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At least 145 records · Page 8

A diagnostic to measure neutral-atom density in fusion-research plasmas

For this study, a femtosecond two-photon-absorption laser-induced-fluorescence (TALIF) diagnostic was designed, installed, and operated on the Princeton-Field-Reversed Configuration-2 device to provide non-invasive measurements of the time and spatially resolved neutral-atom densities in its plasmas. Calibration of the H o density was accomplished by comparison with Kr TALIF. Measurements on plasmas formed of either H 2 or Kr fill gases allowed examination of nominally long and short ionization mean-free-path regimes. With multi-kW plasma heating and H 2 fill gas, a spatially uniform H o density of order 10 17 m –3 was measured with better than ±2 mm and 10 µs resolution. Under similar plasma conditions but with Kr fill gas, a 3-fold decrease in the in-plasma Kr density was observed.

70 PLASMA PHYSICS AND FUSION TECHNOLOGY↗

Motivation in vigilance - Effects of self-evaluation and experimenter-controlled feedback.

Vigilance experiments have been performed to study the relative efficiency of feedback operations in enhancing vigilance performance. Two feedback operations were compared - i.e., experimenter-controlled feedback in the form of knowledge of results (KR) regarding response times to signal detections, and subject-controlled feedback in the form of self-evaluation (SE) of response times to signal detections. The subjects responded to the aperiodic offset of a visual signal during a 1-hr vigil. Both feedback operations were found to enhance performance efficiency: subjects in the KR and SE conditions had faster response times than controls receiving no evaluative feedback. Moreover, the data of the KR and SE groups did not differ significantly from each other. The results are discussed in terms of the hypothesis that self-evaluation is a critical factor underlying the incentive value of KR in vigilance tasks.

Warm, J. S.↗

Motivation in vigilance - A test of the goal-setting hypothesis of the effectiveness of knowledge of results.

This study tested the prediction, derived from the goal-setting hypothesis, that the facilitating effects of knowledge of results (KR) in a simple vigilance task should be related directly to the level of the performance standard used to regulate KR. Two groups of Ss received dichotomous KR in terms of whether Ss response times (RTs) to signal detections exceeded a high or low standard of performance. The aperiodic offset of a visual signal was the critical event for detection. The vigil was divided into a training phase followed by testing, during which KR was withdrawn. Knowledge of results enhanced performance in both phases. However, the two standards used to regulate feedback contributed little to these effects.

Warm, J. S.↗

Cosmic-ray exposure history of North Ray and South Ray material

Cosmic-ray exposure ages for two breccias, 68815 and 69935, in the vicinity of South Ray Crater give consistent values of 2.0 plus or minus 0.2 m.y. when measured by the Kr-81-Kr, Na-22-Ne, and particle track methods. These also agree with estimates of exposure ages made by others using microcrater counts on six rocks in the same vicinity, including 69935. It is likely that this represents the age of South Ray Crater. Soils from stations close to South Ray Crater appear to be mature, well-irradiated materials containing little, if any, of a 2 m.y. component. Reviewing various lines of evidence, it is concluded that there are no compelling reasons to believe that so-called South Ray soils contain a large fraction of South Ray ejecta. However, if they do contain such ejecta, this material must have been well irradiated in situ prior to being thrown out in the South Ray event. A chip from a large boulder on the rim of North Ray Crater gives a Kr-81-Kr age of 50.6 plus or minus 3.8 m.y. Similar ages are found by the Na-22-Ne and the particle track methods. The agreement of this result with other data on large North Ray boulders fixes the age of North Ray Crater as 50 m.y.

Behrmann, C.↗

Neutron capture time scale of the s-process, estimated from s-process krypton in a meteorite

A krypton fraction enriched in s-process isotopes was extracted from a mineral fraction of the Murchison C2 chondrite. The (Kr-86)/(Kr-84) ratio is enhanced by 6 standard deviations, showing that significant amounts of Kr-86 were made in the s-process, despite the short, 10.8 yr beta-decay half-life of its precursor, Kr-85. Judging from this sample, the mean neutron capture time in the s-process was on the order of 5-100 yr for nuclei with cross sections of 125 mb.

