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At least 19 records

Dual-Fuel Ammonia Equivalence Ratio Sweep Data

Ammonia (NH3) has garnered significant interest as an alternative fuel for meeting international emissions reduction mandates in sectors with high weight and distance requirements, such as shipping. Technical barriers and unanswered questions remain on the combustion strategies that can maximize ammonia utilization and minimize emissions. Prior research studies at the US Department of Energy’s Oak Ridge National Laboratory have shown strong performance with NH3 under dual-fuel mode using conventional diesel combustion (CDC) manifold air pressure settings. Diesel airflow was initially used to simplify retrofitting (no turbocharger modification), which resulted in air-fuel equivalence ratios (λ) greater than 1.5. To characterize potential improvements in dual-fuel NH3 combustion performance at richer in-cylinder conditions, a global λ sweep compared the use of early (E-pilot) and late (L-pilot) single diesel injections. The experiments were conducted at 1200 RPM and 12.8 ± 0.2 bar (75 % load), and λ was varied by decreasing the commanded air flow to the engine at greater than 90 % ammonia energy substitution level. A diesel injection timing sweep was conducted for both the injection strategies at fixed λ, and the timing with the lowest engine-out N2O emissions was identified. The results indicated an optimal balance between CO2,eq and thermal efficiency benefits both E-pilot and L-pilot injection strategy cases compared with CDC at a λ of 1.4. The indicated nitrogen-based emissions exhibited a strong correlation to the ratio of CA5–50 and ignition delay for L-pilot, but no apparent trend emerged for the E-pilot injection strategy at the tested boundary conditions. This dataset includes the raw experimental data and documentation of the experiment conditions and methods.

30 DIRECT ENERGY CONVERSION↗

Increased accuracy and signal-to-noise ratio through recent improvements in infra-red video bolometer fabrication and calibration

The infra-red video bolometer (IRVB) is a diagnostic equipped with an infra-red camera that measures the total radiated power in thousands of lines of sight within a large field of view. Recently validated in MAST-U [Fderici et al., Rev. Sci. Instrum. 94, 033502 (2023)], it offers a high spatial resolution map of the radiated power in the divertor region, where large gradients are expected. The IRVB’s sensing element comprises a thin layer of high Z absorbing material, typically platinum, usually coated with carbon to reduce reflections [Peterson et al., Rev. Sci. Instrum. 79, 10E301 (2008)].Here, the possibility of using a relatively inert material such as titanium, is explored that can be produced in layers up to 1 μm compared to 2.5 μm for Pt and then coat it with Pt of the desired thickness (0.3 μm per side here) and carbon. This leads to a higher temperature signal (about 3 times) and better spatial resolution (about 4 times), resulting in higher accuracy in the measured power [Peterson et al., Rev. Sci. Instrum. 79, 10E301 (2008)]. This assembly is also expected to improve foil uniformity, as the Pt layer is obtained via deposition rather than mechanical processes [Mukai et al., Rev. Sci. Instrum. 87, 2014 (2016)].Given its multi-material composition, measuring the thermal properties of the foil assembly is vital. Various methods using a calibrated laser as a heat source have been developed, analyzing the temperature profile shape [Sano et al., Plasma and Fusion Res. 7, 2405039 (2012)] and [Mukai et al., Rev. Sci. Instrum. 89, 10E114 (2018)] or fitting the calculated laser power for different intensities and frequencies [Fderici et al., Rev. Sci. Instrum. 94, 033502 (2023)]. Here, a simpler approach is presented, which relies on analyzing the separate components of the foil heat equation for a single laser exposure in a given area. This can then be iterated over the entire foil to capture local deviations.

