Silicon concentration and pH controls over competitive or simultaneous incorporation of iodate and chromate into calcium carbonate phases
Not Available
Katsenovich, Yelena P.↗
SEARCH · Engineering Papers
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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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A neutron tomography study to visualize fluoride salt (FLiNaK) intrusion in nuclear-grade graphite
Manufactured graphite is a preferred material for in-core components of molten salt reactors and fluoride salt-cooled high-temperature reactors, which are in permanent contact with liquid salts. However, owing to the porous nature of nuclear graphite, under certain conditions, molten salts may intrude graphite's pores and affect graphite's properties and functionality. Therefore, a better understanding of molten salt intrusion (distribution across sample cross section and penetration depth) is needed to assess its effects. Here, in this work, we have demonstrated the use of neutron imaging (computed tomography) in the evaluation of salt penetration and distribution of a wide range of graphite grades with diverse microstructures that have been subjected to FLiNaK (LiF–NaF–KF) intrusion at 750 °C and 5 bar pressure for 12 h. Because of the great neutron attenuation contrast from scattering and adsorption between Li (from FLiNaK) and the graphite matrix, we have obtained direct visualization of FLiNaK salt distribution in the salt-impregnated graphites for the first time. Three-dimensional reconstructed images and cross-sectional concentration profiles demonstrate that salt penetration and density distribution are greatly dependent on the microstructural properties of the graphite grade.
22 GENERAL STUDIES OF NUCLEAR REACTORS↗
Viewing is understanding: Graphite microstructure effects on infiltrated molten salt distribution revealed by 3D neutron tomography
Molten salt infiltration in the pore network of nuclear graphite may cause unwanted changes to graphite's local structure and mechanical and thermal properties. A detailed and comprehensive understanding of molten salt intrusion (distribution across sample cross section and penetration depth) is needed to assess its effects. Here, in this work, we report on an improved methodology for the use of neutron imaging (computed tomography) to evaluate salt penetration and distribution of a wide range of graphite grades with diverse microstructures. Neutron tomography data were acquired on the same graphite sample before and after salt intrusion; the 3D reconstructed volumes were digitally co-registered and subtracted. The difference in neutron attenuation coefficient represents direct visualization of FLiNaK (LiF–NaF–KF) salt distribution in the salt-impregnated graphite samples. This improved methodology was applied to investigate the effect of exposure times (12 h and 336 h) and of graphite microstructure when exposed to FLiNaK at 750 °C and 3 bar (gauge) pressure, starting from flowing argon at near atmospheric pressure. The results show that medium-grained and fine-grained graphites evolve to equilibrium at significantly different rates: fast salt uptake in medium-grained graphites produces salt deposits throughout the volume of graphite specimens, whereas salt infiltration in fine-grained graphites is much slower and limited to exposed surfaces.
FLiNaK infiltration↗
Microstructure modeling of nuclear structural materials: Recent progress and future directions
Modeling and simulation of microstructures are essential to understand the complex responses and behaviors of nuclear materials in extreme environments. The needs to assess the extended life operation as well as the growing interest in accelerating nuclear materials development and qualification have stimulated the use of high-fidelity multiscale models aided by empirical and ab initio data. This paper reviews the role of various models across different length and time scales in investigating irradiation effects on microstructure evolution and degradation, in particular the embrittlement caused by radiation induced or enhanced formation of nanoscale chemical heterogeneities. The strength and limitations of these models, including classical rate theories, cluster dynamics, phase-field methods, and atomistic models informed by ab initio energies, are discussed with seminal examples. Challenges regarding the lack of thermo-kinetic data and theoretical treatments considering chemical complexities and magnetic excitations, as well as the stabilizing effect by excess point defects in nuclear structural materials are presented, along with potential solutions based on ab initio informed surrogate energy models and statistical sampling by Monte Carlo simulations. Further, the review then highlights the opportunities to leverage the advantages of different methods by establishing hybrid models by shared variables or coupled codes and applications. Finally, the review concludes with forward-looking remarks on how the use of physics-based models can aid the improvement of machine-learning models of property degradation and vice versa.
