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NASA NTRS2005

Lunar and Planetary Science XXXVI, Part 19

The topics include: 1) The abundances of Iron-60 in Pyroxene Chondrules from Unequilibrated Ordinary Chondrites; 2) LL-Ordinary Chondrite Impact on the Moon: Results from the 3.9 Ga Impact Melt at the Landing Site of Appolo 17; 3) Evaluation of Chemical Methods for Projectile Identification in Terrestrial and Lunar Impactites; 4) Impact Cratering Experiments in Microgravity Environment; 5) New Achondrites with High-Calcium Pyroxene and Its implication for Igneous Differentiation of Asteroids; 6) Climate History of the Polar Regions of Mars Deduced form Geologic Mapping Results; 7) The crater Production Function for Mars: A-2 Cumulative Power-Law Slope for Pristine Craters Greater than 5 km in Diameter Based on Crater Distribution for Northern Plains Materials; 8) High Resolution Al-26 Chronology: Resolved Time Interval Between Rim and Interior of a Highly Fractionated Compact Type a CAI from Efremovka; 9) Assessing Aqueous Alteration on Mars Using Global Distributions of K and Th; 10) FeNi Metal Grains in LaPaz Mare Basalt Meteorites and Appolo 12 Basalts; 11) Unique Properties of Lunar Soil for In Situ Resource Utilization on the Moon; 12) U-Pb Systematics of Phosphates in Nakhlites; 13) Measurements of Sound Speed in Granular Materials Simulated Regolith; 14) The Effects of Oxygen, Sulphur and Silicon on the Dihedral Angles Between Fe-rich Liquid Metal and Olivine, Ringwoodite and Silicate Perovskite: Implications for Planetary Core Formation; 15) Seismic Shaking Removal of Craters 0.2-0.5 km in Diameter on Asteroid 433 Eros; 16) Focused Ion Beam Microscoopy of ALH84001 Carbonate Disks; 17) Simulating Micro-Gravity in the Laboratory; 18) Mars Atmospheric Sample Return Instrument Development; 19) Combined Remote LIBS and Raman Spectroscopy Measurements; 20) Unusual Radar Backscatter Properties Along the Northern Rim of Imbrium Basin; 21) The Mars Express/NASAS Project at JPL; 22) The Geology of the Viking 2 Lander Site Revisited; 23) An Impact Genesis for Loki Patera? 24) Mars Polar Cap Edges Tracked over 3 Full Mars Years; 25) Elemental Abundance in Presolar SiC: Comparing Grains Separated by Acid Residue and Gently Separation Procedures; 26) First Results from the Descent Imager/Spectral Radiometer (DISR) Experiment on the Huygens Entry Probe of Titan; 27) Minor Element Behavior of Pallasite Olivine: Understanding Pallasite Thermal History and Chronology; 28) Canonical Anorthite in a Grosnaja Forsterite-bearing CAI; 29) Experimental Evidence for Condensation of 'Astrophysical' Carbonate; 30) Distribution and Classification of Multiple Coronae on Venus; 31) Recognition of Rayed Craters on Mars in THEMIS Thermal Infrared Imagery: Implications for Martian Meteorite Source Regions; 32) Geochemical Modeling of Evaporites on Mars: Insight from Meridiani Planum; 33) Hadean Crustal Processes Revealed from Oxygen Isotopes and U-Th-Pb Depth Profiling of Pre-4.0 Ga Detrital Zircons from Western Australia; 34) On Modeling the Seepage of Water into the Martian Subsurface; 35) Martial Gullies and Groundwater: A Series of Unfortunate Exceptions; 36) Olivine and Carbonate Globules in ALH84001: A Terrestrial Analog, and Implications for Water on Mars; 37) A Reevaluation of Mass Movements Within the Valles Marineris Region of Mars Using MOLA and MOC Data; 38) Evidence of Hydrated 109P/Swift-Tuttle Meteoroids from Meteor Spectroscopy; 39) Cr-54 Anomalies in the Solar System: Their Extent and Origin; 40) Reevaluation of the Mn-53-Cr-53 Systematic in the Basaltic Achondrites; 41) Effective Liquid Metal-Silicate Mixing Upon Shock by Power-Law Droplet Size Scaling in Richtmyer-Meshkov Like Perturbations; 42) Post-Impact Deformation of Impact Craters: Towards a Better Understanding Through the Study of Mjolnir Crater; 43) Cutting Silica Aerogel for Particle Extraction; 44) Liquid Hydrocarbons on Titan's Surface? How Cassini ISS Observations Fit into the Story (So Far); and 45) Mesoscale Simulations of Polar Circulations: Late Spring to Late Summe

