Low-Flux NAA Applications at the Savannah River Site

Neutron activation analysis using low-flux isotopic neutron sources is put to use in addressing areas of applied interest in managing the Savannah River Site. Some of the applications are unique due the site's operating history and its chemical processing facilities. Because sensitivity needs for many of the applications are not severe, they can be accomplished using a 6 mg ²⁵²Cf neutron activation analysis facility. Overviews of the facility and several example applications are presented.     

Radiochemical analyses for the defense waste processing facility startup at the Savannah River Site

Highly radioactive waste from defense-related activities at the Savannah River Site in South Carolina are to be incorporated into a borosilicate glass in the Defense Waste Processing Facility (DWPF) for long-tem geological isolation. Processing and repository safety considerations require the determination of 24 radioisotopes that meet the reporting criteria. These isotopes include fission products, activation products, and daughter nuclei that grow into the waste. Four isotopes,¹³⁷Cs,⁹⁰Sr,²³⁸Pu and²³⁸U will be routinely measured in the DWPF operation for process control. This work shows that the concentrations of the other 20 reportable radioisotopes in the final glass product can be predicted from a thorough characterization of the high level waste (HLW) tanks and a knowledge of the concentrations of the major non-radioactive components in the vitrification process.     

Neutron activation analysis applications at the Savannah River Site using an isotopic neutron source

NAA using ²⁵²Cf is used to address important areas of applied interest of the Savanah River Site (SRS). Sensitivity needs for many of the applications are not severe; analyses are accomplished using a 21 mg ²⁵²Cf NAA facility. Because NAA allows analysis of bulk samples, it offers strong advantages for samples in difficult-to-digest matrices when its sensitivity is sufficient. Following radiochemical separation with stable carrier addition, chemical yields for a number of methods are determined by neutron activation of the stable carrier. In some of the cases where no suitable stable carriers exist, the source has been used to generate radioactive tracers to yield separations.     

Analysis of 36Cl in Savannah River Site radioactive waste

The present work shows the activity levels of ²²⁶Ra, ²²⁸Ra, ⁴⁰K and ¹³⁷Cs in bottom sediments collected from eight locations of Mumbai Harbour Bay. The study has shown that ⁴⁰K and ²²⁸Ra concentration is nearly uniform throughout the studied area while ²²⁶Ra and ¹³⁷Cs are more concentrated in the southern regions of the bay. The significant variation in the activity levels of radionuclides within the study site might be due to their sorption/desorption processes onto the surface of sediment materials. The low mean value of ²²⁶Ra/²²⁸Ra ratio (0.72) in the sediments indicates that ²³⁸U has relatively greater solubility and mobility than ²³²Th. Similarly, low activity ratio (0.18) for ¹³⁷Cs/⁴⁰K reflects the presence of very high content of ⁴⁰K in sediment due to presence of primary minerals in sediment. Silt and clay were reported to dominate the composition of the sediment. A significant positive correlation between ²²⁶Ra and ²²⁸Ra and ¹³⁷Cs and ⁴⁰K suggest a similar origin of their geochemical sources and identical behavior during transport in the sediment system.     

Analysis of radioiodine in ground litter samples downwind of the Savannah River Site

Ground litter samples were collected and analyzed for radioiodine (¹²⁹I) content from distances of 1.4–128 km away from the Savannah River Site nuclear fuel reprocessing facility. Analysis methods consisted of thermo-chromatographic separation of the iodine from the sample matrix followed by isotope dilution thermal ionization mass spectrometry (ID-TIMS). The results indicate that measurable quantities of radioiodine are released and that the accumulation decreases as a function of distance from the source in agreement with a simple approximation described in the United Nations Scientific Committee on the Effects of Atomic Radiation (UNSCEAR) report.     

Radium-226 analysis methodology in Savannah River Site high activity waste matrices

Waste cleanup efforts currently underway at the Savannah River Site have created a need to characterize Radium-226 levels in the various high activity waste matrices currently in Site inventories. The traditional method our laboratory used for analyzing Ra-226 in higher activity matrices was based on classic cation exchange methodology. Radiochemical separations were often initiated in remotely operated shielded analytical cells followed by additional hands-on separations in radiological hoods. Methodology based on IBC advanced technologies SuperLig 640 extractant, mounted in 3M Empore filter media has been developed to streamLine the radium analyses.     