36 MATERIALS SCIENCE↗
Optimization-based technoeconomic comparison of multi-stage membrane distillation configurations for hypersaline produced water desalination
Unconventional oil and gas production raises concerns regarding sustainable management of high salinity wastewaters generated in this process. Membrane distillation (MD) is a thermal desalination process capable of treating hypersaline brines such as produced water. The low single pass recovery in MD systems operated in a single stage requires a large recycle stream to achieve the desired recovery, resulting in high energy consumption and operating cost. Multistage configurations in continuous recirculation operation mode offer the potential to reduce the energy intensity of MD systems. However, rigorous analysis is needed to assess the performance of MD configurations when operating in multi-stage mode. Here, we present an optimization-based comparison of economic and energetic performance for five configurations of MD (including DCMD, AGMD, PGMD, CGMD, and VMD) operating in multi-stage continuous recirculation mode. Our findings demonstrate that multistage operation reduces the treatment cost and energy intensity of all MD configurations compared to single stage MD, with the greatest benefit for VMD and PGMD. AGMD with five stages outperforms other configurations with 3.58 $/m 3 feed treatment cost, followed by VMD, CGMD, DCMD, and PGMD with 3.8, 4.2, 5.4, and 9.06$/m 3 feed treatment costs corresponding to twelve, eight, eight, and sixteen stages, respectively.
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
Polycyclic aromatic hydrocarbons and cannabinoids in secondhand cannabis smoke
The legalization of cannabis is exposing more people to secondhand smoke (SHS) generated during cannabis use. Given the serious health effects caused by tobacco SHS, there is a need to assess the potential health effects of exposure to cannabis SHS. As a step toward this, we measured the concentrations of cannabinoids, nicotine and polycyclic aromatic hydrocarbons (PAHs) in air samples collected in public places where cannabis was being consumed. These were compared with concentrations in exhaled aerosols from cannabis smoking and vaping, and in tobacco SHS. Tetrahydrocannabinol concentrations were 22 to 255 µg/m 3 in field samples, below the threshold for psychoactive effects. Nicotine concentrations in field samples did not exceed 1 µg/m 3 . The total PAH concentrations in field samples were from 3.2 to 80.5 ng/m 3 , depending on location type. By contrast, PAH levels averaged 72 ng/m 3 in tobacco SHS and 220 ng/m 3 in the more concentrated, exhaled cannabis aerosols. A total of 22 different PAHs were identified in field samples of cannabis aerosols, from which benz[a]anthracene (B[a]A) was present in the highest concentrations. The PAH profile of cannabis aerosols was different from that of tobacco SHS. A preliminary cancer risk evaluation showed that the dose associated with inhalation of cannabis SHS during an 8-h work shift exceeded the California No Significant Risk Level for B[a]A at all venues where cannabis was consumed primarily via smoking. In summary, the consumption of cannabis, by smoking and by vaporizing, can create aerosols that contain carcinogenic PAHs. Thus breathing secondhand cannabis aerosols increases exposure to carcinogens.
Aerosol↗
Earthquake-triggered submarine canyon flushing transfers young terrestrial and marine organic carbon into the deep sea
Submarine canyons transfer substantial amounts of sediment and organic carbon (OC) into the deep ocean, nourishing deep-sea ecosystems and contributing to the global carbon cycle through OC burial and sequestration. Tracking lateral OC transport through submarine canyon systems is challenged by the deep-ocean setting, difficulties with constraining episodic depositional events, and the need to assess the composition and age of marine and terrestrial organic matter. We apply innovative parallel ramped pyrolysis oxidation accelerator mass spectrometry and pyrolysis-gas chromatography-mass spectrometry with isotope analyses to track OC age and sources in the 2016 Kaikoura earthquake-triggered, canyon-flushing event that deposited along >1300 km of a submarine canyon-channel system, offshore Aotearoa New Zealand. Specifically, these techniques allow us to determine the ages, sources, and partitioning of OC within the Kaikoura turbidite deposit and test hypotheses of how submarine canyon systems contribute to lateral OC flux and burial. Our results show that, despite considerable canyon floor erosion, substantial amounts of young OC were flushed into the deep sea, with relatively little (~2%) pre-Holocene OC contributions. Even without a direct connection between rivers and submarine canyons, most (~55%) of the OC in the Kaikoura event bed is from terrestrial sources. However, the deposit also contains substantial amounts (~22%) of marine-derived OC and ~23% of the material is of unassignable origin. Particle sorting imparts variability on the age and composition of OC within turbidite deposits and along the turbidity current flow path. Terrestrial-derived OC is preferentially older than marine-derived OC and concentrated in coarser particle sizes found more commonly at the deposit base and in proximal settings. Young, marine-derived OC is concentrated at the surface of the deposits and tends to be enriched in finer particle sizes. Such OC partitioning in turbidites supports the relevance of depositional models for predicting and quantifying distribution of OC in deep-sea deposits. Earthquake-triggered, canyon flushing events and resulting turbidites enhance OC burial efficiency and can sequester OC effectively, contributing an important carbon sink to the sedimentary carbon cycle.