Source record↗
NASA NTRS2013

Medicine Delivery Device with Integrated Sterilization and Detection

Sterile delivery devices can be created by integrating a medicine delivery instrument with surfaces that are coated with germicidal and anti-fouling material. This requires that a large-surface-area template be developed within a constrained volume to ensure good contact between the delivered medicine and the germicidal material. Both of these can be integrated using JPL-developed silicon nanotip or cryo-etch black silicon technologies with atomic layer deposition (ALD) coating of specific germicidal layers. The application of semiconductor processing techniques and technologies to the problems of fluid manipulation and delivery has enabled the integration of chemical, electrical, and mechanical manipulation of samples all within a single microfluidic device. This approach has been successfully applied at JPL to the automated processing, detection, and analysis of minute quantities (parts per trillion level) of biomaterials to develop instruments for in situ exploration or extraterrestrial bodies. The same nanofabrication techniques that are used to produce a microfluidics device are also capable of synthesizing extremely high-surface-area templates in precise locations, and coating those surfaces with conformal films to manipulate their surface properties. This methodology has been successfully applied at JPL to produce patterned and coated silicon nanotips (also known as black silicon) to manipulate the hydrophilicity of surfaces to direct the spreading of fluids in microdevices. JPL's ALD technique is an ideal method to produce the highly conformal coatings required for this type of application. Certain materials, such as TiO2, have germicidal and anti-fouling properties when they are illuminated with UV light. The proposed delivery device contacts medicine with this high-surface-area black silicon surface coated with a thin-film germicidal deposited conformally with ALD. The coating can also be illuminated with ultraviolet light for the purpose of sterilization or identification of the medicine itself. This constrained volume that is located immediately prior to delivery into a patient, ensures that the medicine delivery device is inherently sterile. An additional benefit to integrating a high-surface-area template within the fluid channel of a medicine delivery device is that one can envision a number of different functional coatings that could facilitate the capture and analysis of either microbial contaminants or the medicine itself. For example, one could attach antibodies or some other binding agent with a specific affinity to the silicon nanotip template. Once a target molecule or microbe is bound to the high-surface- area template, one could use an optical analytical technique such as fluorescence or adsorption to determine the identity and potentially the concentration of the species of interest. By illuminating the bound species from the back, it may also be possible to probe only the molecules with an evanescent wave, making detection of the species from the front side of the device much simpler.

Shearn, Michael J.↗
NASA NTRS1998

New AFM Techniques for Investigating Molecular Growth Mechanisms of Protein Crystals

Atomic Force Microscopy (AFM) has emerged as a powerful technique for investigating protein crystal growth. Earlier AFM studies were among the first to demonstrate that these crystals grew by dislocation and 2D nucleation growth mechanisms [1]. These investigations were restricted to the micron range where only surface features, such as dislocation hillocks and 2D islands are visible. Most AFM instruments can scan at higher resolutions and have the potential to resolve individual protein molecules at nanometer ranges. Such scans are essential for determining the molecular packing arrangements on crystal faces and for probing the growth process at the molecular level. However, at this resolution the AFM tip influences the image produced, with the resulting image being a convolution of the tip shape and the surface morphology [2]. In most studies this problem is resolved by deconvoluting the image to obtain the true surface morphology. Although deconvolution routines work reasonably well for simple one- dimensional shapes, for complex surfaces this approach does not produce accurate results. In this study we devised a new approach which takes advantage of the precise molecular order of crystal surfaces, combined with the knowledge of individual molecular shapes from the crystallographic data of the protein and the AFM tip shape. This information is used to construct expected theoretical AFM images by convoluting the tip shape with the constructed crystal surface shape for a given surface packing arrangement. By comparing the images from actual AFM scans with the constructed ones for different possible surface packing arrangements, the correct packing arrangement can be conclusively determined. This approach was used in this study to determine the correct one from two possible packing arrangements on (I 10) faces of tetragonal lysozyme crystals. Another novel AFM technique was also devised to measure the dimension of individual growth units of the crystal faces. Measuring these units was not attempted before and most studies have assumed that the growth unit consisted of individual protein molecules. The linescan mode of AFM instruments allows the crystal surface to be scanned along a single line. By scanning across a growth step an image showing the motion of the step is obtained. Normally such an image shows a straight line for continuous and constant step velocity. In this study by increasing the scan rate and by decreasing the step velocity (by decreasing the supersaturation), we were able to capture images of individual growth events, shown by jump discontinuities in the step line. By suitable integration of the image the growth unit dimension in the scanned direction can be obtained. Since multiple units can be involved in the growth process it is necessary to collect a statistically relevant sample before drawing conclusions about the growth mechanism. This technique was successfully employed to obtain the dimensions of growth units for the (110) face, showing that they consisted of various aggregates corresponding to the 43 helices in the crystal structure.

