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At least 451 records · Page 25

Trailblazing Kr/Xe Separation: The Birth of the First Kr-Selective Material

Efficient separation of Kr from Kr/Xe mixtures is pivotal in nuclear waste management and dark matter research. Thus far, scientists have encountered a formidable challenge: the absence of a material with the ability to selectively adsorb Kr over Xe at room temperature. This study presents a groundbreaking transformation of the renowned metal–organic framework (MOF) CuBTC, previously acknowledged for its Xe adsorption affinity, into an unparalleled Kr-selective adsorbent. This achievement stems from an innovative densification approach involving systematic compression of the MOF, where the crystal size, interparticle interaction, defects, and evacuation conditions are synergistically modulated. The resultant densified CuBTC phase exhibits exceptional mechanical resilience, radiation tolerance, and notably an unprecedented selectivity for Kr over Xe at room temperature. Simulation and experimental kinetic diffusion studies confirm reduced gas diffusion in the densified MOF, attributed to its small pore window and minimal interparticle voids. The lighter Kr element demonstrates facile surface passage and higher diffusivity within the material, while the heavier Xe encounters increased difficulty entering the material and lower diffusivity. This Kr-selective MOF not only represents a significant breakthrough in Kr separation but also demonstrates remarkable processability and scalability to kilogram levels. Furthermore, the findings presented herein underscore the transformative potential of engineered MOFs in addressing complex challenges, heralding a new era of Kr separation technologies.

36 MATERIALS SCIENCE↗

Rational design of a genetically encoded NMR zinc sensor

Elucidating the biochemical roles of the essential metal ion, Zn 2+ , motivates detection strategies that are sensitive, selective, quantitative, and minimally invasive in living systems. Fluorescent probes have identified Zn 2+ in cells but complementary approaches employing nuclear magnetic resonance (NMR) are lacking. Recent studies of maltose binding protein (MBP) using ultrasensitive 129 Xe NMR spectroscopy identified a switchable salt bridge which causes slow xenon exchange and elicits strong hyperpolarized 129 Xe chemical exchange saturation transfer (hyper-CEST) NMR contrast. To engineer the first genetically encoded, NMR-active sensor for Zn 2+ , we converted the MBP salt bridge into a Zn 2+ binding site, while preserving the specific xenon binding cavity. The zinc sensor (ZS) at only 1 μM achieved ‘turn-on’ detection of Zn 2+ with pronounced hyper-CEST contrast. This made it possible to determine different Zn 2+ levels in a biological fluid via hyper-CEST. ZS was responsive to low-micromolar Zn 2+ , only modestly responsive to Cu 2+ , and nonresponsive to other biologically important metal ions, according to hyper-CEST NMR spectroscopy and isothermal titration calorimetry (ITC). Protein X-ray crystallography confirmed the identity of the bound Zn 2+ ion using anomalous scattering: Zn 2+ was coordinated with two histidine side chains and three water molecules. Penta-coordinate Zn 2+ forms a hydrogen-bond-mediated gate that controls the Xe exchange rate. Metal ion binding affinity, 129 Xe NMR chemical shift, and exchange rate are tunable parameters via protein engineering, which highlights the potential to develop proteins as selective metal ion sensors for NMR spectroscopy and imaging.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Measurements and models of enhanced recombination following inner-shell vacancies in liquid xenon

Electron-capture decays of 125 Xe and 127 Xe , and double-electron-capture decays of 124 Xe , are backgrounds in searches for weakly interacting massive particles (WIMPs) conducted by dual-phase xenon time projection chambers such as LUX-ZEPLIN (LZ). These decays produce signals with more light and less charge than equivalent-energy 𝛽 decays and correspondingly overlap more with WIMP signals. We measure three electron-capture charge yields in LZ: the 1.1 keV M-shell, 5.2 keV L-shell, and 33.2 keV K-shell at drift fields of 193 and 96.5 V/cm. The LL double-electron-capture decay of 124 Xe exhibits even more pronounced shifts in charge and light. We provide a first model of double-electron-capture charge yields using the link between ionization density and electron-ion recombination, and identify a need for more accurate calculations. Finally, we discuss the implications of the reduced charge yield of these decays and other interactions creating inner-shell vacancies for future dark matter searches.

