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At least 1,783 records · Page 99

Explosive Byproduct Gas Transport Through Sorptive Geomedia

Current underground nuclear explosion (UNE) detection strategies rely heavily on atmospheric noble gas sampling of radioxenon. However, discriminating nuclear weapons testing programs from civilian sources is difficult due to highly variable atmospheric radioxenon backgrounds and processes affecting subsurface transport of parent radionuclides. Here, we aim to study the transport of gases produced by subsurface explosions as novel stable signatures for underground nuclear explosion (UNE) monitoring. These gases may be produced in large quantities with distinct molecular ratios, which will be impacted by subsurface transport processes. To demonstrate how ratios of gases produced by explosions can change during transport in geomaterials, we conducted laboratory benchtop experiments on the transport of carbon dioxide (CO 2 ) and hydrogen (H 2 ) gases through variably saturated zeolitic tuff, which is abundant at the historic US testing site. We observed that zeolitic tuff sorbs substantial quantities of CO 2 while allowing H 2 to transport more freely, leading to changes in the molecular ratios of the two gases along the transport pathway. Gas uptake in the dry zeolitic tuff core was 72.3% for CO 2 , compared with 53.4% for xenon and 7.6% for H 2 . The presence of 20% water saturation disrupted the CO 2 sorption process, though to a lesser extent than observed for noble gases, with a 36.7% drop in xenon sorption compared with a 21.9% drop for CO 2 . These results represent the first observations of zeolite sorption altering explosive gas ratios during transport through geomedia relevant to nuclear proliferation monitoring.

54 ENVIRONMENTAL SCIENCES↗

1 H NMR metabolomics study of metastatic melanoma in C57BL/6J mouse spleen

Melanoma is a malignant tumor of melanocytes. Although extensive investigations have been done to study metabolic changes in primary melanoma in vivo and in vitro, little effort has been devoted to metabolic profiling of metastatic tumors in organs other than lymph nodes. As such, in this work, NMR-based metabolomics combined with multivariate data analysis is used to study metastatic B16-F10 melanoma in C57BL/6J mouse spleen. Principal Component Analysis (PCA), an unsupervised multivariate data analysis method, is used to detect possible outliers, while Orthogonal Projection to Latent Structure (OPLS), a supervised multivariate data analysis method, is employed to find important metabolites responsible for discriminating the control and the melanoma groups. Two different strategies, i.e., spectral binning and spectral deconvolution, are used to reduce the original spectral data before statistical analysis. Spectral deconvolution is found to be superior for identifying a set of discriminatory metabolites between the control and the melanoma groups, especially when the sample size is small. OPLS results show that the melanoma group can be well separated from its control group. It is found that taurine, glutamate, aspartate, O-Phosphoethanolamine, niacinamide ,ATP, lipids and glycerol derivatives are decreased statistically and significantly while alanine, malate, xanthine, histamine, dCTP, GTP, thymidine, 2'-Deoxyguanosine are statistically and significantly elevated. Furthermore, these significantly changed metabolites are associated with multiple biological pathways and may be potential biomarkers for metastatic melanoma in spleen.

1H NMR metabolomics↗

The Influence of Constitutional Supercooling on the Distribution of Te-particles in Melt-Grown CZT

A section of a vertical gradient freeze Cd 0.9 Zn 0.1 Te boule approximately 2100-mm 3 with a planar area of 300-mm 2 was prepared and examined using transmitted IR microscopy at various magnifications to determine the three-dimensional spatial and size distributions of Te-particles over large longitudinal and radial length scales. Te-particle density distributions were determined as a function of longitudinal and radial positions in these strips and exhibited a multi-modal lognormal size density distribution that indicated a slight preference for increasing size with longitudinal growth time, while showing a pronounced cellular network structure. Higher magnification images revealed a typical Rayleigh-instability pearl string morphology with large and small satellite droplets. This study includes solidification experiments in small crucibles of 30:70 mixtures of Cd:Te performed over a wide range of cooling rates that clearly demonstrated a growth instability with Te-particle capture that is suggested to be responsible for one of the peaks in the size distribution using size discrimination visualization. The results are discussed with regard to a manifold Te-particle genesis history as Te-particle direct capture from melt-solid growth instabilities due to constitutional supercooling and as Te-particle formation from the breakup of Te-ribbons via a Rayleigh-Plateau instability.