Matsuda, J.-I.↗

Isotopic Composition of Trapped and Cosmogenic Noble Gases in Several Martian Meteorites

Isotopic abundances of the noble gases were measured in the following Martian meteorites: two shock glass inclusions from EET79001, shock vein glass from Shergotty and Y793605, and whole rock samples of ALH84001 and QUE94201. These glass samples, when combined with literature data on a separate single glass inclusion from EET79001 and a glass vein from Zagami, permit examination of the isotopic composition of Ne, Ar, Kr, and Xe trapped from the Martian atmosphere in greater detail. The isotopic composition of Martian Ne, if actually present in these glasses, remains poorly defined. The Ar-40/Ar-36 ratio of Martian atmospheric Ar may be much less than the ratio measured by Viking and possibly as low as approx. 1900. The atmospheric Ar-36/Ar-38 ratio is less than or equal to 4.0. Martian atmospheric Kr appears to be enriched in lighter isotopes by approx. 0.4%/amu compared to both solar wind Kr and to the Martian composition previously reported. The Martian atmospheric Ar-36/Xe-132 and Kr-84/Xe-132 Xe elemental ratios are higher than those reported by Viking by factors of approx. 3.3 and approx. 2.5, respectively. Cosmogenic gases indicate space exposure ages of 13.9 +/- 1 Myr for ALH84001 and 2.7 +/- 0.6 Myr for QUE94201. Small amounts of Ne-21 produced by energetic solar protons may be present in QUE94201, but are not present in ALH84001 or Y793605. The space exposure age for Y793605 is 4.9 +/- 0.6 Myr and appears to be distinctly older than the ages for basaltic shergottites.

Garrison, Daniel H.↗

Nucleosynthesis Predictions for Intermediate-Mass AGB Stars: Comparison to Observations of Type I Planetary Nebulae

Type I planetary nebulae (PNe) have high He/H and N/O ratios and are thought to be descendants of stars with initial masses of approx. 3-8 Stellar Mass. These characteristics indicate that the progenitor stars experienced proton-capture nucleosynthesis at the base of the convective envelope, in addition to the slow neutron capture process operating in the He-shell (the s-process). We compare the predicted abundances of elements up to Sr from models of intermediate-mass asymptotic giant branch (AGB) stars to measured abundances in Type I PNe. In particular, we compare predictions and observations for the light trans-iron elements Se and Kr, in order to constrain convective mixing and the s-process in these stars. A partial mixing zone is included in selected models to explore the effect of a C-13 pocket on the s-process yields. The solar-metallicity models produce enrichments of [(Se, Kr)/Fe] less than or approx. 0.6, consistent with Galactic Type I PNe where the observed enhancements are typically less than or approx. 0.3 dex, while lower metallicity models predict larger enrichments of C, N, Se, and Kr. O destruction occurs in the most massive models but it is not efficient enough to account for the greater than or approx. 0.3 dex O depletions observed in some Type I PNe. It is not possible to reach firm conclusions regarding the neutron source operating in massive AGB stars from Se and Kr abundances in Type I PNe; abundances for more s-process elements may help to distinguish between the two neutron sources. We predict that only the most massive (M grester than or approx.5 Stellar Mass) models would evolve into Type I PNe, indicating that extra-mixing processes are active in lower-mass stars (3-4 Stellar Mass), if these stars are to evolve into Type I PNe.

