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843 records · Page 47
All sourcesNASA NTRSDOE OSTI
DOE OSTI2020

Accelerating Ab Initio Simulation via Nested Monte Carlo and Machine Learned Reference Potentials

As a corollary of the rapid advances in computing, ab initio simulation is playing an increasingly important role in modeling materials at the atomic scale. Two strategies are possible, ab initio Monte Carlo (AIMC) and molecular dynamics (AIMD) simulation. The former benefits from exact sampling from the correct thermodynamic distribution, while the latter is typically more efficient with its collective all-atom coordinate updates. In this study, using a relatively simple test model comprised of helium and argon, we show that AIMC can be brought up to, and even above, the performance levels of AIMD via a hybrid nested sampling/machine learning (ML) strategy. Here, ML provides an accurate classical reference potential (up to three-body explicit interactions) that can pilot long collective Monte Carlo moves that are accepted or rejected in toto à la nested Monte Carlo (NMC); this is in contrast to the single move nature of a naive implementation. Our proposed method only requires a small up front expense from evaluating the ab initio energies and forces of (100) random configurations for training. Importantly, our method does not totally rely on the trained, assuredly imperfect, interaction. We show that high performance and exact sampling at the desired level of theory can be realized even when the trained interaction has appreciable differences from the ab initio potential. Remarkably, at the highest levels of performance realized via our approach, a pair of statistically uncorrelated atomic configurations can be generated with (1) ab initio calculations.

74 ATOMIC AND MOLECULAR PHYSICS↗
NASA NTRS2015

Technology Candidates for Air-to-Air and Air-to-Ground Data Exchange

Technology Candidates for Air-to-Air and Air-to-Ground Data Exchange is a two-year research effort to visualize the U. S. aviation industry at a point 50 years in the future, and to define potential communication solutions to meet those future data exchange needs. The research team, led by XCELAR, was tasked with identifying future National Airspace System (NAS) scenarios, determining requirements and functions (including gaps), investigating technical and business issues for air, ground, & air-to-ground interactions, and reporting on the results. The project was conducted under technical direction from NASA and in collaboration with XCELAR's partner, National Institute of Aerospace, and NASA technical representatives. Parallel efforts were initiated to define the information exchange functional needs of the future NAS, and specific communication link technologies to potentially serve those needs. Those efforts converged with the mapping of each identified future NAS function to potential enabling communication solutions; those solutions were then compared with, and ranked relative to, each other on a technical basis in a structured analysis process. The technical solutions emerging from that process were then assessed from a business case perspective to determine their viability from a real-world adoption and deployment standpoint. The results of that analysis produced a proposed set of future solutions and most promising candidate technologies. Gap analyses were conducted at two points in the process, the first examining technical factors, and the second as part of the business case analysis. In each case, no gaps or unmet needs were identified in applying the solutions evaluated to the requirements identified. The future communication solutions identified in the research comprise both specific link technologies and two enabling technologies that apply to most or all specific links. As a result, the research resulted in a new analysis approach, viewing the underlying architecture of ground-air and air-air communications as a whole, rather than as simple "link to function" paired solutions. For the business case analysis, a number of "reference architectures" were developed for both the future technologies and the current systems, based on three typical configurations of current aircraft. Current and future costs were assigned, and various comparisons made between the current and future architectures. In general, it was assumed that if a future architecture offers lower cost than the current typical architecture, while delivering equivalent or better performance, it is likely that the future solution will gain industry acceptance. Conversely, future architectures presenting higher costs than their current counterparts must present a compelling benefit case in other areas or risk a lack of industry acceptance. The business case analysis consistently indicated lower costs for the proposed future architectures, and in most cases, significantly so. The proposed future solutions were found to offer significantly greater functionality, flexibility, and growth potential over time, at lower cost, than current systems. This was true for overall, fleet-wide equipage for domestic and oceanic air carriers, as well as for single, General Aviation (GA) aircraft. The overall research results indicate that all identified requirements can be met by the proposed solutions with significant capacity for future growth. Results also illustrate that the majority of the future communication needs can be met using currently allocated aviation RF spectrum, if used in more effective ways than it is today. A combination of such optimized aviation-specific links and commercial communication systems meets all identified needs for the 50-year future and beyond, with the caveat that a new, overall function will be needed to manage all information exchange, individual links, security, cost, and other factors. This function was labeled "Delivery Manager" (DM) within this research. DM employs a distributed client/server architecture, for both airborne and ground communications architectures. Final research results included identifying the most promising candidate technologies for the future system, conclusions and recommendations, and identifying areas where further research should be considered.