Li, Huayu↗
DOE OSTI2021

Deployment of salt sample extraction system at an engineering-scale electrorefiner

The goal of the salt sampling program at Argonne is to develop and deploy automated molten salt sampling approaches for interfacing relevant unit operations with salt analysis to improve the timeliness of sampling-based accountancy measurements. Two technologies under development in support of this goal are a vacuum sampling loop module and a high-throughput pneumatic sample generator module. Compared to traditional point sampling approaches (i.e., dip probes), the vacuum sampling loop facilitates the collection of a larger cross-section of the bulk salt in order to collect more representative samples. The vacuum sampling approach also eliminates the risk of dross contamination of samples and avoids the use of moving parts in the salt. The pneumatic sample generator module is used to facilitate high-throughput sample analysis to improve the measurement precision of any given analytical technique by averaging out random sampling and measurement errors. In FY21, two methods for integrating these two modules were tested including direct fluidic coupling and coupling using a solid salt transfer mechanism. Solid salt transfer was ultimately selected over fluidic coupling, primarily to enable the transport of samples over longer distances to support automated at-line integration with high-precision techniques (such as microcalorimetry) that cannot withstand the conditions near an electrorefining process. To facilitate rapid solid salt coupling, new mechanisms were developed for rapidly charging and discharging salt sample tubes at the vacuum sampling loop and pneumatic sample generator modules, respectively. While the charging mechanism will be deployed in FY22, the discharge mechanism was tested in FY21 and is described here. The solid salt tube transfer method was deployed at one of Argonne’s engineering-scale electrorefiners to implement at-line high-throughput pneumatic micro-sample generation capabilities. The approach was used to generate precise uranium- and lanthanide-bearing electrorefiner micro-samples with the specific dimensions requested by researchers at Los Alamos National Laboratory for use in testing their novel microcalorimeter x-ray techniques. The solid salt transfer mechanism proved not only to be an effective means of integrating the precision sample generator with vacuum sampling, but also improved the performance of the sampler generator. To discharge salt from the sample tubes at the sampler generator, tube segments were inserted directly into the sample generator’s Helmholtz chamber and pressure pulse actuations were used to generate precision molten salt samples directly from the tube segments. The direct insertion of sample tubes into the sample generator enabled rapid loading of the salt and prevented salt from contacting most of the interior surfaces of the sample generator, which eliminated cross-contamination between runs. The vacuum sampling-loop tube charging mechanism will support high-throughput tube sampling operations by employing a dynamic vacuum filling process to fill short charge tubes that are configured to be rapidly connected and disconnected from the loop. The dynamic vacuum sampling operation will be automated, and sample tube handling can be executed with simple overhead actuation. Because the modular sampling approach described here eliminates the need for new high-radiation sample handling capabilities, salt-wetted seals, salt-wetted moving parts, and heated transfer lines outside the electrorefiner, it will address most of the remaining technical challenges for the at-line deployment of high-precision analytical techniques which will enable significant reductions in the time delay for sampling-based high-precision accountancy measurements.