72 PHYSICS OF ELEMENTARY PARTICLES AND FIELDS↗

Development of bubble evolution model for new mechanistic transient fission gas release capability in BISON

This report summarizes efforts within NEAMS to investigate the mechanisms that govern fission gas behavior in UO 2 . In particular, the focus is on understanding how fission gas behavior causes transient fission gas release and fragmentation/pulverization of high burnup structure (HBS) in UO 2 . HBS forms in the periphery of the pellet where temperatures are relatively low. Previously, MD simulations were performed to determine the reaction energies for various Xe and U defects with bubbles, as a function of Xe to vacancy ratio or, equivalently, pressure. As had been shown in FY22, it was found that the unmodified version of the Simple Integrated Fission Gas Release and Swelling (SIFGRS) model within BISON greatly over-predicted the number gas atoms per vacancy in the bubbles in the outer rim of the pellet (a ratio of > 1 million). This was due to slow grain boundary vacancy diffusivity and not accounting for the pressure-dependent reaction energy for Xe interstitials with bubbles. The application of the pressure dependent reaction energies was able to restrict Xe to vacancy ratios to 2:1, which is far more realistic than those originally obtained from SIFGRS.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗

Xenon compatibility in magmatic processes: Hadean to current contexts

Xenon (Xe) behaviour in petrological processes, albeit essential to constrain mantle ingassing and degassing models, is elusive due to its volatile nature, and lack of direct investigation at the pressures (P) and temperatures (T) relevant to magma formation and crystallisation at depth. Xenon stands out amongst noble gases due to its unique reactivity with silicates of the lower crust and upper mantle, which could at least partially explain that published mineral/melt partitioning coefficients span up to six orders of magnitude. We report partition coefficients of Xe using in situ X-ray fluorescence at high P and T, and mass spectrometry analyses. Xenon is found to be moderately incompatible in anorthite-clinopyroxene mix in equilibrium with basalt (partition coefficient value of 0.16 ± 0.06), and compatible in olivine in equilibrium with basalt (partition coefficients in the range 88 ± 22 to 302 ± 46). While Xe is, thus, concentrated in basaltic melts coexisting with crystallising pyroxenes and feldspars, it is strongly retained in olivine at depth. Consequently, Xe originally contained in solid Earth has been preferentially retained at depth throughout Earth’s history, from the magma ocean stages to present day partial mantle melting processes.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Cyclotron production of I-123: An evaluation of the nuclear reactions which produce this isotope

The reactions studied which produce I-123 directly were Sb-121(He-4,2n) I-123, Sb-121(He-3,n) I-123, Te-122(d,n) I-123, Te-122(He-4,p2n) I-123, Te-122(He-3,pn) I-123, and Te-123(He-3,p2n) I-123. Reactions which produce I-123 indirectly through the positron decay of 2.1-hour Xe-123 were Te-122(He-4,3n) Xe-123, Te-122(He-3,2n) Xe-123 and Te-123(He-3,3n) Xe-123. Use of the gas flow I-123 cyclotron target assembly is recommended for the production of I-123 with radiochemical purity greater than 99.995%.

Sodd, V. J.↗

A target for production of radioxenons

A liquid cesium target has been developed which permits the production and identification of the neutron deficient isotopes of xenon. The thick target yields of Xe-127 and Xe-129 m were measured for proton energies between 28 and 40 MeV. Production of Xe-129 m, as indicated by the presence of a 196 keV line in the gamma ray spectra, occurred at all proton energies; Xe-127 was produced at proton energies above 33 MeV. Both accumulated on the target with the same time constant, and the cross sections were comparable in magnitude. The radioxenons were removed from the target by a stream of carrier gas so that chemical separation was unnecessary.

