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At least 37 records · Page 2
All sourcesNASA NTRSDOE OSTI
DOE OSTI2021

Reactive oxygen species alter chemical composition and adsorptive fractionation of soil organic matter

Reactive oxygen species (ROS), formed during redox fluctuations in iron-rich soils, have been known to stimulate lignin degradation, although not much is known about how they alter soil organic matter (SOM) composition and interaction with mineral surfaces. We conducted a laboratory experiment to see how ROS altered SOM composition and adsorptive fractionation onto Fe-mineral surfaces. We reacted water extracts of SOM with ·OH, produced by the Fenton reaction, and then conducted a sorption experiment of the extracts with goethite to analyze the amount and quality of SOM adsorbed. The Fenton reaction preferentially consumed low-O, mostly aromatic molecules, and new high-O molecules were detected post-Fenton, nearly half of which were carbohydrate-like. Although the amount of C adsorbed did not change after oxidation, the post-Fenton adsorbed molecules were more oxidized. Pre-Fenton adsorption was dominated by aromatic molecules (90%), but post-Fenton, the adsorbed molecules were 75% aromatic and 25% carbohydrate-like. We show that the ·OH radical oxidized SOM and shifted patterns of adsorption to a more oxidized pool. Because adsorption to minerals is thought to stabilize SOM, our results suggest that ROS may alter the availability and stabilization patterns of SOM.

Patel, Kaizad F.↗
DOE OSTI2021

Effective Biomass Fractionation through Oxygen-Enhanced Alkaline–Oxidative Pretreatment

The high recalcitrance of plant cell walls is an obstacle for effective chemical or biological conversion into renewable chemicals and transportation fuels. Here, we investigated the utilization of both oxygen (O 2 ) and hydrogen peroxide (H 2 O 2 ) as co-oxidants during alkaline-oxidative pretreatment to improve biomass fractionation and increase enzymatic digestibility. The oxidative pretreatment of hybrid poplar was studied over a variety of conditions. Employing O 2 in addition to H 2 O 2 as a co-oxidant during the two-stage alkaline pre-extraction/copper-catalyzed alkaline hydrogen peroxide (Cu-AHP) pretreatment process resulted in a substantial improvement in delignification relative to using H 2 O 2 alone during the second-stage Cu-AHP pretreatment, leading to high overall sugar yields even at H 2 O 2 loadings as low as 2% (w/w of original biomass). The presence of H 2 O 2 , however, was both critical and synergistic. Performing analogous reactions in the absence of H 2 O 2 resulted in approximately 25% less delignification and a 30% decrease in sugar yields. Here, the lignin isolated from this dual oxidant second stage had high aliphatic hydroxyl group content and reactivity to isocyanate, indicating that it is a promising substrate for the production of polyurethanes. To test the suitability of the isolated lignin as a source of aromatic monomers, the lignin was subjected to a sequential Bobbitt’s salt oxidation followed by formic-acid catalyzed depolymerization process. Monomer yields of approximately 17% (w/w) were obtained, and the difference in yields was not significant between lignin isolated from our Cu-AHP process with and without O 2 as a co-oxidant. Thus, the addition of O 2 did not lead to significant lignin crosslinking, a result consistent with the two-dimensional heteronuclear single-quantum coherence (2D HSQC) NMR spectra of the isolated lignin.

09 BIOMASS FUELS↗
DOE OSTI2024

Design and Validation of a High-Throughput Reductive Catalytic Fractionation Method

Reductive catalytic fractionation (RCF) is a promising method to extract and depolymerize lignin from biomass, and bench-scale studies have enabled considerable progress in the past decade. RCF experiments are typically conducted in pressurized batch reactors with volumes ranging between 50 and 1000 mL, limiting the throughput of these experiments to one to six reactions per day for an individual researcher. Here, we report a high-throughput RCF (HTP-RCF) method in which batch RCF reactions are conducted in 1 mL wells machined directly into Hastelloy reactor plates. The plate reactors can seal high pressures produced by organic solvents by vertically stacking multiple reactor plates, leading to a compact and modular system capable of performing 240 reactions per experiment. Using this setup, we screened solvent mixtures and catalyst loadings for hydrogen-free RCF using 50 mg poplar and 0.5 mL reaction solvent. The system of 1:1 isopropanol/methanol showed optimal monomer yields and selectivity to 4-propyl substituted monomers, and validation reactions using 75 mL batch reactors produced identical monomer yields. To accommodate the low material loadings, we then developed a workup procedure for parallel filtration, washing, and drying of samples and a 1H nuclear magnetic resonance spectroscopy method to measure the RCF oil yield without performing liquid-liquid extraction. As a demonstration of this experimental pipeline, 50 unique switchgrass samples were screened in RCF reactions in the HTP-RCF system, revealing a wide range of monomer yields (21-36%), S/G ratios (0.41-0.93), and oil yields (40-75%). These results were successfully validated by repeating RCF reactions in 75 mL batch reactors for a subset of samples. We anticipate that this approach can be used to rapidly screen substrates, catalysts, and reaction conditions in high-pressure batch reactions with higher throughput than standard batch reactors.

