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NASA NTRS1976

Thermomagnetic analysis of meteorites. III - C3 and C4 chondrites

Results are presented for thermomagnetic analysis in a controlled oxygen atmosphere of samples from thirteen C3 chondrites and two C4 chondrites. The examined meteorites are found to have rather diverse thermomagnetic properties, so they are placed into three groups on the basis of their thermomagnetic behavior and magnetic mineralogy: (1) those possibly containing magnetite before heating, but which display a large increase in saturation moment upon cooling to room temperature; (2) those containing magnetite as their major magnetic phase, but which show little change in saturation moment following the heating-cooling cycle; and (3) those which contain iron metal in addition to other magnetic phases. Upper limits are placed on the magnetite content of the five meteorites in group 1 by assuming that the initial saturation moment is due entirely to magnetite, and quantitative estimates of the magnetite content of the four meteorites in group 2 are determined from ambient-temperature saturation magnetization measurements. The data for the six meteorites in group 3 are discussed in terms of nickel content and troilite oxidation. It is concluded that since the magnetic and bulk mineralogies of carbonaceous chondrites are more varied and complex than indicated by whole-rock elemental analyses, the origin of such meteorites cannot be described by a simple model.

Herndon, J. M.↗

NASA NTRS1994

A quantitative analysis of IRAS maps of molecular clouds

We present an analysis of IRAS maps of five molecular clouds: Orion, Ophiuchus, Perseus, Taurus, and Lupus. For the classification and description of these astrophysical maps, we use a newly developed technique which considers all maps of a given type to be elements of a pseudometric space. For each physical characteristic of interest, this formal system assigns a distance function (a pseudometric) to the space of all maps: this procedure allows us to measure quantitatively the difference between any two maps and to order the space of all maps. We thus obtain a quantitative classification scheme for molecular clouds. In this present study we use the IRAS continuum maps at 100 and 60 micrometer(s) to produce column density (or optical depth) maps for the five molecular cloud regions given above. For this sample of clouds, we compute the 'output' functions which measure the distribution of density, the distribution of topological components, the self-gravity, and the filamentary nature of the clouds. The results of this work provide a quantitative description of the structure in these molecular cloud regions. We then order the clouds according to the overall environmental 'complexity' of these star-forming regions. Finally, we compare our results with the observed populations of young stellar objects in these clouds and discuss the possible environmental effects on the star-formation process. Our results are consistent with the recently stated conjecture that more massive stars tend to form in more 'complex' environments.

Wiseman, Jennifer J.↗

NASA NTRS2002

Investigation of Error Patterns in Geographical Databases

The objective of the research conducted in this project is to develop a methodology to investigate the accuracy of Airport Safety Modeling Data (ASMD) using statistical, visualization, and Artificial Neural Network (ANN) techniques. Such a methodology can contribute to answering the following research questions: Over a representative sampling of ASMD databases, can statistical error analysis techniques be accurately learned and replicated by ANN modeling techniques? This representative ASMD sample should include numerous airports and a variety of terrain characterizations. Is it possible to identify and automate the recognition of patterns of error related to geographical features? Do such patterns of error relate to specific geographical features, such as elevation or terrain slope? Is it possible to combine the errors in small regions into an error prediction for a larger region? What are the data density reduction implications of this work? ASMD may be used as the source of terrain data for a synthetic visual system to be used in the cockpit of aircraft when visual reference to ground features is not possible during conditions of marginal weather or reduced visibility. In this research, United States Geologic Survey (USGS) digital elevation model (DEM) data has been selected as the benchmark. Artificial Neural Networks (ANNS) have been used and tested as alternate methods in place of the statistical methods in similar problems. They often perform better in pattern recognition, prediction and classification and categorization problems. Many studies show that when the data is complex and noisy, the accuracy of ANN models is generally higher than those of comparable traditional methods.

