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At least 577 records · Page 32

Origin of 16 O-rich fine-grained Ca-Al-rich inclusions of different mineralogy and texture

We conducted a coordinated mineralogical and oxygen isotopic study of four fine-grained calcium-, aluminum-rich inclusions (CAIs) from the ALHA77307 CO3.0 carbonaceous chondrite. Three of the inclusions studied, 05, 1-65, and 2-119, all have nodular structures that represent three major groups, melilite-rich, spinel-rich, and hibonite-rich, based on their primary core mineral assemblages. A condensation origin was inferred for these CAIs. However, the difference in their primary core mineralogy reflects unique nebular environments in which multiple gas-solid reactions occurred under disequilibrium conditions to form hibonite, spinel, and melilite with minor perovskite and Al,Ti-rich diopside. A common occurrence of a diopside rim on the CAIs records a widespread event that marks the end of their condensation as a result of isolation from a nebular gas. An exception is a rare inclusion 2-112 that contains euhedral spinel crystals embedded in melilite, suggesting this CAI had been re-melted. All of the fine-grained CAIs analyzed in ALHA77307 are 16 O-rich with an average Δ 17 O value of ~-22 ± 5‰ (2σ), indicating no apparent correlation between their textures and oxygen isotopic compositions. We therefore conclude that a prevalent 16 O-rich gas reservoir existed in a region of the solar nebula where CO3 fine-grained CAIs formed, initially by condensation and then later, some of them were reprocessed by melting event(s).

58 GEOSCIENCES↗

PET waste- and bio-derived imine vitrimers for shape-memory, intrinsic flame-retardant, and recyclable carbon fiber composites

Developing circular multifunctional vitrimers and carbon fiber–reinforced polymers (CFRPs) that are simultaneously recyclable, mechanically robust, and intrinsically flame retardant remains a major challenge. Here, in this study, we report multifunctional vitrimers and their carbon fiber–reinforced vitrimer (CFRV) composites, where the vitrimer design integrates closed-loop recyclability, enhanced interfacial adhesion, and intrinsic flame retardancy within a single materials platform. The vitrimer matrix is synthesized from post-consumer polyethylene terephthalate (PET) waste and a vanillin-derived phosphorus-containing crosslinker, forming an imine-based network. The resulting vitrimer resin exhibits high tensile strength, thermal healability, repeated reprocessability, programmable shape memory, and rapid chemical depolymerization under mild conditions. Amine-functionalized carbon fibers significantly improve fiber–matrix interfacial bonding, yielding CFRVs with tensile strengths up to 789 MPa and complete recovery of structurally intact fibers after chemical recycling. The phosphorus-rich aromatic network further imparts intrinsic flame retardancy, enabling self-extinguishing behavior without external additives. This work advances a materials design paradigm for next-generation multifunctional, sustainable vitrimers and CFRVs, while simultaneously addressing the recycling challenges associated with both plastic and CFRP waste.

Bio-derived crosslinker↗

Amino acid enantiomers in old and young dissolved organic matter: Implications for a microbial nitrogen pump