72 PHYSICS OF ELEMENTARY PARTICLES AND FIELDS↗

Inhibiting Effect of Additives on Pressure Solution of Calcite

The task of protection of cultural heritage requires a better understanding of combined effects of mechanical and chemical factors involved in environmental deterioration of monuments. The present paper deals with extending some known physicochemical methods proposed for inhibiting the decay of unstressed materials to their study during water-assisted deformation. The tests have been carried out on natural limestone samples and calcite powders in CaCO{sub 3} saturated aqueous solutions under static loads causing measurable pressure solution creep. In the solutions containing 1-hydroxyethylidene-1,1-diphosphonic acid, nitrilotriacetic acid, or ethylenediaminetetraacetic acid, the creep rate decreases considerably with increasing concentration of additives. The extent of creep deceleration has been found to be proportional to the independently estimated calcite surface area occupied by adsorbed species. This fact enables us to discriminate the adsorption-induced effect from other variables controlling the pressure solution rate and may be used in screening of compounds able to minimize the environmental impact on marble and limestone objects undergoing mechanical stresses.

36 MATERIALS SCIENCE↗

Exploiting Acoustic Anisotropy to Detect Recrystallization in a Ni Single Crystal Using Ultrasonic Nondestructive Inspection

Ultrasonic inspection was used to detect regions of recrystallization (RX) within a single crystal of Ni. RX can produce polycrystalline regions within single-crystal (SX) materials. Because RX regions act as initiator sites for failure by fatigue-crack growth in otherwise SX Ni-based superalloys, RX is an issue of direct concern for the service life of high-performance turbine blades. Detection and discrimination of RX regions in single-crystal materials are significant challenges for current nondestructive inspection technologies. The present study leverages the elastic anisotropy of single crystals, which produces acoustic anisotropy, to ultrasonically detect and characterize RX regions produced within single-crystal specimens. Single crystals of pure Ni were processed to create controlled regions of RX. These specimens were ultrasonically examined in an immersion tank using a high-resolution, polyvinylidene fluoride transducer to detect acoustic impedance changes across the boundaries between different crystals (i.e., grains) within the RX region. Data from time-of-flight and absolute peak amplitude measurements were used to create acoustic images that were compared against electron microscope images of the RX regions. The ultrasonic inspection technique described here successfully detected not only the locations of RX regions, but also the approximate sizes and shapes of the RX regions.

36 MATERIALS SCIENCE↗

Fatigue of Composite Materials Subjected to Variable Loadings

A model describing the fatigue behavior of composite materials under variable loadings is presented. The approach is based on a two-parameter model fulfilling the principal responses’ features of composite materials subjected to constant amplitude cyclic loadings. It is shown that when coupled with the equivalent residual strength assumption the model can describe the strength degradation of composite materials subjected to variable amplitude loadings without simplifications or substantial reductions of the loading spectrum. Compared to the linear Miner’s rule, the results highlight the importance of the sequence of loads and the approach discriminates the ascending, descending and random patterns. It is shown that for the case under study the ordered descending (high to low) sequence showed the worst scenario in terms of damage accumulation extent, while the random spectrum resulted in an intermediate response between ordered ascending and descending sequences.

36 MATERIALS SCIENCE↗

Mitigating Implicit Bias as a Leader

Bias. It’s a word that makes most of us squirm. Bias implies to us that we are “bad people” and are being accused of deliberately discriminating against others. Yet, if you ask a social scientist, you will find that it doesn't mean that at all; implicit bias is a neurologically based, energy-saving short cut. Our brains apply mental models to make thousands of quick decisions every day: which brand of milk to buy at the store or when to turn the wheel to avoid a traffic accident. Lastly, we form our implicit biases subconsciously over time, influenced by our upbringing, societal norms, and life experiences.

99 GENERAL AND MISCELLANEOUS↗

The high matrix acquisition technique for imaging of atherosclerotic plaque inflammation in fluorine-18 fluorodeoxyglucose positron emission tomography/computed tomography with time-of-flight: Phantom study

Background: Motion artifact and partial volume effect caused underestimation of coronary plaque inflammation. This study evaluated the high matrix acquisition technique using time-of-flight (TOF) positron emission tomography/computed tomography for imaging of atherosclerotic plaque inflammation with fluorine-18 fluorodeoxyglucose in small and moving phantoms. Methods and Results: All images were reconstructed using a conventional algorithm without TOF (4 × 4 × 4 mm{sup 3} voxel size) and a high matrix algorithm with TOF (2 × 2 × 2 mm{sup 3} voxel size). Microsphere phantoms of 10, 7.9, 6.2, 5.0, and 4.0 mm diameters were acquired in 3-dimensional list-mode for 30 minutes. A heart phantom mimicking cardiac motion consisted of a hot spot simulating a plaque (φ 4 mm, φ 2 mm) on the outside of the left ventricle. In the microsphere and heart phantom study, visual discrimination, maximum activity, and target-to-background ratio using the high matrix algorithm with TOF were better than those using the conventional algorithm without TOF. Conclusion: The high matrix algorithm with TOF improves detection of small targets in phantoms.