Magnetic Fusion Energy↗

Particle signal considerations for isotope ratio analysis with single particle multi-collector inductively coupled plasma mass spectrometry

Particle analysis has benefitted from the advent of single particle inductively coupled plasma-mass spectrometry (spICP-MS) due to its robustness, sensitivity, and high-throughput nature. Previous methods of spICP-MS have typically utilized quadrupole or time-of-flight mass analyzers and therefore employ electron multiplier-based detectors (such as secondary electron multipliers or microchannel plates). However, to obtain precise measurements on elemental or isotopic ratios within individual particles, multi-collector ICP-MS (MC-ICP-MS) can be used. Here, we investigate Ce isotope ratios, specifically 142 Ce/ 140 Ce, by spMC-ICP-MS using an all-Faraday cup collector array. Using 1 μm (diameter) cerium dioxide particles, integration times of the Faraday cup detectors were varied from 50–500 ms. The signal from the cerium isotopes in the particles was used to determine isotope ratios, which closely matched the expected natural isotopic abundances. Due to the signal decay response from the Faraday cups, the signal from particles lasts much longer than the expected 1–2 ms (up to 100 s of ms). To explore this effect on isotope ratio analysis, multiple ratio analysis methods were used to determine how to obtain optimal precision and accuracy. Relative differences were around 2% for methods that calculated isotope ratios from summing the total signal of an individual particle before calculating the ratio (rather than using every data point individually). It was found that summing all data points per particle, or integrating under the signal peak, yielded both accurate and precise isotope ratios within the particle population. Particles were also sampled off a solid substrate via microextraction, and isotope ratios were determined with relative differences of 0.13% to 9%. This demonstrates the ability to use spMC-ICP-MS to obtain isotope ratios on particles, with little to no relative difference in comparison to the expected ratio, even when operating Faraday detectors at fast 50 ms integration times.

Szakas, Sarah E. [Oak Ridge National Laboratory (O↗

Revisiting the Relationship Between Induced Polarization and Surface Conductivity: Ratios From Laboratory to Field

Abstract Among the subsurface geophysical methods used in the critical zone investigations, induced polarization (IP) shows great vitality thanks to its unique ability to assess porosity via bulk conduction and estimate permeability through surface conduction and/or polarization. However, such an advantageous separation between bulk and surface is mostly implemented by multi‐salinity experiments in the laboratory, which is incredibly difficult to realize in the field. One promising approach to address such an obstinate issue is to gauge the surface conductivity ( σ s ) from the quadrature conductivity ( σ ″) or normalized chargeability ( M n ) with the ratios between ( l = σ ″/ σ s , l mn = M n / σ s ). While these ratios are known not to be universal, the underlying principles are not fully understood and relevant theoretical studies are rare, which makes quantitative IP applications difficult. Here we scrutinize the conduction and polarization mechanisms of geomaterials and pinpoint that the two ratios are inherently functions of salinities and frequencies rather than only determined by the properties of the electrical double layer (EDL), hence representative samples from the investigated field must be calibrated in the laboratory and a characteristic frequency should be chosen for their usage. Besides the macro‐scale ratios l and l mn , we define two micro‐scale ratios χ and χ mn directly from the EDL, such that the new ratios exclude the effect of salinity and frequency and offer the opportunity to characterize and monitor changes of the EDL. Our study demonstrates that the existing macro‐scale ratios converge toward the values of novel micro‐scale ratios at high water salinity.

Qi, Youzheng [Earth and Environmental Sciences Are↗

Reaction Rate Ratios for Recent Fast Metal Experiments with Large Plutonium Masses

Reaction rate ratios are integral responses that are used within the criticality experiments field because they contain spectral information. While these types of measurements have been utilized for nuclear data validation with historic experiments, few experiments of this type have been utilized for recent experiments, as few exist. This work focuses on measured reaction rate ratios for two nearly bare plutonium critical assemblies with different geometries: one that is cube like (with a Pu mass of 40 kg) and one that is slab like (with a Pu mass of 109 kg). Irradiations were performed with both configurations in which foils were placed near the center of the assembly. Plutonium, highly enriched uranium, depleted uranium, and Au foils were included in the irradiation and counted via high-purity germanium detectors. From these measurements, reaction rate ratios were calculated. Measured and simulated values and uncertainties are presented for the reaction rate ratios. Ratios utilizing the following reactions are given in this work: 197 Au(n, γ), 197 Au(n,2n), 235 U(n,fission), 238 U(n, fission), 238 U(n,2n), 238 U(n,γ), and 239 Pu(n,fission). Uncertainties for the measured reaction rate ratios ranged from 4% to 7%, and the contribution of various parameters to this uncertainty was investigated. The results are compared to historical experiments and should be used for nuclear data validation for future nuclear data library releases. These measurements are part of the EUCLID (Experiments Underpinned by Computational Learning for Improvements in Nuclear Data) project, which utilizes measurement responses in addition to k eff (such as these reaction rate ratios) to help reduce uncertainties in 239 Pu nuclear data.