Dryer, David↗

NASA NTRS2016

Mineralogy, Provenance, and Diagenesis of a Potassic Basaltic Sandstone on Mars: CheMin X-Ray Diffraction of the Windjana Sample (Kimberley Area, Gale Crater)

The Windjana drill sample, a sandstone of the Dillinger member (Kimberley formation, Gale Crater, Mars), was analyzed by CheMin X-ray diffraction (XRD) in the MSL Curiosity rover. From Rietveld refinements of its XRD pattern, Windjana contains the following: sanidine (21% weight, approximately Or(sub 95)); augite (20%); magnetite (12%); pigeonite; olivine; plagioclase; amorphous and smectitic material (approximately 25%); and percent levels of others including ilmenite, fluorapatite, and bassanite. From mass balance on the Alpha Proton X-ray Spectrometer (APXS) chemical analysis, the amorphous material is Fe rich with nearly no other cations-like ferrihydrite. The Windjana sample shows little alteration and was likely cemented by its magnetite and ferrihydrite. From ChemCam Laser-Induced Breakdown Spectrometer (LIBS) chemical analyses, Windjana is representative of the Dillinger and Mount Remarkable members of the Kimberley formation. LIBS data suggest that the Kimberley sediments include at least three chemical components. The most K-rich targets have 5.6% K2O, approximately 1.8 times that of Windjana, implying a sediment component with greater than 40% sanidine, e.g., a trachyte. A second component is rich in mafic minerals, with little feldspar (like a shergottite). A third component is richer in plagioclase and in Na2O, and is likely to be basaltic. The K-rich sediment component is consistent with APXS and ChemCam observations of K-rich rocks elsewhere in Gale Crater. The source of this sediment component was likely volcanic. The presence of sediment from many igneous sources, in concert with Curiosity's identifications of other igneous materials (e.g.,mugearite), implies that the northern rim of Gale Crater exposes a diverse igneous complex, at least as diverse as that found in similar-age terranes on Earth.

Treiman, Allan H.↗

DOE OSTI2021

Manipulating meso-scale solvent structure from Pd nanoparticle deposits in deep eutectic solvents

Deep Eutectic Solvents (DESs) are complex solutions that present unique challenges compared to traditional electrolytes. Unlike most electrolytes and ionic liquids, DESs have delicate hydrogen bond networks that are responsible for their highly sensitive compositional dependence on the melting point. Prior work has demonstrated unique nanoscale structure both experimentally and theoretically that brings both challenges and opportunities to their adoption in traditional electrochemical processes. In this study, we use in-situ sample-rotated ultra-small angle X-ray scattering to resolve the near-interface solvent structure after electrodepositing Pd nanoparticles onto a glassy carbon electrode in choline chloride:urea and choline chloride:ethylene glycol DESs. Our results indicate that solvent structure can be observed on the meso-scale in the choline chloride:urea and choline chloride:ethylene glycol systems. Importantly, this extended solvent structure peaks at -0.5 V (vs. Ag/AgCl) and decreases slightly with higher overpotentials during Pd electrodeposition. Experimentally, the nature of this structure is more pronounced in the ethylene glycol system, as evidenced by both the X-ray scattering as well as the electrochemical impedance spectroscopy (EIS). Here, molecular dynamics simulations and dipolar orientation analysis reveal that chloride delocalization near the Pd interface and long-range interactions between the choline and each hydrogen bond donor are very different and qualitatively consistent with the experimental data. These results show how the long-range solvent-deposit interactions can be tuned by changing the hydrogen bond donor in the DES and the applied potential.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

DOE OSTI2020

Modeling thin layers of analytes on substrates for spectral analysis: use of solid/liquid n and k values to model reflectance spectra