BIOMASS FUELS,INORGANIC, ORGANIC, PHYSICAL, AND AN↗
NASA NTRS1977

Electrophoretic fractional elution apparatus employing a rotational seal fraction collector

Electrophoretic fractional elution apparatus which has a column with a rotating seal joint is described. A thin jet of eluting buffer is directed across the lumen of the electrophoretic column in a direction perpendicular to that of electrophoretic migration. Either the content of the column is rotated with respect to the stationary jet, or the jet is rotated with respect to the column. The system may employ electrophoresis either in free solution or in packed columns.

Bier, M.↗
NASA NTRS2002

Fractional-order Viscoelasticity (FOV): Constitutive Development Using the Fractional Calculus: First Annual Report

This is the first annual report to the U.S. Army Medical Research and Material Command for the three year project "Advanced Soft Tissue Modeling for Telemedicine and Surgical Simulation" supported by grant No. DAMD17-01-1-0673 to The Cleveland Clinic Foundation, to which the NASA Glenn Research Center is a subcontractor through Space Act Agreement SAA 3-445. The objective of this report is to extend popular one-dimensional (1D) fractional-order viscoelastic (FOV) materials models into their three-dimensional (3D) equivalents for finitely deforming continua, and to provide numerical algorithms for their solution.

Freed, Alan↗
DOE OSTI2025

Improved PARE (Pressurized Airborne Release Equipment) for ARF (Airborne Release Fraction) and RF (Respirable Fraction) Testing

An improved version of the PARE (Pressurized Airborne Release Equipment) system (Sutter 1983a and Sutter 1983b and Ballinger et al 1987) has been developed for powder venting testing. This effort seeks to improve the accuracy of risk estimation for the venting of pressurized powders and the venting of gases through pressurized powders.

61 RADIATION PROTECTION AND DOSIMETRY↗
NASA NTRS2004

Control of Initialized Fractional-Order Systems

Fractional-Order systems, or systems containing fractional derivatives and integrals, have been studied by many in the engineering area. Additionally, very readable discussions, devoted specifically to the subject, are presented by Oldham and Spanier, Miller and Ross, and Pudlubny (1999a). It should be noted that there are a growing number of physical systems whose behavior can be compactly described using fractional system theory. Of specific interest to electrical engineers are long lines, electrochemical processes, dielectric polarization, colored noise, viscoelastic materials, and chaos. With the growing number of applications, it is important to establish a theory of control for these fractional-order systems, and for the potential use of fractional-order systems as feedback compensators. This topic is addressed in this paper. The first section discusses the control of fractional-order systems using a vector space representation, where initialization is included in the discussion. It should be noted that Bagley and Calico and Padovan and Sawicki both present a fractional state-space representation, which do not include the important historic effects. Incorporation of these effects based on the initialized fractional calculus is presented . The control methods presented in this paper are based on the initialized fractional order system theory. The second section presents an input-output approach. Some of the problems encountered in these sections are: a) the need to introduce a new complex plane to study the dynamics of fractional-order systems, b) the need to properly define the Laplace transform of the fractional derivative, and c) the proper inclusion of the initialization response in the system and control formulation. Following this, the next section generalizes the proportional-plus-integral-control (PI-control) and PID-control (PI-plus- derivative) concepts using fractional integrals. This is then further generalized using general fractional- order compensators. Finally the compensator concept is generalized by the use of a continuum of fractions in the compensator via the concept of order-distributions. The last section introduces fractional feedback in discrete-time.

