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All sourcesNASA NTRSDOE OSTI
NASA NTRS2018

D/H Isotope Fractionation During H Diffusion Loss from Clinopyroxene Evidenced in Martian Nakhlites

Knowing the distribution and origin of water in terrestrial planets is crucial to understand their formation, evolution and the source of their atmospheres and surface water. Mantle D/H ratios may be used to determine what type of material contributed water to the terrestrial planets [1]. However, other processes, magmatic or surface alteration processes, can also modify D/H ratios, and for Mars, we only have samples from the crust, as meteorites. The D/H ratio of igneous phases of Martian meteorites is generally explained in terms of the mixing contributions of two reservoirs: surficial with high D/H (dD > 700 ‰) related to interaction with the martian atmosphere (dD ~ 5000‰), and mantle-derived with lower D/H (dD < 500 ‰ but the exact value is still debated)[2]. However, our present study evidences that H loss in clinopyroxene during degassing can significantly fractionate H isotopes and increase their D/H ratios. In situ analyses of H isotopes, and of water, major and trace element contents were performed on the pyroxenes of 5 nakhlites. Nakhlites are clinopyroxenites that likely originated from the same lava flow or shallow magma chamber. Water contents decrease (380 to <5 ppm H2O) with increasing dD (-268 to 4860 ‰). Significant influence from spallation, exchange with the martian atmosphere, shock, surface alteration, and hydrothermal processes is ruled out. Together with the evidence of less water at the edge of individual pyroxene grains compared to their interior, we interpret this correlation as the result of preferential diffusive loss of H relative to D from the already crystallized pyroxenes during ascent of the partially-crystallized magma. Similar H isotope fractionations have been observed in another nominally anhydrous mineral, garnet, during experimental dehydration [3]. These results emphasize that caution is warranted when interpreting H isotope analyses of igneous, nominally anhydrous minerals in terms of planetary processes.

Peslier, A. H.↗
DOE OSTI2022

A fractional model for anomalous diffusion with increased variability: Analysis, algorithms and applications to interface problems

Fractional equations have become the model of choice in several applications where heterogeneities at the microstructure result in anomalous diffusive behavior at the macroscale. Here, we introduce a new fractional operator characterized by a doubly-variable fractional order and possibly truncated interactions. Under certain conditions on the model parameters and on the regularity of the fractional order we show that the corresponding Poisson problem is well-posed. Additionally, we introduce a finite element discretization and describe an efficient implementation of the finite-element matrix assembly in the case of piecewise constant fractional order. Through several numerical tests, we illustrate the improved descriptive power of this new operator across media interfaces. Furthermore, we present one-dimensional and two-dimensional h-convergence results that show that the variable-order model has the same convergence behavior as the constant-order model.

97 MATHEMATICS AND COMPUTING↗
DOE OSTI2025

The effect of ion pairing on speciation and transport in ion exchange membranes at varying hydration levels: A four-state model

Understanding ion pairing in ion exchange membranes (IEMs) is essential for advancing IEM applications in energy and environmental technologies. Here, this study introduces a four-state molecular dynamics model to quantify speciation and transport within Nafion-117, specifically examining the role of ion pairing in monovalent and divalent counterions (NaCl, Na 2 SO 4 , and MgSO 4 ). By analyzing radial distribution functions (RDFs) and molecular snapshots, we distinguish ion pairing modes and classify counterions into four states: condensed counterion, condensed ion pair, free ion pair, and free counterion. A key finding is that while divalent counterions (e. g., Mg 2+ ) maintain stable speciation across hydration levels, monovalent counterions (e.g., Na + ) show notable speciation shifts with hydration. Both monovalent and divalent counterions are not diffusive when condensed onto the polymer (sorbed to membrane functional groups). In contrast, free counterions are diffusive across all hydration levels. To evaluate the overall diffusivity of counterions, four-state fractions and diffusivities are computed, each contributing to counterion transport. The condensed/free ion speciation for multivalent sulfate salts aligns with previous revisions to the Donnan-Manning framework that include ion pairing, thereby validating its relevance to established membrane theories. The four-state model's diffusivity results support several current ion exchange assumptions, including that the condensed counterions are immobile, while uncondensed counterions are mobile. The four-state model offers insights into contact ion pairing within IEMs, highlighting its potential even when undetected in aqueous solution experiments. This work advances the theoretical understanding of counterion speciation in IEMs while identifying model limitations that suggest avenues for refinement, such as distinguishing water-mediated ion pairs between fully hydrated ions.

