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A novel method proposed by Korea Atomic Energy Research Institute has been applied to the treatment of chloride salt wastes coming from electrorefining of spent nuclear fuel, which allows to separate uranium from fission products. It is based on a matrix, SAP (SiO2-Al2O3-P2O5), synthesized by a conventional sol-gel process, able to stabilize the volatile salt wastes due to the formation of metalaluminosilicates, metalaluminophosphates and metalphosphates. With this method a higher disposal efficiency and a lower waste volume can be obtained. Eutectic melt LiCl-KCl (59-41 mol%) has been used to simulate the waste salt. The composite SAP has been prepared by using tetraethyl ortosilicate (TEOS), aluminum chloride (AlCl3.6H2O) and phosphoric acid (H3PO4) as sources of Si, Al, and P, respectively. All reagents were dissolved in EtOH/H2O and the mixture, tightly sealed, was placed in an electric oven at 70 C. After a gelling/ageing for 3 days, the transparent hydrogels were dried at 110 C for 3 days and then thermally treated at 600 C for 2 hours. The final product (SAP) was reacted with metal chlorides at increasing temperatures for 20 hours inside an Argon-atmosphere glove-box, after mixing them at a SAP/metal chloride mixing ratio of 2. The obtained products have been characterized by means of density measurements, scanning electron microscopy, thermal analysis, as well as by XRD, FTIR and Raman spectra. Financial support from the Nuclear Fission Safety Program of the European Union (project SACSESS, contract FP7-CP-2012-323282) is gratefully acknowledged.

Two different glass powders (a commercially available glass frit and a borosilicate glass) have been used as blending agents for sodalite, an aluminosilicate mineral able to condition chloride salt wastes from pyrometallurgical processes. The synthesis of the mineral phase has been made through a process recently proposed by Idaho National Laboratory in USA, starting from a homogeneous powder of nepheline, chloride salts and glass. The mix, put into an alumina crucible, was introduced in a furnace inside an argon-atmosphere glove-box. The furnace temperature was then raised to 925 C, where it was kept for 7 hours. Leach tests under static conditions, according to ASTM C1285-02, have then been carried out on the final waste forms at room temperature (23 C) and in an oven at 90 C. SEM investigations have also been made before and after leach tests, in order to check the status of the powders. In particular the effect of the leaching process on the surface of the sodalite grains at 90 C from 30 to 150 days has been evidenced. The results obtained in the present study have been usefully compared to those from a similar test on a sodalite added with a glass frit by Idaho National Laboratory. Financial support from the Nuclear Fission Safety Program of the European Union is gratefully acknowledged (project ACSEPT, contract FP7-CP-2007-211 267).

The effect of the presence of an additional ester or amide carboxy group in the 6position of the pyridine nuclei of calixarenebased picolinamide ligands on the extraction and complexation properties of lanthanideIII and actinideIII metal ions was studied. For this purpose, six new ligands 1–6were synthesized; their conformational properties were studied both in solution and in the solid state, and their binding properties towards lanthanide LnIII and actinide AnIII metal ions were determined under extracting conditions simulating those present in radioactive waste. In the presence of BrCosan as synergizer, a rather high efficiency in the extraction of trivalent metal ions by these ligands was observed even at [HNO3] > 2–3 M. Complexation of LnIIImetal ions was also studied under homogeneous conditions methanol solution, both in chloride and nitrate media, by using spectrophotometry and calorimetry. A comparison with the data obtained with ligands L1–L3, lacking the additional binding sites in the 6position of the pyridine nuclei, is reported and the effects of the structure of the ligands on the stoichiometry of the complexes, coordination of the metal ions, basicity of the pyridine binding groups and efficiency and selectivity in the extractions are also discussed.

A novel method proposed by Korea Atomic Energy Research Institute has been applied to the treatment of chloride salt wastes coming from electrorefining of spent nuclear fuel, which allows to separate uranium from fission products. It is based on a matrix, SAP (SiO2-Al2O3-P2O5), synthesized by a conventional sol-gel process, able to stabilize the volatile salt wastes due to the formation of metalaluminosilicates, metalaluminophosphates and metalphosphates. With this method a higher disposal efficiency and a lower waste volume can be obtained. Eutectic melt LiCl-KCl (59-41 mol%) has been used to simulate the waste salt. The composite SAP has been prepared by using tetraethyl ortosilicate (TEOS), aluminum chloride (AlCl3.6H2O) and phosphoric acid (H3PO4) as sources of Si, Al, and P, respectively. All reagents were dissolved in EtOH/H2O and the mixture, tightly sealed, was placed in an electric oven at 70 C. After a gelling/ageing for 3 days, the transparent hydrogels were dried at 110 C for 3 days and then thermally treated at 600 C for 2 hours. The final product (SAP) was reacted with metal chlorides at increasing temperatures for 20 hours inside an Argon-atmosphere glove-box, after mixing them at a SAP/metal chloride mixing ratio of 2. The obtained products have been characterized by means of density measurements, scanning electron microscopy, thermal analysis, as well as by XRD, FTIR and Raman spectra. Financial support from the Nuclear Fission Safety Program of the European Union (project SACSESS, contract FP7-CP-2012-323282) is gratefully acknowledged.

Two different glass powders (a commercially available glass frit and a borosilicate glass) have been used as blending agents for sodalite, an aluminosilicate mineral able to condition chloride salt wastes from pyrometallurgical processes. The synthesis of the mineral phase has been made through a process recently proposed by Idaho National Laboratory in USA, starting from a homogeneous powder of nepheline, chloride salts and glass. The mix, put into an alumina crucible, was introduced in a furnace inside an argon-atmosphere glove-box. The furnace temperature was then raised to 925 C, where it was kept for 7 hours. Leach tests under static conditions, according to ASTM C1285-02, have then been carried out on the final waste forms at room temperature (23 C) and in an oven at 90 C. SEM investigations have also been made before and after leach tests, in order to check the status of the powders. In particular the effect of the leaching process on the surface of the sodalite grains at 90 C from 30 to 150 days has been evidenced. The results obtained in the present study have been usefully compared to those from a similar test on a sodalite added with a glass frit by Idaho National Laboratory. Financial support from the Nuclear Fission Safety Program of the European Union is gratefully acknowledged (project ACSEPT, contract FP7-CP-2007-211 267).

The cover picture showsthe complexation of actinide metal ions by picolinamidebased calix[6]arenes. These ligands possess remarkable efficiency in the extraction of trivalent metal ions even at very high HNO3concentration and fair selectivity for actinide ions over lanthanide ions, which is useful in the recycling of the spent nuclear fuel. The Partitioning and Transmutation P&T strategy would allow the longlived minor actinides Np, Am, Cm in fast nuclear reactors to be separated and transmutated and would also allow the radiotoxicity in the ultimate waste to be minimized, making nuclear power plants more efficient and sustainable. Details are discussed in the article by M. Mariani, A. Casnati et al. on p. 2675 ff.