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Tank Waste LDR Organics Data Summary for Sample-and-Send (Rev.1A)

The presence of organic chemicals regulated under the Resource Conservation and Recovery Act (RCRA) Land Disposal Restrictions (LDR) adds complexity to treating and disposing of the low activity fraction of Hanford tank waste if a low temperature treatment method such as grouting is used (SRNL-STI-2020-00228). The complexity arises from the fact that the baseline vitrification method is considered by the Washington State Department of Ecology (Ecology) as providing adequate thermal treatment for organics; a status not automatically extended to a lowtemperature process, such as solidifying the waste in a cementitious waste form. In addition, the Environmental Protection Agency (EPA) LDR program is intended to ensure that wastes are properly treated prior to disposal. Proper treatment makes hazardous waste less harmful to groundwater by reducing the mobility and/or toxicity of the hazardous constituents in the waste. EPA guidance indicates that stabilization/solidification of waste for organics could be considered impermissible dilution under the LDR dilution prohibition. In addition, waste storage activities at Hanford have required transferring and blending waste within the tank system and these activities have potentially altered the concentrations of the hazardous constituents. The LDR dilution prohibition found in 40 Code of Federal Regulations (CFR) 268.3 states that “… no generator, transporter, handler, or owner or operator of a treatment, storage, or disposal facility shall in any way dilute a restricted waste or the residual from treatment of a restricted waste as a substitute for adequate treatment …”. Hence, if LAW is to be treated using low temperature stabilization (such as cementation), then it is important to demonstrate both how past storage activities have contributed to the removal (by vacuum evaporation), or destruction (by in situ decomposition) of the LDR organics and how future retrieval and waste feed preparation will contribute to their removal (by filtration and ion exchange). Demonstrating these processes helps validate that cementation without additional organic treatment does not necessarily represent impermissible dilution. To aid in implementing cementitious solidification of Low Activity Waste (LAW), WRPS has been developing a regulatory and processing LDR treatment variance strategy termed “Sampleand-Send” that relies, in part, on demonstrating that in situ decomposition reactions along with historic evaporation of tank waste has destroyed or removed most of the LDR organics possibly associated with Hanford Tank Waste (SRNL-STI-2020-00582, SRNL-STI-2021-00453, SRNL-STI-2022-00391). Under the Sample-and-Send concept, Hanford tank waste would be retrieved, processed through a Tank-Side Cesium Removal-like system, and staged as a candidate feed that would then be sampled to confirm the waste acceptance criteria is met for solidification in an LAW cementitious treatment facility. If it can be shown that LDR organics are at concentrations below the waste acceptance criteria (WAC) for cementitious stabilization and have been sufficiently removed (by historic evaporation or by filtration and ion exchange during Cs removal), destroyed (by historic in situ decomposition), or are not soluble in LAW above the WAC then additional organic treatment is not needed prior to creating a cementitious final waste form and the concept of Sample-and-Send would be proposed to establish a non-rulemaking site-specific treatment variance using the specified method of treatment “STABL” to remove sampling requirements of the waste form after treatment. Waste not meeting the WAC could either be routed to the Hanford Waste Treatment and Immobilization Plant for LAW vitrification, or further processed by evaporation or chemical oxidation before solidifying in a cementitious waste form. A key component in implementing the Sample-and-Send strategy is identifying which of the 207 LDR organic compounds associated with the RCRA Part A permit application waste codes for the Double Shell Tanks (DSTs) and Single Shell Tanks (SSTs) and any applicable Underlying Hazardous Constituents (UHCs) from 40 CFR 268.48 should be considered as potentially present and thus subject to regulation. In addition, it is also necessary to understand the solubility volatility, and reactivity of these compounds in LAW to identify which of the potentially present LDR organic compounds are not soluble above regulatory levels or are likely to have been removed by historic evaporation or destroyed by in situ decomposition reactions. If there are potentially present LDR organic compounds that have not been removed or destroyed and are soluble above regulatorily significant concentrations then a treatability variance may be needed for these species to eliminate any concerns pertaining to impermissible dilution. The spreadsheet accompanying this calculation report contains the data and logic computations needed to screen the list of 207 LDR organics associated with Hanford tank waste to identify those potentially present and to indicate which compounds may need to be included in a treatability variance.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