Since solids are only sometimes seen en masse in a pure bulk form, and for liquids other than water almost never, a capability to model reflectance spectra from analytes deposited on various substrates would be highly advantageous. If available, the real, n ( ν ) , and imaginary, k ( ν ) , components of the complex refractive index, n n + i k , can be used to simulate infrared spectra, accounting for reflection, refraction, and absorption phenomena as a function of wavelength. We focus on using the Pacific Northwest National Laboratory (PNNL) derived n / k vectors for solid and liquid analytes deposited as thin layers on different types of substrates including conductors, such as aluminum, and inorganic dielectrics, such as glass. The model is an adaptation of the Monte Carlo ray trace modeling program, TracePro, extended through the use of its macrolanguage. The model is tested using thin films of organic liquids including silicone oil and no. 2 diesel fuel, as well as organic solids such as caffeine and acetaminophen on aluminum and glass. The predicted spectra for the solid films were compared to experimental hemispherical reflectance data measured using a Fourier transform spectrometer with an integrating sphere. The thickness of the calculated layer is a parameter for predicting the (transflectance) spectra and is obtained using the areal density measured from gravimetric methods to generate the thin-layer samples. Comparison of the calculated spectra with experimental hemispherical reflectance data shows excellent agreement, indicating promise for the use of measured n / k data to synthesize reference spectral data. In particular, accounting for the inhomogeneity of the deposits greatly improved the match with experimental data. Finally, the theoretical modeling shows that for thicker layers (ca. 20 to 100 μm) of typical organics possessing moderately strong k values, the longwave infrared features are often saturated and better spectral contrast is obtained from the overtone/combination bands in the shortwave infrared.

42 ENGINEERING↗

DOE OSTI2020

Retrospective on Recent DOE-Funded Studies Concerning the Extraction of Rare Earth Elements & Lithium from Geothermal Brines (Final Report)

Rare earth elements (REE) and lithium are non-toxic metals that are considered critical materials due to their use in electronics, magnets, batteries, and a wide variety of industrial processes important for the economy and military preparedness. Demand for REE and lithium is increasing and these critical materials are imported, so identifying and exploiting domestic sources of REE and lithium is a national priority. The U.S. Department of Energy (DOE) Geothermal Technologies Office (GTO) has been in the forefront of sponsoring research investigating the potential recovery of REE, lithium, and other critical minerals from geothermal brines. It has been proposed that the future of geothermal energy should include “hybrid systems” that combine electricity generation with other revenue-generating activities, such as recovery of valuable and critical minerals, including REE and lithium. Two recent GTO funding opportunities have focused on the recovery of REE and other valuable minerals from geothermal brines. The research supported by the GTO’s mineral recovery program is focused on three areas: resource characterization, technology for the extraction of REE, and technology for the extraction of lithium (Tables 1 and 2). This report is a retrospective study examining the outcome of GTO’s two recent mineral recovery programs (DE-FOA-0001016 in FY 2014 and DE-FOA-0001376 in FY 2016). In this report, the knowledge, technology, and techniques that were developed by researchers funded by GTO are summarized and discussed. Four projects were funded to assess the concentrations and amounts of REE found in geothermal brines and oil field produced waters. The GTO-funded studies compiled publically available data on REE concentrations from brines and produced water from all over the USA. In addition, new samples were collected and characterized from major geothermal and hydrocarbon basins in the Western USA. The studies examined the relationship between lithology and REE concentrations and developed models examining the influence of geology on REE concentrations in produced brines. It was determined that REE are frequently found at higher concentrations in oil field produced water than geothermal brines, but that some geothermal areas had significant REE resources. Significant reservoirs of REE were identified in the Western USA. In some cases, concentrations of REE were more than 1000 times the concentrations found in seawater. Collectively, these studies represent a comprehensive picture of REE resources associated with geothermal and hydrocarbon systems in the USA. The studies did not examine lithium resources, but in some cases, lithium concentration data was collected. Data from these studies are housed in the Geothermal Data Repository (GDR) and represent a significant information resource and it is recommended that these data be further analyzed in a future study. Eight projects were funded to develop new technology for REE extraction from geothermal fluids. These projects investigated sorption as an approach for removal and recovery of REE from geothermal brines. The projects investigated cutting-edge technology for selective sorption of ions from complex solutions, including the application of metal-organic frameworks and biosorbent proteins. The REE sorption studies tested different combinations of metal-binding ligands and solid supports. The most promising metal-binding ligands for REE included phosphonic acid, thiol, and carboxylic acid functional groups. Ligands were attached or incorporated into a wide variety of solid supports. In most cases, attachment was via covalent bonding to organic resins, polymers, or silica-based supports. Most of the REE projects were conducted at a low technology readiness level (TRL) and showed promise, but direct comparison between technologies was not possible based on the available information. It is recommended that testing and reporting be standardized to the extent possible to facilitate comparisons between technologies. Two projects were directed at novel lithium extraction technology. Both projects investigated the use of inorganic sorbents, including manganese oxides. One study also examined the use of metal- ion imprinted polymers as selective ion-exchange resins for the separation of lithium and manganese from brines. Both approaches showed promise for the selective extraction of lithium from brines, including potentially geothermal brines. Results from these GTO studies indicated that selective REE and lithium extraction is possible, but interference from co-occurring solutes, such as calcium, magnesium, or heavy metals, will interfere with process efficiency and negatively impact process economics. Techno-economic analysis conducted as part of the resource and technology studies suggest extraction of REE from geothermal brines is unlikely to be economically viable, especially since non-geothermal produced waters frequently have higher REE concentrations. It is recommended that benchmarks for techno-economic analysis be established to the extent possible for future studies, to facilitate direct comparison of various technologies. Based on the collective results of this program, it appears that hybrid geothermal power would benefit more from recovery of lithium and other metals, rather than REE. It is recommended that future studies be conducted at a higher- TRL and that sorbents be tested against actual geothermal fluid samples. Prior higher-TRL efforts to extract metals from geothermal brines should be further evaluated for lessons learned.