42 ENGINEERING↗
NASA NTRS2016

Precision Oxygen Isotope Measurements of Two C-Rich Hydrated Interplanetary Dust Particles

Introduction: Chondritic-smooth IDPs (Interplanetary Dust Particles) are low porosity objects whose mineralogy is dominated by aqueous alteration products such as Mg-rich phyllosilicates (smectite and serpentine group) and Mg-Fe carbonate minerals. Their hydrated mineralogy combined with low atmospheric entry velocities have been used to infer an origin largely from asteroidal sources. Spectroscopic studies show that the types and abundance of organic matter in CS IDPs is similar to that in CP IDPs. Although CS IDPs show broad similarities to primitive carbonaceous chondrites, only a few particles have been directly linked to specific meteorite groups such as CM and CI chondrites based on the presence of diagnostic minerals. Many CS IDPs however, have carbon contents that greatly exceed that of known meteorite groups suggesting that they either may derive from comets or represent samples of more primitive parent bodies than do meteorites. It is now recognized that many large, dark primitive asteroids in the outer main belt, as well as some trans-Neptunian objects, show spectroscopic evidence for aqueous alteration products on their surfaces. Some CS IDPs exhibit large bulk D enrichments similar to those observed in the cometary CP IDPs. While hydrated minerals in comets have not been unambiguously identified to date, the presence of the smectite group mineral nontronite has been inferred from infrared spectra obtained from the ejecta from comet 9P/Tempel 1 during the Deep Impact mission. Recent observations of low temperature sulfide minerals in Stardust mission samples suggest that limited aqueous activity occurred on comet Wild-2. All of these observations, taken together, suggest that the high-carbon hydrated IDPs are abundant and important samples of primitive solar system objects not represented in meteorite collections. Oxygen isotopic compositions of chondrites reflect mixing between a 16O-rich reservoir and a 17O,18O-rich reservoir produced via mass-independent fractionation. The composition of the 16O-rich reservoir is well constrained but material representing the 17O,18O-rich end-member is rare. Self-shielding models predict that cometary water, presumed to represent this reservoir, should be enriched in 17O and 18O by greater than 200 per mille. The high-carbon hydrated IDPs may be among the best materials available to search for preserved "cometary" H2O signatures. In order to better understand the origin and evolution of these particles, we have obtained 10 hydrated interplanetary dust particles for coordinated mineralogical, isotopic and organic analyses. We have previously reported the results of mineralogical and O isotopic measurements of two hydrated IDPs; here we present results of O isotopic measurements of three additional IDPs. Samples and Methods: Three interplanetary dust particles (L2079C35, L2083D46 and L2083E46) were embedded in S and partially ultramicrotomed into approximately 70 nanometer sections for analysis via transmission electron microscopy (TEM). The remainders of the unsliced particles were removed from S and pressed into high purity Au foil that was cleaned with HF acid and annealed at 800 degrees Centigrade. The pressed IDPs were analyzed via electron microprobe analysis (EPMA) for quantitative bulk chemical analysis. After EPMA analysis, the IDPs were subjected to precision O isotope analysis with the UCLA Cameca IMS-1270 ion probe. A 20 kiloelectronvolt, 0.5 nanoangstrom Cs+ primary beam of approximately 15 micrometers diameter was used for each measurement. Small particles of San Carlos olivine and Burma spinel were pressed into the Au foil for use as standards to correct for instrumental mass fractionation. The detection system was configured for multicollection, with 16O measured on a Faraday cup, and 17O and 18O measured on electron multipliers (EMs). Individual analyses consisted of 15 cycles of 10 seconds per cycle. Additionally, two microtome thin sections were measured for H isotopic compositions with the JSC NanoSIMS 50L ion probe. An 8 picoangstrom, 16 kiloelectronvolt Cs plus primary beam was used. Measurements consisted of H, C, 12C, 16O, and 18O collected with EMs in multicollection. Terrestrial biotite and kerogen were used for isotopic standards. A significant challenge in O isotope measurement of hydrated minerals is the interference from 16OH at mass 17O. We ensured that the 17O and 16OH peaks were fully resolved by using a mass resolution of greater than 7000 and by careful analyses of San Carlos olivine, Burma spinel and chlorite hydrated mineral standards. The hydride was further suppressed with a cold finger attached to an LN2 dewar to trap volatiles in the sample chamber. All sputtered ions were counted (i.e. presputtering was not used); after applying background, yield and deadtime corrections, we performed a change-point analysis on our data via R in order to determine when the sample reached sputtering equilibrium; data points collected prior to the change point were excluded. Change-point analysis was also used to determine whether the IDP had completely sputtered. Results: Mineralogy. IDPs C35 and E46 exhibited hydrated mineralogies, Fe-Ni sulfide grains, nanoglobules and occasional enstatite grains distributed throughout a fine-grained Mg-Fe saponite matrix. C35 also contained breunnerite (Mg,Fe)CO3; solar flare tracks were observed in enstatite, indicating minimal atmospheric entry heating. The mineralogy of D46 is dominated by a large FeS grain with a minor component of adhering silicate material. D46 was strongly heated during atmorpheric entry as evidenced by a well-developed magnetite rim. EPMA analyses show that both C35 and E46 have high carbon contents of 20 weight percentage (approximately 6X CI). D46 contains approximately 6 wt.weight percentage C. A significant amount of the carbon is present as carbon nanoglobules. Results: Hydrogen isotopes: Although the bulk delta D values of both sections of L2079C35 were within error of SMOW (minus 33 plus or minus 19 per mille, 1 plus or minus 14 per mille 1 sigma), several delta D-rich hotspots were also identified, reaching 2000 per mille. As shown in Fig. 1, these hotspots are clearly associated with discrete carbonaceous inclusions that are akin to nanoglobules found in many meteorites and other IDPs. Oxygen Isotopes. Results of the oxygen isotope measurements are shown in Figure 1. The oxygen isotope composition for L2079C35 was delta 18O equals plus11.6 plus or minus 1.9per mille, delta 17O equals plus 7.9 plus or minus 1.9per mille (2 standard errors). The oxygen isotope composition for L2083D46 was delta 18O equals minus 8.1 plus or minus 1.9 per mille, delta 17O equals minus 6.4 plus or minus 3.1 per mille (2 standard errors). The oxygen isotope composition for L2083E46 was delta 18O equals plus 12.0 plus or minus 1.9 per mille, delta 17O equals plus 9.2 plus or minus 2.0 per mille (2 standard errors). Discussion: Despite mineralogical similarities to highly aqueously altered carbonaceous chondrites, the hydrated IDPs we analyzed have oxygen isotopic compositions that are distinct from matrix materials in the CI, CM, and CR chondrites. The IDPs plot along the Young-Russell line, with delta 17O values for C35 and E46 suggestive of interaction with a 16O-poor reservoir. However, we have thus far not observed evidence of extreme 16O-poor reservoirs expected from self-shielding models and observed in Acfer 094 simplectite. The high carbon contents of the IDPs also set them apart from known meteoritic samples. The lack of atmospheric entry heating effects are consistent with low encounter velocities and suggest either an asteroidal source, or a low inclination, low eccentricity cometary origin. Conclusions: The unusual oxygen isotopic compositions, high carbon contents, and the abundance of Drich nanoglobules, together, suggest that the high-carbon, hydrated IDPs are derived from a primitive source that is not yet represented in meteorite collections.