73 NUCLEAR PHYSICS AND RADIATION PHYSICS↗

Plutonium isotope ratio measurements by total evaporation-thermal ionization mass spectrometry (TE-TIMS): an evaluation of uncertainties using traceable standards from the New Brunswick Laboratory

The accuracy and precision of isotope amount ratio measurements using thermal ionization mass spectrometry (TIMS) instrumentation are described, and the measurement of Pu materials is emphasized. The mass fractionation observed for Am, Ga, Pu, and U for isotope amount ratio measurements using the total evaporation (TE) technique is compared with theoretical estimates to demonstrate the advantage of the TE methodology and to investigate systematic biases in the major isotope amount ratios of U and Pu certified reference material (CRM) standards from the U.S. provider of CRMs. The quality of the Pu isotopic data generated by TIMS instruments in an analytical laboratory is demonstrated by the application of the double ratio technique to estimate the 241 Pu half-life. Analytical data on traceable Pu CRMs from the New Brunswick Laboratory (NBL), generated as part of routine measurements supporting various programs, are used for this half-life estimation. Although the 241 Pu abundances in CRMs of 136, 137, 138, and 126-A are approximately 200–2000× smaller than those in the 241 Pu material used in the previous Institute for Reference Materials and Measurements (IRMM) evaluation of the 241 Pu half-life, the half-life value estimated in this work shows excellent agreement with the currently accepted value from the IRMM. This agreement also demonstrates the pedigree of the Pu isotopic standards from the NBL and the quality of the isotope amount ratio measurements using TIMS instrumentation. For both the major and minor Pu isotope amount ratios, this report describes the relative importance of the factors affecting the uncertainty of TIMS measurements, which are considered the gold standard in isotope ratio measurements (LA-UR-24-29199).

07 ISOTOPE AND RADIATION SOURCES↗

Characterizing chemical abundance ratios in extremely metal-poor star-forming galaxies in DESI EDR

We present a search for galaxies in the local Universe with extremely low oxygen abundance, that is, more than 25 times lower than solar, which corresponds to 12 + log(O/H) < 7.3. To determine the oxygen abundance, we apply the directT e method for objects where the [O III]λ4363 line is detected. We identified 21 extremely metal-poor galaxies in the early data release of the Dark Energy Spectroscopic Instrument (DESI EDR), for some of which we also derived N/O, Ne/O, Ar/O, and S/O ratios. We find that many DESI galaxies with extremely low oxygen abundance exhibit a higher N/O ratio in comparison to the reference low-metallicity sample collected from the literature. We suggest that the elevation in N/O ratio may be explained by a contamination with metal-rich gas caused by gas inflow or a merger event. Moreover, contrary to some recent studies, we find that Ar/O and S/O ratios are enhanced as well, while the Ne/O ratio does not show such elevation. One of the galaxies, J0713+5608, has a remarkably low oxygen abundance of 6.978 ± 0.095 dex. This measurement aligns with the lowest known oxygen abundances in galaxies to date. Given the relatively high uncertainty, this galaxy may have the lowest oxygen abundance ever found. Additionally, J0713+5608 exhibited an enhanced N/O ratio compared to the typical N/O ratio observed in metal-poor galaxies within the local Universe.