Karakas, Amanda I.↗

Isotopic Evidence for a Martian Regolith Component in Martian Meteorites

Noble gas measurements in gas-rich impact-melt (GRIM) glasses in EET79001 shergottite showed that their elemental and isotopic composition is similar to that of the Martian atmosphere [1-3]. The GRIM glasses contain large amounts of Martian atmospheric gases. Those measurements further suggested that the Kr isotopic composition of Martian atmosphere is approximately similar to that of solar Kr. The (80)Kr(sub n) - (80)Kr(sub M) mixing ratio in the Martian atmosphere reported here is approximately 3%. These neutron-capture reactions presumably occurred in the glass-precursor regolith materials containing Sm- and Br- bearing mineral phases near the EET79001/ Shergotty sites on Mars. The irradiated materials were mobilized into host rock voids either during shock-melting or possibly by earlier aeolian / fluvial activity.

Rao, M. N.↗

Real-time monitoring of trace noble gases using laser-induced breakdown spectroscopy—An investigation of the impact of bulk gas on plasma properties and sensitivity

The impact of Ar and He bulk gases on laser-induced breakdown spectroscopy (LIBS) real-time monitoring of trace Xe and Kr was assessed. LIBS is being developed as a monitoring tool for measuring noble gas transport in molten salt systems, in which traditional sensors may face challenges associated with radiation, corrosive materials, and/or mixed phases. The plasma temperature and electron densities of LIBS plasmas were measured in both static and various flowing Ar and He streams (0–5 L min −1 ). The use of an Ar bulk gas resulted in higher plasma temperature, greater electron densities by an order of magnitude, and extended plasma lifetime compared with when He bulk gas was used. Gas flow rate was found to have little impact on plasma temperature; however, its effect on electron density was significant, indicating the need to consider flow rate–specific models. Matrix effects on emission peaks were reported for both bulk gases. Due to these matrix effects, multivariate models were developed for Xe and Kr ranging from 0 to 700 ppm in both bulk gases. Although the predictive behavior was similar (root mean square error of prediction ranging from 11.1 to 20.6 ppm), the limits of detection were superior in He (Xe: 22.9 ppm, Kr: 30.4 ppm). Furthermore, these models were employed in demonstrative real-time tests (>1 h), which showed strong predictive precision (relative standard deviation <5 %) regardless of the bulk gas. Ultimately, this study provides a guide for the considerations required when developing gaseous LIBS models for real-time monitoring.

Gas flow effects↗

Materials Data on KrF2 by Materials Project

KrF2 is Cyanogen Chloride-derived structured and crystallizes in the tetragonal I4/mmm space group. The structure is zero-dimensional and consists of two KrF2 clusters. Kr is bonded in a linear geometry to two equivalent F atoms. Both Kr–F bond lengths are 1.94 Å. F is bonded in a single-bond geometry to one Kr atom.

36 MATERIALS SCIENCE↗

Materials Data on KrF2 by Materials Project

KrF2 is Cyanogen Chloride-derived structured and crystallizes in the tetragonal P4_2/mnm space group. The structure is zero-dimensional and consists of two KrF2 clusters. Kr is bonded in a linear geometry to two equivalent F atoms. Both Kr–F bond lengths are 1.94 Å. F is bonded in a single-bond geometry to one Kr atom.