36 MATERIALS SCIENCE↗

NASA NTRS1994

Chemical transitions for interstellar C2 and CN in cloud envelopes

Observations were made of absorption from CH, C2, and CN toward moderately reddened stars in Sco, OB2, Ceo OB3, and Taurus/Auriga. For these directions, most of the reddening is associated with a single cloud complex, for example, the rho Ophiuchus molecular cloud, and as a result, the observations probe moderately dense material. When combined with avaliable data for nearby directions, the survey provides the basis for a comprehensive analysis of the chemistry for these species. The chemical transitions affecting C2 and CN in cloud envelopes were analyzed. The depth into a cloud at which a transition takes place was characterized by tau(sub uv), the grain optical depth at 1000 A. One transition at tau(sub uv) approx. = 2, which arises from, the conversion of C(+) into CO, affects the chemistries for both molecules because of the key role this ion plays. A second one involving production terms in the CN chemistry occurs at tau(sub uv) of approx. = 3; neutral reactions which C2 and CH is more important at larger values for tau(sub uv). The transition from photodissociation to chemical destruction takes place at tau(sub uv) approx. = 4.5 for C2 and CN. The observational data for stars in Sco OB2, Cep OB3, and Taurus/Auriga were studied with chemical rate equations containing the most important production and destruction mechanisms. Because the sample of stars in Sco OB2 includes sight lines with A(sub v) ranging from 1-4 mag, sight lines dominated by photochemistry could be analyzed separately from those controlled by gas-phase destruction. The analysis yielded values for two poorly known rate constants for reactions involved in the production of CN; the reactions are C2 + N yields CN + C and C(+) + NH yields all products. The other directions were analyzed with the inferred values. The predicted column densities for C2 and CN agree with the observed values to better than 50%, and in most instances 20%. When combining the estimates for density and temperature derived from chemical modeling and molecular excitation for a specific cloud, such as the rho Ophiuchus molecular cloud, the portion of the cloud envelope probed by C2 and CN absorption was found to be in pressure equilibrium.

Federman, S. R.↗

NASA NTRS2014

Development of an Autonomous, Dual Chamber Bioreactor for the Growth of 3-Dimensional Epithelial-Stromal Tissues in Microgravity

