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The radiolytic degradation of three N,N-dialkyl amide ligands relevant to nuclear fuel reprocessing was studied. The degradation of these ligands: N,N di-2-ethyhexylbutyramide (DEHBA), N,N di-2-ethyhexylisobutyramide (DEHiBA) and N,N di-2-ethyhexyl-3-dimethylbutanamide (DEHDMBA) was examined to evaluate the effect of the structure on the formation of degradation products as well as to compare alpha induced degradation to gamma induced degradation. In situ alpha radiolysis by introduction of plutonium(IV) as the alpha source in the solution and ex situ gamma radiolysis with 60Co as the gamma source were compared. Upon identification of the main degradation products, a degradation scheme was proposed. The effects of radiation on the stability of Pu-monoamide complexes were discussed. Theoretical calculations were also performed to determine bond dissociation energy and estimate the relative strength of the bond in the molecule. The results show that neither the type of radiation (alpha vs. gamma) nor the structure modification (introduction of branching on the alkyl chain off the carbonyl carbon) of the molecule significantly impact the formation of degradation products under the conditions studied. Moreover, it was observed that the overall stability of the monoamide remains good and that Pu complexation is not greatly affected by either alpha or gamma irradiation.

For more than 50 years, CETAMA, the Commission for establishment of analytical methods from the French Alternative Energies and Atomic Energy Commission, has provided Certified Reference Materials and Interlaboratory Comparisons for the development and validation of analytical methods in the nuclear field. In the future, the nuclear spent fuel reprocessing industry will require new standards and methods to comply with high content plutonium fuel and new extraction solvents. These standards and methods will have to be fully validated in order to ensure the quality of the analytical results obtained by the laboratories. In this context, a new 242 Pu reference material, certified for its isotopic composition, has been recently produced. A novel statistical approach for data processing has been used and has led to a certified value of 0.985459 ± 0.000052 for the n ( 242 Pu)/ n (Pu) atomic ratio. In addition, an interlaboratory comparison has also been organized for the validation of a method for the analysis of DMDOHEMA, and its degradation products. This compound is considered as a new extractant candidate in the frame of separation processes for transmutation of long-lived radionuclides. The methodology and results obtained in both cases are presented.

An interlaboratory comparison has been organized by CETAMA Working Group 24 “Organic analysis” for the validation of a malonamide analysis method, DMDOHEMA, by Gas Chromatography coupled with a Flame Ionization Detector (GC-FID). This compound is studied as a new extraction solvent in nuclear reprocessing processes. Most of the results for DMDOHEMA showed an agreement between the laboratory values and the reference value better than 10%. Repeatability and reproducibility of the method were evaluated by robust statistics and detection limits were also estimated from laboratory data. The description of the method has been published in the CETAMA ANASOR collection book.