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At least 379 records · Page 21

Bismuth Detection in Alkaline Electrolyte via Anodic Stripping Voltammetry for Battery Separator Evaluation

Abstract Anodic stripping voltammetry (ASV) has been widely used for the detection of several heavy metal ions in neutral and acidic solution, in many cases employing electrodes and/or solutions incorporating Bi. In this work we demonstrate that Bi(OH) 4 − ion concentration can be measured in highly alkaline 8.5 M KOH solution using ASV. The addition of Pb in similar concentrations to the Bi(OH) 4 − being measured is shown to improve both the sensitivity and precision of the method. When the Pb additive is employed, a formal limit of detection of 8.5 ppb is achieved, compared to 17.3 ppb when the Pb additive is not used. Due to the use of Bi additives in alkaline battery chemistries, it follows that separators which limit Bi(OH) 4 − diffusion into the bulk electrolyte and away from the electrodes are of interest. For this purpose, we utilize ASV to determine Bi(OH) 4 − diffusion rates through Celgard 3501, cellophane 350P00, and Nafion 211. Bi(OH) 4 − crossover rates, as determined by ASV, are shown to be repeatable and consistent with expectations from the known separator structure.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Direct Bayesian inference for fault severity assessment in Digital-Twin-Based fault diagnosis

For applications in condition-based maintenance of nuclear systems, the assessment of fault severity is crucial. In this work, we developed a framework that allows for direct inference of the probability distributions of possible faults in a system. Here, we employed a model-based approach with model residuals generated from analytical redundancy relations provided by physics-based models of the system components. From real-time sensor readings, the values of the model residuals can be calculated, and the posterior probability distributions of the faults can be computed directly using the methods of Bayesian networks. From the posterior distribution of each fault, one can estimate the fault probability based on a chosen threshold and assess the severity of the fault. By eliminating the discretization and simplifications in middle steps, this approach allows us to leverage the available computational resources to provide more accurate fault probability estimates and severity assessments.

73 NUCLEAR PHYSICS AND RADIATION PHYSICS↗

TransformerG2G: Adaptive time-stepping for learning temporal graph embeddings using transformers

Dynamic graph embedding has emerged as a very effective technique for addressing diverse temporal graph analytic tasks (i.e., link prediction, node classification, recommender systems, anomaly detection, and graph generation) in various applications. Such temporal graphs exhibit heterogeneous transient dynamics, varying time intervals, and highly evolving node features throughout their evolution. Hence, incorporating long-range dependencies from the historical graph context plays a crucial role in accurately learning their temporal dynamics. In this paper, we develop a graph embedding model with uncertainty quantification, TransformerG2G, by exploiting the advanced transformer encoder to first learn intermediate node representations from its current state (t) and previous context (over timestamps [t–1,t–l], l is the length of context). Moreover, we employ two projection layers to generate lower-dimensional multivariate Gaussian distributions as each node's latent embedding at timestamp t. We consider diverse benchmarks with varying levels of "novelty" as measured by the TEA (Temporal Edge Appearance) plots. Here, our experiments demonstrate that the proposed TransformerG2G model outperforms conventional multi-step methods and our prior work (DynG2G) in terms of both link prediction accuracy and computational efficiency, especially for high degree of novelty. Furthermore, the learned time-dependent attention weights across multiple graph snapshots reveal the development of an automatic adaptive time stepping enabled by the transformer. Importantly, by examining the attention weights, we can uncover temporal dependencies, identify influential elements, and gain insights into the complex interactions within the graph structure. For example, we identified a strong correlation between attention weights and node degree at the various stages of the graph topology evolution.