Dissolved organic nitrogen (DON) represents the largest reservoir of fixed N in the surface ocean and a significant portion accumulates in the deep sea, where it can persist for millennial time scales. However, like the dissolved organic carbon (DOC) pool, the origin and composition of long-lived, refractory DON remains largely unknown. In recent years, the “microbial carbon pump” hypothesis has emerged from abundant evidence showing that microbial processes are primarily responsible for refractory DOC accumulation. However, a similar mechanism for DON has rarely been investigated. In the study of DON, spectroscopic evidence has indicated a primarily amide composition, implying a dominant contribution from peptides. Therefore, if an analogous “microbial nitrogen pump” controls refractory DON accumulation, the amino acid component should bear increasing signatures of microbial origin with increasing age. Here we investigate the microbial sequestration of N via the production of refractory DON, for the first time considering together DOM Δ 14 C with amino acid (AA) molar abundance (Mol%) and D/L ratio (as a tracer for prokaryotic input). Measurements were made on a unique set of high and low molecular weight (HMW, LMW) DOM isolates with 14 C ages and chemical compositions generally consistent with semi-labile and refractory DOM respectively. The samples were collected in the North Pacific Subtropical Gyre where deep waters contain some of the oldest DOC in the world ocean. We observe higher D/L ratios in older, LMW DOM isolates for almost all analyzed AAs. Using mass spectral data, we also quantify three D-AAs in all samples (D-valine, D-phenylalanine, and D-leucine), which have not previously been confirmed in ocean DOM. These newly identified D-AAs are concentrated in the LMW refractory DOM fraction and have oceanographically consistent depth profiles. Our results suggest that several novel D-AA subgroupings may be unique tracers for different prokaryotic source processes. D-alanine appears to have largely independent cycling from the other D-AAs with a connection to the production of HMW DON, which we hypothesize is linked to water column peptidoglycan. In contrast, D-leucine, D-valine, and D-phenylalanine appear to be most strongly related to the production of LMW DON. Trends in both the HMW and LMW fractions suggest a linkage to sinking particles and local microbial transformations, implying that LMW DON has a direct biological source rather than originating from successive microbial reprocessing of HMW DON. In conclusion, taken together, our observations are consistent with the dominant production of refractory LMW DON by prokaryotic organisms and suggests that different AA sub-groupings that can be used to track different processes within the DON pool.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Quantifying fission gas adsorption onto natural clinoptilolite in the presence of environmental air and water

Adsorption of noble gas fission products onto naturally occurring minerals is of interest for its potential to retain or retard emissions from nuclear fuel reprocessing operations or underground nuclear explosions. However, experimental studies of trace noble gas adsorption in the presence of air and water have largely focused on synthetic materials, such as activated carbon or metal-organic frameworks. Here, in this study, adsorption of Kr and Xe onto the naturally occurring zeolitic mineral clinoptilolite is studied in the presence of nitrogen and water. By varying the composition of the gas phase and monitoring the change in the combined adsorbate mass, the adsorbed concentration of noble gas is calculated gravimetrically. For dry clinoptilolite, the concentration of adsorbed Kr and Xe is linearly correlated with noble gas pressure and Henry's Law appears satisfactory, despite the presence of nitrogen at atmospheric pressures. However, the presence of water significantly reduces the adsorbed concentration of both Kr and Xe, which is typical in nanoporous sorbents. Here, an empirical bivariate model is presented, combining the Henry's Law adsorption model for a dry adsorbent with the exponential reduction in the presence of water, as reported by Lungu and Underhill in 1999. This model provides a means to estimate the adsorbate concentration at the trace partial pressures and higher water contents relevant to field-scale modeling of fission gas transport through the vadose zone.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

Reductive removal of pertechnetate and chromate by zero valent iron under variable ionic strength conditions

Radioactive technetium-99 (Tc) present in waste streams and subsurface plumes at legacy nuclear reprocessing sites worldwide poses potential risks to human health and the environment. This research comparatively evaluated efficiency of zero valent iron (ZVI) toward reductive removal of Tc(VII) in presence of Cr(VI) from NaCl and Na 2 SO 4 electrolyte solutions under aerobic conditions. In both electrolytes, anticorrosive Cr(VI) suppressed oxidation of ZVI at elevated concentrations resulting in the delay of initiation of Tc(VII) reduction to Tc(IV)). In the absence of Cr(VI), no such delay was observed in the analogous systems. At low ionic strength, retarded ZVI oxidation inhibited Tc(VII) reduction in part due to the competing thermodynamically more favorable reduction of Cr(VI) to Cr(III); this effect was particularly pronounced in the chloride medium at the ionic strength ? 0.1. Higher ionic strength favored reduction of both Tc(VII) and Cr(VI), which followed a second-order reaction rate in both electrolytes attributed to the more efficient iron oxidation as evident from x-ray diffraction and electron microscopy measurements. Magnetite was the primary iron oxide phase, and its higher fraction in the SO 4 2- solutions facilitated reductive removal of Tc(VII) and Cr(VI). In the Cl- matrix, Cr(VI) promoted further oxidation of magnetite as well as formation of chromite diminishing overall reductive capacity of this system and resulting in less effective removal of Tc(VII) compared to the SO 4 2- solutions.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