Ion exchange membranes↗
NASA NTRS1993

Diffusion-controlled magnesium isotopic fractionation of a single crystal forsterite evaporated from the solid state

Though the origin of calcium- and aluminum-rich inclusions (CAI's) in carbonaceous chondrites is till a disputed issue, evaporation is no doubt one of the most important processes for the formation of CAI's in the early solar nebula. The mechanism for production of large isotopic mass fractionation effects in magnesium, silicon, oxygen, and chromium in CAI's can be better understood by examining isotopic fractionation during the evaporation of minerals. New evaporation experiments were performed on single-crystal forsterite. The magnesium isotopic distribution near the evaporating surfaces of the residues using a modified AEI IM-20 ion microprobe to obtain rastered beam depth profiles was measured. A theoretical model was used to explain the profiles and allowed determination of the diffusion coefficient of Mg(++) in forsterite at higher temperatures than previous measurements. The gas/solid isotopic fractionation factor for magnesium for evaporation from solid forsterite was also determined and found to be nearly the same as that for evaporation of liquid Mg2SiO4.

Wang, Jianhua↗
NASA NTRS2002

Modelling the effect of diffuse light on canopy photosynthesis in controlled environments

A layered canopy model was used to analyze the effects of diffuse light on canopy gross photosynthesis in controlled environment plant growth chambers, where, in contrast to the field, highly diffuse light can occur at high irradiance. The model suggests that high diffuse light fractions (approximately 0.7) and irradiance (1400 micromoles m-2 s-1) may enhance crop life-cycle canopy gross photosynthesis for hydroponic wheat by about 20% compared to direct light at the same irradiance. Our simulations suggest that high accuracy is not needed in specifying diffuse light fractions in chambers between approximately 0.7 and 1, because simulated photosynthesis for closed canopies plateau in this range. We also examined the effect of leaf angle distribution on canopy photosynthesis under growth chamber conditions, as these distributions determine canopy extinction coefficients for direct and diffuse light. We show that the spherical leaf angle distribution is not suitable for modeling photosynthesis of planophile canopies (e.g., soybean and peanut) in growth chambers. Also, the absorption of the light reflected from the surface below the canopy should generally be included in model simulations, as the corresponding albedo values in the photosynthetically active range may be quite high in growth chambers (e.g., approximately 0.5). In addition to the modeling implications, our results suggest that diffuse light conditions should be considered when drawing conclusions from experiments in controlled environments.

Non-NASA Center↗
NASA NTRS1992

Fractionation of CO in the diffuse clouds toward Zeta Ophiuchi

An analysis of CO A-X bands in diffuse clouds toward Zeta Ophiuchi is presented. The results provide isotopic ratios that constitute the strongest observational evidence for highly localized isotopic fractionation of CO in diffuse portions of an interstellar cloud. The value of the fractionation implies that selective photodissociation is the controlling influence of the fractionation. The molecule's excitation temperature is discussed and a lower limit to the O-16/O-18 ratio is provided. The absence of CO lines from the gas that provides broad CH+ and CH lines commonly attributed to warm gas behind a shock front is addressed.

Sheffer, Yaron↗
DOE OSTI2021

Error Estimates for the Optimal Control of a Parabolic Fractional PDE

In this work, we consider the integral definition of the fractional Laplacian and analyze a linear-quadratic optimal control problem for the so-called fractional heat equation; control constraints are also considered. We derive existence and uniqueness results, first order optimality conditions, and regularity estimates for the optimal variables. To discretize the state equation we propose a fully discrete scheme that relies on an implicit finite difference discretization in time combined with a piecewise linear finite element discretization in space. We derive stability results and a novel $L^2(0,T;L^2(\Omega))$ a priori error estimate. On the basis of the aforementioned solution technique, we propose a fully discrete scheme for our optimal control problem that discretizes the control variable with piecewise constant functions, and we derive a priori error estimates for it. We illustrate the theory with one- and two-dimensional numerical experiments.

97 MATHEMATICS AND COMPUTING↗
NASA NTRS1990

Mass fractionation of noble gases in diffusion-limited hydrodynamic hydrogen escape

The theory of mass fractionation by hydrogen is presently extended to atmospheres in which hydrogen is not the major constituent. This theoretical framework is applied to three different cases. In the first, it is shown that the fractionation of terrestrial atmospheric neon with respect to mantle neon is explainable as a consequence of diffusion-limited hydrogen escape from a steam atmosphere toward the end of the accretion process. In the second, the anomalously high Ar-38/Ar-36 ratio of Mars is shown to be due to hydrodynamic fractionation by a vigorously escaping and very pure hydrogen wind. In the last case, it is speculated that the currently high Martian D/H ratio emerged during the hydrodynamic escape phase which fractionated Ar.