97 MATHEMATICS AND COMPUTING↗

Phase control of nonlinear Breit-Wheeler pair creation

Electron-positron pair creation occurs throughout the universe in the environments of extreme astrophysical objects, such as pulsar magnetospheres and black hole accretion disks. The difficulty of emulating these environments in the laboratory has motivated the use of ultrahigh-intensity laser pulses for pair creation. Here we show that the phase offset between a laser pulse and its second harmonic can be used to control the relative transverse motion of electrons and positrons created in the nonlinear Breit-Wheeler process. Analytic theory and particle-in-cell simulations of a head-on collision between a two-color laser pulse and electron beam predict that with an appropriate phase offset, the electrons will drift in one direction and the positrons in the other. The resulting current may provide a collective signature of nonlinear Breit-Wheeler, while the spatial separation resulting from the relative motion may facilitate isolation of positrons for subsequent applications or detection. Published by the American Physical Society 2024

79 ASTRONOMY AND ASTROPHYSICS↗

metabCombiner 2.0: Disparate Multi-Dataset Feature Alignment for LC-MS Metabolomics

Liquid chromatography–high-resolution mass spectrometry (LC-HRMS), as applied to untargeted metabolomics, enables the simultaneous detection of thousands of small molecules, generating complex datasets. Alignment is a crucial step in data processing pipelines, whereby LC-MS features derived from common ions are assembled into a unified matrix amenable to further analysis. Variability in the analytical factors that influence liquid chromatography separations complicates data alignment. This is prominent when aligning data acquired in different laboratories, generated using non-identical instruments, or between batches from large-scale studies. Previously, we developed metabCombiner for aligning disparately acquired LC-MS metabolomics datasets. Here, we report significant upgrades to metabCombiner that enable the stepwise alignment of multiple untargeted LC-MS metabolomics datasets, facilitating inter-laboratory reproducibility studies. To accomplish this, a “primary” feature list is used as a template for matching compounds in “target” feature lists. We demonstrate this workflow by aligning four lipidomics datasets from core laboratories generated using each institution’s in-house LC-MS instrumentation and methods. We also introduce batchCombine, an application of the metabCombiner framework for aligning experiments composed of multiple batches. metabCombiner is available as an R package on Github and Bioconductor, along with a new online version implemented as an R Shiny App.

97 MATHEMATICS AND COMPUTING↗

A semi–automatic analytical methodology for characterizing the energy consumption of MRI systems using load duration curves

Background and purpose: Magnetic resonance imaging (MRI) scanners are a major contributor to greenhouse gas emissions from the healthcare sector, and efforts to improve energy efficiency and reduce energy consumption rely on quantification of the characteristics of energy consumption. The purpose of this work was to develop a semi-automatic analytical methodology for the characterization of the energy consumption of MRI systems using only the load duration curve (LDC). LDCs are a fundamental tool used across various fields to analyze and understand the behavior of loads over time. Methods: An electric current transformer sensor and data logger were installed on two 3T MRI scanners from two vendors, termed M1 (outpatient scanner) and M2 (inpatient/emergency scanner). Data was collected for 1 month (7/11/2023 to 8/11/2023). Active power was calculated, assuming a balanced three-phase system, using the average current measured across all three phases, a 480 V reference voltage for both machines, and vendor-provided power factors. An LDC was constructed for each system by sorting the active power values in descending order and computing the cumulative time (in units of percentage) for each data point. The first derivative of the LDC was then computed (LDC’), smoothed by convolution with a window function (sLDC’), and used to detect transitions between different system modes including (in descending power levels): scan, prepared-to-scan, idle, low-power, and off. The final, segmented LDC was used to measure time (% total time), total energy (kWh), and mean power (kW) for each system mode on both scanners. The method was validated by comparing mean power values, computed using the segmented 1-month LDC, for each nonproductive system mode (i.e., prepared-to-scan, idle, lower-power, and off) against power levels measured after a deliberate system shutdown was performed for each scanner (1 day worth of data). Results: The validation revealed differences in mean power values <1.4% for all nonproductive modes and both scanners. In the scan system mode, the mean power values ranged from 29.8 to 37.2 kW and the total energy consumed for 1 month ranged from 11 106 to 14 466 kWh depending on the scanner. Over the course of 1 month, the portion of time the scanners were in nonproductive modes ranged from 76% to 80% across scanners and the nonproductive energy consumption ranged from 8010 to 6722 kWh depending on the scanner. The M1 (outpatient) scanner consumed 99.9 and 183.9 kWh/day in idle mode for weekdays and weekends, respectively, because the scanner spent 23% more time proportionally in idle mode on the weekends. Conclusions: A semi-automatic method for quantifying energy consumption characteristics of MRI scanners was introduced and validated. This method is relatively simple to implement as it requires only power data from the scanners and avoids the technical challenges associated with extracting and processing scanner log files. Finally, the methodology enables quantitative evaluation of the power, time, and energy characteristics of MRI scanners in scan and nonproductive system modes, providing baseline data and the capability of identifying potential opportunities for enhancing the energy efficiency of MRI scanners.