Astronomy & Astrophysics↗

Ratio-preserving approach to cosmological concordance

Cosmological observables are particularly sensitive to key ratios of energy densities and rates, both today and at earlier epochs of the Universe. Well-known examples include the photon-to-baryon and the matter-to-radiation ratios. Equally important, though less publicized, are the ratios of pressure-supported to pressureless matter and the Thomson scattering rate to the Hubble rate around recombination, both of which observations tightly constrain. Preserving these key ratios in theories beyond the Λ Cold-Dark-Matter ( Λ CDM ) model ensures broad concordance with a large swath of datasets when addressing cosmological tensions. We demonstrate that a mirror dark sector, reflecting a partial Z 2 symmetry with the Standard Model, in conjunction with percentage level changes to the visible fine-structure constant and electron mass which represent a phenomenological change to the Thomson scattering rate, maintains essential cosmological ratios. Incorporating this ratio-preserving approach into a cosmological framework significantly improves agreement to observational data ( Δ χ 2 = - 35.72 ) and completely eliminates the Hubble tension with a cosmologically inferred H 0 = 73.80 ± 1.02 km / s / Mpc when including the S H 0 ES calibration in our analysis. While our approach is certainly nonminimal, it emphasizes the importance of keeping key ratios constant when exploring models beyond Λ CDM .

79 ASTRONOMY AND ASTROPHYSICS↗

Refining a Novel Process Monitoring Method to Safeguard Continuously Cycling Designs Using Isotopic Ratios

In advanced reactor (AR) designs, a common feature is continuous chemical processing and circulation of the nuclear material. This work bridges a significant measurement gap in safeguarding reactors with circulating fuel or continuous refueling by leveraging and building on the isotope ratio method first developed by our team under an FY21 Advanced Reactors International Safeguards Engagement (ARISE) project (Uribe et al. 2021). In circulating fuel designs, the radioisotope inventory changes from traditional effects (e.g., radioactive decay, fission) but also includes material transport due to pressure and temperature gradients. Such designs may also require regular or continuous additions or removals during operation, which significantly increases the rate of inventory change compared to traditional pressurized water reactor (PWR)s. Thus, directly tracking the nuclear inventory is ineffective since the isotopes are continuously added and removed. The isotope ratio method instead focuses on detecting changes to the input and output flows of radioisotopes. Previous work showed that for well-chosen pairs of isotopes, the isotopic ratio provides a sensitive and lasting indicator of deviation from normal conditions (e.g., startup, shutdown, diversion). The isotope ratio method is a process monitoring method with potential for application in for forward-looking approaches to International Atomic Energy Agency (IAEA) safeguards. The original process monitoring method was developed for a specific case—the decay tank of a thorium-fueled molten salt breeder reactor. In this expanded work, we explored other types of reactors and processes with nonstationary (e.g., flowing) nuclear material, which are difficult to safeguard with traditional methods because of the transient nature of the systems. The goal of the present work is to generalize the isotope ratio method for use in processes with continuously flowing nuclear material. All continuous processes have an average time for isotopes to be replaced in the system. The isotope ratio method works by choosing radioisotopes with half-lives both above and below the processing time. The present work seeks to explore which isotopes are suitable for the method by simulating the nuclear inventory, radioisotope emissions, and detector responses for several classes of advanced reactors. While the method can in principle be applied to other processes (e.g., enrichment or reprocessing facilities), the present work limits scope to ARs with continuously flowing fuel. Section 2 details the mathematics supporting the isotope ratio method, and Section 3 introduces the representative ARs selected for this work. Section 4 discusses how each reactor was analyzed, and Section 5 showcases the results for each representative reactor. Finally, Section 6 provides concluding remarks and suggests pathways for further analysis.

98 NUCLEAR DISARMAMENT, SAFEGUARDS, AND PHYSICAL P↗

Measurement of 𝐵 meson production fraction ratios in proton-proton collisions at √𝑠 = 13 TeV using open-charm and charmonium decays