Effects of composition and canister centerline cooling on microstructure, phase distribution, and chemical durability of dehalogenated iron phosphate waste forms

This paper discusses the effects of composition and canister centerline cooling (CCC) on the microstructures, phase distribution, and chemical durability of dehalogenated iron phosphate waste forms starting from chloride-based salt simulants including KCl (Simple-1), NdCl3 (Simple-2), SrCl2 (Simple-3), LaCl3 (Simple-4), LiCl (Simple-5), CsCl (Simple-6), as well as a complex simulant containing LiCl, KCl, NaCl, CsI, SrCl2, CeCl3, and NdCl3 called ERV2. The simulants represent salt constituents present in salt wastes from electrorefiners used for electrochemical reprocessing. These salts are reacted with ammonium dihydrogen phosphate (ADP) resulting in a NH4Cl (dechlorination) byproduct that is captured and phosphate product containing oxides of the salt cations. This product is further stabilized using Fe2O3 through vitrification at higher temperatures. The results presented herein describe the properties of CCC-treated materials following dechlorination and vitrification including phase identification and quantification, elemental distributions, and chemical durabilities. The chemical durability in the CCC-cooled samples are lower durability than quenched materials for the ERV2 samples. The phases formed upon CCC cooling are very complex compositionally and microstructurally.

iron phosphate glass, iron phosphate waste forms, ↗

Component effects on crystallization of RE-containing aluminoborosilicate glass

Lanthanide-aluminoborosilicate (LABS) glass is one option for immobilizing rare earth (RE) oxide fission products generated during reprocessing of pyroprocessed fuel. This glass system can accommodate a high loading of RE oxides and has excellent chemical durability. The present study describes efforts to model equilibrium crystallinity as a function of glass composition and temperature as well as liquidus temperature (TL) as a function of glass composition. The experimental method for determining TL was ASTM C1720-11. Typically, three crystalline phases were formed in each glass: Ce-borosilicate (Ce 3 BSi 2 O 10 ), mullite (Al 10 Si 2 O 19 ), and corundum (Al 2 O 3 ). Cerianite (CeO 2 ) was a common minor crystalline phase and Nd-silicate (Nd 2 Si 2 O 7 ) occurred in some of the glasses. In the composition region studied, TL decreased as SiO 2 and B 2 O 3 fractions increased and strongly increased with increasing fractions of RE oxides; Al 2 O 3 had a moderate effect on the TL but, as expected, it strongly affected the precipitation of Alcontaining crystals.

36 MATERIALS SCIENCE↗

Postirradiation examination on metallic fuel in the AFC-2 irradiation test series

In this paper, irradiation experiments on metallic fuel alloys containing rare earth additions to simulate potential carry-over from pyro-metallurgical reprocessing and minor actinide additions were performed in the Idaho National Laboratory Advanced Test Reactor. These tests were designated AFC-2A and AFC-2B. Additionally irradiation experiments were also performed on metallic fuel alloys containing minor actinide additions that were fabricated by different techniques. These tests were designated AFC-2E. These pins were removed from the reactor after achieving burnups between 6 and 11% fission per initial heave metal atom. Examination of these pins revealed that they were unintentionally operated beyond their desired power and temperature conditions. Highlights from the postirradiation examination of these experiments is discussed. A variety of issue contributed to the poor performance of these irradiation tests including capsule design, reactor power variations and fabrication issues. While all the issues contributed, the major issue was determined to be unanticipated variations in reactor power. Through comparisons between these experiments and historical off-normal experiments, it was possible to conclude bound the operating temperatures of these experiments. There likely was some in-pile melting in the rare earth addition experiments (AFC-2A, AFC-2B), but it is not likely that there was in-pile melting in the fabrication technique experiments (AFC-2E).

