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Search indexed NASA NTRS and DOE OSTI research on propulsion, heat transfer, battery materials and energy systems. Follow report and document links to the original sources.

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At least 469 records · Page 26

Measuring Hydroxylammonium, Nitrate, and Nitrite Concentration with Raman Spectroscopy for 238 Pu Supply Program

Optical spectroscopy has great potential to improve the timeliness of important analytical measurements for the 238 Pu Supply Program by enabling real-time analysis of process solutions within radiochemical hot cells. Hydroxylammonium (H 3 NOH + ]), nitrate (NO 3 - ), and nitrite (NO 2 - ) are three important molecular species present in multiple aqueous streams throughout the program’s flow sheet. The concentration of each species normally goes uncharacterized during processing. However, rapid quantification may benefit the program because uncertainties in kinetic redox expressions describing hydroxylammonium (HA) and nitrite reactions with Np and Pu leads to uncertainty in process model predictions for solvent extraction runs. HA concentration is normally quantified using ion chromatography, a technique that requires diluted grab samples taken out of the hot cell and analyzed off-line. Here we evaluate Raman spectroscopy for determining the concentration of H 3 NOH + , NO 3 - , and NO 2 - in benchtop tests to determine limits of detection. We also consider the possibility of using Raman spectroscopy in both glove box and hot cell environments for rapid analysis and pinpoint additional development opportunities needed to make this application successful.

38 RADIATION CHEMISTRY, RADIOCHEMISTRY, AND NUCLEA↗

BioGeoChemistry at Interfaces (LLNL SFA OBER FY21 Program Management and Performance Report)

The focus of the BioGeoChemistry at Interfaces (formerly BioGeoChemistry of Actinides) SFA is to identify and quantify the biogeochemical processes and the underlying mechanisms that control actinide mobility in an effort to reliably predict and control the cycling and migration of actinides in the environment. The research approach includes: (1) Field Studies (Research Thrust 1) that capture actinide behavior on the timescale of decades and (2) Fundamental Laboratory Studies (Research Thrust 2) that isolate specific biogeochemical processes observed in the field. These Research Thrusts are underpinned by the unique capabilities and staff expertise at Lawrence Livermore National Laboratory, allowing the BioGeoChemistry at Interfaces SFA to advance our understanding of actinide migration behavior in the environment, and serve as an international resource for environmental radiochemistry research (Figure 1).

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FY2020 Annual Report on Subcontract B631779 with UC Berkeley: Reactive Precursors Additive Manufacturing Report

This work succeeded in reaching each of the stated milestones for developing, printing, reacting, and characterizing the uranium carbide final products. Leveraging experience gained from creating magnesium oxide inks (milestone #1) and prior reactive precursor work with boron carbide (milestone #2) a uranium carbide reactive precursor ink was developed. The chosen composition of ink utilized a mixture of wax, petrolatum, and stearic acid as the binder. The reactive precursor portion of the ink was comprised of uranium oxide and nano particle activated carbon for production of uranium carbide via carbothermal reduction. Following an in-air burnout of the binder at 160C the printed samples were reacted and sintered at 1750C in an argon environment induction furnace. The resulting product has an open porosity dense, foam-like internal structure with a calculated density of 89% in the solid fraction.

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Deeply Rooted: Evaluating Plant Rooting Depth as a Means for Enhanced Soil Carbon Sequestration (Full Technical Report)

Soils store three times as much carbon (C) as the atmosphere, but are not at capacity, and enhanced soil C storage is considered an essential strategy to mitigate rising atmospheric CO 2 levels. Agricultural soils have experienced substantial C loss in the past century due to poor agricultural practices and erosion. A shift towards deep-rooting crops and low-impact soil management could potentially increase long-term sequestration of C fixed by plants and stored in their root tissues, particularly for crops that have naturally deep root systems (>1 meter). A substantial amount of the CO 2 taken up by plants is allocated to their root systems, and because C deposited in deep soil layers has a longer residence time (up to millennia, in contrast to C deposited in topsoils), C increases at depth may have better long-term C sequestration potential than topsoils. However, the accrual, turnover, and stabilization of C in subsoils is a critical knowledge gap. We investigated a deeply rooted plant, switchgrass (Panicum virgatum), as a means of increasing carbon stocks in marginal and agricultural soils. We hypothesized that deep (>30 cm) SOC stocks would be greater under bioenergy crops relative to stocks under shallow-rooted conventional crop cover. To test this hypothesis, we compared soil depth profiles beneath deeply rooted switchgrass (cultivated for 4-30 years) and paired shallowrooted annual controls. We studied 12 field sites, 3 that were collected in 2018 before the start of the project as part a Department of Energy (DOE) Sustainable Biofuels study, and 9 that we collected in 2019 on a national field sampling campaign across the eastern US. In our publication from the 2018 study, which was written in collaboration with the LLNL Soil Microbiome Scientific Focus Area (SFA), we found that C stocks increased under switchgrass, but that the increases were dependent on soil texture. In the 2019 study, we found that carbon accrual tended to occur most consistently in low C soil in the southern US, which could indicate that perennial grasses may be a viable strategy to increase SOC in marginals soils in this region. We have published two studies from the 2019 sampling campaign thus far, we measured microbial growth parameters that will aid in modeling subsoil carbon cycling, and we found that switchgrass appears to move water upward in the soil profile and could promote drought tolerance, which a phenomenon commonly performed by trees known as ‘hydraulic redistribution;’ our study is the first to show this can occur in deep-rooted grasses. Finally, we published a modeling paper in collaboration with the LLNL Soil Microbiome SFA, where we found that poorly crystalline minerals are abundant and strongly correlated with organic C in geographically limited zones with enhanced weathering rates. Our results will inform technological development in the agricultural carbon sequestration sector as well as future negative emissions policies.