54 ENVIRONMENTAL SCIENCES↗
Overview of oxygen opacity experiments at the National Ignition Facility and investigation of potential systematic errors
Experiments to measure oxygen opacity at stellar interior conditions have been performed at the National Ignition Facility in a Discovery Science campaign. These experiments utilize the Opacity-on-NIF platform with a sample comprised of O, Mg, and Si. The spectral data from the Opacity Spectrometer cover the 1000–2000 eV photon energy range showing bound-free continuum absorption from O and line absorption from Mg and Si. DANTE and the Gated X-ray Detector are employed to measure the sample plasma’s temperature and density, respectively. Initial data show lower transmission than expected by theoretical models, raising questions of whether potential background or data uniformity concerns could produce systematic errors in the inferred transmission. Here, we investigate three concerns thought to be important for the oxygen opacity data, including instrumental scattered background, sample self-emission non-uniformity, and backlight continuum non-uniformity. Additionally, we show the effect of a recently developed method to account for 2nd order crystal reflection. The total effect of these concerns on one experiment is found to be small compared to the observed difference between the inferred transmission and a model calculation at the inferred temperature and density. Thus, we conclude that these potential sources of systematic error cannot account for the observed difference, increasing the likelihood of a real effect due to the high temperature and density conditions. However, because this is only a single experiment, we cannot make a firm conclusion. More experiments measuring the opacity and necessary calibrations are needed to assess the reproducibility and uncertainty of this result.
79 ASTRONOMY AND ASTROPHYSICS↗
Call attention to using DRT and EIS to quantify the contributions of solid oxide cell components to the total impedance
The contributions of anode and cathode processes to solid oxide fuel cell (SOFC) impedance were studied using electrochemical impedance spectroscopy (EIS) and distribution of relaxation time (DRT). Specifically, the role of gas composition at both anode and cathode was explored in a systematic study aimed at deconvoluting, identifying and quantifying the contributions of different anode and cathode processes. Further, five distinct relaxation time distributions were observed in the DRT spectra; although the peaks were ascribed to diffusion and charge transfer processes at the electrodes, it was found that both electrodes contributed to various peaks at the same time. Moreover, it was found that two distinctive operating conditions could return equivalent DRT spectra. While DRT analysis allows to obtain useful information regarding cell performance, extra consideration is needed when assessing and quantifying anodic and cathodic resistances within the SOFC.
08 HYDROGEN↗
Effects of ingested nanocellulose on intestinal microbiota and homeostasis in Wistar Han rats
Micron scale crystalline and fibrillar cellulose materials are “generally regarded as safe” (GRAS) as binders and thickeners in food products. Yet, partly due to a lack of relevant toxicological data, nanocellulose (NC) materials, which have unique properties that can be exploited to improve food quality and safety, have yet to receive FDA approval as food ingredients. Results of in vitro and in vivo toxicological studies of ingested NC, detailed in a recent companion report, revealed minimal acute in vitro cytotoxicity, and no toxicity in a subacute rat gavage model, suggesting that NC materials are non-hazardous. However, ingested materials may also modulate gut microbial populations, or alter aspects of intestinal function not evaluated in standard totoxicity testing, which could have important health implications. Here, we report the results of studies of the effects of ingested cellulose nanofibrils (CNF) on the fecal microbiome and metabolome, intestinal (ileal) epithelial cell mRNA expression of cell junction genes, and ileal cytokine production. Feces, plasma, and ileum samples were collected from Wistar Han rats before and after five weeks of biweekly gavages of water or cream, with or without 1% w/w CNF. Analysis of fecal microbial populations revealed that CNF caused changes in both genus and species diversity, with specific effects on species that produce short chain fatty acids, and that have been associated with increased IgA production and elevation of insulin levels. Fecal metabolomic analysis revealed relatively few effects of CNF, with significant changes in the levels of only ten metabolites out of 366 measured. Exposure to CNF also caused differential regulation of mRNA expression of several genes involved in epithelial cell junctions, and increased production of cytokines that both promote and inhibit proliferation of CD8 T cells. These perturbations in intestinal homeostasis contrast somewhat with the absence of in vitro and in vivo toxicity observed previously but would appear to represent minor effects. Additionally, the gut microbiome is highly sensitive to ingested substances, and such disturbances of the intestinal microbial ecosystem do not necessarily represent or predict meaningful pathology. Further studies, including chronic feeding studies, are needed to assess the real health implications, if any, of these changes.