Communications↗
DOE OSTI2020

Machine learning Frenkel Hamiltonian parameters to accelerate simulations of exciton dynamics

In this manuscript, we develop multiple machine learning (ML) models to accelerate a scheme for parameterizing site-based models of exciton dynamics from all-atom configurations of condensed phase sexithiophene systems. This scheme encodes the details of a system’s specific molecular morphology in the correlated distributions of model parameters through the analysis of many single-molecule excited-state electronic-structure calculations. These calculations yield excitation energies for each molecule in the system and the network of pair-wise intermolecular electronic couplings. In this work, we demonstrate that the excitation energies can be accurately predicted using a kernel ridge regression (KRR) model with Coulomb matrix featurization. We present two ML models for predicting intermolecular couplings. The first one utilizes a deep neural network and bi-molecular featurization to predict the coupling directly, which we find to perform poorly. The second one utilizes a KRR model to predict unimolecular transition densities, which can subsequently be analyzed to compute the coupling. We find that the latter approach performs excellently, indicating that an effective, generalizable strategy for predicting simple bimolecular properties is through the indirect application of ML to predict higher-order unimolecular properties. Such an approach necessitates a much smaller feature space and can incorporate the insight of well-established molecular physics.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2023

Accelerating full-waveform inversion using source stacking: synthetic experiments at the global scale in a realistic 3-D earth model

SUMMARY The spectral element method is currently the method of choice for computing accurate synthetic seismic wavefields in realistic 3-D earth models at the global scale. However, it requires significantly more computational time, compared to normal mode-based approximate methods. Source stacking, whereby multiple earthquake sources are aligned on their origin time and simultaneously triggered, can reduce the computational costs by several orders of magnitude. We present the results of synthetic tests performed on a realistic radially anisotropic 3-D model, slightly modified from model SEMUCB-WM1 with three component synthetic waveform ‘data’ for a duration of 10 000 s, and filtered at periods longer than 60 s, for a set of 273 events and 515 stations. We consider two definitions of the misfit function, one based on the stacked records at individual stations and another based on station-pair cross-correlations of the stacked records. The inverse step is performed using a Gauss–Newton approach where the gradient and Hessian are computed using normal mode perturbation theory. We investigate the retrieval of radially anisotropic long wavelength structure in the upper mantle in the depth range 100–800 km, after fixing the crust and uppermost mantle structure constrained by fundamental mode Love and Rayleigh wave dispersion data. The results show good performance using both definitions of the misfit function, even in the presence of realistic noise, with degraded amplitudes of lateral variations in the anisotropic parameter ξ. Interestingly, we show that we can retrieve the long wavelength structure in the upper mantle, when considering one or the other of three portions of the cross-correlation time series, corresponding to where we expect the energy from surface wave overtone, fundamental mode or a mixture of the two to be dominant, respectively. We also considered the issue of missing data, by randomly removing a successively larger proportion of the available synthetic data. We replace the missing data by synthetics computed in the current 3-D model using normal mode perturbation theory. The inversion results degrade with the proportion of missing data, especially for ξ, and we find that a data availability of 45 per cent or more leads to acceptable results. We also present a strategy for grouping events and stations to minimize the number of missing data in each group. This leads to an increased number of computations but can be significantly more efficient than conventional single-event-at-a-time inversion. We apply the grouping strategy to a real picking scenario, and show promising resolution capability despite the use of fewer waveforms and uneven ray path distribution. Source stacking approach can be used to rapidly obtain a starting 3-D model for more conventional full-waveform inversion at higher resolution, and to investigate assumptions made in the inversion, such as trade-offs between isotropic, anisotropic or anelastic structure, different model parametrizations or how crustal structure is accounted for.