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Laboratory Analysis for Radiological Events

Presentation for an International Atomic Energy Agency sponsored workshop on Consequence Management (virtual). Presentation sponsored by DOE NA-81

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Development of Solid Isotope Harvesting Methods in Preparation for FRIB (Closeout Report)

This project developed the techniques necessary to isolate hydrolysable radiometals from irradiated accelerator components. It was a collaborative project headed by Dr. Jennifer Shusterman at Hunter College in coordination with Dr. Nick Scielzo at Lawrence Livermore National Laboratory and Dr. Gregory Severin at Michigan State University. To develop the methods for harvesting hydrolysable radiometals, both non-radioactive and radioactive experiments were conducted. Non-radioactive tests involved dissolving common accelerator materials (tungsten, copper, aluminum, and gold), adding trace amounts of Zr 4+ and Y 3+ , and then separating the added ions out again using a variety of column-based approaches. These methods were then tested on surrogate materials that were created by irradiating tungsten, copper, aluminum and gold foils with a low-purity 88 Zr beam at the National Superconducting Cyclotron Laboratory. The implanted 88 Zr (and co-implanted and daughter-product 88 Y) were recovered, validating the developed methods. MSU’s role in the project was to develop the chemistry for recovering Zr and Y from tungsten; build the target station for irradiating the foils; conduct the irradiations with the collaborators; to validate the tungsten methodology using the irradiated foils; and to disseminate the results.

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Effects of Electron Irradiation on Candidate Materials for Target Window in Accelerator-Driven Mo-99 Production

Room-temperature (RT) axial tensile tests were conducted in 2018 and 2021 with flat, sub-sized, dog-boned samples of non-irradiated and irradiated Inconel 718 and irradiated beryllium (Be). The sample gauge length was 7.62 mm. Tensile properties of interest are the engineering yield stress (YS), ultimate tensile stress (UTS), uniform elongation (UE) and total elongation (TE). The electron dose of the 2021 samples was ≈2 times the dose of samples tested in 2018. Relative dose rates of 0, 1 (2018), and 2 (2021) are assigned to these samples. The 2021 electron-irradiated Be samples were brittle with a low failure stress of 338±64 MPa based on two samples. The failures occurred in the gauge section. The 2018 results for electron-irradiated Be indicated a slight decrease in ductility and strength for the one electron-irradiated sample that failed in the gauge section.

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Oxidative degradation in polyethylene: the microscopic properties responsible for macroscopic weathering

Radiation-initiated crosslinking of polyethylene has proven to be an effective method of reducing creep and wear. This has allowed polyethylene to find widespread use in engineering and medical sectors where extreme conditions would otherwise cause it to degrade. However, despite their resilience, irradiated polyethylene products are still vulnerable to oxidative degradation in some long-term applications. A good deal of literature exists to discuss the effects that irradiation and oxidative degradation have on polyethylene’s mechanical properties, but not much literature exists to describe the microscopic properties that make irradiated polyethylene susceptible to this process. This review presents a micro-scale look at polyethylene’s morphology and chemistry, with the intention of describing which characteristics make the material more or less favorable for oxidation. By describing the factors that make irradiated polyethylene vulnerable to oxidation in the first place, the hope is to provide insight on how to mitigate oxidation in future applications.

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National User Resource for Biological Accelerator Mass Spectrometry Annual Report

The National User Resource for Biological Accelerator Mass Spectrometry (User Resource) will provide isotopic analysis (primarily radiocarbon or 14C) by accelerator mass spectrometry (AMS) for NIH-funded researchers across the United States and will be the only User Resource of its type in the United States. The User Resource will provide measurement capability and expertise to a research community that requires highly sensitive, quantitative isotope analyses. Since commissioning a new accelerator mass spectrometer in June 2014, we have measured over 4000 samples a year for collaborators and service users. The User Resource will enable us to continue to meet these research needs, as well as provide for new users whose research programs would benefit from AMS as a measurement tool.