Zahnle, Kevin↗
DOE OSTI2021

Analysis of Anisotropic Nonlocal Diffusion Models: Well-posedness of Fractional Problems for Anomalous Transport

We analyze the well-posedness of an anisotropic, nonlocal diffusion equation. Establishing an equivalence between weighted and unweighted anisotropic nonlocal diffusion operators in the vein of unified nonlocal vector calculus, we apply our analysis to a class of fractional-order operators and present rigorous estimates for the solution of the corresponding anisotropic anomalous diffusion equation. Furthermore, we extend our analysis to the anisotropic diffusion-advection equation and prove well-posedness for fractional orders s ∊ [0.5, 1). We also present an application of the advection-diffusion equation to anomalous transport of solutes.

97 MATHEMATICS AND COMPUTING↗
NASA NTRS1985

Measurement and Modeling of the Optical Scattering Properties of Crop Canopies

The specular reflection process is shown to be a key aspect of radiation transfer by plant canopies. Polarization measurements are demonstrated as the tool for determining the specular and diffuse portions of the canopy radiance. The magnitude of the specular fraction of the reflectance is significant compared to the magnitude of the diffuse fraction. Therefore, it is necessary to consider specularly reflected light in developing and evaluating light-canopy interaction models for wheat canopies. Models which assume leaves are diffuse reflectors correctly predict only the diffuse fraction of the canopy reflectance factor. The specular reflectance model, when coupled with a diffuse leaf model, would predict both the specular and diffuse portions of the reflectance factor. The specular model predicts and the data analysis confirms that the single variable, angle of incidence of specularly reflected sunlight on the leaf, explains much of variation in the polarization data as a function of view-illumination directions.

Vanderbilt, V. C.↗
NASA NTRS2007

Isotopic Measurements in CAIs with the Nanosims: Implications to the understanding of the Formation process of Ca, Al-Rich Inclusions

Ca, Al-rich Inclusions (CAIs) preserve evidence of thermal events that they experienced during their formation in the early solar system. Most CAIs from CV and CO chondrites are characterized by large variations in O-isotopic compositions of primary minerals, with spinel, hibonite, and pyroxene being more O-16-rich than melilite and anorthite, with delta 17, O-18 = approx. -40%o (DELTA O-17 = delta O-17 - 0.52 x delta O-18 = approx. - 20%o ). These anomalous compositions cannot be accounted for by standard mass dependent fractionation and diffusive process of those minerals. It requires the presence of an anomalous oxygen reservoir of nucleosynthetic origin or mass independent fractionations before the formation of CAIs in the early solar system. The CAMECA NanoSIMS is a new generation ion microprobe that offers high sensitivity isotopic measurements with sub 100 nm spatial resolution. The NanoSIMS has significantly improved abilities in the study of presolar grains in various kind of meteorites and the decay products of extinct nuclides in ancient solar system matter. This instrument promises significant improvements over other conventional ion probes in the precision isotopic characterization of sub-micron scales. We report the results of our first O isotopic measurements of various CAI minerals from EK1-6-3 and 7R19-1(a) utilizing the JSC NanoSIMS 50L ion microprobe. We evaluate the measurement conditions, the instrumental mass fractionation factor (IMF) for O isotopic measurement and the accuracy of the isotopic ratio through the analysis of a San Carlos olivine standard and CAI sample of 7R19-1(a).

Ito, M.↗
DOE OSTI2022

Single-Axis Tracker Control Optimization Potential for the Contiguous United States

Conventional tracker control algorithms maximize collection of direct irradiance with no regard for collection of diffuse irradiance. Therefore, a tracker control algorithm that optimizes for maximal total irradiance, not just direct, might realize improved insolation collection. Using weather data gridded at 0.25° by 0.25° latitude/longitude spacing covering the contiguous United States, we evaluate the insolation gain of two alternative control algorithms optimized for improved total irradiance collection in monofacial arrays and present annual and monthly geographic heatmaps showing the gains across the contiguous United States. Certain locations show potential annual insolation gains approaching 1.0%, but most locations with recently-built tracker systems show annual gains between 0.1% and 0.4%. We also demonstrate a relationship between a climate's annualized diffuse insolation fraction and its potential tracker optimization insolation gain.

diffuse↗
DOE OSTI2022

Single-Axis Tracker Control Optimization Potential for the Contiguous United States: Preprint

Conventional tracker control algorithms maximize collection of direct irradiance with no regard for collection of diffuse irradiance. Therefore, a tracker control algorithm that optimizes for maximal total irradiance, not just direct, might realize improved insolation collection. Using weather data gridded at 0.25° by 0.25° latitude/longitude spacing covering the contiguous United States, we evaluate the insolation gain of two alternative control algorithms optimized for improved total irradiance collection in monofacial arrays and present annual and monthly geographic heatmaps showing the gains across the contiguous United States. Certain locations show potential annual insolation gains approaching 1.0%, but most locations with recently-built tracker systems show annual gains between 0.1% and 0.4%. We also demonstrate a relationship between a climate's annualized diffuse insolation fraction and its potential tracker optimization insolation gain.