We are developing a novel, autonomous bioreactor that can provide for the growth and maintenance in microgravity of 3‐D organotypic epithelial‐stromal cultures that require an air‐liquid interface. These complex 3‐D tissue models accurately represent the morphological features, differentiation markers, and growth characteristics observed in normal human epithelial tissues, including the skin, esophagus, lung, breast, pancreas, and colon. However, because of their precise and complex culture requirements, including that of an air‐liquid interface, these 3‐D models have yet to be utilized for life sciences research aboard the International Space Station. The development of a bioreactor for these cultures will provide the capability to perform biological research on the ISS using these realistic, tissue‐like human epithelial‐stromal cell models and will contribute significantly to advances in fundamental space biology research on questions regarding microgravity effects on normal tissue development, aging, cancer, and other disease processes. It will also allow for the study of how combined stressors, such as microgravity with radiation and nutritional deficiencies, affect multiple biological processes and will provide a platform for conducting countermeasure investigations on the ISS without the use of animal models. The technology will be autonomous and consist of a cell culture chamber that provides for air‐liquid, liquid‐liquid, and liquid‐air exchanges within the chambers while maintaining the growth and development of the biological samples. The bioreactor will support multiple tissue types and its modular design will provide for incorporation of add‐on capabilities such as microfluidics drug delivery, media sampling, and in situ biomarker analysis. Preliminary flight testing of the hardware will be conducted on a parabolic platform through NASA's Flight Opportunities Program.

Patel, Zarana S.↗

DOE OSTI2018

Thermodynamics of Reactions Affected by Medium Reorganization

We present a thermodynamic analysis of the activation barrier for reactions which can be monitored through the difference in the energies of reactants and products defined as the reaction coordinate (electron and atom transfer, enzyme catalysis, etc). The free-energy surfaces along the reaction coordinate are separated into the enthalpy and entropy surfaces. For the Gaussian statistics of the reaction coordinate, the free-energy surfaces are parabolas, and the entropy surface is an inverted parabola. Its maximum coincides with the transition state for reactions with zero value of the reaction free energy. Maximum entropic depression of the activation barrier, anticipated by the concept of transition-state ensembles, can be achieved for such reactions. From Onsager’s reversibility, the entropy of equilibrium fluctuations encodes the entropic component of the activation barrier. The reorganization entropy thus becomes the critical parameter of the theory reducing the problem of activation entropy to the problem of reorganization entropy. Standard solvation theories do not provide reorganization entropy sufficient for the barrier depression. Complex media, characterized by many relaxation processes, need to be involved and proteins provide several routes for achieving large entropic effects related to incomplete (nonergodic) sampling of the complex energy landscape and active role of water in the reaction mechanism.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

DOE OSTI2018

Parametric Sensitivity and Uncertainty Quantification in the Version 1 of E3SM Atmosphere Model Based on Short Perturbed Parameter Ensemble Simulations

Abstract The atmospheric component of Energy Exascale Earth System Model version 1 has included many new features in the physics parameterizations compared to its predecessors. Potential complex nonlinear interactions among the new features create a significant challenge for understanding the model behaviors and parameter tuning. Using the one‐at‐a‐time method, the benefit of tuning one parameter may offset the benefit of tuning another parameter, or improvement in one target variable may lead to degradation in another target variable. To better understand the Energy Exascale Earth System Model version 1 model behaviors and physics, we conducted a large number of short simulations (three days) in which 18 parameters carefully selected from parameterizations of deep convection, shallow convection, and cloud macrophysics and microphysics were perturbed simultaneously using the Latin hypercube sampling method. From the perturbed parameter ensemble simulations and use of different skill score functions, we identified the most sensitive parameters, quantified how the model responds to changes of the parameters for both global mean and spatial distribution, and estimated the maximum likelihood of model parameter space for a number of important fidelity metrics. Comparison of the parametric sensitivity using simulations of two different lengths suggests that perturbed parameter ensemble using short simulations has some bearing on understanding parametric sensitivity of longer simulations. Results from this analysis provide a more comprehensive picture of the Energy Exascale Earth System Model version 1 behavior. The difficulty in reducing biases in multiple variables simultaneously highlights the need of characterizing model structural uncertainty (so‐called embedded errors) to inform future development efforts.