Hartley, Tom T.↗
DOE OSTI2025

Equilibrium Fe isotope fractionation between olivine, pyroxene, spinel and MORB glass: Implications for mantle partial melting to generate MORBs

Primitive mid-ocean ridge basalts (MORBs) exhibit Fe isotopic compositions heavier than the upper mantle by +0.074 ± 0.028 ‰ for δ 56 Fe. The processes responsible for this isotopic difference remain unclear. Modeling of Fe isotope fractionation during mantle partial melting requires reliable equilibrium Fe isotope fractionation factors between minerals and melts, for which consistent data are still lacking. Here, in this study, we used Nuclear Resonant Inelastic X-ray Scattering (NRIXS) technique to measure Fe force constants for a MORB glass (ALV 519-4-1) and natural mantle minerals (olivine, orthopyroxene, clinopyroxene, and spinel) to determine the equilibrium Fe isotope fractionation factors between them. The force constants determined in this study, in increasing order, are 167 ± 26 N/m for spinel, 175 ± 17 N/m for olivine, 176 ± 20 N/m for MORB glass, 205 ± 26 N/m for clinopyroxene, and 219 ± 36 N/m for orthopyroxene. We evaluated the previously proposed mechanisms for the heavy Fe isotopic composition of MORBs, including (i) mantle partial melting, (ii) mantle lithological heterogeneity, with pyroxenite in the source, (iii) mantle metasomatism by low-degree melts, and (iv) fractional crystallization of olivine from melts. For (i), we used the pMELTS program to simulate adiabatic decompression melting of mantle peridotites, and calculated Fe isotope fractionation based on Fe 3+ –Fe 2+ equilibrium-controlled fractionation, where Fe 3+ forms stronger bonds and is more incompatible than Fe 2+ . At 10 wt% peridotite melting, corresponding to MORB generation, only +0.03 ‰ Fe isotope fractionation between the melt and the original bulk composition (Δ 56 Fe = δ 56 Fe melt - δ 56 Fe 0 ) was produced, insufficient to account for the observed MORB-upper mantle difference. For (ii), melting of pyroxenites yields smaller Fe isotope fractionation than melting of peridotites, making it unlikely the cause for the MORB-upper mantle isotopic difference. For (iii), both the Fe 3+ /ΣFe ratio and the δ 56 Fe of melts increase with the degree of partial melting, indicating that low-degree melts are not isotopically heavy enough to significantly alter the isotopic composition of lithospheric mantle through metasomatism. For (iv), equilibrium isotope fractionation between olivine and melt is near zero. These results suggest that equilibrium Fe isotope fractionation alone cannot explain the MORB isotopic signature, highlighting the potential role of kinetic isotope fractionation. Using a diffusion model, we calculated kinetic Fe and Mg isotope fractionations associated with (iv) olivine crystallization from a melt, and found that the predicted Fe and Mg isotope fractionations were inconsistent with observations in MORBs. Qualitatively, two processes could have induced kinetic Fe isotope fractionation during MORB generation: (a) Fe-Mg interdiffusion between melt and solid during melt migration and (b) reactive melt-rock interactions during melt focusing. However, a quantitative understanding of their role in modifying the melt isotopic composition remains limited and requires further investigation.

Fe isotopes↗
DOE OSTI2021

TEA Modeling to Quantify Economic Implications for Biorefinery Processing of Isolated Anatomical Fractions of Corn Stover