diffuse↗
NASA NTRS2004

Lunar and Planetary Science XXXV: From Ancient Mists: Presolar and Nebular Processes

The session "From Ancient Mists: Presolar and Nebular Processes" included the following reports: Interpretation of the Meteoritic Extinct Radioactivity - Mean Life Relation; On the Issue of Molybdenum Isotopic Anomalies in Meteorites: Is It Still "FUN"?; (26Al/27Al)o of the Solar Nebula Inferred from Al-Mg Systematic in Bulk CAIs from CV3 Chondrites; Magnesium Isotopic Compositions of Igneous CAIs in the CR Carbonaceous Chondrites: Evidence for an Early and Late-stage Melting of CAIs; The 26Al-26Mg Chronology of a Type C CAI and POIs in Ningqiang Carbonaceous Chondrite; Bulk Compositions of CAIs and Al-rich Chondrules: Implications of the Reversal of the Anorthite / Forsterite Condensation Sequence at Low Nebular Pressures; Synthesis of Refractory Minerals by High-Temperature Condensation of a Gas of Solar Composition; Elemental and Isotopic Fractionation by Diffusion-limited Evaporation; "Nonideal" Isotopic Fractionation Behavior of Magnesium in Evaporation Residues; Determination of Primordial Refractory Inclusion Compositions; Zoning Patterns in Spinel from Type B Ca-Al-rich Inclusions: Constraints on Sub-Solidus Thermal History; Radial Migration of Materials from Inner to Outer Solar Nebula: Evidence from Meteorite Matrix; and Refractory Forsterites in Chondritic Meteorites, a Link Between CAIs and Chondrules.

Source record↗
DOE OSTI2021

The influence of fire aerosols on surface climate and gross primary production in the Energy Exascale Earth System Model (E3SM)

Fire-emitted aerosols play an important role in influencing Earth’s climate, directly by scattering and absorbing radiation and indirectly by influencing cloud microphysics. The quantification of fire-aerosol interactions, however, remains challenging and subject to uncertainties in emissions, plume parameterizations, and aerosol properties. Here we optimized fire-associated aerosol emissions in the Energy Exascale Earth System Model (E3SM) using the Global Fire Emissions Database (GFED) and AERONET aerosol optical depth (AOD) observations during 1997-2016. Furthermore, we distributed fire emissions vertically using smoke plume heights from Multi-angle Imaging SpectroRadiometer (MISR) satellite observations. From the optimization, we estimate that global fires emit 45.5 Tg y -1 of primary particulate organic matter and 3.9 Tg y -1 of black carbon. We then performed two climate simulations with and without the optimized fire emissions. We find that fire aerosols significantly increase global AOD by 14 ± 7% and contribute to a reduction in net shortwave radiation at the surface (-2.3 ± 0.5 W m -2 ). Together, fire-induced direct and indirect aerosol effects cause annual mean global land surface air temperature to decrease by 0.17 ± 0.15°C, relative humidity to increase by 0.4 ± 0.3%, and diffuse light fraction to increase by 0.5 ± 0.3%. In response, GPP declines by 2.8 Pg C y -1 , as a result of large positive drivers (decreases in temperature and increases in humidity and diffuse light) nearly cancelling out large negative drivers (decreases shortwave radiation and soil moisture). Our analysis highlights the importance of fire aerosols in modifying surface climate and photosynthesis across the tropics.

54 ENVIRONMENTAL SCIENCES↗
NASA NTRS1986

Solar wind helium, neon and argon released by oxidation of metal grains from the Weston chondrite

A set of experiments were carried out to test the feasibility of determining unfractionated elemental and isotopic ratios for the noble gases in the presumably ancient solar wind present in the gas rich meteorites. The problems of diffusive loss was avoided by analyzing metal rather than the usual silicates. In order to avoid chemical, and even harsh physical, treatment of the sample, which might have affected the surfaces of metal grains, a means of analyzing the metal in the presence of residual silicate not removed by gentle crushing and magnetic separation was devised. Preliminary results given were obtained by taking advantage of the differing properties of metal and silicates with regard to diffusion. The results suggests that, with some modifications in the choice of pyrolysis and combustion temperatures and in the amount of O2 used, it should be possible, by oxidizing the surfaces of metal grains from gas rich meteorites, to obtain data on solar wind that has not been fractionated by diffusive loss.

Becker, R. H.↗