Microscopic Measurement: Need for Nuclear Material Sample Specimen Characterization Capability

The Surveillance, Fabrication, and Off-Site Operations team at Lawrence Livermore National Laboratory is beginning an update to the nuclear material machining lab in Superblock. Plutonium and other nuclear materials tend to accelerate the aging process for equipment and machines that would otherwise be maintainable for long lives. They have their lifespans shortened from deteriorated seals, embrittled polymer components, accelerated corrosion, and damage to electronics from exposure to radioactive materials. The cost of installation of equipment into a glove box (GB) tends to outstrip the cost of the equipment itself. Due to the magnification of cost, the historical approach to equipment installs has been to purchase and install the highest-quality and most robust equipment available to maximize time between failures and updates. To make room for the installation of a new lathe, the inspection GB is being moved to a different location within the machining lab. As part of the overall effort, the equipment within the inspection GB is being revisited. Current measurement capabilities are antiquated and starting to become problematic due to age. Advances in metrology are sought for more comprehensive characterization of scientific samples. This document aims to identify several options for the replacement of current measurement equipment and identify a system for purchase and eventual installation. The intention is not to select the cheapest system, but rather to identify a system that best meets the needs of both the operators and principal investigators (PI). Following the convention of the SYSM-5620 Design Thinking and System Engineering, it was determined that a laser confocal measurement system from Keyence is the most suitable option for our programmatic need. Form factor, capability, and maintainability were considered. Along with stakeholder input, to ensure the best decision for the Nuclear Material Technology Program.

36 MATERIALS SCIENCE↗

Evaluation of the Reconstruction Accuracy of the Ultrasound Model–Based Image Reconstruction (U-MBIR) Method for Concrete to Optimize Damage Detection

Reinforced concrete is a critical structural material used to construct nuclear power plants (NPPs). As such, its safety and performance must be thoroughly examined throughout the life cycle of the NPP infrastructure system. Ultrasonic measurements have been an industry standard for both surface and subsurface inspections. To support the development of these techniques, Oak Ridge National Laboratory (ORNL) has researched and developed advanced image reconstruction algorithms to capture internal damage. The results and discussion presented herein summarize the current state of the ultrasonic model–based iterative reconstruction (U-MBIR) algorithm developed at ORNL. In the work documented in this report, the U-MBIR methodology was applied to four sets of ultrasonic data collected from concrete specimens. The results demonstrate that the U-MBIR algorithm can successfully detect defects within the four concrete samples. The reconstruction images help identify the specimen thickness, regions of delamination, and location of rebar embedded within the concrete. The reconstruction images allow engineers and technicians to characterize the internal defects within concrete specimens and structural members. Ultimately, this knowledge can guide engineers in making informed decisions regarding the performance, safety, and reliability of structural materials (i.e., reinforced concrete) throughout the life cycle of NPPs.

22 GENERAL STUDIES OF NUCLEAR REACTORS↗

SNM Radiation Signature Classification Using Different Semi-Supervised Machine Learning Models

The timely detection of special nuclear material (SNM) transfers between nuclear facilities is an important monitoring objective in nuclear nonproliferation. Persistent monitoring enabled by successful detection and characterization of radiological material movements could greatly enhance the nuclear nonproliferation mission in a range of applications. Supervised machine learning can be used to signal detections when material is present if a model is trained on sufficient volumes of labeled measurements. However, the nuclear monitoring data needed to train robust machine learning models can be costly to label since radiation spectra may require strict scrutiny for characterization. Therefore, this work investigates the application of semi-supervised learning to utilize both labeled and unlabeled data. As a demonstration experiment, radiation measurements from sodium iodide (NaI) detectors are provided by the Multi-Informatics for Nuclear Operating Scenarios (MINOS) venture at Oak Ridge National Laboratory (ORNL) as sample data. Anomalous measurements are identified using a method of statistical hypothesis testing. After background estimation, an energy-dependent spectroscopic analysis is used to characterize an anomaly based on its radiation signatures. In the absence of ground-truth information, a labeling heuristic provides data necessary for training and testing machine learning models. Supervised logistic regression serves as a baseline to compare three semi-supervised machine learning models: co-training, label propagation, and a convolutional neural network (CNN). In each case, the semi-supervised models outperform logistic regression, suggesting that unlabeled data can be valuable when training and demonstrating value in semi-supervised nonproliferation implementations.

