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At least 199 records · Page 11

Rapid Analytical Methodology for Chloride Molten Salt Reactor Safeguards and Process Monitoring

Technologies that enable near real-time isotopic analysis of advanced molten salt reactor (MSR) fuels are critically needed to safeguard these reactors, increase their operational efficiency, and enable their widespread deployment with confidence. We present a systematic approach to developing near real-time dissolution and chemical isolation of U, Pu, and major fission products from highly radioactive chloride molten salt samples. Chemical yields greater than 95% were observed for both uranium and the lanthanides. Interference reduction enabled the detection and quantification of key diagnostic isotopes (including 112Ag, 147Nd, and 153Sm) that were previously undetectable in the original sample. The results from this initial scoping study lay the foundation for the development of future automated systems that can enable cost-efficient, near-real time chemical separation and analysis of extremely highly radioactive molten salt samples.

38 - RADIATION CHEMISTRY, RADIOCHEMISTRY, AND NUCL↗

Savannah River Site Composite Analysis (FY2019 Annual Review)

The Savannah River Site (SRS) is a Department of Energy (DOE) site encompassing approximately 310 square miles in South Carolina. It is bounded on the southwest by the Savannah River (SR) and is situated approximately 12 miles south of Aiken, South Carolina, and 15 miles southeast of Augusta, Georgia. Construction of and subsequent operations at the SRS began in 1951 under the direction of the Atomic Energy Commission. The primary mission of the SRS was to produce tritium and plutonium for the national nuclear weapons complex. Between 1953 and 1955, SRS brought five reactors and various support facilities into operation in support of its primary mission. Support facilities included two chemical separations plants, a heavy water extraction plant, a nuclear fuel and target fabrication facility, a tritium extraction facility and waste management facilities. With the declining need for a large nuclear weapons stockpile since the end of the Cold War, many SRS facilities no longer produce or process nuclear materials. All reactors were shut down by 1993. However, the SRS Tritium Extraction Facility continues to supply DOE with tritium. Additionally, operations at the K-Area Complex currently provide interim safe storage for much of DOE’s excess plutonium (Pu) and high enriched uranium, in a building which formerly housed K Reactor. As the SRS mission has changed, many surplus facilities are being dispositioned safely and economically. SRS has completed extensive decommissioning activities in D-Area, M-Area, P-Area, R-Area, and T-Area, with groundwater (GW) remediation ongoing. High-level waste tanks continue to be emptied and closed.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

Fundamental Studies on the Recovery of Rare Earth Elements from Coal and Coal Byproducts (Final Product Report)

The objective of this project was to collect fundamental information that can be used to develop disruptive physical and chemical separation methods that may be used to extract the rare earth elements (REEs) from coal-based feedstocks in a highly efficient, cost-effective, and environmentally benign manner. To meet the stated objective, a set of interrelated fundamental studies have been conducted. The project has been subdivided into three broad areas of tasks as follows, (1) measurement of surface forces in the thin liquid films (TLFs) of water confined between two macroscopic surfaces to establish the optimal conditions for efficiently collecting the ultrafine particles of rare earth minerals (REMs) present in the coal-based feedstocks using the flotation and/or the hydrophobic-hydrophilic separation process(es), (2) identification of the fundamental mechanisms by which REE ions adsorb and desorb on clay minerals present in coal byproducts, and the characterization of the ion-adsorption clays (IACs) present in U.S. coals, and (3) developing methods of extracting the REEs from the REMs and IACs present in US coal byproducts in a cost-effective and sustainable manner.

01 COAL, LIGNITE, AND PEAT↗

Thermal Characterization of Acid Treated Anion Exchange Resins

Anion exchange is a chemical separation and purification technique in which a solid phase ion exchanging material (i.e., anion exchange resin beads) interchanges its anions with the desired anions from a solution phase. Typical anion exchange resins (e.g., Bio-Rad AG 1-X8 strongly basic anion exchange resin) consist of a polymer resin bead of cross-linked polystyrene with quaternary ammonium functional groups (Figure 1). Anion exchange occurs at the resin functional groups by exchange of the counter ion of the quaternary ammonium (typically chloride or nitrate) for the anionic species of interest. Other resin polymers have been developed—such as cross-linked vinylpyridine/divinylbenzene utilized in Reillex HPQ anion exchange resin—to improve the resins’ resistance against degradation by oxidizing agents, strong acids, and radiation. Anion exchange is performed for the separation of transuranic (TRU) elements throughout the Department of Energy complex. At the Los Alamos National Laboratory (LANL), production scale quantities of these resins are handled at the Chemistry and Metallurgy Research Facility, the Plutonium Facility, and the Transuranic Waste Facility. Spent anion exchange resin will eventually be disposed of as TRU waste. This has prompted concerns regarding its safe disposal under potential hazard scenarios, in particular a thermal excursion of a TRU waste drum. There is a concern that a potential thermal excursion of a TRU waste drum containing anion exchange resin previously contacted with nitric acid may result in energetic side reactions and pressure buildup due to resin degradation by nitric acid and heat. Therefore, the objective of the experiments described in this report was to gather qualitative and quantitative data to support decisions regarding the thermal stability and safe disposal strategy of nitric acid treated anion exchange resins utilized in TRU processing operations.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

