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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. The availability of on-line, real-time techniques that directly measure process concentrations of nuclear materials will enhance the 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 paper reviews the current state of development of the spectroscopic on-line monitoring techniques for such solutions. To further examine the applicability of optical spectroscopy for this application, segments of a spent nuclear fuel, with approximate burn-up values of 70 MW d/kg M, were dissolved in concentrated nitric acid and adjusted to varying final concentrations of HNO 3 . The resulting spent fuel solutions were batch-contacted with tributyl phosphate/n-dodecane organic solvent. The feed and equilibrium aqueous and loaded organic solutions were subjected to optical measurements. The obtained spectra showed the presence of quantifiable Raman bands due to NO 3 − and UO 2 2+ 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. This result justifies spectroscopic techniques as a promising methodology for monitoring spent fuel processing solutions in real-time. The fuel solution was quantitatively evaluated based on spectroscopic measurements and was compared to inductively coupled plasma-mass spectroscopy analysis and Oak Ridge Isotope Generator (ORIGEN)-based estimates.

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During World War II, the Hanford Site in Washington became the location for U.S. plutonium production. In 2004, a bottle containing a sample of plutonium was recovered from a Hanford waste trench. Here, state-of-the-art instrumental analyses, reactor model simulations, and investigative science techniques were used to provide insights as to the origin of this unknown sample, a process collectively termed as nuclear archeology. Isotopic age dating conducted on the sample in 2007 indicated the sample was separated from the spent fuel 61.6 +/- 4.5 years earlier. The isotope (22)Na, a detectable product of a secondary nuclear reaction, proved useful as a powerful tool for nuclear forensic analysis as (1) an easily detectable signifier of the presence of alpha emitting actinides, (2) an indicator of sample splitting, and (3) a measure of the time since sample splitting. Analytical results of minor actinide isotopes and reactor model simulations confirmed the material originated from the X-10 reactor in Oak Ridge, TN. Corroborated by historical documents, we concluded this sample was part of the first batch of Pu separated at T-Plant, Hanford, the world's first industrial-scale reprocessing facility, on December 9, 1944. This sample represents the oldest known collection of man-made (239)Pu in the world.

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There is little information available on the variation in lignin content of growth rings in hardwoods. This study examines whether infrared microscopy can detect intra-incremental differences in the chemical composition of three hardwoods (R. pseudoacacia, P. Americana, and G. triacanthos) and the effect of such differences on the delignification of the hardwoods during weathering. Earlywood has higher lignin content than latewood in R. pseudoacacia and P. americana, but the opposite was found for G. triacanthos. The delignification of the earlywood and latewood during weathering varied for the three species. It was greater in the earlywood of R. pseuoacacia, whereas in P. americana and G. triacanthus it was more pronounced in latewood. Differences in density and lignin content of earlywood and latewood help explain these differences. In addition, a deconvoluting software package was used to determine whether it is possible to estimate the lignin/hemicellulose ratio in softwoods and hardwoods. Results from the 1760-1580 cm(-1) region provided data that can be used to estimate the lignin/hemicellulose ratio of softwoods and hardwoods. This information can be obtained far more easily using infrared microscopy than with conventional wet chemical techniques, potentially allowing characterization of greater numbers of species than has hitherto been possible.

SummaryPacific Northwest National Laboratory (PNNL) is developing the concept of an automated UF 6 cylinder verification station that would be located at key measurement points to positively identify each cylinder, measure its mass and enrichment, store the collected data in a secure database, and maintain continuity of knowledge on measured cylinders until the arrival of International Atomic Energy Agency (IAEA) inspectors. At the center of this unattended system is a hybrid enrichment assay technique that combines the traditional enrichment-meter method (based on the 186-keV peak from 235 U) with nontraditional neutron-induced high-energy gamma-ray signatures (spawned primarily by 234 U alpha emissions and 19 F(α,n) reactions). Previous work by PNNL provided proof-of-principle for the nontraditional signatures to support accurate, full-volume interrogation of the cylinder enrichment, thereby reducing the systematic uncertainties in enrichment assay due to UF 6 heterogeneity and providing greater sensitivity to material substitution scenarios [Smith 2009;Smith In press].The work described here builds on that preliminary evaluation of the non-traditional signatures, but focuses on a prototype field system utilizing NaI(Tl) and LaBr 3 (Ce) spectrometers, and enrichment analysis algorithms that integrate the traditional and non-traditional signatures. Results for the assay of Type-30B cylinders ranging from 0.2 to 4.95 wt% 235 U, at an AREVA fuel fabrication plant in Richland, WA, are described for the following enrichment analysis methods: 1) traditional enrichment meter signature (186-keV peak) as calculated using a square-wave convolute (SWC) algorithm; 2) nontraditional high-energy gamma-ray signature that provides neutron detection without neutron detectors and 3) hybrid algorithm that merges the traditional and non-traditional signatures. Uncertainties for each method, relative to the declared enrichment for each cylinder, are calculated and compared to the uncertainties from an attended HPGe verification station at AREVA, and the IAEA's uncertainty target values for feed, tail and product cylinders. Table 1 provides a summary of those results below. Traditional NaI (SWC method) 3.5 7.9 13Non-Traditional NaI 3.7 4.9 32Hybrid NaI (simple average) 2.5 4.6 9.71 The target uncertainties are estimated from the combination of systematic and random errors given in Kuhn and should be used only to set the scale of the target uncertainties.iv A summary of the major findings from the field measurements and subsequent analysis follows:• Traditional enrichment-meter assay using specially collimated NaI spectrometers and a SquareWave-Convolute algorithm can achieve uncertainties comparable to HPGe and LaBr for product, natural and depleted cylinders.• Non-traditional signatures measured using NaI spectrometers enable interrogation of the entire cylinder volume and accurate measurement of absolute 235 U mass in product, natural and depleted cylinders.• A hybrid enrichment assay method can achieve lower uncertainties than e...

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