Blue, J. W.↗

Comparisons between observed and predicted cosmogenic noble gases in lunar samples

Comparisons are made between cosmogenic production rates and isotopic ratios predicted on the basis of nuclear systematics with those observed in well-documented lunar samples. Although some significant differences are found, the agreement in general is surprisingly good. The predicted production rates for Ar-38 and Xe-126 agree reasonably well with observation but the predicted rate for Ne-21 appears to be too high; in most cases the predicted rate for Kr-83 agrees to within 50%, although some larger differences are apparent. There are some prominent cases in which predicted isotopic compositons differ from observation: Kr-78/Kr-83 trends in the wrong sense with the Zr/Sr ratio; Xe-124/Xe-126 is too large by about 13%; Xe-128/Xe-126 is too small by about 6%; Xe-130/Xe-126 is too low by 30-40%.

Hohenberg, C. M.↗

Xenon, osmium, and lead formed in O-shells and C-shells of massive stars

In this paper it is shown that the explosive products from O-shells of massive stars which contain Xe-124 with large overproduction factors do not contain any of the naturally occurring isotopes of Os and Pb. Further, it is shown that the explosive products from C-shells (explosive carbon burning) do contain Os and Pb along with Xe which is strongly enriched in r-Xe of anomalous isotopic composition. The composition of Os in this matter is probably s-like rather than r-like. Pb in this matter is enriched in Pb-208. The results and arguments of this paper have implications for studies of isotopic compositions of Xe, Os, and Pb in residues of the Allende and other carbonaceous chondrites.

Heymann, D.↗

On the presolar origin of the 'normal planetary' noble gas component in meteorites

Several components of planetary noble gases, including CCFXe (Xe-X), s-process Kr and Xe, and Ne-E, are now thought to have had a presolar origin. It is proposed that the 'normal planetary' noble gas component, which contains most of the planetary Ar, Kr, and Xe, is also presolar. This component was trapped in carbonaceous mantles as the mantles formed on grain surfaces in the molecular cloud. The presolar dust grains and their carbonaceous mantles were then incorporated into primitive meteorites. This model naturally explains: (1) the affinity of 'normal planetary' noble gases for carbonaceous material in primitive chondrites; (2) the near absence of He and Ne in the 'normal planetary' component; (3) the elemental fractionation patterns of the 'exotic' and 'normal planetary' components; (4) the similarity of the isotopic compositions of 'normal planetary' and trapped solar Ar, Kr, and Xe; (5) the high noble gas content of the 'normal planetary' gas carrier; (6) several aspects of the chemistry of the 'normal planetary' gas carrier; (7) the correlation of planetary noble gases with the fine-grained material in primitive chondrites; and (8) the widespread occurrence of the planetary fractionation pattern throughout the solar system.

Huss, Gary R.↗

The early solar system abundance of Pu-244 as inferred from the St. Severin chondrite

The isotopic composition of Xe released in stepwise heating of neutron-irradiated samples of the St. Severin chondrite was measured. This analysis shows that at the time of formation of most chondritic meteorites, approximately 4.56 x 10 to the 9th yr ago, the atomic ratio of Pu-244/U-238 was 0.0068 + or - 0.0010 in chondritic meteorites. This value is believed to be more reliable that inferred from earlier analyses of St. Severin and is the best estimate for the early solar system abundance of Pu-244. The comparison of Xe compositions between irradiated and unirradiated samples shows that the composition of trapped (ambient) Xe in St. Severin has a significantly lower value of Xe-136/Xe-130 than average carbonaceous chondrites.