32 ENERGY CONSERVATION, CONSUMPTION, AND UTILIZATI↗

Conformational Panorama and Chirality Controlled Structure–Energy Relationship in a Chiral Carboxylic Acid Dimer

Chirality recognition in dimers of tetrahydro-2-furoic acid (THFA) was studied in a conformer-specific manner using rotational spectroscopy and theoretical approaches. THFA shows a strong preference for the trans- over the cis-COOH configuration. Two drastically different scenarios are possible for the detectable (THFA) 2 : a kinetically preferred dimer bound by feeble interactions between two trans-THFAs or a thermodynamically favored dimer with a double hydrogen-bonded ring structure between two cis subunits. To identify the conformers responsible for the extremely dense rotational spectra observed, it was essential not only to locate several hundred homo/heterochiral (THFA) 2 minima in ab initio calculations but also to evaluate the energetic connectivities among the minima. The study further reveals an interesting chirality dependent structure-energy ordering relationship. A method for enantiomeric excess (ee) determination of THFA is presented using a recently proposed chiral self-tag approach.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Generation of random geological models using multi-randomization for machine learning

Generating high-fidelity geological models is essential for advancing machine learning (ML) methods in automated seismic interpretation. For instance, seismic images paired with corresponding fault labels are foundational for ML-based fault detection from seismic migration sections. While several open-access datasets of random geological models exist, open-source tools specifically designed to produce large volumes of such models for ML applications remain scarce. To address this gap, we present RGM (Random Geological Model), an open-source software package for efficiently generating 2D and 3D synthetic geological models tailored for ML workflows. RGM supports the creation of diverse model components, including medium property distributions (P-/S-wave velocities and density), seismic reflectivity images (i.e., synthetic migration sections), relative geological time, and discrete fault attributes such as probability, dip, strike, rake, and displacement. It also accommodates the creation of complex geological features such as salt bodies and unconformities. The model generation algorithm employs a multi-randomization strategy, yielding an effectively infinite-dimensional model space that encompasses a wide range of geological scenarios and associated seismic features. Furthermore, RGM incorporates a method to generate synthetic elastic migration images using analytical elastic reflection coefficients combined with frequency-dependent scaling. This functionality enables the creation of training datasets for ML models that leverage elastic seismic images. RGM is implemented in modern object-oriented Fortran, allowing users to flexibly control statistical parameters governing model variability. We demonstrate the capability, performance, and geological realism of the package through comprehensive 2D and 3D examples.

58 GEOSCIENCES↗

Detecting compounds in microfluidic droplets using mass spectrometry

Disclosed herein are devices and methods for detecting compounds in droplets using mass spectrometry. In some embodiments, the device comprises: a microfluidics-MS (microMS) device, wherein the microMS device comprises: a droplet-to-digital microfluidic device, wherein the droplet-to-digital microfluidic device comprises: a glass layer; an electrode layer comprising chrome electrodes etched onto one side of the glass layer; a dielectric layer configured for electrowetting; and a microfluidics layer comprising channels, pockets, and a droplet generator, for example a T-junction droplet generator, wherein the pockets are connected to the channels; and a mass spectrometry plate, wherein the mass spectrometry plate is reversibly sealed to the microfluidic device.