Production fraction ratios of 𝐵 + , 𝐵 0 , and 𝐵$^{0}_{𝑠}$ mesons are measured in proton-proton collisions at √𝑠 = 13 TeV using a special dataset recorded in 2018 with high-rate triggers designed to collect an unbiased sample of 1⁢010 𝑏 hadrons with the CMS experiment at the LHC. These data allow the study of the open-charm decays of 𝐵 mesons (𝐵 (𝑠) → 𝜋⁢𝐷 (𝑠) ) where the 𝐷 meson decays into fully hadronic final states. By utilizing known branching fractions and precise theoretical calculations, production fraction ratios as functions of 𝐵 meson transverse momentum (𝑝 T ) and rapidity (𝑦) are measured using open-charm decays in the kinematic range of 8 < 𝑝 T < 60 GeV and |𝑦| <2.25. In addition, the same dataset is used to measure the relative production fraction ratios with the charmonium decay channels [𝐵 (𝑠) →𝑋⁢𝐽/𝜓 with 𝑋 indicating a 𝐾 + , 𝐾*(892) 0 , or 𝜙⁡(1020) meson] where the 𝐽/𝜓 meson decays into a pair of muons. The open-charm results are used to normalize the relative production fraction ratios obtained from the charmonium samples. Measurements of the ratios of branching fractions of 𝐵 meson decays to charmonium and open-charm final states are also reported, which will improve the world-average values of these ratios. Finally, we test isospin invariance in 𝐵 meson production in proton-proton collisions and observe that it holds within the experimental precision.

Bottom mesons↗

Experimental demonstration of accelerating a beam with a large transverse emittance ratio in the relativistic heavy ion collider for the electron-ion collider

The electron-ion collider (EIC), to be constructed at Brookhaven National Laboratory, will collide polarized high-energy electron beams with hadron beams, achieving luminosities of up to 1.0 × 10 34 cm −2 s −1 in the center-of-mass energy range of 20–140 GeV. To reach such high luminosity, the EIC will employ small, flat beams at the interaction point. According to the design of the EIC hadron storage ring (HSR), hadron beams with a large transverse emittance ratio of 11:1 will be generated at the injection energy using an electron cooling technique and then accelerated to high energies for collisions. Accelerating hadron beams with such a large emittance ratio had never been demonstrated elsewhere—until our recent beam experiment at the relativistic heavy ion collider (RHIC). In this experiment, we successfully generated a large transverse emittance ratio of 13:1 with a gold-ion beam at 31 GeV/nucleon using stochastic cooling. We then accelerated this beam, with a transverse emittance ratio of 11:1, from 31 to 100 GeV/nucleon. Thanks to RHIC’s high-performance orbit, tune, and decoupling feedback systems, the large emittance ratio was well maintained throughout the 5-min-long acceleration process. This experiment fully validated the EIC/HSR design assumptions—namely, that large-emittance-ratio hadron beams can be generated at injection energy and then accelerated to high energies for collisions.

73 NUCLEAR PHYSICS AND RADIATION PHYSICS↗

A preliminary investigation into the feasibility of laser ablation U–Pb isotope ratio measurement via all‐faraday cup detection with 10 11 ‐ and 10 13 ‐Ω amplifiers on the Neoma multicollector‐inductively coupled plasma‐mass spectrometer

Rationale Signal detection for uranium–lead (U–Pb) dating of zircon is typically performed via ion counters. Here, we develop a preliminary understanding of the strengths and limitations of faraday‐cup‐based detection. Methods A suite of zircon reference materials and the NIST‐610 glass were sampled using laser ablation followed by U–Pb isotope ratio measurement on a Neoma multicollector‐inductively coupled plasma‐mass spectrometer. Results We were able to produce geologically accurate 207 Pb/ 206 Pb, 206 Pb/ 238 U, and 207 Pb/ 235 U ratios for the NIST‐610 glass and the zircon standards, with ages ranging from ~2.5 Ga to ~337 Ma (TanBrown A, Oracle, 91550, Mud Tank, Temora, and Plešovice). Two of the younger zircon standards examined (94‐35, ~55.6 Ma, and Fish Canyon, 28.6 Ma) yielded accurate 206 Pb/ 238 U but not 207 Pb/ 235 U or 207 Pb/ 206 Pb ratios, whereas the youngest zircon standard (Penglai, ~4.4 Ma) failed for all three ratios of interest. The accuracy and precision of the all‐faraday method are directly tied to signal intensity, with reliable data capable of being produced even when both isotopes in a ratio have signals below ~0.001 V (equivalent to ~62 500 cps on an ion counter). Conclusion The all‐faraday cup multicollection method provides sufficient sensitivity to obtain geologically meaningful U–Pb data, with possible advantages being that laser pit depth‐dependent changes in the observed interelemental fractionation behavior may be easier to correct using a static collector configuration compared to when the ion beam is swept across a single detector while also removing the need for an interdetector‐type calibration. Further work is needed to refine the all‐faraday cup method (e.g., application of background subtraction and common Pb corrections, outlier removal, and interelement as well as down‐hole fractionation corrections), but our initial results demonstrate that the faraday detector method has sufficient sensitivity to warrant further study.