54 ENVIRONMENTAL SCIENCES↗

DOE OSTI2022

Tritium Transport Modeling at the Pore Scale in Ceramic Breeder Materials Using TMAP8

Fusion reactors depend on the blanket material to breed and release tritium at the same rate or faster than it is consumed by the fusion reaction. Cellular ceramic breeders (CCBs) are dense materials that can maintain a high tritium breeding ratio while promoting tritium release because of highly connected pores. Assessing the tritium breeding capabilities of these materials requires a combination of extensive experimental and modeling efforts. In this work, we develop and calibrate a multiphysics model of tritium transport. This novel model accounts for ceramic and pore diffusion, trapping and detrapping, and several surface reactions at the pore surface. We perform a sensitivity analysis and calibrate the model by comparing its predictions against experimental measurements of deuterium absorption. The calibrated model is then used to model tritium absorption in samples with different pore microstructures to investigate the effect of pore interconnectivity on tritium absorption. The model is part of the development of the multiscale, multiphysics framework for tritium transport [i.e., the Tritium Migration Analysis Program (TMAP8)], which is itself built on top of the finite-element multiphysics framework multiphysics object-oriented simulation environment (MOOSE). This study demonstrates some of TMAP8’s capabilities and is the first step toward assessing the tritium breeding capabilities of ceramic breeder material designs.

70 PLASMA PHYSICS AND FUSION TECHNOLOGY↗

DOE OSTI2020

Measurement Error and Resolution in Quantitative Stable Isotope Probing: Implications for Experimental Design

Quantitative stable isotope probing (qSIP) estimates isotope tracer incorporation into DNA of individual microbes and can link microbial biodiversity and biogeochemistry in complex communities. As with any quantitative estimation technique, qSIP involves measurement error, and a fuller understanding of error, precision, and statistical power benefits qSIP experimental design and data interpretation. We used several qSIP data sets—from soil and seawater microbiomes—to evaluate how variance in isotope incorporation estimates depends on organism abundance and resolution of the density fractionation scheme. We assessed statistical power for replicated qSIP studies, plus sensitivity and specificity for unreplicated designs. As a taxon’s abundance increases, the variance of its weighted mean density declines. Nine fractions appear to be a reasonable trade-off between cost and precision for most qSIP applications. Increasing the number of density fractions beyond that reduces variance, although the magnitude of this benefit declines with additional fractions. Our analysis suggests that, if a taxon has an isotope enrichment of 10 atom% excess, there is a 60% chance that this will be detected as significantly different from zero (with alpha 0.1). With five replicates, isotope enrichment of 5 atom% could be detected with power (0.6) and alpha (0.1). Finally, we illustrate the importance of internal standards, which can help to calibrate per sample conversions of %GC to mean weighted density. These results should benefit researchers designing future SIP experiments and provide a useful reference for metagenomic SIP applications where both financial and computational limitations constrain experimental scope.

59 BASIC BIOLOGICAL SCIENCES↗

DOE OSTI2020

Non-destructive simulation of node defects in additively manufactured lattice structures

Additive Manufacturing (AM), commonly referred to as 3D printing, offers the ability to not only fabricate geometrically complex lattice structures but parts in which lattice topologies in-fill volumes bounded by complex surface geometries. However, current AM processes produce defects on the strut and node elements which make up the lattice structure. This creates an inherent difference between the as-designed and as-fabricated geometries, which negatively affects predictions (via numerical simulation) of the lattice’s mechanical performance. Although experimental and numerical analysis of an AM lattice’s bulk structure, unit cell and struts have been performed, there exists almost no research data on the mechanical response of the individual as-manufactured lattice node elements. Here we propose a methodology that, for the first time, allows non-destructive quantification of the mechanical response of node elements within an as-manufactured lattice structure. A custom-developed tool is used to extract and classify each individual node geometry from micro-computed tomography scans of an AM fabricated lattice. Voxel-based finite element meshes are generated for numerical simulation and the mechanical response distribution is compared to that of the idealised computer-aided design model. The method demonstrates compatibility with Uncertainty Quantification methods that provide opportunities for efficient prediction of a population of nodal responses from sampled data. Overall, the non-destructive and automated nature of the node extraction and response evaluation is promising for its application in qualification and certification of additively manufactured lattice structures.