59 BASIC BIOLOGICAL SCIENCES↗
Burst pressure models and validations for thick-walled pipelines containing corrosion defects
Corrosion is one major threat to pipeline integrity. Over the past decades, many corrosion models have been developed for determining the remaining strength of corroded pipelines, including ASME B31.G, Modified B31.G, LPC, PCORRC and their modified models. All these corrosion models are applicable only to large diameter, thin-walled pipelines with a diameter to wall thickness ratio D/t ≥ 20. In practice, many pipelines have a small diameter and thick wall with a D/t ratio < 20, and thus an adequate corrosion model is needed for assessing remaining strength for corroded thick-walled pipelines. This paper briefly reviews the theoretical burst pressure models for defect-free thin and thick-walled pipelines and four representative corrosion assessment models for thin-walled corroded pipelines. On this basis, two modified corrosion models are proposed to thick-walled pipelines in terms of the average shear stress yield theory. To verify the proposed corrosion models, comprehensive validations are performed. Numerical validations include the elastic-plastic finite element analysis to determine burst pressure for pipelines without and with corrosion defects and the model evaluation using a large dataset of available FEA results of burst pressure for machined defects. Experimental validations include a set of burst pressure tests for defect-free thick-walled pipes with different thicknesses and the model evaluation using one large burst dataset for machined defects with flat bottoms and another large dataset for real corrosion defects with curved river bottom profiles. Both numerical and experimental validations show that the proposed corrosion models can more accurately predict the remaining strength for corroded thin and thick-walled pipelines.
Pipeline↗
A multistep enrichment process with custom growth medium improves resuscitation of chlorine-stressed coliforms from secondary sewage effluents
Resuscitation and detection of stressed coliforms in treated water samples is needed to assess and prevent health effects from adverse exposure. Herein, we developed a custom growth media that improved total coliform resuscitation from chlorine-stressed samples from secondary effluent to see if detection time could be reduced from 18 to 8 hours.
59 BASIC BIOLOGICAL SCIENCES↗
Comparing structure-property evolution for PM-HIP and forged alloy 625 irradiated with neutrons to 1 dpa
The nuclear power industry has growing interest in qualifying powder metallurgy with hot isostatic pressing (PM-HIP) to replace traditional alloy fabrication methods for reactor structural components. But there is little known about the response of PM-HIP alloys to reactor conditions. This study directly compares the response of PM-HIP to forged Ni-base Alloy 625 under neutron irradiation doses ~0.5–1 displacements per atom (dpa) at temperatures ranging ~321–385 °C. Post-irradiation examination involves microstructure characterization, ASTM E8 uniaxial tensile testing, and fractography. Up through 1 dpa, PM-HIP Alloy 625 appears more resistant to irradiation-induced cavity nucleation than its forged counterpart, and consequently experiences significantly less hardening. This observed difference in performance can be explained by the higher initial dislocation density of the forged material, which represents an interstitial-biased sink that leaves a vacancy supersaturation to nucleate cavities. These findings show promise for qualification of PM-HIP Alloy 625 for nuclear applications, although higher dose studies are needed to assess the steady-state irradiated microstructure.