Snead, C. J.↗
NASA NTRS2007

Derivation and Application of a Global Albedo yielding an Optical Brightness To Physical Size Transformation Free of Systematic Errors

Orbital object data acquired via optical telescopes can play a crucial role in accurately defining the space environment. Radar systems probe the characteristics of small debris by measuring the reflected electromagnetic energy from an object of the same order of size as the wavelength of the radiation. This signal is affected by electrical conductivity of the bulk of the debris object, as well as its shape and orientation. Optical measurements use reflected solar radiation with wavelengths much smaller than the size of the objects. Just as with radar, the shape and orientation of an object are important, but we only need to consider the surface electrical properties of the debris material (i.e., the surface albedo), not the bulk electromagnetic properties. As a result, these two methods are complementary in that they measure somewhat independent physical properties to estimate the same thing, debris size. Short arc optical observations such as are typical of NASA's Liquid Mirror Telescope (LMT) give enough information to estimate an Assumed Circular Orbit (ACO) and an associated range. This information, combined with the apparent magnitude, can be used to estimate an "absolute" brightness (scaled to a fixed range and phase angle). This absolute magnitude is what is used to estimate debris size. However, the shape and surface albedo effects make the size estimates subject to systematic and random errors, such that it is impossible to ascertain the size of an individual object with any certainty. However, as has been shown with radar debris measurements, that does not preclude the ability to estimate the size distribution of a number of objects statistically. After systematic errors have been eliminated (range errors, phase function assumptions, photometry) there remains a random geometric albedo distribution that relates object size to absolute magnitude. Measurements by the LMT of a subset of tracked debris objects with sizes estimated from their radar cross sections indicate that the random variations in the albedo follow a log-normal distribution quite well. In addition, this distribution appears to be independent of object size over a considerable range in size. Note that this relation appears to hold for debris only, where the shapes and other properties are not primarily the result of human manufacture, but of random processes. With this information in hand, it now becomes possible to estimate the actual size distribution we are sampling from. We have identified two characteristics of the space debris population that make this process tractable and by extension have developed a methodology for performing the transformation.