Conceptual Model Testing Related to SDU 6 Drainwell Observations

From its inception in the early 1950s through the end of the Cold War in the early 1990s, the Savannah River Site (SRS) produced nuclear materials for national defense in five reactors. Additionally, irradiated reactor fuel and target tubes were dissolved in nitric acid to recover plutonium and uranium using the PUREX (Plutonium Uranium Reduction EXtraction) process. Liquid waste from these chemical separations processes was then stored onsite in 51 underground tanks. Eight waste storage tanks have been operationally closed (i.e. cleaned and grouted) and the remaining tanks hold a mixture of liquids, insoluble solids, and precipitated salts (SRMC-LWP-2022-00001), the latter generated by evaporating water from the liquid waste. Waste is currently being retrieved from tanks and separated into 1) high-radioactivity, low-volume, and 2) low-radioactivity, high-volume components, principally through the Salt Waste Processing Facility (SWPF) (SRMC-LWP-2023-00001). The former waste stream is vitrified in the Defense Waste Processing Facility (DWPF), stored onsite, and destined for offsite disposal in a deep geologic repository. The latter stream is mixed with dry cementitious materials in the Saltstone Production Facility (SPF) and the wet slurry placed in onsite Saltstone Disposal Units (SDUs) within the Saltstone Disposal Facility (SDF), where it hardens into a cement waste form termed saltstone. A low-infiltration surface cover system will be placed over the SDF at closure, where SDUs will then be in the subsurface post-closure (SRR-CWDA-2019-00001).

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

Efficient and Selective Chemical Transformations in Highly Charged and Confined Nanodroplets

The acceleration of chemical reaction rates and the increased product selectivity in microdroplets compared to that in bulk solutions has become a topic of increasing interest that has been extensively characterized by electrospray ionization mass spectrometry (ESI-MS). However, the sources of this acceleration and the detailed relationships between droplet properties and resulting reaction rate acceleration are still under debate. Moreover, droplet properties are governed by multiple interrelated experimental parameters, i.e., electrospray voltage, solution flow rate, etc., which makes it difficult and time-consuming to explore this diverse parameter space using traditional manual experimental or computational approaches. In this work, we developed an automated experimental platform integrating reactions in controlled charged microdroplet environments with ESI-MS characterization and sequential hybrid Bayesian modeling, as well as an optimal experimental design framework, to achieve multidimensional parameter optimization for higher reaction turnover rates, based on a model reaction of tetraethylenepentamine (TEPA) with carbon dioxide. With the current platform, we have achieved automated scans with a range of electrospray voltages and solution flow rates, and determined and optimized parameter settings to achieve increased reaction turnovers. We have also linked this platform to the underlying properties of droplets via a hybrid model incorporating physics, high-level theoretical calculations, and machine learning (ML) approaches. The autonomous platform is broadly applicable to a range of chemical reactions relevant to DOE’s mission in chemical separations, catalysis, and materials synthesis.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

OB200-DV-1 Treatability Testing: Final Results

The Hanford Site in Washington state previously generated plutonium for nuclear weapons. During operations, radionuclide byproducts and chemical process fluids were intentionally and/or unintentionally released to the subsurface, resulting in more than 800 contaminated waste sites across the Central Plateau, where historical chemical separations and waste management activities took place. As the Hanford Site mission transitioned from operations to site cleanup, remediation of the vadose zone and groundwater became a priority. However, given the depth of the unsaturated zone contamination above the groundwater, the unique nature of the waste, and the continuing impacts on groundwater quality, technologies needed to be identified and evaluated for in situ remediation in the deep vadose zone (DVZ). A laboratory treatability study has been completed to evaluate site-relevant effectiveness for nine in situ technologies that may be used to treat continuing sources of contaminants in specific areas of the Central Plateau waste sites that are grouped into the 200-DV-1 Operable Unit (OU). The 200-DV-1 OU was established in 2010 to address 43 Central Plateau waste sites with complex DVZ remediation challenges. Eight of these technologies were identified through a prescreening effort that evaluated remedial technologies potentially applicable to DVZ contamination in the Central Plateau . These eight technologies were selected for further study based on site specific knowledge gaps about their effectiveness. A ninth technology was added to the treatability study based on new information from separate laboratory investigations (conducted following the prescreening effort) demonstrating the technology’s potential effectiveness (see Section 1.2 for more information) and value for inclusion in the treatability study.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