Recovery and determination of adsorbed technetium on Savannah River Site charcoal stack samples

Experimental results are provided for the sample analyses for technetium in charcoal samples placed in-line with a Savannah River Site (SRS) processing stack effluent stream as a part of an environmental surveillance program. The method for Tc removal from charcoal was based on that originally developed with high purity charcoal. Presented is the process that allowed for the quantitative analysis of ⁹⁹Tc in SRS charcoal stack samples with and without ⁹⁷Tc as a tracer. The results obtained with the method using the ⁹⁷Tc tracer quantitatively confirm the results obtained with no tracer added. All samples contain ⁹⁹Tc at the pg·g⁻¹ level.     

Gamma-pulse-height evaluation of a USA Savannah River Site Burial Ground special configuration waste item

The Savannah River Site (SRS) Burial Ground had a container labeled as Box 33 for which they had no reliable solid waste stream designation. The container consisted of an outer box of dimensions 48″ × 46″×66″ and an inner box that contained high density and high radiation dose material. From the outer box Radiation Control measured an extremity dose rate of 22 mrem/h. With the lid removed from the outer box, the maximum dose rate measured from the inner box was 100 mrem/h extremity and 80 mrem/h whole body. From the outer box the material was sufficiently high in density that the Solid Waste Management operators were unable to obtain a Co-60 radiograph of the contents. Solid Waste Management requested that the Analytical Development Section of Savannah River National Laboratory perform a γ-ray assay of the item to evaluate the radioactive content and possibly to designate a solid waste stream. This paper contains the results of three models used to analyze the measured γ-ray data acquired in an unusual configuration.     

Diverse active well neutron coincidence counter utility at the Savannah River National Laboratory

In this paper we describe use of the Aquila active well neutron coincidence counter for nuclear material assays of ²³⁵U in multiple analytical techniques at Savannah River Site (SRS), at the Savannah River National Laboratory (SRNL), and at Argonne West National Laboratory (AWNL). The uses include as a portable passive neutron counter for field measurements searching for evidence of ²⁵²Cf deposits and storage; as a portable active neutron counter using an external activation source for field measurements searching for trace ²³⁵U deposits and holdup; for verification measurements of U-Al reactor fuel elements; for verification measurements of uranium metal; and for verification measurements of process waste of impure uranium in a challenging cement matrix. The wide variety of uses described demonstrate utility of the technique for neutron coincidence verification measurements over the dynamic ranges of 100–5000 g for U metal, 200–1300 g for U-Al, and 8–35 g for process waste. In addition to demonstrating use of the instrument in both the passive and active modes, we also demonstrate its use in both the fast and thermal neutron modes.     

Separation and purification and beta liquid scintillation analysis of 151Sm in Savannah River Site and Hanford Site DOE high level waste

This paper describes development work to obtain a product phase of ¹⁵¹Sm pure of any other radioactive species so that it can be determined in US Department of Energy high level liquid waste and low level solid waste by liquid scintillation b-spectroscopy. The technique provides separation from mCi/ml levels of ¹³⁷Cs, Pu a- and ²⁴¹Pu b-decay activity, and ⁹⁰Sr/⁹⁰Y activity. The separation technique is also demonstrated to be useful for the determination of ¹⁴⁷Pm.     

Observation and Measurement of 79Se in Savannah River Site High Level Waste Tank Fission Product Waste

We report the first observation of confirmed ⁷⁹Se activity in Savannah River Site high level fission product waste. ⁷⁹Se was measured after a seven step chemical treatment to remove interfering activity from ¹³⁷Cs, ⁹⁰Sr, and plutonium at levels 10⁵ times higher than the observed ⁷⁹Se content and to remove ⁹⁹Tc at levels 300 times higher than observed ⁷⁹Se. ⁷⁹Se was measured by liquid scintillation -decay counting after specific tests to eliminate uncertainties from possible contributions from ⁹⁹Tc, ¹⁴⁷Pm, ¹⁵¹Sm, ⁹³Zr, or ²⁴¹Pu, whose -decay spectra could appear similar to that of ⁷⁹Se, and whose content would be expected at levels near or greater than ⁷⁹Se.     