98 NUCLEAR DISARMAMENT, SAFEGUARDS, AND PHYSICAL P↗

Virulence and Genetic Diversity of Puccinia spp., Causal Agents of Rust on Switchgrass (Panicum virgatum L.) in the USA

Switchgrass (Panicum virgatum L.) is an important cellulosic biofuel grass native to North America. Rust, caused by Puccinia spp. is the most predominant disease of switchgrass and has the potential to impact biomass conversion. In this study, virulence patterns were determined on a set of 38 switchgrass genotypes for 14 single-spore rust isolates from 14 field samples collected in seven states. Single nucleotide polymorphism (SNP) variation was also assessed in 720 sequenced cloned amplicons representing 654 base pairs of the elongation factor 1-α gene from the field samples. Five major haplotypes were identified differing by 11 out of the 39 SNP positions identified. STRUCTURE, Principal Coordinate Analysis, and phylogenetic analyses divided the rust population into two genetic clusters. Virginia and Georgia had the highest and lowest rust genetic diversity, respectively. Only nine accessions showed a differential disease response between the 14 isolates, allowing the identification of eight races, differing by 1–3 virulence factors. Overall, the results suggested clonal reproduction of the pathogen and a North–South differentiation via local adaptation. However, similar haplotypes and races were also recovered from several states, suggesting migration events, and highlighting the need to further investigate the switchgrass rust population structure and evolution in the USA.

Bahri, Bochra A. (ORCID:0000000159055880)↗

The Evolution of AGN Activity in Brightest Cluster Galaxies

We present the results of an analysis of Wide-field Infrared Survey Explorer (WISE) observations of the full 2500 deg 2 South Pole Telescope (SPT)-Sunyaev–Zel'dovich cluster sample. We describe a process for identifying active galactic nuclei (AGN) in brightest cluster galaxies (BCGs) based on WISE mid-IR color and redshift. Applying this technique to the BCGs of the SPT-SZ sample, we calculate the AGN-hosting BCG fraction, which is defined as the fraction of BCGs hosting bright central AGNs over all possible BCGs. Assuming an evolving single-burst stellar population model, we find statistically significant evidence (>99.9%) for a mid-IR excess at high redshift compared to low redshift, suggesting that the fraction of AGN-hosting BCGs increases with redshift over the range of 0 < z < 1.3. The best-fit redshift trend of the AGN-hosting BCG fraction has the form (1 + z) 4.1±1.0 . These results are consistent with previous studies in galaxy clusters as well as as in field galaxies. One way to explain this result is that member galaxies at high redshift tend to have more cold gas. While BCGs in nearby galaxy clusters grow mostly by dry mergers with cluster members, leading to no increase in AGN activity, BCGs at high redshift could primarily merge with gas-rich satellites, providing fuel for feeding AGNs. If this observed increase in AGN activity is linked to gas-rich mergers rather than ICM cooling, we would expect to see an increase in scatter in the P cav versus L cool relation at z > 1. Last, this work confirms that the runaway cooling phase, as predicted by the classical cooling-flow model, in the Phoenix cluster is extremely rare and most BCGs have low (relative to Eddington) black hole accretion rates.