62 RADIOLOGY AND NUCLEAR MEDICINE↗

Transfer learning for probabilistic localization of hidden cracks in concrete structures

Abstract The utility of discriminative supervised learning models built using multiple training-data sources is investigated for hidden crack localization in concrete. Feed-forward neural network (FFNN) is chosen as the model architecture, and transfer learning is used to assimilate the information obtained from different sources (computational physics simulations and laboratory experiments). The labeled training data consists of values of a damage index and the known locations of hidden cracks. The classification models need to learn how the presence of damage (hidden cracks) affects the damage index at different sensors for different test conditions. To this end, diagnostic FFNN models are built by sequentially adding and training new hidden layers to assimilate labeled information from computer models (different model geometries, test conditions, crack lengths, crack locations) and laboratory experiments on a plain cement slab. These transfer learning-based models are then used to localize damage in concrete specimens that reflect real-world conditions (i.e., specimens with steel reinforcement and randomly distributed aggregate). The actual damage state in these specimens is determined by extracting cores and performing petrographic studies on the extracted cores. The damage probability estimated by transfer learning-based models is compared with the petrographic damage rating index (DRI) to identify the most suitable approach to train the diagnostic models. The transfer learning-based diagnostic methodology shows promise and could be used in various structural health monitoring applications, where sufficient labeled data are typically not available from a single data source.

Miele, S.↗

Electron Transfer Dissociation of All Ions at All Times, MS{sup ETD}, in a Quadrupole Time-of-Flight (Q-ToF) Mass Spectrometer

Data-independent mass spectral acquisition is particularly powerful when combined with ultra-performance liquid chromatography (LC) that provides excellent separation of most components present in a given sample. Data-independent analysis (DIA) consists of alternating full MS scans and scans with fragmentation of all ions within a selected m/z range, providing precursor masses and structure information, respectively. Fragmentation spectra are acquired either by sequential isolation and fragmentation of sliding m/z ranges or fragmenting all ions entering the MS instrument with no ion isolation, termed broadband DIA. Previously, broadband DIA has only been possible using collision induced dissociation (CID). Here, we report the use of electron transfer dissociation (ETD) as the fragmentation technique in broadband DIA instead of traditional collision induced dissociation (CID) during MS{sup E}. In this approach, which we refer to as MS{sup ETD}, we implement the inherent benefits provided by ETD, such as discrimination of leucine and isoleucine, in a DIA setup. The combination of DIA analysis and ETD fragmentation with supplemental CID energy provides a powerful platform to obtain information on all precursors and their sequence from a single experiment. .

46 INSTRUMENTATION RELATED TO NUCLEAR SCIENCE AND ↗

Investigation and Applications of In-Source Oxidation in Liquid Sampling-Atmospheric Pressure Afterglow Microplasma Ionization (LS-APAG) Source

A liquid sampling-atmospheric pressure afterglow microplasma ionization (LS-APAG) source is presented for the first time, which is embedded with both electrospray ionization (ESI) and atmospheric pressure afterglow microplasma ionization (APAG) techniques. This ion source is capable of analyzing compounds with diverse molecule weights and polarities. An unseparated mixture sample was detected as a proof-of-concept, giving complementary information (both polarities and non-polarities) with the two ionization modes. It should also be noted that molecular mass can be quickly identified by ESI with clean and simple spectra, while the structure can be directly studied using APAG with in-source oxidation. The ionization/oxidation mechanism and applications of the LS-APAG source have been further explored in the analysis of nonpolar alkanes and unsaturated fatty acids/esters. A unique [M + O – 3H]{sup +} was observed in the case of individual alkanes (C{sub 5}–C{sub 19}) and complex hydrocarbons mixture under optimized conditions. Moreover, branched alkanes generated significant in-source fragments, which could be further applied to the discrimination of isomeric alkanes. The technique also facilitates facile determination of double bond positions in unsaturated fatty acids/esters due to diagnostic fragments (the acid/ester-containing aldehyde and acid oxidation products) generated by on-line ozonolysis in APAG mode. Finally, some examples of in situ APAG analysis by gas sampling and surface sampling were given as well. .