Geochemistry & Geophysics↗
NASA NTRS1998

Analysis and Testing of Plates with Piezoelectric Sensors and Actuators

Piezoelectric material inherently possesses coupling between electrostatics and structural dynamics. Utilizing linear piezoelectric theory results in an intrinsically coupled pair of piezoelectric constitutive equations. One equation describes the direct piezoelectric effect where strains produce an electric field and the other describes the converse effect where an applied electrical field produces strain. The purpose of this study is to compare finite element analysis and experiments of a thin plate with bonded piezoelectric material. Since an isotropic plate in combination with a thin piezoelectric layer constitutes a special case of a laminated composite, the classical laminated plate theory is used in the formulation to accommodated generic laminated composite panels with multiple bonded and embedded piezoelectric layers. Additionally, the von Karman large deflection plate theory is incorporated. The formulation results in laminate constitutive equations that are amiable to the inclusion of the piezoelectric constitutive equations yielding in a fully electro-mechanically coupled composite laminate. Using the finite element formulation, the governing differential equations of motion of a composite laminate with embedded piezoelectric layers are derived. The finite element model not only considers structural degrees of freedom (d.o.f.) but an additional electrical d.o.f. for each piezoelectric layer. Comparison between experiment and numerical prediction is performed by first treating the piezoelectric as a sensor and then again treating it as an actuator. To assess the piezoelectric layer as a sensor, various uniformly distributed pressure loads were simulated in the analysis and the corresponding generated voltages were calculated using both linear and nonlinear finite element analyses. Experiments were carried out by applying the same uniformly distributed loads and measuring the resulting generated voltages and corresponding maximum plate deflections. It is found that a highly nonlinear relationship exists between maximum deflection and voltage versus pressure loading. In order to assess comparisons of predicted and measured piezoelectric actuation, sinusoidal excitation voltages are simulated/applied and maximum deflections are calculated/measured. The maximum deflection as a function of time was determined using the linear finite elements analysis. Good correlation between prediction and measurement was achieved in all cases.

Bevan, Jeffrey S.↗
DOE OSTI2026

Mixed stochastic-deterministic density functional theoretic decomposition of Kubo–Greenwood conductivities in the projector augmented wave formalism

Pairing the accuracy of the Kohn–Sham density-functional framework with the efficiency of a stochastic algorithmic approach, mixed stochastic-deterministic density functional theory (mDFT) achieves a favorable computational scaling with system sizes and electronic temperatures. We employ the recently developed mDFT formalism to investigate the dynamic charge-transport properties of systems in the warm dense matter regime. The optical conductivity spectra are computed for single- and multi- component mixtures of carbon, hydrogen, and beryllium using two complementary approaches: Kubo–Greenwood in the mDFT picture and real-time time-dependent mDFT. We further devise a decomposition of the Onsager coefficients leading up to the Kubo–Greenwood spectra to exhibit contributions from the deterministic, stochastic, and mixed electronic state transitions at different incident photon energies.

36 MATERIALS SCIENCE↗
DOE OSTI2024

Innovating the next generation of commercial smart building software

Nearly 30% of commercial building energy use is wasted due to equipment faults and HVAC controls problems. The result is increased emissions, compromised comfort and productivity, and less reliable coordination of building power needs with a clean grid. The energy impact alone represents $17 billion in potential savings. Today’s smart building software provides a robust solution to address these operational deficiencies. Energy management and information systems (EMIS) are saving up to 9% on average, with two-year paybacks. They are being incorporated into energy management processes, commissioning services, and utility programs. As effective as they are, two barriers prevent even deeper benefits; limited personnel to fix problems once they are identified, and the expense and time to manually implement changes in control systems. In partnership with the research community, the EMIS industry is developing new capabilities to overcome these barriers. Moving beyond siloed products for either fault detection and diagnostics, or optimal control, these new capabilities empower users to not only automatically identify faults, but also to push corrective action, and control improvements to their buildings. In this paper, several areas for enhancements are documented: ‘one-time’ correction of faults such as setpoints, schedules, and economizer lockouts; short-term active testing for automated proportional integral derivative (PID) loop tuning and functional testing; and continuous supervisory control for demand flexibility and year-round efficiency. Results are presented from a pair of partner implementations out of a dozen providers integrating these enhancements into their products, including field tests from across the country, and insights into operator acceptance and integration into operations and maintenance practices.

Casillas, Armando↗
NASA NTRS1998

Cardiogenic oscillation phase relationships during single-breath tests performed in microgravity

We studied the phase relationships of the cardiogenic oscillations in the phase III portion of single-breath washouts (SBW) in normal gravity (1 G) and in sustained microgravity (microG). The SBW consisted of a vital capacity inspiration of 5% He-1.25% sulfurhexafluoride-balance O2, preceded at residual volume by a 150-ml Ar bolus. Pairs of gas signals, all of which still showed cardiogenic oscillations, were cross-correlated, and their phase difference was expressed as an angle. Phase relationships between inspired gases (e.g., He) and resident gas (n2) showed no change from 1 G (211 +/- 9 degrees) to microG (163 +/- 7 degrees). Ar bolus and He were unaltered between 1 G (173 +/- 15 degrees) and microG (211 +/- 25 degrees), showing that airway closure in microG remains in regions of high specific ventilation and suggesting that airway closure results from lung regions reaching low regional volume near residual volume. In contrast, CO2 reversed phase with He between 1 G (332 +/- 6 degrees) and microG (263 +/- 27 degrees), strongly suggesting that, in microG, areas of high ventilation are associated with high ventilation-perfusion ratio (VA/Q). This widening of the range of VA/Q in microG may explain previous measurements (G.K. Prisk, A.R. Elliott, H.J.B. Guy, J.M. Kosonen, and J.B. West J. Appl. Physiol. 79: 1290-1298, 1995) of an overall unaltered range of VA/Q in microG, despite more homogeneous distributions of both ventilation and perfusion.