HEU measurements of holdup and recovered residue in the deactivation and decommission activities of the 321-M Reactor Fuel Fabrication Facility at the Savannah River Site

Summary This paper contains a summary of the holdup and material control and accountability (MC&A) assays conducted for the determination of highly enriched uranium (HEU) in the deactivation and decommissioning (D&D) of the Reactor Fuel Fabrication Facility at the Savannah River Site (SRS). The facility was used to fabricate HEU fuel assemblies, lithium-aluminum target tubes, neptunium assemblies, and miscellaneous components for the SRS production reactors. The facility operated for more than 35 years. During this time thousands of uranium-aluminum alloy (U-Al) production reactor fuel tubes were produced. After the facility ceased operations in 1995, all of the easily accessible U-Al was removed from the building, and only residual amounts remained. The bulk of this residue was located in the equipment that generated and handled small U-Al particles and in the exhaust systems for this equipment (e.g., chip compactor, casting furnaces, log saw, lathes A & B, cyclone separator, Freon?cart, riser crusher, …, etc). The D&D project is likely to represent an important example for D&D activities across SRS and across the Department of Energy weapons complex. The Savannah River National Laboratory was tasked to conduct holdup assays to quantify the amount of HEU on all components removed from the facility prior to placing in solid waste containers. The ²³⁵U holdup in any single component of process equipment must not exceed 50 g in order to meet the container limit. This limit was imposed to meet criticality requirements of the low level solid waste storage vaults. Thus, the holdup measurements were used as guidance to determine if further decontamination of equipment was needed to ensure that the quantity of ²³⁵U did not exceed the 50 g limit and to ensure that the waste met the Waste Acceptance Criteria (WAC) of the solid waste storage vaults. Since HEU is an accountable nuclear material, the holdupassays and assays of recovered residue were also important for material control and accountability purposes. In summary, the results of the holdup assays were essential for determining compliance with the Waste Acceptance Criteria, Material Control & Accountability, and to ensure that administrative criticality safety controls were not exceeded. This paper discusses theg-ray assay measurements conducted and the modeling of the acquired data to obtain measured holdup in process equipment, exhaust components, and fixed geometry scrap cans. It also presents development work required to model new acquisition configurations and to adapt available instrumentation to perform the assays.     

Determination of long-lived fission products and actinides in Savannah River Site HLW sludge and glass for waste acceptance

Savannah River Site (SRS) is immobilizing the radioactive, high-level waste sludge in Tank 51 into a borosilicate glass for disposal in a geologic repository. A requirement for repository aceeptance is that SRS report the concentrations of certain fission product and actinide radionuclides in the glass. This paper presents measurements of many of these concentrations in both Tank 51 sludge and the final glass. The radionuclides were measured by inductively coupled plasma mass spectrometry and α, β, and γ counting methods. Examples of the radionuclides are⁹⁰Sr,¹³⁷Cs,²³⁸U and,²³⁹Pu. Concentrations in the glass are 3.1 times lower due to dilution of the sludge with a nonradio-active glass forming frit in the vitrification process. Results also indicated that in both the sludge and glass the relative concentrations of the long lived fission products insoluble in caustic are in proportion to their yields from the fission of²³⁵U waste in the SRS reactors. This allowed the calculation of a fission yield scaling factor. This factor in addition to the sludge dilution factor can be used to estimate concentrations of waste acceptance radionuclides that cannot be measured in the glass. Examples of these radionuclides are⁷⁹Se,⁹³Zr, and¹⁰⁷Pd.     

Measurement of <Superscript>99</Superscript>Tc in Savannah River Site high activity waste

Summary Waste cleanup efforts currently underway at the Savannah River Site have created a need to characterize ⁹⁹Tc in the various high activity waste matrices currently in Site inventories. The traditional method our laboratory used for analyzing ⁹⁹Tc in higher activity matrices was a solvent-solvent extraction method using Aliquat-336 in xylene. In an effort to eliminate the resulting generation of mixed wastes, a variety of different separation methodologies have been studied. Eichrom TEVA solid phase extractions using column technology have been employed in a case by case basis over the last several years. More recently, applications using Eichrom TEVA extraction discs and 3M Empore Tc extraction discs have also been explored.     