Hudson, G. B.↗

Carbon and nitrogen in Type 2 supernova diamonds

Abundant diamonds found in meteorites seem either to have condensed within supernova interiors during their expansions and coolings or to have been present around those explosions. Either alternative allows implantation of Xe-HL prior to interstellar mixing. A puzzling feature is the near normalcy of the carbon isotopes, considering that the only C-rich matter, the He-burning shell, is pure C-12 in that region. That last fact has caused many to associate supernova carbon with C-12 carbon, so that its SUNOCONS have been anticipated as very C-12-rich. We show that this expectation is misleading because the C-13-rich regions of Type 2's have been largely overlooked in this thinking. We here follow the idea that the diamonds nucleated in the C-12-rich He shell, the only C-rich site for nucleation, but then attached C-13-rich carbon during turbulent encounters with overlying C-13-rich matter. That is, the initial diamonds continued to grow during the same collisional encounters that cause the Xe-HL implantation. Instead of interacting with the small carbon mass having 13/12 = 0.2 in the upper He zone, however, we have calculated the remnants of the initial H-burning core, which left behind C-13-rich matter as it receded during core hydrogen burning. Howard et al. described why the velocity mixing would be essential to understanding the implantation of both the Xe-H and Xe-L components. Velocity mixing is now known to occur from the X-ray and gamma-ray light curves of supernova 1987A. Using the stellar evolution code developed at Goettingen, we calculated at Clemson the evolution of a grid of massive stars up to the beginning of core He burning. We paid attention to all H-burning reactions throughout the star, to the treatment of both convection and semiconvection, and to the recession of the outer boundary of the convective H-burning core as the star expands toward a larger redder state. This program was to generate a careful map of the CNO isotope distribution as He burning begins. Our result for the 30 solar mass star is shown.

Clayton, Donald D.↗

Noble gases in presolar diamonds I: Three distinct components and their implications for diamond origins

High-purity separates of presolar diamond were prepared from 14 primitive chondrites from 7 compositional groups. Their noble gases were measured using stepped pyrolysis. Three distinct noble gas components are present in diamonds, HL, P3, and P6, each of which is found to consist of five noble gases. P3, released between 200 C and 900 C, has a 'planetary' elemental abundance pattern and roughly 'normal' isotopic ratios. HL, consisting of isotopically anomalous Xe-HL and Kr-H, Ar with high Ar-38/Ar-36, and most of the gas making up Ne-A2 and He-A, is released between 1100 C and 1600 C. HL has 'planetary' elemental ratios, except that it has much more He and Ne than other known 'planetary' components. HL gases are carried in the bulk diamonds, not in some trace phase. P6 has a slightly higher median release temperature than HL and is not cleanly separated from HL by stepped pyrolysis. Our data suggest that P6 has roughly 'normal' isotopic compositions and 'planetary' elemental ratios. Both P3 and P6 seem to be isotopically distinct from P1, the dominant 'planetary' noble-gas component in primitive chondrites. Release characteristics suggest that HL and P6 are sited in different carriers within the diamond fractions, while P3 may be sited near the surfaces of the diamonds. We find no evidence of separability of Xe-H and Xe-L or other isotopic variations in the HL component. However, because approximately 10(exp 10) diamonds are required to measure a Xe composition, a lack of isotopic variability does not constrain diamonds to come from a single source. In fact, the high abundance of diamonds in primitive chondrites and the presence of at least three distinct noble-gas components strongly suggest that diamonds originated in many sources. Relative abundances of noble-gas components in diamonds correlate with degree of thermal processing, indicating that all meteorites sampled essentially the same mixture of diamonds. That mixture was probably inherited from the Sun's parent molecular cloud.

Huss, Gary R.↗

Fractionated martian atmosphere in the nakhlites?

