PNNL

Abstract

The potential of using optical spectroscopic techniques, such as Raman and Visible/Near Infrared (Vis/NIR), for on-line process control and special nuclear materials accountability applications at a spent nuclear fuel reprocessing facility was evaluated. Availability of on-line real-time techniques that directly measure process concentrations of nuclear materials will enhance performance and proliferation resistance of the solvent extraction processes. Further, on-line monitoring of radiochemical streams will also improve reprocessing plant operation and safety. This report reviews current state of development of the spectroscopic on-line monitoring techniques for such solutions. To further examine applicability of optical spectroscopy for monitoring reprocessing solutions, segments of a spent nuclear fuel, with approximate burn-up values of 70 MWd/kgM, were dissolved in concentrated nitric acid and adjusted to varying final concentrations of HNO3. The resulting spent fuel solutions were batch-contacted with tributyl phosphate/dodecane organic solvent. The feed and equilibrium aqueous and loaded organic solutions were subjected to optical measurements. The obtained spectra showed the presence of the quantifiable Raman bands due to NO3- and UO22+ and Vis/NIR bands due to multiple species of Pu(IV), Pu(VI), Np(V), the Np(V)-U(VI) cation-cation complex, and Nd(III) in fuel solutions, justifying spectroscopic techniques as a promising methodology for monitoring spent fuel processing solutions in real-time. Quantitative evaluation of the fuel solution was performed based on spectroscopic measurements and compared to ICP-MS analysis.