36 MATERIALS SCIENCE↗

Materials Data on Hg2Te4Kr3(O2F13)2 by Materials Project

(KrF2)3(HgTe2(OF5)2)2 crystallizes in the monoclinic P2_1/c space group. The structure is zero-dimensional and consists of four HgTe2(OF5)2 clusters and six KrF2 clusters. In each HgTe2(OF5)2 cluster, Hg is bonded in a linear geometry to two O atoms. There are one shorter (2.06 Å) and one longer (2.08 Å) Hg–O bond lengths. There are two inequivalent Te sites. In the first Te site, Te is bonded in an octahedral geometry to one O and five F atoms. The Te–O bond length is 1.89 Å. There is three shorter (1.88 Å) and two longer (1.89 Å) Te–F bond length. In the second Te site, Te is bonded in an octahedral geometry to one O and five F atoms. The Te–O bond length is 1.88 Å. There are a spread of Te–F bond distances ranging from 1.87–1.89 Å. There are two inequivalent O sites. In the first O site, O is bonded in a bent 120 degrees geometry to one Hg and one Te atom. In the second O site, O is bonded in a bent 120 degrees geometry to one Hg and one Te atom. There are ten inequivalent F sites. In the first F site, F is bonded in a single-bond geometry to one Te atom. In the second F site, F is bonded in a single-bond geometry to one Te atom. In the third F site, F is bonded in a single-bond geometry to one Te atom. In the fourth F site, F is bonded in a single-bond geometry to one Te atom. In the fifth F site, F is bonded in a single-bond geometry to one Te atom. In the sixth F site, F is bonded in a single-bond geometry to one Te atom. In the seventh F site, F is bonded in a single-bond geometry to one Te atom. In the eighth F site, F is bonded in a single-bond geometry to one Te atom. In the ninth F site, F is bonded in a single-bond geometry to one Te atom. In the tenth F site, F is bonded in a single-bond geometry to one Te atom. In each KrF2 cluster, Kr is bonded in a linear geometry to two equivalent F atoms. Both Kr–F bond lengths are 1.94 Å. F is bonded in a single-bond geometry to one Kr atom.

36 MATERIALS SCIENCE↗

Self-Adjusting Metal–Organic Framework for Efficient Capture of Trace Xenon and Krypton

The capture of the xenon and krypton from nuclear reprocessing off-gas is essential to the treatment of radioactive waste. Although various porous materials have been employed to capture Xe and Kr, the development of high-performance adsorbents capable of trapping Xe/Kr at very low partial pressure as in the nuclear reprocessing off-gas conditions remains challenging. Herein, we report a self-adjusting metal-organic framework based on multiple weak binding interactions to capture trace Xe and Kr from the nuclear reprocessing off-gas. The self-adjusting behavior of ATC-Cu and its mechanism have been visualized by the in-situ single-crystal X-ray diffraction studies and theoretical calculations. The self-adjusting behavior endows ATC-Cu unprecedented uptake capacities of 2.65 and 0.52 mmol g -1 for Xe and Kr respectively at 0.1 bar and 298 K, as well as the record Xe capture capability from the nuclear reprocessing off-gas. Further, our work not only provides a benchmark Xe adsorbent but proposes a new route to construct smart materials for efficient separations.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Experimental measurement of the rapid mixing of fuel and air in a multi-element diffusion (Hencken) burner

Flat flame burners are valuable tools for studying complex combustion phenomena like particle synthesis due to the well-controlled and well-behaved initial and boundary conditions. In this study, the methane/air flame temperature and tracer density profiles of a multi-element diffusion burner equipped with a central tube were characterized using krypton (Kr) x-ray fluorescence at the Advanced Photon Source at Argonne National Laboratory. The experiments were performed using a fuel-to-oxygen equivalence ratio of 0.8 and 3.3% Kr by volume was added to the reactant gases. One- and two-dimensional scans of non-combusting (i.e., cold flow) and combusting conditions, both with and without flow through the central tube were performed. Spatially-resolved Kr number density profiles were obtained at different planar locations and heights above the surface of the burner. The results show rapid mixing occurred near the exit-plane of the burner and increased spatial uniformity was achieved from 0.1 mm to 0.5 mm above the surface of the burner. Further, the data also showed the impact of the central tube flow on the main methane/air flame, including evidence of the central tube flow mixing with the main flow. Flame temperatures were calculated from the fluorescence measurements at various heights above the burner surface and were in good agreement with model predictions for a burner stabilized flame. These high-fidelity measurements provide accurate baseline data that are particularly valuable for understanding the effects of fuel and air mixing on downstream phenomena, such as the formation of condensed-phase products.

