. The Am(C5-BPP)3 NMR sample is furthermore spiked with Cm(III) and characterized by time-resolved laser fluorescence spectroscopy (TRLFS), yielding important information on the speciation of trace amounts of minor complex species

Homogenous recycling of transuranium elements from irradiated fast reactor fuel by the EURO-GANEX solvent extraction process

The EURO-GANEX process was developed forco-separating transuranium elements from irradiatednuclear fuels. A hot flow-sheet trial was performed in acounter-current centrifugal contactor setup, using a genuinehigh active feed solution. Irradiated mixed (carbide,nitride) U80Pu20 fast reactor fuel containing 20 % Pu wasthermally treated to oxidise it to the oxide form which wasthen dissolved in HNO3. From this solution uranium wasseparated to >99.9 % in a primary solvent extraction cycleusing 1.0 mol/L DEHiBA (N,N-di(2-ethylhexyl)isobutyramidein TPH (hydrogenated tetrapropene) as the organicphase. The raffinate solution from this process, containing10 g/L Pu, was further processed in a second cycle of solventextraction. In this EURO-GANEX flow-sheet, TRU andfission product lanthanides were firstly co-extracted intoa solvent composed of 0.2 mol/L TODGA (N,N,N′,N′-tetran-octyl diglycolamide) and 0.5 mol/L DMDOHEMA (N,N′-dimethyl-N,N′-dioctyl-2-(2-hexyloxy-ethyl) malonamide)dissolved in Exxsol D80, separating them from most otherfission and corrosion products. Subsequently, the TRUwere selectively stripped from the collected loaded solventusing a solution containing 0.055 mol/L SO3-Ph-BTP(2,6-bis(5,6-di(3-sulphophenyl)-1,2,4-triazin-3-yl)pyridinetetrasodium salt) and 1 mol/L AHA (acetohydroxamicacid) in 0.5 mol/L HNO3; lanthanides were finally strippedusing 0.01 mol/L HNO3. Approximately 99.9 % of the TRUand less than 0.1 % of the lanthanides were found in theproduct solution, which also contained the major fractionsof Zr and Mo