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗

Dehalogenation of electrochemical processing salt simulants with ammonium phosphates and immobilization of salt cations in an iron phosphate glass waste form

This study demonstrates the conversion of simulated pyroprocessing salt wastes [i.e., ER(SF) and ERV2] into chemically durable iron phosphate glass waste forms through reactions with ammonium hydrogen phosphate precursors [i.e., NH4H2PO4 and (NH4)2HPO4] and added Fe2O3. The reaction of the salt simulants with the phosphate precursors resulted in dehalogenation of the salt through the production of NH4Cl and NH4I (along with water), of which the NH4Cl can be used to produce UCl3 oxidant for use in the electrorefiner during pyroprocessing. These iron phosphate glasses contain a notably higher waste loading than the baseline glass-bonded sodalite ceramic waste form, which requires about 70 vol% sodalite to accommodate Cl from the salt, because they are dehalogenated prior to vitrification. The high waste loadings coupled with higher bulk densities (~3×103 kg/m3) than glass-bonded sodalite (~2.3×103 kg/m3) mean that these glasses have a higher storage volume, i.e., the volume required to immobilize a given mass of waste. The iron phosphate glass waste forms were characterized using a variety of techniques including physical property measurements and chemical durability testing. Following initial testing, a proof-of-concept demonstration was conducted to show that the NH4Cl generated from this process could be used to produce UCl3 using depleted uranium dendrites as a feedstock.

phosphate glass, pyroprocessing, waste forms, salt↗

Glass-bonded ceramic waste forms for immobilization of radioiodine from caustic scrubber wastes

Glass-bonded sodalite composite waste forms have been developed for the immobilization of liquid radioactive wastes resulting from off-gas treatment during aqueous reprocessing of used nuclear fuel, with a particular focus on 129I. The proposed composite waste form is comprised of aluminosilicate ceramic phases containing volatile radionuclides bonded with a glassy matrix. In this work, a suite of ten candidate low-temperature glass binders (ZnO-Bi2O3-based glasses and a Na2O-B2O3-SiO2 glass) were examined. Six glasses were mixed with caustic scrubber waste simulant previously converted into a sodalite-rich material (to provide glass fractions of 10 and 20 wt.%), uniaxially pressed into pellets, and sintered at 350 °C or 550 °C for 8 h in air. Iodine retention after heat treatment was assessed by neutron activation analysis, showing retention of 67-100 % of expected iodine. The aqueous durabilities of the resulting materials were then determined, following the ASTM C1308 standard test, showing iodine releases of 1 to 23 g m-2 after 4 d. The cumulative iodine release for the best performing system (a zinc-bismuth-borate glass binder) was <1 g m-2, and its iodine retention from processing was 67 %. The iodine releases compared favorably with other waste forms. In parallel, this best-performing composition was also consolidated via hot isostatic pressing (HIP) in a stainless-steel canister at 550 °C for 2 h under 100 MPa pressure. The HIPed sample was produced at the ~20 g scale and showed improved densification and minimal reaction with the canister.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗

Assessment of uranium nitride interatomic potentials

Uranium mononitride (UN) is a promising nuclear fuel due to its high fissile density, high thermal conductivity, and suitability for reprocessing. In this study, two uranium nitride interatomic potentials are assessed: Tseplyaev and Starikov's angular-dependent potential and Kocevski et al.'s embedded atom model potential. Predictions of the thermophysical and elastic properties of UN, UN 2 , and α- and β-U 2 N 3 computed using both potentials are assessed and compared to available experimental data. Notably, the Tseplyaev potential performs better with the energetic aspects of UN, e.g., specific heat capacity and point defect formation energies, whereas the Kocevski potential performs better with the structural aspects of UN, e.g., thermal expansion as well as with the elastic properties. The reasons why the Kocevski potential underestimates the UN specific heat are explained by examining the UN phonon properties modeled using both potentials. The Kocevski potential shows better identification of the mechanical stability ranges of UN, UN 2 , and α- and β-U 2 N 3 , reasonably predicting the melting point of UN and predicting stable structures for UN 2 and α- and β-U 2 N 3 . On the other hand, the Tseplyaev potential predicts a premature phase change of both UN and UN 2 and cannot stabilize α- nor β-U 2 N 3 . However, the Kocevski potential cannot predict a stable α-U phase and is thus not suitable for the calculation of formation energies for non-stoichiometric point defects.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