Non-NASA Center↗
NASA NTRS2020

Using Two-Stream Theory to Capture Fluctuations of Satellite-Perceived TOA SW Radiances Reflected from Clouds Over Ocean

Shortwave (SW) fluxes estimated from broadband radiometry rely on empirically gathered and hemispherically resolved fields of outgoing top-of-atmosphere (TOA) radiances. This study aims to provide more accurate and precise fields of TOA SW radiances reflected from clouds over ocean by introducing a novel semiphysical model predicting radiances per narrow sun-observer geometry. This model was statistically trained using CERES-measured radiances paired with MODIS-retrieved cloud parameters as well as reanalysis-based geophysical parameters. By using radiative transfer approximations as a framework to ingest the above parameters, the new approach incorporates cloud-top effective radius and above-cloud water vapor in addition to traditionally used cloud optical depth, cloud fraction, cloud phase, and surface wind speed. A two-stream cloud albedo – serving to statistically incorporate cloud optical thickness and cloud-top effective radius – and Cox–Munk ocean reflectance were used to describe an albedo over each CERES footprint. Effective-radius-dependent asymmetry parameters were obtained empirically and separately for each viewing-illumination geometry. A simple equation of radiative transfer, with this albedo and attenuating above-cloud water vapor as inputs, was used in its log-linear form to allow for statistical optimization. We identified the two-stream functional form that minimized radiance residuals calculated against CERES observations and outperformed the state-of-the-art approach for most observer geometries outside the sun-glint and solar zenith angles between 20 and 70∘, reducing the median SD of radiance residuals per solar geometry by up to 13.2 % for liquid clouds, 1.9 % for ice clouds, and 35.8 % for footprints containing both cloud phases. Geometries affected by sun glint (constituting between 10 % and 1 % of the discretized upward hemisphere for solar zenith angles of 20 and 70∘, respectively), however, often showed weaker performance when handled with the new approach and had increased residuals by as much as 60 % compared to the state-of-the-art approach. Overall, uncertainties were reduced for liquid-phase and mixed-phase footprints by 5.76 % and 10.81 %, respectively, while uncertainties for ice-phase footprints increased by 0.34 %. Tested for a variety of scenes, we further demonstrated the plausibility of scene-wise predicted radiance fields. This new approach may prove useful when employed in angular distribution models and may result in improved flux estimates, in particular dealing with clouds characterized by small or large droplet/crystal sizes.

Two- stream theory↗
NASA NTRS2014

A Revised Calibration Function and Results for the Phoenix Mission TECP Relative Humidity Sensor

The original calibration function of the R(sub H) sensor on the Phoenix Thermal and Electrical Conductivity Sensor (TECP) has been revised in order to extend the range of the valid calibration, and to improve accuracy. The original function returned non-physical R(sub H) values at the lowest temperatures. To resolve this, and because the original calibration was performed against a pair of hygrometers that measured frost point (T(sub f)), the revised calibration equation is also cast in terms of frost point. Because of the complexity of maintaining very low temperatures and high R(sub H) in the laboratory, no calibration data exists at T is greater than 203K. However, sensor response during the mission was smooth and continuous down to 181 K. Therefore we have opted to include flight data in the calibration data set; selection was limited to data acquired during periods when the atmosphere is known to have been saturated. T(sub f) remained below 210 K throughout the mission(P is greater than 0.75 Pa). R(sub H), conversely, ranged from 1 to well under 0.01 diurnally, due to approximately 50 K temperature variations. To first order, both vapor pressure and its variance are greater during daylight hours. Variance in overnight humidity is almost entirely explained by temperature, while atmospheric turbulence contributes substantial variance to daytime humidity. Likewise, data gathered with the TECP aloft reflect higher H2O abundances than at the surface, as well as greater variance. There is evidence for saturation of the atmosphere overnight throughout much of the mission. In virtually every overnight observation, once the atmosphere cooled to T(sub f), water vapor begins to decrease, and tracks air temperature. There is no evidence for substantial decreases in water vapor prior to saturation, as expected for adsorptive exchange. Likewise, there is no evidence of local control of vapor by phases such as perchlorate hydrates hydrated minerals. The daytime average H2O pressure does not change substantially over the course of the mission, although the H2O column abundance varies by a factor of 2. Column abundances calculated from TECP data are lower than orbital measurements if one assumes that H2O is uniformly mixed through a single scale height. These results argue that the vertical distribution of H2O begins to change well in advance of surface concentrations as northern autumn approaches.