36 MATERIALS SCIENCE↗

DOE OSTI2022

Position-specific carbon isotope analysis of serine by gas chromatography/Orbitrap mass spectrometry, and an application to plant metabolism

Position-specific 13 C/ 12 C ratios within amino acids remain largely unexplored in environmental samples due to methodological limitations. We hypothesized that natural-abundance isotope patterns in serine may serve as a proxy for plant metabolic fluxes including photorespiration. Here we describe an Orbitrap method optimized for the position-specific carbon isotope analysis of serine to test our hypothesis and discuss the generalizability of this method to other amino acids. Position-specific carbon isotope ratios of serine were measured using a Thermo Scientific™ Q Exactive™ GC Orbitrap™. Amino acids were hydrolyzed from Arabidopsis biomass, purified from potential matrix interferences, and derivatized alongside standards. Derivatized serine (N,O-bis(trifluoroacetyl)methyl ester) was isolated using gas chromatography, trapped in a reservoir, and purged into the electron ionization source over tens of minutes, producing fragment ions containing different combinations of atoms from the serine-derivative molecule. The 13 C/ 12 C ratios of fragments with monoisotopic masses of 110.0217, 138.0166, and 165.0037 Da were monitored in the mass analyzer and used to calculate position-specific δ 13 C values relative to a working standard. This methodology constrains position-specific δ 13 C values for nanomole amounts of serine isolated from chemically complex mixtures. The δ 13 C values of fragment ions of serine were characterized with ≤1‰ precisions, leading to propagated standard errors of 0.7–5‰ for each carbon position. Position-specific δ 13 C values differed by up to ca 28 ± 5‰ between serine molecules hydrolyzed from plants grown under contrasting pCO 2 , selected to promote different fluxes through photosynthesis and photorespiration. The method was validated using pure serine standards characterized offline. Here this study presents the first Orbitrap-based measurements of natural-abundance, position-specific carbon isotope variation in an amino acid isolated from a biological matrix. We present a method for the precise characterization of isotope ratios in serine and propose applications probing metabolism in plants. We discuss the potential for extending these approaches to other amino acids, paving the way for novel applications.

59 BASIC BIOLOGICAL SCIENCES↗

DOE OSTI2026

Surface Reconstruction in Hydrated Amphiphilic Block Copolymer Thin Films Probed by Fluid Cell Atomic Force Microscopy

In many thin film materials, nuanced interplays of interfacial energies control the surface morphology and rearrangement. This work evaluates polymer−solvent interactions and solvent-driven surface reconstructions via ex situ and in situ fluid cell Atomic Force Microscopy (fc-AFM) analysis of amphiphilic block copolymer (BCP) thin films upon exposure to deionized (DI) water. We examine the differences in surface morphology, whole-film swelling, and force response in thin films of polystyrene-block-poly(ethylene oxide) (PS-b-PEO) and polystyrene- block-poly[(allyl glycidyl ether)-co-(ethylene oxide)] (PS-b- P[AGE-co-EO]) processed into standing-up cylinder morphologies perpendicular to a silicon substrate (⊥C). Using Amplitude Modulation AFM (AM-AFM) and Amplitude-Phase Distance (APD) force spectroscopy, this work probes the mechanoresponsive nature of the dynamic surface layers of these films, unveiling surface layer stratification and surface chain rearrangement via minimal tip−sample stimulation. To help rationalize the observed reconfigurations, the energetic driving forces were estimated using the harmonic mean approximations of interfacial energies. Given the nonionizable nature of the minority P(AGE-co-EO) block and the energetic driving forces for chain mobility, this work shows how the elimination of unfavorable PS−water interfaces drives chain rearrangement and coverage of the PS surface by chains of the hydrophilic block. This work highlights considerations for increasing the heterogeneity and complexity of BCP thin films via random blocks and how those changes to local interfacial energies may drive larger scale film morphology reconstructions, with broader implications for tuning interface hydrophilicity.