46 INSTRUMENTATION RELATED TO NUCLEAR SCIENCE AND ↗

pH Effects on Electrospray Ionization Efficiency

Electrospray ionization efficiency is known to be affected by mobile phase composition. In this paper, a detailed study of analyte ionization efficiency dependence on mobile phase pH is presented. The pH effect was studied on 28 compounds with different chemical properties. Neither pK{sub a} nor solution phase ionization degree by itself was observed to be sufficient at describing how aqueous phase pH affects the ionization efficiency of the analyte. Therefore, the analyte behavior was related to various physicochemical properties via linear discriminant analyses. Distinction between pH-dependent and pH-independent compounds was achieved using two parameters: number of potential charge centers and hydrogen bonding acceptor capacity (in the case of 80% acetonitrile) or polarity of neutral form of analyte and pK{sub a} (in the case of 20% acetonitrile). It was also observed that decreasing pH may increase ionization efficiency of a compound by more than two orders of magnitude. .

46 INSTRUMENTATION RELATED TO NUCLEAR SCIENCE AND ↗

Detection of Metastatic Breast and Thyroid Cancer in Lymph Nodes by Desorption Electrospray Ionization Mass Spectrometry Imaging

Ambient ionization mass spectrometry has been widely applied to image lipids and metabolites in primary cancer tissues with the purpose of detecting and understanding metabolic changes associated with cancer development and progression. Here, we report the use of desorption electrospray ionization mass spectrometry (DESI-MS) to image metastatic breast and thyroid cancer in human lymph node tissues. Our results show clear alterations in lipid and metabolite distributions detected in the mass spectra profiles from 42 samples of metastatic thyroid tumors, metastatic breast tumors, and normal lymph node tissues. 2D DESI-MS ion images of selected molecular species allowed discrimination and visualization of specific histologic features within tissue sections, including regions of metastatic cancer, adjacent normal lymph node, and fibrosis or adipose tissues, which strongly correlated with pathologic findings. In thyroid cancer metastasis, increased relative abundances of ceramides and glycerophosphoinisitols were observed. In breast cancer metastasis, increased relative abundances of various fatty acids and specific glycerophospholipids were seen. Trends in the alterations in fatty acyl chain composition of lipid species were also observed through detailed mass spectra evaluation and chemical identification of molecular species. The results obtained demonstrate DESI-MSI as a potential clinical tool for the detection of breast and thyroid cancer metastasis in lymph nodes, although further validation is needed. .

46 INSTRUMENTATION RELATED TO NUCLEAR SCIENCE AND ↗

Optimization of a New Aerodynamic Cylindrical FAIMS Device for Small Molecule Analysis

The implementation of an aerodynamic mechanism to improve ion sampling between nanoelectrospray (n-ESI) and FAIMS was recently reported for proteomic analyses. This investigation explores the new FAIMS interface for small molecule analysis at high liquid flow rates and includes an examination of key differences in ionization between heated-ESI (HESI) and n-ESI. The sheath gas, critical for desolvation with HESI, affects FAIMS operation as higher FAIMS gas flow rates are required to achieve sufficient desolvation. Gas flow rate experiments also uncovered m/z discrimination with the conventional design as larger (slower moving) m/z ions experienced larger signal intensity losses than smaller m/z ions due to the desolvation gas flow having a greater drag effect on slower moving ions. The modified inlet in new FAIMS dampens the gas drag, making the HESI source more amenable as less m/z bias and significantly lower %RSD values were observed. Furthermore, a larger radius inner electrode in new FAIMS enables significantly higher E/N (electric field/number gas density) to be achieved using the existing waveform generator. Thus, new FAIMS signal intensities using only nitrogen improved 1.25- to 2-fold compared with the conventional design and 50% helium. Adding helium to the new FAIMS gave no significant improvements. The larger inner electrode also decreased ion focusing capabilities, and the effect on peak separation and ion intensity was examined in detail. The peak capacity of new FAIMS was approximately double that of conventional FAIMS; separation of seven low m/z ions gave a peak capacity of 37.7 using the gas additive 2-propanol. .