21 SPECIFIC NUCLEAR REACTORS AND ASSOCIATED PLANTS↗
A call to standardize metrics for monitoring baleen whales near marine construction activities
Effective monitoring is necessary to protect marine mammal species during the construction of offshore infrastructure. The tools for detecting or monitoring marine mammals span traditional (e.g., visual observers, optical cameras), to newer (e.g., passive acoustic monitoring, infrared cameras, tags), and emerging (e.g., satellite imagery, environmental DNA, dimethyl sulfide concentration) technologies. Some are better suited for use during offshore development; however, peer-reviewed literature does not typically evaluate and report on the performance of these various technologies. We define a minimum set of metrics related to efficacy (i.e., confusion matrix, precision and recall, probability of missed mitigation), detection range (i.e., maximum and reliable detection range, spatial resolution), and data delivery (i.e., detection latency, system reliability, temporal resolution) that we recommend are needed to assess the utility of monitoring technologies for this purpose. Following a literature review of relevant studies, we highlight which publications reported these metrics and used multiple technologies to compare relative performance. We also emphasize the benefits of multi-modal approaches and recommend performance assessments through modeling or large-scale collaborative field testing. These metrics will standardize data collection, reporting, and analysis; promote consistent and comparable results; and foster collaboration among developers, regulatory agencies, and scientists. This may lead to the co-development of technology that achieves multiple goals, has greater application, and can answer research questions while collecting data to fulfill permitting requirements. These metrics may also inform decisions on what systems regulatory agencies might consider using and reduce monitoring costs, which is critical to support the marine sector's rapid growth alongside marine mammal conservation.
32 ENERGY CONSERVATION, CONSUMPTION, AND UTILIZATI↗
Large seasonal fluctuations of groundwater radioiodine speciation and concentrations in a riparian wetland in South Carolina
Recent studies evaluating multiple years of groundwater radioiodine ( 129 I) concentration in a riparian wetland located in South Carolina, USA identified strong seasonal concentration fluctuations, such that summer concentrations were much greater than winter concentrations. These fluctuations were observed only in the wetlands but not in the upland portion of the plume and only with 129 I, and not with other contaminants of anthropogenic origin: nitrate/nitrite, strontium-90, technecium-99, tritium, or uranium. This unexplained observation was hypothesized to be the result of strongly coupled processes involving hydrology, water temperature, microbiology, and chemistry. To test this hypothesis, an extensive historical groundwater database was evaluated, and additional measurements of total iodine and iodine speciation were made from recently collected samples. During the summer, the water table decreased by as much as 0.7 m, surface water temperature increased by as much as 15 °C, and total iodine concentrations were consistently greater (up to 680%) than the following winter months. Most of the additional iodine observed in the summer could be attributed to proportional gains in organo-iodine, and not iodide or iodate. Furthermore, 129 I concentrations were observed to be two-orders-of-magnitude greater at the bottom of the upland aquifer than at the top. A coupled hydrological and biogeochemical conceptual model is proposed to tie these observations together. First, as the surface water temperature increased during the summer, microbial activity was enhanced, which in turn stimulated the formation of mobile organo-I. Hydrological processes were also likely involved in the observed iodine seasonal changes: (1) as the water table decreased in summer, the remaining upland water entering the wetland was comprised of a greater proportion of water containing elevated iodine concentrations from the low depths, and (2) water flow paths in summer changed such that the wells intercepted more of the contaminant plume and less of the diluting rainwater (due to evapotranspiration) and streamwater (as the lower levels promote a predominantly recharging system). Furthermore, these results underscore the importance of coupled processes influencing contaminant concentrations, and the need to assess seasonal contaminant variations to optimize long-term monitoring programs of wetlands.