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M4SF-22LL010301052-SUPCRTNE Thermodynamic Database Integration

This progress report (Level 4 Milestone Number M4SF-22LL010301052) summarizes research conducted at Lawrence Livermore National Laboratory (LLNL) within the Argillite Activity Number SF-22LL01030105. SUPCRTNE (starting with v. 1.0) is being developed as the primary engine for future thermodynamic database development. It replaces SUPCRT92 (Johnson et al., 1992), which was earlier used on the Yucca Mountain Project (Wolery and Jove-Colon, 2007). Various changes to SUPCRT92 were and are presently being made. A major change is replacing the original water properties module H2O92D. For this, we have developed a modularized form of the program H2OI95. H2OI95 (Wolery, 2018, 2020) evaluates a newer equation of state for water (IAPWS-95, (Wagner and Pruß, 2002)) that is the present international standard. Thermochemical properties including Gibbs energy, enthalpy, and entropy are now tied to the CODATA standard (Cox et al., 1989).

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Developing a Th Resonance Ionization Scheme: for Future Use in Age Dating SNM by Resonance Ionization Mass Spectrometry

We report the development of a Th resonance ionization scheme (RIS) for analyzing Th isotopes by resonance ionization mass spectrometry (RIMS) to enable age-dating via the 230 Th/ 234 U inter-elemental pair. This report summarizes the work that completes the first of two tasks that are required for developing U-Th dating via RIMS at the Laser Ionization of Neutrals (LION) laboratory at Lawrence Livermore National Laboratory (LLNL). The first task involves choosing and vetting an appropriate Th RIS for the LION instrument and simultaneous U and Th analysis.

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National Technology & Engineering Solutions of Sandia, LLC Technical Assistance With Dine College (Final CTAP Report)

Under the CTAP Statement of Work, Sandia was tasked with providing technical assistance to Dine College to create a testing program to determine hazardous contaminant levels in donated hand sanitizer. Sandia will loan instrumentation, provide a procedure, and act as technical advisor. The challenge for on-site testing lies in a balance of testing capability/speed, complexity, and cost of operations. Instruments that allow fastest and least expensive operation will be validated for performance for this sample problem (hand sanitizer w/ poisonous methanol or 1-propanol). The objective of this project is to enable Dine College personnel to perform on-site testing.

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Impact of Irradiation and Decay Time on Chemical Speciation in Uranyl Sulfate Solution

A pH-1, 200-g U/L, highly enriched uranyl sulfate solution was neutron-irradiated using an accelerator-driven neutron source (the Universal Neutron Irradiator, UNI) to fission U-235 under conditions similar to those used by SHINE to produce Mo-99 in a subcritical assembly. We completed a series of five uranyl sulfate irradiations to assess the impact of irradiation and decay time on uranium precipitation and iodine speciation in solution. The duration of each irradiation was increased in order, with the shortest irradiation taking 2.9 hours and the longest, 64.5 hours. A total of 9.5E16 U-235 nuclei were fissioned in all irradiations, and a maximum fission power density of 0.26 W/mL was reached in the final irradiation. We observed no evidence of uranyl peroxide or other precipitates, demonstrating that the addition of Fe 2+ to a final Fe concentration of 200 ppm in the target solution was successful at preventing precipitation under representative irradiation conditions. Nonvolatile I - was found to be the dominant (>70%) iodine species in solution, both immediately after irradiation and after days to weeks of decay time.

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LDRD External Report Summary

Matrix-Assisted Ionization is a new and highly promising mass spectrometry technique for rapid analysis of uranium; however, the chemistry and physics underlying this ionization mechanism are largely unknown. This effort seeks to understand the fundamental ionization phenomena by characterizing both ionization matrix materials themselves and analyte chemistry ionization trends.

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Radiolysis of Organic Solvents in the Presence of Plutonium

In this report, we describe a set of organic solvent radiolysis experiments performed at Lawrence Livermore National Laboratory. The goal of these experiments was to test for radiolytic solvent damage due to the presence of plutonium (Pu) particulates in solvent baths that are part of a materials production and cleaning workflow. The solvents (NOVEC 72DE and NOVEC 7500) were tested at a Pu activity level of ~1 microCi/mL using weapons grade Pu -- equivalent to 0.35 g Pu dispersed in a 5 gallon fluid bath filled to 4.5 gallons. Experiments were performed using fresh solvent and solvent that was 95% evaporated; the evaporated solvent was meant to represent fluids that may be in the solvent bath and subjected to evaporation and refilling without a full solvent replacement.

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