79 ASTRONOMY AND ASTROPHYSICS↗

Compact Steep Spectrum Radio Sources with Enhanced Star Formation Are Smaller Than 10 kpc

Compact steep spectrum (CSS) radio sources are active galactic nuclei (AGN) that have radio jets propagating only on galactic scales, defined as having projected linear size (LS) of up to 20 kpc. CSS sources are generally hosted by massive early-type galaxies with little ongoing star formation; however, a small fraction are known to have enhanced star formation. Using archival data from the Faint Images of the Radio Sky at Twenty cm survey, the Very Large Array Sky Survey, and the Sloan Digital Sky Survey, we identify a volume-limited sample of 166 CSS sources at z < 0.2 with L 1.4 GHz > 10 24 W Hz -1 . Comparing the star formation rates and linear sizes of these CSS sources, we find that the ≈14% of CSS sources with specific star formation rates above 0.01 Gyr -1 all have LS < 10 kpc. We discuss the possible mechanisms driving this result, concluding that it is likely the excess star formation in these sources occurred in multiple bursts and ceased prior to the AGN jet being triggered.

79 ASTRONOMY AND ASTROPHYSICS↗

Development of toughened epoxy polymers for high performance composite and ablative applications

A survey of current procedures for the assessment of state of cure in epoxy polymers and for the evaluation of polymer toughness as related to nature of the crosslinking agent was made to facilitate a cause-effect study of the chemical modification of epoxy polymers. Various conformations of sample morphology were examined to identify testing variables and to establish optimum conditions for the selected physical test methods. Dynamic viscoelasticity testing was examined in conjunction with chemical analyses to allow observation of the extent of the curing reaction with size of the crosslinking agent the primary variable. Specifically the aims of the project were twofold: (1) to consider the experimental variables associated with development of "extent of cure" analysis, and (2) to assess methodology of fracture energy determination and to prescribe a meaningful and reproducible procedure. The following is separated into two categories for ease of presentation.

Allen, V. R.↗

Absolute isotopic abundances of Ti in meteorites

A general formalism is presented for determining possible isotope compositions of exotic Ti, and illustrated with results from Ti isotope abundances measured in Ca-Al-rich inclusions of the Allende and Leoville meteorites and samples of other meteorites. Previously identified correlations between Ti-50 and Ca-48 in FUN (isotope fractionation effects and unknown nucleosynthetic effects) inclusions is shown to hold true, thereby supporting contributions from a neutron-rich equilibrium or nucleosynthetic equilibrium during formation of the meteorites. Extension of the study to carbonaceous meteorites indicated that condensation, volatilization and recondensation occurred during formation, although the isotope fractionation observed cannot yet be explained.

Niederer, F. R.↗

Reaction of iron with hydrogen chloride-oxygen mixtures at 550 C

The reaction of iron with 1 percent HCl/0-50 percent O2/Ar has been studied at 550 C with thermogravimetry to monitor kinetics and scanning electron microscopy to characterize product morphologies. In addition, the volatile species were identified with an atmospheric pressure sampling mass spectrometer. The reaction of 1 percent HCl/Ar produces FeCl2. The reactions of 1 percent HCl/1, 10, 50 percent O2/Ar produce Fe2O3, Fe3O4, FeCl2, and FeCl3. In each case condensed phase chlorides form at the oxide/metal interface where the oxygen potential is low. The 10 and 50 percent oxygen mixtures have kinetics in the first 3 hr similar to pure oxidation with some deviations due to iron-chloride formation. The 1 percent oxygen mixture shows enhanced reaction rates over oxidation, very likely due to the formation of a porous scale.

Jacobson, N. S.↗

The effect of nitrogen on xenon ion engine erosion

Erosion studies were performed on a 30-cm diameter J-series ion engine modified for operation on xenon propellant. The erosion rates of molybdenum and tantalum badges placed at different locations within the discharge chamber were measured as a function of the percentage of nitrogen (by mass) added to the xenon propellant. Reductions in the erosion rates of these badges of a factor of 8 to 50 were observed at nitrogen addition fractions between 0.5 to 2.0 percent. Reductions in cathode-side baffle erosion were achieved by adding nitrogen to the xenon propellant or by increasing the cathode orifice diameter. Analyses show that no significant degradation in ion engine performance should be expected at these nitrogen mass fractions. XRD, XPS and Auger analyses indicate the existence of nitrogen and nitrides in the surface of some but not all of the badges used in the tests where nitrogen was added to the xenon. Difficulty in identifying surface nitrides in the samples may be due to the existence of surface oxides and contaminants, or to the small thicknesses of the nitride layers.