42 ENGINEERING↗

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↗

Engineering Polyketide Stereocenters with Ketoreductase Domain Exchanges

Polyketide synthases (PKSs) are versatile biosynthetic megasynthases capable of producing a diverse range of natural products with many applications, including in pharmaceuticals. The stereochemical precision of PKSs makes them a powerful tool for engineering tailored, unnatural polyketides; however, modifying the stereocenters of a PKS product while maintaining production levels remains a significant challenge. In this study, we systematically tested and evaluated strategies for ketoreductase (KR) domain exchanges, the domain responsible for setting stereocenters of polyketide products. After first optimizing the method for KR exchanges, we then performed 44 KR domain exchanges on three different PKSs to obtain high production of all four stereoisomers in vivo. By testing both one- and two-module PKS systems, we investigated how downstream modules process intermediates with altered stereochemistry and found that the configuration of the α-substituents was critical for gatekeeping by the ketosynthase (KS). To overcome this constraint, we investigated two different strategies for altering the KS domain, including introducing targeted mutations in the downstream KS, and exploring boundaries in exchanging the entire functional unit from the donor PKS. Both strategies successfully modified the KS stereocontrol with distinct trade-offs; the functional unit exchange resulted in higher titer improvements, though it was more likely to break the entire PKS. This study demonstrates a comprehensive approach to successfully engineering all four stereochemical configurations in multiple PKS systems, advancing our understanding of and ability to rationally modify polyketide stereochemistry through multiple engineering strategies.

Keiser, Leah S. [Joint BioEnergy Institute (JBEI),↗

Radiation-resistant metal-organic framework enables efficient separation of krypton fission gas from spent nuclear fuel

Capture and storage of volatile radionuclides that result from processing of used nuclear fuel is a major challenge. Solid adsorbents, in particular ultra-microporous metal-organic frameworks, could be effective in capturing these volatile radionuclides, including 85 Kr. However, metal-organic frameworks are found to have higher affinity for xenon than for krypton, and have comparable affinity for Kr and N 2 . Also, the adsorbent needs to have high radiation stability. To address these challenges, here we evaluate a series of ultra-microporous metal-organic frameworks, SIFSIX-3-M (M = Zn, Cu, Ni, Co, or Fe) for their capability in 85 Kr separation and storage using a two-bed breakthrough method. These materials were found to have higher Kr/N 2 selectivity than current benchmark materials, which leads to a notable decrease in the nuclear waste volume. The materials were systematically studied for gamma and beta irradiation stability, and SIFSIX-3-Cu is found to be the most radiation resistant.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗

Electron scattering with ethane adsorbed on rare gas multilayers: Hole transfer, coulomb decay, and ion dissociation

Positive ion desorption following electron impact dissociative ionization of ethane adsorbed on Ar, Kr, and Xe multilayers has been studied as a function of incident electron energy from threshold to 100 eV. Based on the dependence of ion yields on the identity of the rare gas, it is likely that the majority of ethane molecules undergo indirect ionization following hole transfer from the ionized underlying rare gas. Further, this has also been corroborated by density of states calculations showing the energetic alignment of the outer valence states of ethane and the condensed rare gas ionization energies. Due to the near-resonant nature of charge transfer for single-hole states, the ethane molecular ion is excited to different final ionic states on different rare gases, which leads to differences in ion desorption yields and branching ratios. The quantitative yields increase with increasing ionization energy gap between the rare gas and ethane, in the order Ar > Kr >Xe. The large increase in yields from 25 eV onwards for all rare gases is likely due to the formation and decay of two-hole states on neighboring rare gas and ethane molecules due to interatomic and intermolecular Coulomb decay (ICD) and not electron transfer mediated decay (ETMD). The ICD and ETMD pathways become accessible when the incoming electron has sufficient energy to excite the inner valence ns level of the rare gas to a Rydberg state or ionize it. The experimental findings are supported by calculations of thresholds, density of states for the final configurations of these processes, and coupling strengths for hole transfer between ethane and rare gases. The fragment ion branching ratios vary with energy from threshold to about 35 eV, showing the fragmentation pattern changes with the mode of hole transfer and availability of excess energy. Sigma C–C bonds are more likely to break than C–H bonds in the mid-20 eV range, and this effect is most pronounced for Xe, followed by Kr, and then Ar.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