Mulrooney, Dr. Mark K.↗
DOE OSTI2025

Probing Ice-Rule-Breaking Transition in Dy 2 Ti 2 O 7 Thin Film by Proximitized Transport and Magnetic Torque

While the spin-ice state of bulk pyrochlores such as Dy 2⁢ Ti 2 ⁢O 7 and Ho 2⁢ Ti 2 ⁢O 7 has been extensively studied in the past several decades due to its unique degenerate ground state and emergent monopole excitation, whether it survives in the thin-film form remains a mystery. The limited volume of the thin-film sample makes it challenging to study the intrinsic magnetic properties. Here, we synthesized 18-nm-thick Dy 2⁢ Ti 2 ⁢O 7 thin film on yttria-stabilized zirconia with 9.5 mol% Y 2 ⁢O 3 substrate and capped it by a thin conductive Bi 2 ⁢Ir 2 ⁢O 7 layer and performed the proximitized magnetoresistance measurements. Our Letter found that the ice-rule-breaking phase transition survives but with a modified effective nearest-neighbor interaction (𝐽 eff =1.054 K) and distorted Ising spin axes (𝜀 = +0.051) compared to the bulk crystal. Furthermore, the results are supported by the simultaneously measured capacitive torque magnetometry. Our Letter demonstrates that proximitized transport is an effective tool for thin films of insulating frustrated magnets.

Magnetic interactions↗
NASA NTRS2011

Demonstration of a Fiber Optic Regression Probe in a High-Temperature Flow

The capability to provide localized, real-time monitoring of material regression rates in various applications has the potential to provide a new stream of data for development testing of various components and systems, as well as serving as a monitoring tool in flight applications. These applications include, but are not limited to, the regression of a combusting solid fuel surface, the ablation of the throat in a chemical rocket or the heat shield of an aeroshell, and the monitoring of erosion in long-life plasma thrusters. The rate of regression in the first application is very fast, while the second and third are increasingly slower. A recent fundamental sensor development effort has led to a novel regression, erosion, and ablation sensor technology (REAST). The REAST sensor allows for measurement of real-time surface erosion rates at a discrete surface location. The sensor is optical, using two different, co-located fiber-optics to perform the regression measurement. The disparate optical transmission properties of the two fiber-optics makes it possible to measure the regression rate by monitoring the relative light attenuation through the fibers. As the fibers regress along with the parent material in which they are embedded, the relative light intensities through the two fibers changes, providing a measure of the regression rate. The optical nature of the system makes it relatively easy to use in a variety of harsh, high temperature environments, and it is also unaffected by the presence of electric and magnetic fields. In addition, the sensor could be used to perform optical spectroscopy on the light emitted by a process and collected by fibers, giving localized measurements of various properties. The capability to perform an in-situ measurement of material regression rates is useful in addressing a variety of physical issues in various applications. An in-situ measurement allows for real-time data regarding the erosion rates, providing a quick method for empirically anchoring any analysis geared towards lifetime qualification. Erosion rate data over an operating envelope could also be useful in the modeling detailed physical processes. The sensor has been embedded in many regressing media to demonstrate the capabilities in a number of regressing environments. In the present work, sensors were installed in the eroding/regressing throat region of a converging-diverging flow, with the working gas heated to high temperatures by means of a high-pressure arc discharge at steady-state discharge power levels up to 500 kW. The amount of regression observed in each material sample was quantified using a later profilometer, which was compared to the in-situ erosion measurements to demonstrate the efficacy of the measurement technique in very harsh, high-temperature environments.