Garner, Charles E.↗

Ammonia-water mixtures at high pressures - Melting curves of ammonia dihydrate and ammonia monohydrate and a revised high-pressure phase diagram for the water-rich region

The phase relations of some mixtures of ammonia and water are investigated to create a phase diagram in pressure-temperature-composition space relevant to the geophysical study of bodies in the outer solar system. The mixtures of NH3(x)H2O(1-x), where x is greater than 0.30 but less than 0.51, are examined at pressures and temperatures ranging from 0-6.5 GPa and 125-400 K, respectively. The ruby luminescence technique monitors the pressure and a diamond-anvil cell compresses the samples, and the phases are identified by means of normal- and polarized-light optical microscopy. The melting curve for NH3H2O(2) is described by the equation T = 176 + 60P - 8.5P squared for the ranges of 0.06-1.4 GPa and 179-243 K. The equation for NH3H2O is T = 194 + 37P - P squared, which represents a minor correction of a previous description by Johnson et al. (1985). Observed phase transitions are consistent with the high-pressure stability limit of NH3H2O(2), and the transition boundary is found to be linear.

Boone, S.↗

Impact melt breccias at the Apollo 17 landing site

Impact melt breccias are by far the most common highland rock type collected on the Apollo 17 mission. They tend to be fine grained, with virtually no clast-free impact melt rocks having been identified. All the highland boulders sampled are impact melt breccia, with the possible exception of one South Massif boulder that might have a friable matrix (but nonetheless consists dominantly of impact melt) and a shocked igneous norite boulder from the North Massif. The impact melt breccias were originally described as metaclastic, but their melt origin became apparent as work progressed. Chemical compositions appear to allow natural groupings of the impact melt breccias. Various groupings of the impact melt breccias are discussed.

Ryder, Graham↗

V/V(max) test applied to SMM gamma-ray bursts

We have applied the V/V(max) test to candidate gamma-ray bursts detected by the Gamma-Ray Spectrometer (GRS) aboard the SMM satellite to examine quantitatively the uniformity of the burst source population. For a sample of 132 candidate bursts identified in the GRS data by an automated search using a single uniform trigger criterion we find average V/V(max) = 0.40 +/- 0.025. This value is significantly different from 0.5, the average for a uniform distribution in space of the parent population of burst sources; however, the shape of the observed distribution of V/V(max) is unusual and our result conflicts with previous measurements. For these reasons we can currently draw no firm conclusion about the distribution of burst sources.

Matz, S. M.↗

Si-29 NMR spectroscopy of naturally-shocked quartz from Meteor Crater, Arizona: Correlation to Kieffer's classification scheme

We have applied solid state Si-29 nuclear magnetic resonance (NMR) spectroscopy to five naturally-shocked Coconino Sandstone samples from Meteor Crater, Arizona, with the goal of examining possible correlations between NMR spectral characteristics and shock level. This work follows our observation of a strong correlation between the width of a Si-29 resonance and peak shock pressure for experimentally shocked quartz powders. The peak width increase is due to the shock-induced formation of amorphous silica, which increases as a function of shock pressure over the range that we studied (7.5 to 22 GPa). The Coconino Sandstone spectra are in excellent agreement with the classification scheme of Kieffer in terms of presence and approximate abundances of quartz, coesite, stishovite, and glass. We also observe a new resonance in two moderately shocked samples that we have tentatively identified with silicon in tetrahedra with one hydroxyl group in a densified form of amorphous silica.

Boslough, M. B.↗

Characterization of the microstructure of Nb-1wt.%Zr-0.1wt.%C tubes as affected by thermomechanical processing

Microstructure of Nb-1Zr-0.1C tubes were characterized as affected by extrusion temperature of the tube shell and its thermomechanical processing to tubing. Two tube shells of about 40-mm outside diameter (OD) and 25-mm inside diameter (ID) were extruded 8:1 from a vacuum arc-melted ingot at 1900 and 1550 K. Two different OD tubes of approximately 0.36-mm wall thickness were fabricated from each tube shell by a series of 26 cold drawing operations with two in process anneals. The microstructure of tube shells and the tubing before and after a 2-step heat treatment were characterized. Residue extracted chemically from each sample was also analyzed to identify the precipitates. The results concerning the effect of the initial extrusion temperature and subsequent processing on the microstructure of the tubes are presented together with a review of results from similar work on Nb-1Zr-0.1C sheet stock.