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Time-resolved luminescence detection of peroxynitrite using a reactivity-based lanthanide probe

Peroxynitrite (ONOO - ) is a powerful and short-lived oxidant formed in vivo, which can react with most biomolecules directly. To fully understand the roles of ONOO - in cell biology, improved methods for the selective detection and real-time analysis of ONOO - are needed. We present a water-soluble, luminescent europium(III) probe for the rapid and sensitive detection of peroxynitrite in human serum, living cells and biological matrices. We have utilised the long luminescence lifetime of the probe to measure ONOO - in a time-resolved manner, effectively avoiding the influence of autofluorescence in biological samples. To demonstrate the utility of the Eu(III) probe, we monitored the production of ONOO - in different cell lines, following treatment with a cold atmospheric plasma device commonly used in the clinic for skin wound treatment.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Sample Preparation Method for Low-Level Total 129 I Measurements by ICP-MS

Trace-level measurements of iodine’s isotopic ( 129 I and 127 I) and chemical species distributions are needed for an accurate understanding of radioiodine migration in the Hanford subsurface. Pacific Northwest National Laboratory (PNNL) previously developed a novel analytical method for iodine characterization that uses ion chromatography (IC) coupled to inductively coupled mass spectrometry (ICP-MS). While the method can measure speciated forms of 129 I at levels below the drinking water standard, an interference from molybdenum (Mo) prevents the assay from quantifying the $\underline{total}$ 129 I concentration in many Hanford sample matrices. In this work, solvent extraction was evaluated as a sample preparation method for eliminating the Mo interference. A series of 10 experiments was conducted in which solutions containing known amounts of iodate or iodide were treated by solvent extraction, and the extracted solutions were analyzed for total iodine concentrations by ICP MS. Several extraction parameters such as reagent concentrations and chemical reaction times were systematically adjusted in attempts to optimize the extraction process. While solvent extraction was shown to be effective at removing Mo, there was a consistent inability to recover more than approximately 75% of the total iodine in most experiments. This would reduce the ability to detect 129 I at levels near the drinking water standard. Additionally, the extraction efficiencies in several experiments were highly variable, suggesting that solvent extraction could add significant uncertainty to radioiodine measurements. We recommend evaluating ion exchange as an alternative sample preparation approach in fiscal year (FY) 2024.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

$t_1$-Noise eliminated dipolar heteronuclear multiple-quantum coherence solid-state NMR spectroscopy

Heteronuclear correlation (HETCOR) spectroscopy is one of the key tools in the arsenal of the solid-state NMR spectroscopist to probe chemical and spatial proximities between two different nuclei and enhance spectral resolution. Dipolar heteronuclear multiple-quantum coherence (D-HMQC) is a powerful technique that can be potentially utilized to obtain 1 H detected 2D HETCOR solid-state NMR spectra of any NMR active nucleus. A long-standing problem in 1 H detected D-HMQC solid-state NMR experiments is the presence of t 1 -noise which reduces sensitivity and impedes spectral interpretation. In this contribution, we describe novel pulse sequences, termed t 1 -noise eliminated (TONE) D-HMQC, that minimize t 1 -noise and can provide higher sensitivity and resolution than conventional D-HMQC. Monte-Carlo and numerical simulations confirm that t 1 -noise in conventional D-HMQC primarily occurs because random MAS frequency fluctuations cause variations in the NMR signal amplitude from scan to scan, leading to imperfect cancellation of uncorrelated signals by phase cycling. The TONE D-HMQC sequence uses 1 H π-pulses to refocus the evolution of 1 H CSA across each SR4 2 1 recoupling block, improving the stability of the pulse sequence to random MAS frequency fluctuations. The 1 H refocusing pulses also restore the orthogonality of in-phase and anti-phase magnetization for all crystallite orientations at the end of each recoupling block, enabling the use of 90° flip-back or LG spin-lock trim pulses to reduce the intensity of uncorrelated signals. We demonstrate the application of these methods to acquire 1 H detected 2D 1 H{ 35 Cl} and 1 H{ 13 C} HETCOR spectra of histidine·HCl·H 2 O with reduced t 1 -noise. To show generality, we also apply these methods to obtain 2D 1 H{ 17 O} spectra of 20%- 17 O fmoc-alanine and for the first time at natural abundance, 2D 1 H{ 25 Mg} HETCOR spectra of magnesium hydroxide. The TONE D-HMQC sequences are also used to probe 1 H– 25 Mg and 1 H– 27 Al proximities in Mg–Al layered double hydroxides and confirm the even mixing of Mg and Al in these materials.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Probing the hydrolytic degradation of UF 4 in humid air