Korman, Valentin↗
DOE OSTI2026

Pattern-enhanced Resonant Soft X-ray Scattering for Operando monitoring of electrochemical solid-liquid interfaces

Unveiling interfaces at sub-nanometer scales is essential for advancing the understanding of complex chemical transformations. However, characterizing solid-liquid interfaces with high dimensional sensitivity and temporal resolution remains challenging, due to their dynamic nature and inaccessibility by conventional probes. Here we present an approach, Pattern-enhanced Resonant Soft X-ray Scattering, to overcome the challenges. Rooted in a “sample-as-optics” philosophy, this technique utilizes precisely engineered line-grating nanopatterns to modulate near-field X-ray illumination, coherently enhancing scattering signals from the line-gratings. We implement the method using Ni line-grating nanopatterns in electrochemical water oxidation. The periodic nanostructures serve as diffractive optical elements to reveal the Ni oxidation gradients and structural dynamics at the electrode-electrolyte interfaces. Finite-element simulations corroborate the observed trends by modeling variations in compositions and structures during electrocatalysis. Through integrating advanced sample design with coherent wave nature of soft X-rays, our approach opens accessible pathways to operando exploring chemical evolution and sub-nanometer dimensional variations simultaneously in electrochemical systems. This non-destructive method is efficient and element-specific, making it valuable for probing chemical and dimensional dynamics with appropriate modeling.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2011

Montana Cropland Enrolled Farm Fields Carbon Sequestration Field Sampling, Measurement, Monitoring, and Verification: Application of Visible-Near Infrared Diffuse Reflectance Spectroscopy (VNIR) and Laser-induced Breakdown Spectroscopy (LIBS)

There is growing need for rapid, accurate, and inexpensive methods to measure, and verify soil organic carbon (SOC) change for national greenhouse gas accounting and the development of a soil carbon trading market. Laboratory based soil characterization typically requires significant soil processing, which is time and resource intensive. This severely limits application for large-region soil characterization. Thus, development of rapid and accurate methods for characterizing soils are needed to map soil properties for precision agriculture applications, improve regional and global soil carbon (C) stock and flux estimates and efficiently map sub-surface metal contamination, among others. The greatest gains for efficient soil characterization will come from collecting soil data in situ, thus minimizing soil sample transportation, processing, and lab-based measurement costs. Visible and near-infrared diffuse reflectance spectroscopy (VisNIR) and laser-induced breakdown spectroscopy (LIBS) are two complementary, yet fundamentally different spectroscopic techniques that have the potential to meet this need. These sensors have the potential to be mounted on a soil penetrometer and deployed for rapid soil profile characterization at field and landscape scales. Details of sensor interaction, efficient data management, and appropriate statistical analysis techniques for model calibrations are first needed. In situ or on-the-go VisNIR spectroscopy has been proposed as a rapid and inexpensive tool for intensively mapping soil texture and organic carbon (SOC). While lab-based VisNIR has been established as a viable technique for estimating various soil properties, few experiments have compared the predictive accuracy of on-the-go and lab-based VisNIR. Eight north central Montana wheat fields were intensively interrogated using on-the-go and lab-based VisNIR. Lab-based spectral data consistently provided more accurate predictions than on-the-go data. However, neither in situ nor lab-based spectroscopy yielded even semi-quantitative SOC predictions. There was little SOC variability to explain across the eight fields, and on-the-go VisNIR was not able to capture the subtle SOC variability in these Montana soils. With more variation in soil clay content compared to SOC, both lab and on-the-go VisNIR showed better explanatory power. There are several potential explanations for poor on-the-go predictive accuracy: soil heterogeneity, field moisture, consistent sample presentation, and a difference between the spatial support of on-the-go measurements and soil samples collected for laboratory analyses. Though the current configuration of a commercially available on-the-go VisNIR system allows for rapid field scanning, on-the-go soil processing (i.e. drying, crushing, and sieving) could improve soil carbon predictions. Laser-induced breakdown spectroscopy (LIBS) is an emerging elemental analysis technology with the potential to provide rapid, accurate and precise analysis of soil constituents, such as carbon, in situ across landscapes. The research team evaluated the accuracy of LIBS for measuring soil profile carbon in field-moist, intact soil cores simulating conditions that might be encountered by a probe-mounted LIBS instrument measuring soil profile carbon in situ. Over the course of three experiments, more than120 intact soil cores from eight north central Montana wheat fields and the Washington State University (WSU) Cook Agronomy Farm near Pullman, WA were interrogated with LIBS for rapid total carbon (TC), inorganic carbon (IC), and SOC determination. Partial least squares regression models were derived and independently validated at field- and regional scales. Researchers obtained the best LIBS validation predictions for IC followed by TC and SOC. Laser-induced breakdown spectroscopy is fundamentally an elemental analysis technique, yet LIBS PLS2 models appeared to discriminate IC from TC. Regression coefficients from initial models suggested a reliance upon stoichiometric relationships between carbon (247.8 nm) and other elements related to total and inorganic carbon in the soil matrix [Ca (210.2 nm, 211.3 nm, and 220.9 nm), Mg (279.55-280.4 nm, 285.26 nm), and Si (251.6 nm, 288.1 nm)]. Expanding the LIBS spectral range to capture emissions from a broader range of elements related to soil organic matter was explored using two spectrometer systems to improve SOC predictions. Results for increasing the spectral range of LIBS to the full 200-800 nm found modest gains in prediction accuracy for IC, but no gains for predicting TC or SOC. Poor SOC predictions are likely a function of (1) the lack of a consistent/definable molecular composition of SOC, (2) relatively little variation in SOC across field sites, and (3) inorganic carbon constituting the primary form of soil carbon, particularly for Montana soils.