54 ENVIRONMENTAL SCIENCES↗
Sliding friction and wear behavior of nuclear graphite in high temperature inert environment: Influence of contact load, speed and temperature
Repeated dynamic interactions of graphitic components in pebble-bed gas-cooled nuclear reactors can cause abrasive wear-induced pebble surface damage, generate hazardous fine graphite debris, and alter fuel circulation dynamics due to changes in friction behavior. Comprehensive tribological characterization of nuclear graphitic materials in conditions relevant to reactor operation is needed to assess reactor long-term safety and performance. This work reports sliding friction and wear behavior of self-mated nuclear graphite ET-10 at various elevated temperatures (650 °C and 750 °C), sliding speeds (1 and 10 mm/s) and contact loads (20 and 40 N) in a controlled argon environment. The results revealed nonmonotonic frictional behavior with a higher running-in coefficient of friction (COF) followed by a lower steady-state COF, as a result of transition from two-body abrasion to three-body abrasion along with formation of a tribofilm. A key finding of this work is the sensitivity of the running-in COF to experimental conditions; maximum running-in values were lower at either elevated temperature (0.52–0.54) or reduced sliding speed (0.51–0.54). Conversely, the steady-state COF remained invariant at approximately 0.3 across all tested parameters. Transmission electron microscopy revealed a 0.5–2.0 μm thick nanocrystalline tribofilm that was thought to be formed by the compaction of the graphitic wear debris on the contact surface during the sliding process. The nanocrystalline nature of the tribofilm was further confirmed by Raman spectroscopy. As a result, the combination of tribological testing and morphological characterization provided a mechanistic understanding of the frictional behavior of nuclear graphite upon sliding.
Friction↗
The Influence of Residual Copper Catalyst on the Polymer-to-Ceramic Conversion of a Click-Derived Polycarbosilane
Preceramic polymers (PCPs) are a key class of materials for the preparation of advanced ceramic components. Following conventional polymer processing and subsequent pyrolysis, polymer-derived ceramic (PDC) fibers, monoliths, and composites offer novel engineering opportunities for aerospace applications. Despite the rapidly emerging commercial applications of PDCs, many basic scientific questions remain regarding the structural transformation of the polymer to the final ceramic and how processing variables affect PDC materials properties. PCPs prepared using a mild and scalable copper (Cu) catalyzed azide/alkyne “click” reaction have been demonstrated as a unique class of material that can bind with transition metals, ultimately producing ultrahigh temperature ceramics (UHTCs) upon pyrolysis. Unexpectedly, it was found that the removal of residual Cu catalyst from a model click-derived polycarbosilane PCP significantly reduced the ceramic yield during pyrolysis. Herein, we report the influence of Cu impurities on polycarbosilane-derived SiC ceramics and present a mechanistic understanding of the unintended role of Cu in the polymer-to-ceramic conversion process. Synchrotron-based scattering and spectroscopy methods were implemented to track the evolution of different atomic species and local structures as well as the influence of Cu toward atomic-scale structures in the final ceramics. It was determined that Cu impurities catalyze the formation of silicon carbide through the formation of an intermediate molten copper/copper silicide, ultimately increasing the ceramic yield. Overall, this contribution highlights the need to carefully assess the interplay between the chemistries needed for PCP synthesis and their potential influence on final PDCs following processing.
Ponder, Jr., James F. [Air Force Research Laborato↗
Geospace Plume and Its Impact on Dayside Magnetopause Reconnection Rate
The role a geospace plume in influencing the efficiency of magnetopause reconnection is an open question with two contrasting theories being debated. A local-control theory suggests that a plume decreases both local and global reconnection rates, whereas a global-control theory argues that the global reconnection rate is controlled by the solar wind rather than local physics. Observationally, limited numbers of point measurements from spacecraft cannot reveal whether a local change affects the global reconnection. A distributed observatory is hence needed to assess the validity of the two theories. We use THEMIS and Los Alamos National Laboratory spacecraft to identify the occurrence of a geospace plume and its contact with the magnetopause. Global evolution and morphology of the plume is traced using GPS measurements. SuperDARN is then used to monitor the distribution and the strength of dayside reconnection. Two storm-time geospace plume events are examined and show that as the plume contacts the magnetopause, the efficiency of reconnection decreases at the contact longitude. The amount of local decrease is 81% and 68% for the two events, and both values are consistent with the mass loading effect of the plume if the plume's atomic mass is ~4 amu. Reconnection in the surrounding is enhanced, and when the solar wind driving is stable, little variation is seen in the cross polar cap potential. This study illuminates a pathway to resolve the role of cold dense plasma on solar wind-magnetosphere coupling, and the observations suggest that plumes redistribute magnetopause reconnection activity without changing the global strength substantially.
79 ASTRONOMY AND ASTROPHYSICS↗