46 INSTRUMENTATION RELATED TO NUCLEAR SCIENCE AND ↗

Calibration-free analysis of Li isotope ratios using laser ablation and laser absorption spectroscopy

We introduce a rapid, calibration-free, all-optical method for high-precision lithium isotope ratio measurements in solid materials using laser ablation combined with tunable laser absorption spectroscopy. A new asynchronous acquisition method is used to acquire time-resolved, high-resolution spectra of the 6Li and 7Li D1 and D2 transitions near 671 nm. Isotope ratios and atomic column densities are extracted from measured spectra via a physics-based fitting model including hyperfine structure. Under 1 Torr air, spectra recorded = 0.75 ms after plasma onset exhibit narrow linewidths corresponding to Doppler temperatures = 400 K, enabling resolution of the isotope peaks with high signal-to-noise ratios. Analysis of LiAlO2 samples with varying 6Li:7Li ratios demonstrates isotopic precisions of 0.6–1.7% for spectra acquired in 30 s. Isotope ratios determined from the spectral fits show accuracy within –0.3% to –1.7% of reference ICP-MS measurements without requiring calibration to external standards. By eliminating sample preparation and enabling spatially resolved isotopic mapping, this method offers a rapid analysis approach to lithium isotope determination in solid materials relevant to nuclear energy, safeguards, and geochemistry.

Phillips, Mark C.↗

Novel cross section ratios as possible signals of saturation in ultraperipheral collisions

We propose new cross section ratios in ultraperipheral A + A and p + A collisions (UPCs) as a potential experimental signal of saturation physics. We consider the ratio R 1 of elastic vector meson photoproduction cross section to the inclusive hadron or jet photoproduction cross section. The ratio can be measured in the γ + A and γ + p collisions taking place in the UPCs. We label the ratios R 1 ( A ) and R 1 ( p ) , respectively. Constructing the double ratio R UPC ( A ) = R 1 ( A ) / R 1 ( p ) , and performing a small- x calculation both in the quasiclassical approximation and by including small- x evolution, we observe that R UPC ( A ) exhibits a markedly different dependence on the nuclear atomic number inside and outside the saturation region. This result indicates that R UPC ( A ) and R 1 ( A ) measurements in UPCs may help in the experimental searches for the evidence of saturation physics. Published by the American Physical Society 2024

73 NUCLEAR PHYSICS AND RADIATION PHYSICS↗

Effects of Critical Compression Ratio on Rating Gasoline Knock Propensity

It is common practice in the automotive industry to explore the knock limits of fuels on an engine by a comparison of the knock limited spark advance (KLSA) at threshold knock intensity. However, the knock propensity of gasolines can be rated by changing one of three metrics on a variable compression ratio Cooperative Fuels Research (CFR) octane rating engine while holding the other two variables constant: knock intensity, spark timing, and critical compression ratio. The operational differences between the standard research octane number (RON) rating and modern engine operation have been explored in three parts. The first part focused on the effects of lambda and knock characterization. The second part studied the effects of spark timing. This third part explores the knock ratings of several gasolines by comparing the critical compression ratios at constant combustion phasing and knock intensity. The threshold knock intensity was based on the standard octane rating D1 pickup or by maximum amplitude of pressure oscillations (MAPO) measured by a piezoelectric cylinder pressure transducer. Several Fuels for Advanced Combustion Engines (FACE) gasolines, primary reference fuels (PRFs), and toluene standardization fuels (TSFs) were tested on a CFR octane rating engine with advanced data acquisition equipment and a piezoelectric cylinder pressure transducer. These tests deviated from the ASTM D2699 standard octane rating procedure. For each test fuel, the CFR engine was operated at stoichiometry at a constant combustion phasing (CA50) and the compression ratio was modified until a threshold knock intensity was realized. It was found that the chemical composition of the fuels affected the relationship of critical compression ratios between the D1 knockmeter and piezoelectric pressure transducer knock intensity thresholds, as well as the measured combustion maximum pressure rise rate and spark timing setting for constant CA50. For highly aromatic fuels tested at a constant MAPO knock intensity threshold, it was found that the maximum pressure rise rate was two to three times higher than that of highly paraffinic fuels with similar RON and the spark advance was several crank angle degrees less for constant combustion phasing.