Considerable evidence points to a martian origin of the shergottite-nakhlite-chassignite (SNC) meteorites. Noble gas isotopic compositions have been measured in most SNC meteorites. The Xe-129/Xe-132 vs. Kr-84/Xe-132 ratios in Chassigny, most shergottites, and lithology C of EETA 79001 define a linear array. This array is thought to be a mixing line between martian mantle and martian atmosphere. One of the SNC meteorites, Nakhla, contains a leachable component that has an elevated Xe-129/Xe-132 ratio relative to its Kr-84/Xe-132 ratio when compared to this approximately linear array. The leachable component probably consists in part of iddingsite, an alteration product produced by interaction of olivine with aqueous fluid at temperatures lower than 150 C. The elevated Xe isotopic ratio may represent a distinct reservoir in the martian crust or mantle. More plausibly, it is elementally fractionated martian atmosphere. Formation of sediments fractionates the noble gases in the correct direction. The range of sediment/atmosphere fractionation factors is consistent with the elevated Xe-129/Xe-132 component in Nakhla being contained in iddingsite, a low temperature weathering product. The crystallization age of Nakhla is 1.3 Ga. Its low-shock state suggests that it was ejected from near the surface of Mars. As liquid water is required for the formation of iddingsite, these observations provide further evidence for the near surface existence of aqueous fluids on Mars more recently than 1.3 Ga.

Drake, Michael J.↗

Acquisition and Early Losses of Rare Gases from the Deep Earth

Direct observations show that the deep Earth contains rare gases of solar composition distinct from those in the atmosphere. We examine the implications of mantle rare gas characteristics on acquisition of rare gases from the solar nebula and subsequent losses due to a large impact. Deep mantle rare gas concentrations and isotopic compositions can be obtained from a model of transport and distribution of mantle rare gases. This model assumes the lower mantle closed early, while the upper mantle is open to subduction from the atmosphere and mass transfer from the lower mantle. Constraints are derived that can be incorporated into models for terrestrial volatile acquisition: (1) Calculated lower-mantle Xe-isotopic ratios indicate that the fraction of radiogenic Xe produced by I-129 and Pu-244 during the first about 10(exp 8) yr was lost, a conclusion also drawn for atmospheric Xe. Thus, either the Earth was made from materials that had lost >99% of rare gases about (0.7-2) x 10(exp 8) yr after the solar system formed, or gases were then lost from the fully formed Earth. (2) Concentrations of 3He and 20Ne in the lower mantle were established after these losses. (3) Neon-isotopic data indicates that mantle Ne has solar composition. The model allows for solar Ar/Ne and Xe/Ne in the lower mantle if a dominant fraction of upper mantle Ar and Xe are subduction-derived. If Earth formed in the presence of the solar nebula, it could have been melted by accretional energy and the blanketing effect of a massive, nebula-derived atmosphere. Gases from this atmosphere would have been sequestered within the molten Earth by dissolution at the surface and downward mixing. It was found that too much Ne would be dissolved in the Earth unless the atmosphere began to escape when the Earth was only partially assembled. Here we consider conditions required to initially dissolve sufficient rare gases to account for the present lower mantle concentrations after subsequent losses at 10(exp 8) yr. It is assumed that equilibration of the atmosphere with a thoroughly molten mantle was rapid, so that initial abundances of gases retained in any mantle layer reflected surface conditions when the layer solidified. For subsequent gas loss of 99.5% and typical solubility coefficients, a total pressure of 100 atm was required for an atmosphere of solar composition. Calculations of the pressure at the base of a primordial atmosphere indicate that this value might be exceeded by an order of magnitude or more for an atmosphere supported by accretional energy. Surface temperatures of about 4000 K would have been produced, probably high enough to melt the deep mantle. Initial distributions of retained rare gases would then be determined by the history of surface pressure and temperature during mantle cooling and solidification, i.e., the coupled cooling of Earth and atmosphere. The Earth's thermal state was determined by its surface temperature and the efficiency of convection in the molten mantle, estimated to be sufficient to maintain an adiabatic gradient. Because the melting curve is steeper than the adiabat, solidification of the mantle proceeded outward from the interior. Incorporation of atmospheric gases in the mantle therefore occurred over a range in surface temperature of a few thousand degrees Kelvin. The thermal state of the atmosphere was controlled by total luminosity of the Earth (energy) released by accreting planetesimals and the cooling Earth), nebular temperature and pressure, and atmospheric opacity. The energy released by accretion declined with time as did nebular pressure. Analytical solutions for an idealized (constant opacity radiative atmosphere show that declining energy sources under constant nebular conditions result in slowly diminishing surface temperature but dramatically increasing surface pressure. For such an atmosphere with declining nebular pressure but constant total luminosity, surface pressure decreases gradually with decreasing temperaure. A decline in accretion luminosity might be compensated by energy released as the mantle cools for about 10(exp 5) year, after which luminosity must decline. The total complement of dissolved rare gases will depend on the particular evolutionary path determined by the declining accretional luminosity, the Earth thermal history, removal of the nebula, and opacity variations of the atmosphere. Models for these coupled evolutionary histories for Earth's acquisition of nebular-derived noble gases are in progress. The later losses required at about 10(exp 8) yr (depleting the interior concentrations of the sequestered solar gases by a factor of > 100) were presumably related to the major impact in which the Moon formed.