Phoenix Thermal and Electrical Conductivity Sensor↗
DOE OSTI2022

High Performance Computing to Quantify the Evolution of Microscopic Concentration Gradients During Flash Processing

During the Flash process, the cross section of a plain-carbon or a low-alloy steel is austenitized through rapid heating and transformed on rapid cooling to a predominantly martensite + bainite structure with small amounts of retained austenite. Unlike conventional heat treating, homogeneity is intentionally avoided during Flash processing of steels. The Flash process assembly consists of a pair of rolls that transfer the steel sheets through the heating and cooling stage of the thermal cycle. The initial microstructure of the steel consists of ferrite (body-centered cubic iron) + carbide ((Fe,X)mCn) mixture. The heating rate through the peak temperature is a function of temperature and reaches a peak of about 300-400°C/s and the cooling rate has a maximum value of 3,000-4,000°C/s. The on-heating phase transformations include carbide dissolution, austenite (face-centered cubic iron) nucleation and growth, and diffusion of carbon and other substitutional elements in the steel. The on-cooling phase transformations include formation of martensite (body-centered tetragonal phase containing supersaturated solute) and bainite (ferrite plates with or without fine carbides). In this project, the focus is on Fe-C-Cr steels that are currently Flash processed for armor applications. The modeling effort proposed here will help optimize the Flash thermal cycle for these low alloy steels to achieve the target performance, which is an ongoing effort at SFP Works. A significant feature of Flash processed Fe-C-Cr steels is the presence of scatter in the through-thickness in the sheet. The variability in hardness results from a variability in the bainite + martensite microstructure that is sensitive to the local chemical concentration of C and Cr. Such a chemical inhomogeneity is intentionally obtained in the Flash process. Although such a microstructural gradient is presumably responsible for the exceptional properties of the Flash processed steel, it is very important to quantify the gradients as a function of Flash variabilities in processing parameters and the input microstructure. Understanding the mechanistic pathway that leads to microstructural gradients could be ground-breaking and instrumental for achieving better process control and optimized microstructural state to meet application-specific strength-ductility requirements. Since the final microstructure depends on setting up precise solute concentration gradients through a rapid heating process, and transforming these regions into various phases, it is important to understand how small changes in steel chemistry, input microstructure (carbide size and distribution), and process variables (Flash thermal cycle) will impact the solute concentration gradients.

97 MATHEMATICS AND COMPUTING↗
NASA NTRS1999

Experimental Investigation of Pool Boiling Heat Transfer Enhancement in Microgravity in the Presence of Electric Fields