Expanding the tools available for direct ortho cupration--targeting lithium phosphidocuprates

Reaction of in situ generated lithium phosphides with 0.5 eq. Cu(I) is employed as a means of targeting lithium phosphidocuprates of either Gilman- or Lipshutz-type formulation--e.g., (R(2)P)(2)CuLi·n(LiX) (n = 0, 1). For R = Ph, X = CN in toluene followed by thf or R = Ph, X = I in thf/toluene an unexpected product results. [(Ph(2)P)(6)Cu(4)][Li·4thf](2)1 reveals an ion-separated structure in the solid state, with solvated lithium cations countering the charge on an adamantyl dianion [(Ph(2)P)(6)Cu(4)](2-). Deployment of R = Ph, X = CN in thf affords a novel network based on the dimer of Ph(2)PCu(CN)Li·2thf 2 with trianions based on 6-membered (PCu)(3) rings acting as nodes in the supramolecular array and solvated alkali metal counter-ions completing the linkers. Cy(2)PLi (Cy = cyclohexyl) has been reacted with CuCN in thf/toluene to yield Gilman-type lithium bis(phosphido)cuprate (Cy(2)P)(2)CuLi·2thf 3 by the exclusion of in situ generated LiCN. A polymer is noted in the solid state.     

Metavanadate at the Active Site of the Phosphatase VHZ

Vanadate is a potent modulator of a number of biological processes and has been shown by crystal structures and NMR spectroscopy to interact with numerous enzymes. Although these effects often occur under conditions where oligomeric forms dominate, the crystal structures and NMR data suggest that the inhibitory form is usually monomeric orthovanadate, a particularly good inhibitor of phosphatases because of its ability to form stable trigonal-bipyramidal complexes. We performed a computational analysis of a 1.14 ? structure of the phosphatase VHZ in complex with an unusual metavanadate species and compared it with two classical trigonal-bipyramidal vanadate-phosphatase complexes. The results support extensive delocalized bonding to the apical ligands in the classical structures. In contrast, in the VHZ metavanadate complex, the central, planar VO(3)(-) moiety has only one apical ligand, the nucleophilic Cys95, and a gap in electron density between V and S. A computational analysis showed that the V-S interaction is primarily ionic. A mechanism is proposed to explain the formation of metavanadate in the active site from a dimeric vanadate species that previous crystallographic evidence has shown to be able to bind to the active sites of phosphatases related to VHZ. Together, the results show that the interaction of vanadate with biological systems is not solely reliant upon the prior formation of a particular inhibitory form in solution. The catalytic properties of an enzyme may act upon the oligomeric forms primarily present in solution to generate species such as the metavanadate ion observed in the VHZ structure.     

Kinase Sensing Based on Protein Interactions at the Catalytic Site

The role kinases play in regulating cellular processes makes them potential biomarkers for detecting the onset and prognosis of various diseases, including many types of cancer. Current kinase biosensors, including electrochemical and radiometric methods, rely on sensing the ATP-dependant enzymatic phosphorylation reaction. Here we introduce a new type of interaction-based electrochemical kinase biosensor that does not require any chemical labelling or modification. The basis for sensing is the interactions between the catalytic site of the kinase and the phosphorylation site of its substrate rather than the phosphorylation reaction. We demonstrated this concept with the ERK2 kinase and its substrate protein HDGF, which is involved in lung cancer. A peptide monolayer derived from the HDGF phosphorylation site was adsorbed onto a gold electrode and was used to sense ERK2 without ATP. The sensitivity of the assay was down to 10 nM of ERK2, corresponding with the range of its cellular concentrations. Surface chemistry analysis confirmed that ERK2 was bound to the HDGF peptide monolayer. This increased the permeability of redox-active species through the monolayer and resulted in ERK2 electrochemical sensing. Since our detection approach is based on protein-protein interactions and not on the enzymatic reaction, it can be further utilized for more selective detection of different types of enzymes.