Porcelli, D.↗

Mineralogical Variations Among High Albedo E-Type Asteroids: Implications for Asteroid Igneous Processes

The link between the E-type asteroids and the enstatite achondrites (aubrites) was first proposed for the original E-asteroid, 44 Nysa. The association was based on the high albedos and the featureless spectra shared by the E-asteroids and the aubrites. Among the plausible geologic and meteoritic materials, only enstatite (the magnesium end-member of the pyroxene solid solution series) is sufficiently abundant to comprise asteroid-sized bodies. However, the presence of a weak 0.89 m absorption feature in the spectrum of 44 Nysa indicates that its pyroxene contains a small amount of Fe(2+) but still substantially more than any aubrite present in the meteorite collection. The original E-class was defined based on its high albedo and flat to slightly reddish spectrum. In the absence of albedo data, the E-type was degenerate with the M- and P-types, and together these were designated as X-types. Recently, a taxonomy has been proposed to identify E-types in the absence of albedo data. In this newer classification system three subdivisions of the X-type have been proposed, including Xc, Xe and Xk. Of nine albedo-defined E-types [d], this newer non-albedo based taxonomy produced the following classifications: X-1 asteroid; Xc-2 asteroids; Xe-5 asteroids; and Xk-1 asteroid. Although the Xe subtype includes the largest number of albedo-defined E-types, most of the remaining 24 Xe-types can be excluded based on their low measured IRAS albedos, ranging from 0.116 to 0.329, which are below the lower albedo limit of the E-class (0.34) and substantially below that of the lowest albedo an actual E-type asteroid (0.41). The present discussion will be limited to unambiguous E-type asteroids determined on albedo criteria.

Gaffey, Michael J.↗

Spatially-Resolved Beam Current and Charge-State Distributions for the NEXT Ion Engine

Plume characterization tests with the 36-cm NEXT ion engine are being performed at The Aerospace Corporation using engineering-model and prototype-model thrusters. We have examined the beam current density and xenon charge-state distribution as functions of position on the accel grid. To measure the current density ratio j++/j+, a collimated Eprobe was rotated through the plume with the probe oriented normal to the accel electrode surface at a distance of 82 cm. The beam current density jb versus radial position was measured with a miniature planar probe at 3 cm from the accel. Combining the j++/j+ and jb data yielded the ratio of total Xe+2 current to total Xe+1 current (J++/J+) at forty operating points in the standard throttle table. The production of Xe+2 and Xe+3 was measured as a function of propellant utilization to support performance and lifetime predictions for an extended throttle table. The angular dependence of jb was measured at intermediate and far-field distances to assist with plume modeling and to evaluate the thrust loss due to beam divergence. Thrust correction factors were derived from the total doubles-to-singles current ratio and from the far-field divergence data

Pollard, James E.↗

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↗