In boiling high heat fluxes are possible driven by relatively small temperature differences, which make its use increasingly attractive in aerospace applications. The objective of the research is to develop ways to overcome specific problems associated with boiling in the low gravity environment by substituting the buoyancy force with the electric force to enhance bubble removal from the heated surface. Previous studies indicate that in terrestrial applications nucleate boiling heat transfer can be increased by a factor of 50, as compared to values obtained for the same system without electric fields. The goal of our research is to experimentally explore the mechanisms responsible for EHD heat transfer enhancement in boiling in low gravity conditions, by visualizing the temperature distributions in the vicinity of the heated surface and around the bubble during boiling using real-time holographic interferometry (HI) combined with high-speed cinematography. In the first phase of the project the influence of the electric field on a single bubble is investigated. Pool boiling is simulated by injecting a single bubble through a nozzle into the subcooled liquid or into the thermal boundary layer developed along the flat heater surface. Since the exact location of bubble formation is known, the optical equipment can be aligned and focused accurately, which is an essential requirement for precision measurements of bubble shape, size and deformation, as well as the visualization of temperature fields by HI. The size of the bubble and the frequency of bubble departure can be controlled by suitable selection of nozzle diameter and mass flow rate of vapor. In this approach effects due to the presence of the electric field can be separated from effects caused by the temperature gradients in the thermal boundary layer. The influence of the thermal boundary layer can be investigated after activating the heater at a later stage of the research. For the visualization experiments a test cell was developed. All four vertical walls of the test cell are transparent, and they allow transillumination with laser light for visualization experiments by HI. The bottom electrode is a copper cylinder, which is electrically grounded. The copper block is heated with a resistive heater and it is equipped with 6 thermocouples that provide reference temperatures for the measurements with HI. The top electrode is a mesh electrode. Bubbles are injected with a syringe into the test cell through the bottom electrode. The working fluids presently used in the interferometric visualization experiments, water and PF 5052, satisfy requirements regarding thermophysical, optical and electrical properties. A 30kV power supply equipped with a voltmeter allows to apply the electric field to the electrodes during the experiments. The magnitude of the applied voltage can be adjusted either manually or through the LabVIEW data acquisition and control system connected to a PC. Temperatures of the heated block are recorded using type-T thermocouples, whose output is read by a data acquisition system. Images of the bubbles are recorded with 35mm photographic and 16mm high-speed cameras, scanned and analyzed using various software packages. Visualized temperature fields HI allows the visualization of temperature fields in the vicinity of bubbles during boiling in the form of fringes. Typical visualized temperature distributions around the air bubbles injected into the thermal boundary layer in PF5052 are shown. The temperature of the heated surface is 35 C. The temperature difference for a pair of fringes is approximately 0.05 C. The heat flux applied to the bottom surface is moderate, and the fringe patterns are regular. In the image a bubble penetrating the thermal boundary layer is visible. Because of the axial symmetry of the problem, simplified reconstruction techniques can be applied to recover the temperature field. The thermal plume developing above the heated surface for more intensive heating is shown. The temperature distribution in the liquid is clearly 3D, and tomographic techniques have to be applied to recover the temperature distribution in such a physical situation. A sequence of interferometric images showing the temperature distribution around the rising bubble, recorded with a high-speed camera is shown. Again, the temperature distribution is 3D, and a more complex approach to the evaluation, the tomographic reconstruction has to be taken. Measurement of the temperature distribution from the fringe pattern temperature distributions that yield important information regarding heat transfer are determined. Two algorithms that allow the quantitative evaluation of interferometric fringe patterns and the reconstruction of temperature fields during boiling have been developed at the Heat Transfer Laboratory of the Johns Hopkins University. In the first algorithm the bubble is assumed to be axially symmetrical, which significantly reduces the computational effort for quantifying the temperature distribution around the bubble. For this purpose the thermal boundary layer around the bubble is divided into equidistant concentric shells, and the refractive index is assumed to be constant in each of the shells. Since large temperature gradients are expected in the vicinity of the bubble during boiling, the deflection of the light beam cannot be neglected in boiling experiments. Since the exit angle of the light beam is known, this allows to account for the deflections and phase shifts outside the boundary layer (in the bulk fluid and in the windows of the test cell). Three dimensional temperature distributions in the vicinity of the bubble are reconstructed using tomographic techniques. In tomography, the measurement volume is sliced into 2D planes. In the present study these planes are parallel to the heated surface. The objective is to determine the values of the field parameter of interest in form of the field function in these 2D planes. The field parameter is the change of the refractive index of the liquid in the measurement volume caused by temperature changes. By superimposing data for many 2D planes recorded at the same time instant, the 3D temperature distribution in the measurement volume is recovered.

Herman, Cila↗
DOE OSTI2024

Atmospheric H 2 observations from the NOAA Cooperative Global Air Sampling Network

