and glass-making processes that can potentially incorporate technetium at temperatures <700 °C to avoid volatilization. Three candidate technetium feed streams are considered: (1) dilute sodium pertechnetate loaded on a non-elutable ion exchange resin; (2) dilute sodium-bearing aqueous eluent from ion exchange recovery of pertechnetate, or (3) technetium(IV) oxide precipitate containing Sn and Cr solids in an aqueous slurry. From the technical literature, promising candidate glasses are identified based on their processing temperatures and chemical durability data. The suitability and technical risk of three low-temperature glass processing routes (vitrification, encapsulation by sintering into a glass composite material, and sol-gel chemical condensation) for the three waste streams was assessed, based on available low-temperature glass data. For a subset of candidate glasses, their long-term thermodynamic behavior with exposure to water and oxygen was modeled using Geochemist's Workbench, with and without addition of reducing stannous ion. For further evaluation and development, encapsulation of precipitated TcO2/Sn/Cr in a glass composite material based on lead-free sealing glasses is recommended as a high priority. Vitrification of pertechnetate in aqueous anion exchange eluent solution using a high lead content borate glass, or other low melting glass is also recommended for further evaluation and development. Additional laboratory studies of phase behavior and chemical durability of low-temperature glasses is also recommended to provide risk mitigation if one of the primary development paths proves infeasible. This report is a deliverable for the task "Candidate Low-T Glass Waste Forms for EMF Bottoms On-Site Disposition Alternative Option."

The direct current (DC) arc plasma has been assessed with an emphasis on excitation temperature (T (exe)) and ionization/excitation efficiency by monitoring magnesium ionic:atomic ratios (Mg II:I). The primary goal is to improve the analytical performance of the DC arc instrumentation such that more sensitive and reproducible measurements can be achieved when analyzing trace impurities in nuclear materials. Due to the variety of sample types requiring DC arc analysis, an understanding of the plasma's characteristics will significantly benefit the experimental design when moving forward with LANL's capabilities for trace metal analysis of plutonium metals.

Advances in sample nebulization and injection technology have significantly reduced the volume of solution required for trace impurity analysis in plutonium and uranium materials. Correspondingly, we have designed and tested a novel chip-based microfluidic platform, containing a 100-µL or 20-µL solid-phase microextraction column, packed by centrifugation, which supports nuclear material mass and solution volume reductions of 90% or more compared to standard methods. Quantitative recovery of 28 trace elements in uranium was demonstrated using a UTEVA chromatographic resin column, and trace element recovery from thorium (a surrogate for plutonium) was similarly demonstrated using anion exchange resin AG MP-1. Of nine materials tested, compatibility of polyvinyl chloride (PVC), polypropylene (PP), and polytetrafluoroethylene (PTFE) chips with the strong nitric acid media was highest. The microcolumns can be incorporated into a variety of devices and systems, and can be loaded with other solid-phase resins for trace element assay in high-purity metals.

A simple, robust analytical chemistry method has been developed to dissolve plutonium containing particles in a complex matrix. The aerosol particles collected on Marple cascade impactor substrates were shown to be dissolved completely with an acid mixture of 12 M HNO3 and 0.1 M HF. A pressurized closed vessel acid digestion technique was utilized to heat the samples at 130 °C for 16 h to facilitate the digestion. The dissolution efficiency for plutonium particles was 99 %. The resulting particle digestate solution was suitable for trace elemental analysis and isotope composition determination, as well as radiochemistry measurements.

A new methodology for trace elemental analysis in plutonium metal samples was developed by interfacing the novel micro-FAST sample introduction system with an ICP-OES instrument. This integrated system, especially when coupled with a low flow rate nebulization technique, reduced the sample volume requirement significantly. Improvements to instrument sensitivity and measurement precision, as well as long term stability, were also achieved by this modified ICP-OES system. The sample size reduction, together with other instrument performance merits, is of great significance, especially to nuclear material analysis.

Solid debris was recovered from the previously-emptied nitrate salt waste drum S855793. The bulk sample was nondestructively assayed for radionuclides in its as-received condition. Three monoliths were selected for further characterization. Two of the monoliths, designated Specimen 1 and 3, consisted primarily of sodium nitrate and lead nitrate, with smaller amounts of lead nitrate oxalate and lead oxide by powder x-ray diffraction. The third monolith, Specimen 2, had a complex composition; lead carbonate was identified as the predominant component, and smaller amounts of nitrate, nitrite and carbonate salts of lead, magnesium and sodium were also identified. Microfocused x-ray fluorescence (MXRF) mapping showed that lead was ubiquitous throughout the cross-sections of Specimens 1 and 2, while heteroelements such as potassium, calcium, chromium, iron, and nickel were found in localized deposits. MXRF examination and destructive analysis of fragments of Specimen 3 showed elevated concentrations of iron, which were broadly distributed through the sample. With the exception of its high iron content and low carbon content, the chemical composition of Specimen 3 was within the ranges of values previously observed in four other nitrate salt samples recovered from emptied waste drums.