46 INSTRUMENTATION RELATED TO NUCLEAR SCIENCE AND ↗

MALDI Orbitrap Mass Spectrometry Profiling of Dysregulated Sulfoglycosphingolipids in Renal Cell Carcinoma Tissues

Matrix-assisted laser desorption/ionization coupled with Orbitrap mass spectrometry (MALDI-Orbitrap-MS) is used for the clinical study of patients with renal cell carcinoma (RCC), as the most common type of kidney cancer. Significant changes in sulfoglycosphingolipid abundances between tumor and autologous normal kidney tissues are observed. First, sulfoglycosphingolipid species in studied RCC samples are identified using high mass accuracy full scan and tandem mass spectra. Subsequently, optimization, method validation, and statistical evaluation of MALDI-MS data for 158 tissues of 80 patients are discussed. More than 120 sulfoglycosphingolipids containing one to five hexosyl units are identified in human RCC samples based on the systematic study of their fragmentation behavior. Many of them are recorded here for the first time. Multivariate data analysis (MDA) methods, i.e., unsupervised principal component analysis (PCA) and supervised orthogonal partial least square discriminant analysis (OPLS-DA), are used for the visualization of differences between normal and tumor samples to reveal the most up- and downregulated lipids in tumor tissues. Obtained results are closely correlated with MALDI mass spectrometry imaging (MSI) and histologic staining. Important steps of the present MALDI-Orbitrap-MS approach are also discussed, such as the selection of best matrix, correct normalization, validation for semiquantitative study, and problems with possible isobaric interferences on closed masses in full scan mass spectra. .

46 INSTRUMENTATION RELATED TO NUCLEAR SCIENCE AND ↗

Improved Precision and Accuracy of Quantification of Rare Earth Element Abundances via Medium-Resolution LA-ICP-MS

Laser ablation ICP-MS enables streamlined, high-sensitivity measurements of rare earth element (REE) abundances in geological materials. However, many REE isotope mass stations are plagued by isobaric interferences, particularly from diatomic oxides and argides. In this study, we compare REE abundances quantitated from mass spectra collected with low-resolution (m/Δm = 300 at 5% peak height) and medium-resolution (m/Δm = 2500) mass discrimination. A wide array of geological samples was analyzed, including USGS and NIST glasses ranging from mafic to felsic in composition, with NIST 610 employed as the bracketing calibrating reference material. The medium-resolution REE analyses are shown to be significantly more accurate and precise (at the 95% confidence level) than low-resolution analyses, particularly in samples characterized by low (<μg/g levels) REE abundances. A list of preferred mass stations that are least susceptible to isobaric interferences is reported. These findings impact the reliability of REE abundances derived from LA-ICP-MS methods, particularly those relying on mass analyzers that do not offer tuneable mass-resolution and/or collision cell technologies that can reduce oxide and/or argide formation. .

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Novel Selectivity-Based Forensic Toxicological Validation of a Paper Spray Mass Spectrometry Method for the Quantitative Determination of Eight Amphetamines in Whole Blood

Paper spray tandem mass spectrometry is used to identify and quantify eight individual amphetamines in whole blood in 1.3 min. The method has been optimized and fully validated according to forensic toxicology guidelines, for the quantification of amphetamine, methamphetamine, 3,4-methylenedioxyamphetamine (MDA), 3,4-methylenedioxy-N-methylamphetamine (MDMA), 3,4-methylenedioxy-N-ethylamphetamine (MDEA), para-methoxyamphetamine (PMA), para-methoxymethamphetamine (PMMA), and 4-fluoroamphetamine (4-FA). Additionally, a new concept of intrinsic and application-based selectivity is discussed, featuring increased confidence in the power to discriminate the amphetamines from other chemically similar compounds when applying an ambient mass spectrometric method without chromatographic separation. Accuracy was within ±15% and average precision was better than 15%, and better than 20% at the LLOQ. Detection limits between 15 and 50 ng/mL were obtained using only 12 μL of whole blood. .

46 INSTRUMENTATION RELATED TO NUCLEAR SCIENCE AND ↗

Multivariate Analysis of MALDI Imaging Mass Spectrometry Data of Mixtures of Single Pollen Grains

Mixtures of pollen grains of three different species (Corylus avellana, Alnus cordata, and Pinus sylvestris) were investigated by matrix-assisted laser desorption/ionization time-of-flight imaging mass spectrometry (MALDI-TOF imaging MS). The amount of pollen grains was reduced stepwise from > 10 to single pollen grains. For sample pretreatment, we modified a previously applied approach, where any additional extraction steps were omitted. Our results show that characteristic pollen MALDI mass spectra can be obtained from a single pollen grain, which is the prerequisite for a reliable pollen classification in practical applications. MALDI imaging of laterally resolved pollen grains provides additional information by reducing the complexity of the MS spectra of mixtures, where frequently peak discrimination is observed. Combined with multivariate statistical analyses, such as principal component analysis (PCA), our approach offers the chance for a fast and reliable identification of individual pollen grains by mass spectrometry. .

46 INSTRUMENTATION RELATED TO NUCLEAR SCIENCE AND ↗