This manuscript describes the chemical transformations that occur during hydrolysis of uranium tetrafluoride (UF 4 ) due to its storage in humid air (85% and 50% relative humidity) at ambient temperatures. This hydrolysis was previously reported to proceed slowly or not at all (depending on the percent relative humidity); however, previous reports relied primarily on X-ray diffraction methods to probe uranium speciation. Here, we employ a battery of physiochemical probing techniques to explore potential hydrolysis, including Raman spectroscopy, powder X-ray diffraction, 19 F nuclear magnetic resonance spectroscopy, scanning electron microscopy, and focused ion beam microscopy with energy-dispersive X-ray spectroscopy. Of these, only Raman spectroscopy proved to be particularly useful at observing chemical changes to UF 4 . It was found that anhydrous UF 4 slightly oxidizes over the course of thirteen days to Schoepite-like uranium complexes and possibly UO 3 . In contrast, UF 4 exposed to 50% relative humidity slightly decomposes into UO 2 F 2 , Schoepite-like uranium complexes, and possibly a high order uranium oxide that eluded chemical assignment (U x O y ). Despite the rich chemical speciation observed in our Raman spectroscopy measurements, X-ray diffraction and 19 F NMR measurements on the same material showed no changes. Microscopy measurements suggest that the observed reactions between UF 4 and water occur primarily on the surface of UF 4 particulates via a method that is visually similar to surface corrosion of metals. Therefore, we postulate that NMR spectroscopy and X-ray diffraction, which are well-suited for bulk analysis, are less suited than Raman spectroscopy to observe the surface-based reactions that occur to UF 4 when exposed to humid air. Considering the importance of UF 4 in the production of nuclear fuel and weapons, the results presented herein are widely applicable to numerous nuclear science fields where uranium detection and speciation in humid environments is of value, including nuclear nonproliferation and nuclear forensics.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Using Raman scattering to study reacting gas flow over a catalyst

l present a series of computational methods for analyzing and correcting Raman scattering from a reacting gas flow. My work focused on the laser diagnostic measurements of formaldehyde production over a silver catalyst, specifically the Raman spectroscopy component. This technique offers a non-intrusive, in situ way to measure the coupling between the gas phase and surface activity of a catalytic reaction at relevant industrial conditions. This report outlines the steps followed for correcting the non-idealities in the data due to both the detection optics and scattering mechanics. By implementing such refinement steps, l can generate an accurate 2D spatial map of the temperature profile, number densities for major species, and relative consumption of reactants throughout the reactor cell.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Structural modification of fentanyls for their retrospective identification by gas chromatographic analysis using chloroformate chemistry

Abstract The one-step breakdown and derivatization of a panel of nine fentanyls to yield uniquely tagged products that can be detected by Electron Ionization Gas Chromatography-Mass Spectrometry (EI-GC-MS) is presented. The method involves the treatment of the synthetic opioids with 2,2,2-trichloroethoxycarbonyl chloride (TrocCl) at 60 °C for 3 h in dichloromethane and furnishes two products from one fentanyl molecule that can be used to retrospectively identify the original opioid. Parameters that were studied and fully optimized for the method included temperature, solvent, nature of scavenging base and reaction time. One of the two resulting products from the reaction bears the trichloroethoxycarbonyl (Troc) tag attached to the norfentanyl portion of the original opioid and greatly aids in the opioid detection and identification process. The methodology has been applied to the chemical modification of a panel of nine fentanyls and in all cases the molecular ion peak for the Troc-norfentanyl product bearing the distinctive trichloroethyl isotopic signature can be clearly observed. The method’s LLOD was determined to be 10 ng/mL while its LLOQ was found to be 20 ng/mL. This methodology represents the first application of chloroformates in the chemical modification of this class of synthetic opioids that are notoriously inert to common derivatization strategies available for GC–MS analysis.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Highly sensitive 2D X-ray absorption spectroscopy via physics informed machine learning