Uz, Mehmet↗

Comet coma sample return instrument

The sample collection technology and instrument concept for the Sample of Comet Coma Earth Return Mission (SOCCER) are described. The scientific goals of this Flyby Sample Return are to return to coma dust and volatile samples from a known comet source, which will permit accurate elemental and isotopic measurements for thousands of individual solid particles and volatiles, detailed analysis of the dust structure, morphology, and mineralogy of the intact samples, and identification of the biogenic elements or compounds in the solid and volatile samples. Having these intact samples, morphologic, petrographic, and phase structural features can be determined. Information on dust particle size, shape, and density can be ascertained by analyzing penetration holes and tracks in the capture medium. Time and spatial data of dust capture will provide understanding of the flux dynamics of the coma and the jets. Additional information will include the identification of cosmic ray tracks in the cometary grains, which can provide a particle's process history and perhaps even the age of the comet. The measurements will be made with the same equipment used for studying micrometeorites for decades past; hence, the results can be directly compared without extrapolation or modification. The data will provide a powerful and direct technique for comparing the cometary samples with all known types of meteorites and interplanetary dust. This sample collection system will provide the first sample return from a specifically identified primitive body and will allow, for the first time, a direct method of matching meteoritic materials captured on Earth with known parent bodies.

Albee, A. L.↗

Post-impact fatigue of cross-plied, through-the-thickness reinforced carbon/epoxy composites

An experimental investigation of the post-impact fatigue response of integrally woven carbon/epoxy composites was conducted. Five different through-the-thickness (TTT) reinforcing fibers were used in an experimental textile process that produced an integrally woven (0/90/0/90/0/90/0/90/0)(sub T) ply layup with 21K AS4 carbon tow fiber. The resin was Hercules 3501-6, and the five TTT reinforcing fibers were Kevlar, Toray carbon, AS4 carbon, glass, and IM6 carbon. The purpose of this investigation was to study the post-impact fatigue response of these material systems and to identify the optimum TTT fiber. Samples were impacted with one half inch diameter aluminum balls with an average velocity of 543 ft/sec. Post-impact static compression and constant amplitude tension-compression fatigue tests were conducted. Fatigue tests were conducted with a loading ratio of R=-5, and frequency of 4 Hz. Damage growth was monitored using x-radiographic and sectioning techniques and by examining the stress-strain response (across the impact site) throughout the fatigue tests. The static compressive stress versus far-field strain response was nearly linear for all material groups. All the samples had a transverse shear failure mode. The average compressive modulus (from far-field strain) was about 10 Msi. The average post-impact static compressive strength was about 35.5 Ksi. The IM6 carbon sample had a strength of over 40 Ksi, more than 16 percent stronger than average. There was considerable scatter in the S-N data. However, the IM6 carbon samples clearly had the best fatigue response. The response of the other materials, while worse than IM6 carbon, could not be ranked definitively. The initial damage zones caused by the impact loading and damage growth from fatigue loading were similar for all five TTT reinforcing materials. The initial damage zones were circular and consisted of delaminations, matrix cracks and ply cracks. Post-impact fatigue loading caused delamination growth, ply cracking and fiber bundle failures, typically 45 deg from impact load direction. During the initial 97 percent of fatigue life, delaminations, ply cracks and fiber bundle failures primarily grew at and near the impact site. During the final 3 percent of life, damage grew rapidly transverse to the loading direction as a through-the-thickness transverse shear failure. The stress-strain response was typically linear during the initial 50 percent of life, and stiffness dropped about 20 percent during this period. During the next 47 percent of life, stiffness dropped about 34 percent, and the stress-strain response was no longer linear. The stiffness decreased about 23 percent during the final 3 percent of life. These trends were typical of all the materials tested. Therefore, by monitoring stiffness loss, fatigue failure could be accurately anticipated.

Serdinak, Thomas E.↗