The Feedstock-Conversion Interface Consortium (FCIC; https://www.energy.gov/sites/prod/files/2020/01/f70/beto-fcic-overview-web.pdf), a collaboration of nine national laboratory partners, seeks to understand impacts of feedstock attributes on biorefinery performance. It is hypothesized that different individual anatomical fractions of corn stover vary in composition and recalcitrance, such that processing each fraction on its own through dedicated campaigns may enable better biorefinery economics overall relative to processing the whole stover material. This presentation focuses on techno-economic analysis (TEA) modeling to quantify the yield and cost ramifications for processing isolated anatomical fractions of corn stover through a low-temperature conversion biorefinery, reflecting a biochemical processing pathway consisting of biomass deconstruction through pretreatment and enzymatic hydrolysis, sugar fermentation and upgrading to hydrocarbon fuels, and lignin upgrading to value-added coproducts. Commercial-scale process simulation and economic evaluation leveraged experimental and analytical data from FCIC researchers for conversion of whole corn stover plus three individual anatomical fractions (cobs, husks, and stalks) across key steps of the conversion process. Our assessment found encouraging potential for biorefinery economic gains that may be achieved through this approach. TEA results indicated fuel yields varying from 29-44 gallons gasoline equivalent (GGE)/dry ton for the individual anatomical fractions compared to whole stover at 34 GGE/ton, equating to minimum fuel selling prices (MFSPs) between $6.37-$10.18/GGE for the fractions versus $8.76/GGE for whole stover (when lignin is burned), or $9.15-$15.19/GGE for the fractions versus $13.11/GGE for whole stover (when lignin is upgraded to coproducts, based on current experimental performance levels). Cobs and husks demonstrated the ability to achieve the highest fuel yields and lowest MFSPs, outperforming whole stover, while stalks led to the opposite result, as a composite reflection of compositional differences and process convertibility. Notably, even when taking the weighted average of the results reflecting each anatomical fraction weighted by its corresponding makeup of corn stover, this feasibility TEA screening supports feedstock cost allowances on the order of roughly $22-$29/ton as may reflect accommodating additional biomass fractionation equipment during feedstock pre-processing upstream of the conversion biorefinery gate to separate corn stover into such constituent fractions. Or viewed differently, the weighted average MFSP for the fractions was found to be $0.31-$0.32/GGE lower than the MFSP for the whole stover basis across either lignin scenario, when maintaining a fixed biomass feedstock cost. These findings highlight favorable implications for biorefinery economics as may be achieved by moving to a staged campaign approach for processing different corn stover fractions sequentially. Further opportunities exist for future work to fill in data gaps for remaining anatomical constituents (e.g. leaves) that were not included in the initial experimental studies, though are expected to maintain similar trends.

biochemical processing pathway↗
NASA NTRS2002

Fractionation of the Early Terrestrial Atmospheres: Dynamical Escape

Hydrodynamic escape may have played a significant role in the early fractionation of the atmospheres of the terrestrial planets. This possibility has been demonstrated in the last two decades by numerous models that show radial, transonic flow of hydrogen can occur in the presence of sufficient solar EUV Hydrodynamic escape may have played a significant role in the early fractionation of the atmospheres of the terrestrial planets. This possibility has been demonstrated in the last two decades by numerous models that show radial, transonic flow of hydrogen can occur in the presence of sufficient solar EUV flux, thought to exist in the first 500 My. The models show that the larger the solar flux the greater the mass of the fractionating species, which are accelerated to escape speeds by the hydrogen wind through drag processes. As the atmospheres evolve and the solar EUV flux wanes, the maximum mass of flowing gas constituents decreases until all gases become static. We show that fractionation can continue beyond this point when non-radial flow and dynamically enhanced Jeans escape are considered. For example, the early terrestrial atmospheres are thought to have had large hydrogen contents, resulting in exobase altitudes of a planetary radius or more. In this case, rotational speeds at the exobases of Earth and Mars would be large enough so that light constituents would "spin" off and fractionate, especially at equatorial latitudes. Also, in the presence of transonic flow of hydrogen only, non-radial expansion throws heavier gases to high altitudes in the exosphere, accompanied by strong bulk speeds at the exobase, which results in enhanced thermal escape fluxes and fractionation. flux, thought to exist in the first 500 My. The models show that the larger the solar flux the greater the mass of the fractionating species, which are accelerated to escape speeds by the hydrogen wind through drag processes. As the atmospheres evolve and the solar EUV flux wanes, the maximum mass of flowing gas constituents decreases until all gases become static. We show that fractionation can continue beyond this point when non-radial flow and dynamically enhanced Jeans escape are considered. For example, the early terrestrial atmospheres are thought to have had large hydrogen contents, resulting in exobase altitudes of a planetary radius or more. In this case, rotational speeds at the exobases of Earth and Mars would be large enough so that light constituents would "spin" off and fractionate, especially at equatorial latitudes. Also, in the presence of transonic flow of hydrogen only, non-radial expansion throws heavier gases to high altitudes in the exosphere, accompanied by strong bulk speeds at the exobase, which results in enhanced thermal escape fluxes and fractionation.

Hartle, Richard E.↗