Abstract. The NOAA Global Monitoring Laboratory (GML) measures atmospheric hydrogen (H2) in grab samples collected weekly as flask pairs at over 50 sites in the Cooperative Global Air Sampling Network. Measurements representative of background air sampling show higher H2 in recent years at all latitudes. The marine boundary layer (MBL) global mean H2 was 552.8 ppb in 2021, 20.2 ± 0.2 ppb higher compared to 2010. A 10 ppb or more increase over the 2010–2021 average annual cycle was detected in 2016 for MBL zonal means in the tropics and in the Southern Hemisphere. Carbon monoxide measurements in the same-air samples suggest large biomass burning events in different regions likely contributed to the observed interannual variability at different latitudes. The NOAA H2 measurements from 2009 to 2021 are now based on the World Meteorological Organization Global Atmospheric Watch (WMO GAW) H2 mole fraction calibration scale, developed and maintained by the Max Planck Institute for Biogeochemistry (MPI-BGC), Jena, Germany. GML maintains eight H2 primary calibration standards to propagate the WMO scale. These are gravimetric hydrogen-in-air mixtures in electropolished stainless steel cylinders (Essex Industries, St. Louis, MO), which are stable for H2. These mixtures were calibrated at the MPI-BGC, the WMO Central Calibration Laboratory (CCL) for H2, in late 2020 and span the range 250–700 ppb. We have used the CCL assignments to propagate the WMO H2 calibration scale to NOAA air measurements performed using gas chromatography and helium pulse discharge detector instruments since 2009. To propagate the scale, NOAA uses a hierarchy of secondary and tertiary standards, which consist of high-pressure whole-air mixtures in aluminum cylinders, calibrated against the primary and secondary standards, respectively. Hydrogen at the parts per billion level has a tendency to increase in aluminum cylinders over time. We fit the calibration histories of these standards with zero-, first-, or second-order polynomial functions of time and use the time-dependent mole fraction assignments on the WMO scale to reprocess all tank air and flask air H2 measurement records. The robustness of the scale propagation over multiple years is evaluated with the regular analysis of target air cylinders and with long-term same-air measurement comparison efforts with WMO GAW partner laboratories. Long-term calibrated, globally distributed, and freely accessible measurements of H2 and other gases and isotopes continue to be essential to track and interpret regional and global changes in the atmosphere composition. The adoption of the WMO H2 calibration scale and subsequent reprocessing of NOAA atmospheric data constitute a significant improvement in the NOAA H2 measurement records.

Pétron, Gabrielle↗
DOE OSTI2020

Spirometric traits show quantile-dependent heritability, which may contribute to their gene-environment interactions with smoking and pollution

Background: “Quantile-dependent expressivity” refers to a genetic effect that is dependent upon whether the phenotype (e.g., spirometric data) is high or low relative to its population distribution. Forced vital capacity (FVC), forced expiratory volume in 1 second (FEV 1 ), and the FEV 1 /FVC ratio are moderately heritable spirometric traits. The aim of the analyses is to test whether their heritability (h 2 ) is constant over all quantiles of their distribution. Methods: Quantile regression was applied to the mean age, sex, height and smoking-adjusted spirometric data over multiple visits in 9,993 offspring-parent pairs and 1,930 sibships from the Framingham Heart Study to obtain robust estimates of offspring-parent (β OP ), offspring-midparent (β OM ), and full-sib regression slopes (β FS ). Nonparametric significance levels were obtained from 1,000 bootstrap samples. β OP s were used as simple indicators of quantile-specific heritability (i.e.,h 2 = 2β OP /(1+r spouse ), where r spouse was the correlation between spouses). Results: β OP ± standard error (SE) decreased by 0.0009 ± 0.0003 (P = 0.003) with every one-percent increment in the population distribution of FEV 1 /FVC, i.e., β OP ± SE were: 0.182 ± 0.031, 0.152 ± 0.015; 0.136 ± 0.011; 0.121 ± 0.013; and 0.099 ± 0.013 at the 10th, 25th, 50th, 75th, and 90th percentiles of the FEV 1 /FVC distribution, respectively. These correspond to h 2 ± SEs of 0.350 ± 0.060 at the 10th, 0.292 ± 0.029 at the 25th, 0.262 ± 0.020 at the 50th, 0.234 ± 0.025 at the 75th, and 0.191 ± 0.025 at the 90th percentiles of the FEV 1 /FVC ratio. Maximum mid-expiratory flow (MMEF) h 2 ± SEs increased 0.0025 ± 0.0007 (P = 0.0004) with every one-percent increment in its distribution, i.e.: 0.467 ± 0.046, 0.467 ± 0.033, 0.554 ± 0.038, 0.615 ± 0.042, and 0.675 ± 0.060 at the 10th, 25th, 50th, 75th, and 90th percentiles of its distribution. This was due to forced expiratory flow at 75% of FVC (FEF75%), whose quantile-specific h 2 increased an average of 0.0042 ± 0.0008 for every one-percent increment in its distribution. It is speculated that previously reported gene-environment interactions may be partially attributable to quantile-specific h 2 , i.e., greater heritability in individuals with lower FEV 1 /FVC due to smoking or airborne particles exposure vs. nonsmoking, unexposed individuals. Conclusion: Heritabilities of FEV 1 /FVC, MMEF, and FEF75% from quantile-regression of offspring-parent and sibling spirometric data suggest their quantile-dependent expressivity.