Abstract Improving the spatial and spectral resolution of 2D X-ray near-edge absorption structure (XANES) has been a decade-long pursuit to probe local chemical reactions at the nanoscale. However, the poor signal-to-noise ratio in the measured images poses significant challenges in quantitative analysis, especially when the element of interest is at a low concentration. In this work, we developed a post-imaging processing method using deep neural network to reliably improve the signal-to-noise ratio in the XANES images. The proposed neural network model could be trained to adapt to new datasets by incorporating the physical features inherent in the latent space of the XANES images and self-supervised to detect new features in the images and achieve self-consistency. Two examples are presented in this work to illustrate the model’s robustness in determining the valence states of Ni and Co in the LiNi x Mn y Co 1-x-y O 2 systems with high confidence.

36 MATERIALS SCIENCE↗

Trace Impurities Identified as Forensic Signatures in CMX-5 Fuel Pellets Using X-ray Spectroscopic Techniques

We report that small-particle analysis is a highly promising emerging forensic tool for analysis of interdicted special nuclear materials. Integration of microstructural, morphological, compositional, and molecular impurity signatures could provide significant advancements in forensic capabilities. We have applied rapid, high-sensitivity, hard X-ray synchrotron chemical imaging to analyze impurity signatures in two differently fabricated fuel pellets from the 5th Collaborative Materials Exercise (CMX5) of the IAEA Nuclear Forensics International Working Group. The spatial distributions, chemical compositions, and morphological and molecular characteristics of impurities were evaluated using X-ray absorption near-edge structure (XANES) and X-ray fluorescence chemical imaging to discover principal impurities, their granularity, particle sizes, modes of occurrence (distinct grains vs incorporation in the UO 2 lattice), and sources and mechanisms of incorporation. Differences in UO 2+x stoichiometry were detected at the microscale in nominally identical UO 2 ceramics (CMX5-A and CMX5-B), implying the presence of multiple UO 2 host phases with characteristic microstructures and feedstock compositions. Al, Fe, Ni, W, and Zr impurities and integrated impurity signature analysis identified distinctly different pellet synthesis and processing methods. For example, two different Al, W, and Zr populations in the CMX5-B sample indicated a more complex processing history than the CMX5-A sample. K-edge XANES measurements reveal both metallic and oxide forms of Fe and Ni but with different proportions between each sample. Altogether, these observations suggest multiple sources of impurities, including fabrication (e.g., force-sieving) and feedstock (mineral oxides). This study demonstrates the potential of synchrotron techniques to integrate different signatures across length scales (angstrom to micrometer) to detect and differentiate between contrasting UO 2 fuel fabrication techniques.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Real-Time Nitrate Ion Monitoring with Poly(3,4-ethylenedioxythiophene) (PEDOT) Materials

Nitrate (NO 3 ) pollution in groundwater, caused by various factors both natural and synthetic, contributes to the decline of human health and well-being. Current techniques used for nitrate detection include spectroscopic, electrochemical, chromatography, and capillary electrophoresis. It is highly desired to develop a simple cost-effective alternative to these complex methods for nitrate detection. Therefore, a real-time poly (3,4-ethylenedioxythiophene) (PEDOT)-based sensor for nitrate ion detection via electrical property change is introduced in this study. Vapor phase polymerization (VPP) is used to create a polymer thin film. Variations in specific parameters during the process are tested and compared to develop new insights into PEDOT sensitivity towards nitrate ions. Through this study, the optimal fabrication parameters that produce a sensor with the highest sensitivity toward nitrate ions are determined. With the optimized parameters, the electrical resistance response of the sensor to 1000 ppm nitrate solution is 41.79%. Furthermore, the sensors can detect nitrate ranging from 1 ppm to 1000 ppm. The proposed sensor demonstrates excellent potential to detect the overabundance of nitrate ions in aqueous solutions in real time.

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