Kolodziej, Christopher P↗

Parametric optimization of the liquid sampling-atmospheric pressure glow discharge ionization source coupled to an Orbitrap mass spectrometer for neodymium isotope ratio determinations

Isotope ratio determinations are a valuable tool in several application areas. In nuclear forensics, the isotope ratios of uranium and plutonium are commonly used as a signature for the nuclear material's provenance and processing history. However, signatures from other coexisting elements, such as neodymium and samarium, can offer additional insights. Here, the liquid sampling-atmospheric pressure glow discharge (LS-APGD) ionization source coupled to an Orbitrap mass spectrometer (MS) has demonstrated its utility for actinide measurements. This instrumental platform can leverage the high resolution offered by the Orbitrap MS to overcome potential isobaric interferences, such as 144 Nd- 144 Sm, 148 Nd- 148 Sm, and 150 Nd- 150 Sm pairs. The work presented herein demonstrates the rapid, accurate, and precise determination of the isotope ratios for neodymium using the LS-APGD/Orbitrap MS. Both the LS-APGD and Orbitrap MS parameters were optimized systematically, with NdO + found to be the most abundant, most reduced species after applying the optimal collision-induced dissociation modalities. A limit of detection of 3 pg of 142 Nd was achieved when data was acquired and processed using the FTMS Booster, an external data acquisition and processing system offered by Spectroswiss. Excellent accuracy of better than 99 % and precision of <1 % RSD were achieved when a solution of the well-characterized neodymium standard (JNdi-1 standard) was analyzed under the optimized condition, indicating the LS-APGD/Orbitrap's great potential for isotope ratio analysis of Nd and other REEs for diverse applications.

47 OTHER INSTRUMENTATION↗

Structure–property relations of sodium iron phosphate nuclear waste glasses: Effects of iron redox ratio and glass composition

Iron phosphate glasses, known for their exceptional chemical durability and potential applicability in nuclear waste management, have gained significant attention over the years. The structures of these glasses are complicated by the coexistence of Fe 3+ and Fe 2+ , which plays a crucial role in determining their structures and properties. Here, this work uses molecular dynamics simulations to study the structural changes in Na 2 O–Fe 2 O 3 –P 2 O 5 glasses with varying glass composition and Fe 2+ /Fe 3+ redox ratio. It was found that the redox ratio and modifier contents significantly affected the short-range and medium-range orders in the glasses. Significant changes in the local environments around P 5+ and Fe 3+ were observed, as reflected by the bond distances and coordination numbers. Na + cations are found to preferentially associate with Fe 3+ (rather than Fe 2+ ), whereas Fe 2+ has stronger association with P 5+ than Na + , confirming the structural role of Fe 2+ as a glass modifier. The disruptions in P–O–P linkages upon increasing FeO suggest that FeO causes glass depolymerization. These glasses achieved higher connectivity with increasing Fe 3+ / (Fe 3+ + Fe 2+ ) ratios, conerting phosphorous Q 2 to Q 3 units and iron Q 5 units to Q 4 units. The decrease of nonbridging oxygen fractions with increasing Fe 3+ / (Fe 3+ + Fe 2+ ) ratios, through creating P–O–Fe linkages, is the main reason of enhanced network connectivity. Quantitative structure–property relationship analyses with different structural descriptors were used to correlate with measured properties. The analyses provided valuable insights into structure–property relationships, emphasizing the importance of choosing relevant energy parameters and defining glass network connectivity, particularly in F net descriptors. It was found the Fe–O–P linkage density exhibits strong correlations to measured dissolution rates, supporting the importance of these linkages in improving the chemical durability in iron phosphate glasses.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