Examination of Gamma-irradiated Calcium Silicate Hydrates. Part II: Mechanical Properties

Mechanical properties of calcium silicate hydrates (C-S-H) with C/S ratios of 0.75, 1, and 1.33 were examined with nanoindentation after gamma-adsorbed doses of 0.145, 0.280, 0.500, and 0.784 MGy, and were compared with control samples. Young' s modulus and stress relaxation tests showed no apparent trend with irradiation dose. Qualitatively, most of the irradiated samples were found to relax more than their respective controls, but not always in a statistically significant manner. Most of the Young' s modulus irradiated–control pairs showed marginally higher stiffness in the irradiated samples, but overall trends with irradiation dose were not obvious. Creep compliance was obtained for the samples irradiated at the highest dose and their respective controls. Two of the three irradiated samples exhibited less creep than their respective controls, but only one of which was statistically significant. The lack of clear changes in mechanical properties for these samples correlates with separate chemical analyses that showed no loss of interlayer water by exposure to irradiation or changes in the mean silicate chain length. Further research evaluating higher doses (25 and 200 MGy) representative of those received by concrete structures in nuclear power plants at prolonged operation is being carried out to complement the present study.

36 MATERIALS SCIENCE↗

Accelerator-Based Production of Scandium Radioisotopes for Applications in Prostate Cancer: Toward Building a Pipeline for Rapid Development of Novel Theranostics

In the field of nuclear medicine, the β + -emitting 43 Sc and β - -emitting 47 Sc are promising candidates in cancer diagnosis and targeted radionuclide therapy (TRT) due to their favorable decay schema and shared pharmacokinetics as a true theranostic pair. Additionally, scandium is a group-3 transition metal (like 177 Lu) and exhibits affinity for DOTA-based chelators, which have been studied in depth, making the barrier to implementation lower for 43/47 Sc than for other proposed true theranostics. Before 43/47 Sc can see widespread pre-clinical evaluation, however, an accessible production methodology must be established and each isotope’s radiolabeling and animal imaging capabilities studied with a widely utilized tracer. As such, a simple means of converting an 18 MeV biomedical cyclotron to support solid targets and produce 43 Sc via the 42 Ca(d,n) 43 Sc reaction has been devised, exhibiting reasonable yields. The Nat Ti(γ,p) 47 Sc reaction is also investigated along with the successful implementation of chemical separation and purification methods for 43/47 Sc. The conjugation of 43/47 Sc with PSMA-617 at specific activities of up to 8.94 MBq/nmol and the subsequent imaging of LNCaP-ENZaR tumor xenografts in mouse models with both 43/47 Sc-PSMA-617 are also presented.

62 RADIOLOGY AND NUCLEAR MEDICINE↗

Synthesis of DOTA-Based 43 Sc Radiopharmaceuticals Using Cyclotron-Produced 43 Sc as Exemplified by [ 43 Sc]Sc-PSMA-617 for PSMA PET Imaging

The implementation of theranostics in oncologic nuclear medicine has exhibited immense potential in improving patient outcomes in prostate cancer with the implementation of [ 68 Ga]Ga-PSMA-11 PET and [ 177 Lu]Lu-PSMA-617 into clinical practice. However, the correlation between radiopharmaceutical biodistributions seen with [ 68 Ga]Ga-PSMA-11 PET imaging and downstream [ 177 Lu]Lu-PSMA-617 therapy remains imperfect. This suggests that prostate cancer theranostics could potentially be further refined through the implementation of true theranostics, tandem pairs of diagnostic and therapeutic radiopharmaceuticals that utilize the same ligand and element, thus yielding identical pharmacokinetics. The radioscandiums are one such group of true theranostic radiopharmaceuticals. The radioscandiums consist of two β+ emitting scandium isotopes ( 43 Sc/ 44 Sc), as well as a β − emitting therapeutic isotope ( 47 Sc), which can all conjugate with PSMA-targeting PSMA-617. This potential has led to extensive investigations into the production of the radioscandiums as well as pre-clinical assessments with several ligands; however, there is a lack of literature extensively describing the complete synthesis of scandium radiopharmaceuticals. which therefore limits the accessibility of radioscandium research in theranostics. As such, this work aims to present an easily translatable protocol for the synthesis of [ 43 Sc]Sc-PSMA-617 from a [ 42 Ca]CaCO 3 starting material, including target formation, nuclear production via 42 Ca(d,n) 43 Sc reaction, chemical separation, radiolabeling, solvent reformulation, and target recycling.

