PNNL

Abstract

There is a renewed interest worldwide to promote the use of nuclear power and close the nuclear fuel cycle. The long term successful use of nuclear power is critically dependent upon adequate and safe processing and disposition of the spent nuclear fuel. Liquid-liquid extraction is a separation technique commonly employed for the processing of the dissolved spent nuclear fuel. The instrumentation used to monitor these processes must be robust, require little or no maintenance, and be able to withstand harsh environments such as high radiation fields and aggressive chemical matrices. In addition, the ability for continuous online monitoring allows for numerous benefits. This paper reviews application of the absorption and vibrational spectroscopic techniques supplemented by physicochemical measurements for radiochemical process monitoring. In this context, our team experimentally assessed the potential of Raman and spectrophotometric techniques for on-line real-time monitoring of the U(VI)/nitrate ion/nitric acid and Pu(IV)/Np(V)/Nd(III), respectively, in solutions relevant to spent fuel reprocessing. Both techniques demonstrated robust performance in the repetitive batch measurements of each analyte in a wide concentration range using simulant and commercial dissolved spent fuel solutions. Static spectroscopic measurements served as training sets for the multivariate data analysis to obtain partial least squares predictive models, which were validated using on-line centrifugal contactor extraction tests. Satisfactory prediction of the analytes concentrations in these preliminary experiments warrants further development of the spectroscopy-based methods for radiochemical safeguards and process control.