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Understanding the fundamental rates of transfer and complex formation is crucial in maintaining optimal efficiency and effectivity in solvent extraction. Methodologies to analyze solvent ex...

Understanding the fundamental rates of transfer and complex formation is crucial in maintaining optimal efficiency and effectivity in solvent extraction. Methodologies to analyze solvent extraction systems are lacking in that they are commonly performed off-line in subsequent experiments. Thus, a method to proficiently investigate solvent extraction systems in a Lewis cell using in situ Raman spectroscopy paired with chemometric modeling has been developed to allow for on-line analysis and monitoring. Forward and reverse interfacial transfer coefficients for the extraction of nitric acid by tributyl phosphate, a process crucial to used nuclear fuel reprocessing, were measured by spectroscopic monitoring of both phases simultaneously in a two-phase solvent extraction system. Concentration data was derived from the chemometric modeling using Raman spectra. The concentration data was fit to a nonlinear least squares regression model to allow for the calculation of the transfer coefficients in the system. The reverse interfacial transfer coefficient, kr, was determined along with the parameter 95% confidence intervals and 95% prediction intervals. The forward interfacial transfer coefficient, kf, was then back calculated from kr and the aqueous phase and organic phase equilibrium concentrations. The average calculated values of kr and kf were 2.56 (± 0.50) × 10−5 m s−1 and 4.75 (± 1.13) × 10−6 m s−1, respectively. The information obtained regarding solvent extraction parameters and transfer can be applied in the study of systems of higher complexity, involving complex formation and their transfer across a liquid:liquid interface.

For many nuclear material safeguards inspections, spectroscopic gamma detectors are required which can achieve high event rates (in excess of 106 s−1) while maintaining very good energy resolution for discrimination of neighboring gamma signatures in complex backgrounds. Such spectra can be useful for non-destructive assay (NDA) of spent nuclear fuel with long cooling times, which contains many potentially useful low-rate gamma lines, e.g., Cs-134, in the presence of a few dominating gamma lines, such as Cs-137. Detectors in use typically sacrifice energy resolution for count rate, e.g., LaBr 3 , or vise-versa, e.g., CdZnTe. In contrast, we anticipate that beginning with a detector with high energy resolution, e.g., high-purity germanium (HPGe), and adapting the data acquisition for high throughput will be able to achieve the goals of the ideal detector. In this work, we present quantification of Cs-134 and Cs-137 activities, useful for fuel burn-up quantification, in fuel that has been cooling for 22.3 years. A segmented, planar HPGe detector is used for this inspection, which has been adapted for a high-rate throughput in excess of 500k counts/s. Using a very-high-statistic spectrum of 2.4 × 1011 counts, isotope activities can be determined with very low statistical uncertainty. However, it is determined that systematic uncertainties dominate in such a data set, e.g., the uncertainty in the pulse line shape. This spectrum offers a unique opportunity to quantify this uncertainty and subsequently determine required counting times for given precision on values of interest.

Progress in the second year of this project is described by the series of technical reports and manuscripts that make up the content of this report. These documents summarize successes in our goals to develop our robust image-hash templating and material-discrimination techniques and apply them to test image data.

Future arms control treaties may push nuclear weapons limits to unprecedented low levels and may entail precise counting of warheads as well as distinguishing between strategic and tactical nuclear weapons. Such advances will require assessment of form and function to confidently verify the presence or absence of nuclear warheads and/or their components. Imaging with penetrating radiation can provide such an assessment and could thus play a unique role in inspection scenarios. Yet many imaging capabilities have been viewed as too intrusive from the perspective of revealing weapon design details, and the potential for the release of sensitive information poses challenges in verification settings. A widely held perception is that verification through radiography requires images of sufficient quality that an expert (e.g., a trained inspector or an image-matching algorithm) can verify the presence or absence of components of a device. The concept of information barriers (IBs) has been established to prevent access to relevant weapon-design information by inspectors (or algorithms), and has, to date, limited the usefulness of radiographic inspection. The challenge of this project is to demonstrate that radiographic information can be used behind an IB to improve the capabilities of treaty-verification weapons-inspection systems.