62 RADIOLOGY AND NUCLEAR MEDICINE↗

The Measurement of Radiation Exposure of Astronauts by Radiochemical Techniques

The principal gamma-ray-omitting radioisotopes produced in the body of astronauts by cosmic-ray bombardment which have half-lives long enough to be useful for radiation dose evaluation are Be-7, Na-22, and Na-24. The sodium isotopes were measured in the preflight and postflight urine and feces, and those feces specimens collected during the manned Apollo missions, by analysis of the urine salts and the raw feces in large crystal multidimensional gamma-ray spectrometers. The Be-7 was chemically separated, and its concentration measured in an all Na(T1), anticoincidence shielded, scintillation well crystal. The overall sensitivity of the experiment was reduced by almost all variables such as low concentrations of excreted cosmogenic radionuclides, high concentrations of injected radionuclides, low sample sizes, long delay periods before analysis, and uncertain excretion rates. The astronaut radiation dose in millirads, as determined by this technique, for the Apollo 7, 8, 9, 10, 11, 12, and 13 missions was 330, 160, 315, 870 ? 550, 31, 110, and 250 respectively. In view of these limitations this technique would be best applied to cases of unusually high exposures, such as that encountered from solar flares.

R L Brodzinski↗

The measurement of radiation exposure of astronauts by radiochemical techniques

The principal gamma-ray emitting radioisotopes, produced in the body of astronauts by cosmic-ray bombardment, which have half-lives long enough to be useful for radiation dose evaluation, are Be-7, Na-22, and Na-24. The sodium isotopes were measured in the preflight and postflight urine and feces, and those feces specimens collected during the manned Apollo missions, by analysis of the urine salts and the raw feces in large crystal multidimensional gamma-ray spectrometers. The Be-7 was chemically separated, and its concentration measured in an all NaI (TL), anticoincidence shielded, scintillation well crystal. The astronaut radiation dose in millirads, as determined for the Apollo 7, 8, 9, 10, 11, 12, and 13 missions, was 330, 160, smaller than 315, 870 plus or minus 550, 31, 110, and smaller than 250, respectively.

Brodzinski, R. L.↗

On convection and gravitational layering in Jupiter and in stars of low mass.

Neutral helium is probably insoluble in metallic hydrogen below some critical temperature. When Jupiter has cooled sufficiently, helium droplets can form, grow, and fall under gravity, leading to chemical separation and gravitational layering in spite of rapid convection. Applications to cool stars are discussed.

Salpeter, E. E.↗

Materials processing in zero gravity

Manufacturing processes which are expected to show drastic changes in a space environment due to the absence of earth gravity are classified according to (1) buoyancy and thermal convection sensitive processes and (2) processes where molecular forces like cohesion and adhesion remain as the relatively strongest and hence controlling factors. Some specific process demonstration experiments carried out during the Apollo 14 mission and in the Skylab program are described. These include chemical separation by electrophoresis, the M551 metals melting experiment, the M552 exothermic brazing experiment, the M553 sphere forming experiment, the M554 composite casting experiment, and the M555 gallium arsenide crystal growth experiment.

Wuenscher, H. F.↗

Isotopic composition of lithium, potassium, rubidium, and strontium in lunar surface material

The isotopic composition of alkali and alkaline earth elements in the Luna 16 regolith was investigated by the method of thermionic emission, without chemical separation. The isotopic composition of the lithium in two regolith samples did not differ (within the limits 0.5 percent) from the mean of the terrestrial reference standard. At the same time, the observed difference (1 percent) in the isotopic composition of lithium between the samples requires further investigation and confirmation. The isotopic compositions of K and Rb did not differ within the limits of experimental error from the isotopic composition of the reference standard.

Zaslavskiy, V. G.↗

A target for production of radioxenons

A liquid cesium target has been developed which permits the production and identification of the neutron deficient isotopes of xenon. The thick target yields of Xe-127 and Xe-129 m were measured for proton energies between 28 and 40 MeV. Production of Xe-129 m, as indicated by the presence of a 196 keV line in the gamma ray spectra, occurred at all proton energies; Xe-127 was produced at proton energies above 33 MeV. Both accumulated on the target with the same time constant, and the cross sections were comparable in magnitude. The radioxenons were removed from the target by a stream of carrier gas so that chemical separation was unnecessary.

Blue, J. W.↗

The state of meteoritic material on the moon

Velocity distributions obtained from earth-based meteor observations and corrected to constant meteoroid mass are transformed to meteoroid impact velocity distributions at the moon. Average velocities at the moon thus obtained range from 13 to 18 km/sec. This information is then combined with impact heating estimates to determine the amounts of resident lunar material and incoming meteoritic material that is melted or vaporized. It is found that about 5% of the resulting melt and about 25% of the impact generated vapor should be of meteoritic content. The uncertainties in these estimates are rather large, however, because of uncertainties in the various experimental results required to establish the parameters used in this analysis. The impact generated melts and impact generated vapor deposits, if the latter can be found, should provide additional means for chemically separating out the meteoritic component in the lunar soil.

Zook, H. A.↗