Copolymers↗

DOE OSTI2019

Fast response of fungal and prokaryotic communities to climate change manipulation in two contrasting tundra soils

Climate models predict substantial changes in temperature and precipitation patterns across Arctic regions, including increased winter precipitation as snow in the near future. Soil microorganisms are considered key players in organic matter decomposition and regulation of biogeochemical cycles. However, current knowledge regarding their response to future climate changes is limited. Here, we explore the short-term effect of increased snow cover on soil fungal, bacterial and archaeal communities in two tundra sites with contrasting water regimes in Greenland. In order to assess seasonal variation of microbial communities, we collected soil samples four times during the plant-growing season. The analysis revealed that soil microbial communities from two tundra sites differed from each other due to contrasting soil chemical properties. Fungal communities showed higher richness at the dry site whereas richness of prokaryotes was higher at the wet tundra site. We demonstrated that fungal and bacterial communities at both sites were significantly affected by short-term increased snow cover manipulation. Our results showed that fungal community composition was more affected by deeper snow cover compared to prokaryotes. The fungal communities showed changes in both taxonomic and ecological groups in response to climate manipulation. However, the changes were not pronounced at all sampling times which points to the need of multiple sampling in ecosystems where environmental factors show seasonal variation. Further, we showed that effects of increased snow cover were manifested after snow had melted. We demonstrated rapid response of soil fungal and bacterial communities to short-term climate manipulation simulating increased winter precipitation at two tundra sites. In particular, we provide evidence that fungal community composition was more affected by increased snow cover compared to prokaryotes indicating fast adaptability to changing environmental conditions. Since fungi are considered the main decomposers of complex organic matter in terrestrial ecosystems, the stronger response of fungal communities may have implications for organic matter turnover in tundra soils under future climate.

54 ENVIRONMENTAL SCIENCES↗

NASA NTRS2012

Optical and Scanning Electron Microscopy of the Materials International Space Station Experiment (MISSE) Spacecraft Silicone Experiment

Under a microscope, atomic oxygen (AO) exposed silicone surfaces are crazed and seen as "islands" separated by numerous crack lines, much analogous to mud-tile cracks. This research characterized and compared the degree of AO degradation of silicones by analyzing optical microscope images of samples exposed to low Earth orbit (LEO) AO as part of the Spacecraft Silicone Experiment. The Spacecraft Silicone Experiment consisted of eight DC 93-500 silicone samples exposed to eight different AO fluence levels (ranged from 1.46 to 8.43 10(exp 21) atoms/sq cm) during two different Materials International Space Station Experiment (MISSE) missions. Image analysis software was used to analyze images taken using a digital camera. To describe the morphological degradation of each AO exposed flight sample, three different parameters were selected and estimated: (1) average area of islands was determined and found to be in the 1000 to 3100 sq mm range; (2) total length of crack lines per unit area of the sample surface were determined and found to be in the range of 27 to 59 mm of crack length per sq mm of sample surface; and (3) the fraction of sample surface area that is occupied by crack lines was determined and found to be in the 25 to 56 percent range. In addition, average crack width can be estimated from crack length and crack area measurements and was calculated to be about 10 mm. Among the parameters studied, the fraction of sample surface area that is occupied by crack lines is believed to be most useful in characterizing the degree of silicone conversion to silicates by AO because its value steadily increases with increasing fluence over the entire fluence range. A series of SEM images from the eight samples exposed to different AO fluences suggest a complex sequence of surface stress due to surface shrinkage and crack formation, followed by re-distribution of stress and shrinking rate on the sample surface. Energy dispersive spectra (EDS) indicated that upon AO exposure, carbon content on the surface decreased relatively quickly at the beginning, to 32 percent of the pristine value for the least exposed sample in this set of experiments (1.46 10(exp 21) atoms/sq cm), but then decreased slowly, to 22 percent of the pristine value for the most exposed sample in this set of experiment (8.43 10(exp 21) atoms/sq cm). The oxygen content appears to increase at a slower rate. The least and most AO exposed samples were, respectively, 52 and 150 percent above the pristine values. The silicone samples with the greater AO exposure (7.75 10(exp 21) atoms/sq cm and higher) appear to have a surface layer which contains SiO2 with perhaps small amounts of unreacted silicone, CO and CO2 sealed inside.

Hung, Ching-cheh↗