59 BASIC BIOLOGICAL SCIENCES↗
DOE OSTI2022

Pauling’s rules for oxide-based minerals: A re-examination based on quantum mechanical constraints and modern applications of bond-valence theory to Earth materials

Since their introduction in 1929, Pauling’s five rules have been used by scientists from many disciplines to rationalize and predict stable arrangements of atoms and coordination polyhedra in crystalline solids; amorphous materials such as silicate glasses and melts; nanomaterials, poorly crystalline solids; aqueous cation and anion complexes; and sorption complexes at mineral-aqueous solution interfaces. The predictive power of these simple yet powerful rules was challenged recently by George et al. (2020), who performed a statistical analysis of the performance of Pauling’s five rules for about 5000 oxide crystal structures. They concluded that only 13% of the oxides satisfy the last four rules simultaneously and that the second rule has the most exceptions. They also found that Pauling’s first rule is satisfied for only 66% of the coordination environments tested and concluded that no simple rule linking ionic radius to coordination environment will be predictive due to the variable quality of univalent radii. We address these concerns and discuss quantum mechanical calculations that complement Pauling’s rules, particularly his first (radius sum and radius ratio rule) and second (electrostatic valence rule) rules. We also present a more realistic view of the bonded radii of atoms, derived by determining the local minimum in the electron density distribution measured along trajectories between bonded atoms known as bond paths, i.e., the bond critical point (rc). Electron density at the bond critical point is a quantum mechanical observable that correlates well with Pauling bond strength. Moreover, a metal atom in a polyhedron has as many bonded radii as it has bonded interactions, resulting in metal and O atoms that may not be spherical. O atoms, for example, are not spherical in many oxide-based crystal structures. Instead, the electron density of a bonded oxygen is often highly distorted or polarized, with its bonded radius decreasing systematically from ~1.38 Å when bonded to highly electropositive atoms like sodium to 0.64 Å when bonded to highly electronegative atoms like nitrogen. Bonded radii determined for metal atoms match the Shannon (1976) radii for more electropositive atoms, but the match decreases systematically as the electronegativities of the M atoms increase. As a result, significant departures from the radius ratio rule in the analysis by George et al. (2020) is not surprising. We offer a modified, more fundamental version of Pauling’s first rule and demonstrate that the second rule has a one-to-one connection between the electron density accumulated between the bonded atoms at the bond critical point and the Pauling bond strength of the bonded interaction. Pauling’s second rule implicitly assumes that bond strength is invariant with bond length for a given pair of bonded atoms. Many studies have since shown that this is not the case, and Brown and Shannon (1973) developed an equation and a set of parameters to describe the relation between bond length and bond strength, now redefined as bond valence to avoid confusion with Pauling bond-strength. Brown (1980) used the valence-sum rule, together with the path rule and the valence-matching principle, as the three axioms of bond-valence theory (BVT), a powerful method for understanding many otherwise elusive aspects of crystals and also their participation in dynamic processes. We show how a priori bond-valence calculations can predict unstrained bond-lengths and how bond-valence mapping can locate low-Z atoms in a crystal structure (e.g., Li) or examine possible diffusion pathways for atoms through crystal structures. In addition, we briefly discuss Pauling’s third, fourth, and fifth rules, the first two of which concern the sharing of polyhedron elements (edges and faces) and the common instability associated with structures in which a polyhedron shares an edge or face with another polyhedron and contains high-valence cations. The olivine [α-(MgxFe1–x)2SiO4] crystal structure is used to illustrate the distortions from hexagonal close-packing of O atoms caused by metal-metal repulsion across shared polyhedron edges. We conclude by discussing several applications of BVT to Earth materials, including the use of BVT to: (1) locate H+ ions in crystal structures, including the location of protons in the crystal structures of nominally anhydrous minerals in Earth’s mantle; (2) determine how strongly bonded (usually anionic) structural units interact with weakly bonded (usually cationic) interstitial complexes in complex uranyl-oxide and uranyl-oxysalt minerals using the valence-matching principle; (3) calculate Lewis acid strengths of cations and Lewis base strengths of anions; (4) determine how (H2O) groups can function as bond-valence transformers by dividing one bond into two bonds of half the bond valence; (5) help characterize products of sorption reactions of aqueous cations (e.g., Co2+ and Pb2+) and oxyanions [e.g., selenate (Se6+O4)2- and selenite (Se4+O3)2-] at mineral-aqueous solution interfaces and the important role of protons in these reactions; and (6) help characterize the local coordination environments of highly charged cations (e.g., Zr4+, Ti4+, U4+, U5+, and U6+) in silicate glasses and melts.

Geochemistry & Geophysics↗