54 ENVIRONMENTAL SCIENCES↗
DOE OSTI2010

Light absorption and electrical transport in Si:O alloys for photovoltaics

Thin films (100-500 nm) of the Si:O alloy have been systematically characterized in the optical absorption and electrical transport behavior, by varying the Si content from 43 up to 100 at. %. Magnetron sputtering or plasma enhanced chemical vapor deposition have been used for the Si:O alloy deposition, followed by annealing up to 1250 deg. C. Boron implantation (30 keV, 3-30x10{sup 14} B/cm{sup 2}) on selected samples was performed to vary the electrical sheet resistance measured by the four-point collinear probe method. Transmittance and reflectance spectra have been extracted and combined to estimate the absorption spectra and the optical band gap, by means of the Tauc analysis. Raman spectroscopy was also employed to follow the amorphous-crystalline (a-c) transition of the Si domains contained in the Si:O films. The optical absorption and the electrical transport of Si:O films can be continuously and independently modulated by acting on different parameters. The light absorption increases (by one decade) with the Si content in the 43-100 at. % range, determining an optical band gap which can be continuously modulated into the 2.6-1.6 eV range, respectively. The a-c phase transition in Si:O films, causing a significant reduction in the absorption coefficient, occurs at increasing temperatures (from 600 to 1100 deg. C) as the Si content decreases. The electrical resistivity of Si:O films can be varied among five decades, being essentially dominated by the number of Si grains and by the doping. Si:O alloys with Si content in the 60-90 at. % range (named oxygen rich silicon films), are proved to join an appealing optical gap with a viable conductivity, being a good candidate for increasing the conversion efficiency of thin-film photovoltaic cell.

36 MATERIALS SCIENCE↗
DOE OSTI2015

Imaging transient melting of a nanocrystal using an X-ray laser

Significance Despite phase transitions, such as melting, being ubiquitous in nature, understanding what occurs at the nanoscale (such as in nanocrystals) has so far remained challenging. With ensemble studies of nanocrystals it is often difficult to discriminate between intrinsic size-dependent properties and effects due to sample size and shape dispersity. Here, using an X-ray free electron laser we image the reversible melting of an individual nanocrystal induced by an ultrashort laser. It is revealed that the melting occurs transiently, repeatably, and inhomogeneously. This is consistent with a core-shell model where the exterior is melted and a solid core remains. These findings reveal, unambiguously, that core-shell melting occurs, which has important implications for understanding nanoscale phenomena.

Clark, Jesse N.↗
DOE OSTI2025

Structure–Activity Relationships for Ethanol Dehydrogenation to Acetaldehyde by Silica-Supported Zinc Oxide Catalysts

Silica-supported ZnO efficiently catalyzes the nonoxidative dehydrogenation of ethanol to acetaldehyde, which is relevant for production of 1,3-butadiene from bioethanol. Characterization with in situ spectroscopies under dehydrated conditions (high sensitivity-low energy ion scattering (HS-LEIS), diffuse reflectance (DR) UV–vis, X-ray absorption spectroscopy (XAS), diffuse reflectance Fourier transform infrared spectroscopy (DRIFTS), inelastic neutron scattering (INS), and UV Raman), and ammonia adsorption probed by temperature-programmed desorption followed by DRIFTS and mass spectrometry (DRIFTS-MS NH 3 -TPD), and DFT calculations revealed that the supported ZnO x phase was present as isolated surface ZnO x sites on SiO 2 , with the vast majority coordinated by two siloxane bonds and one silicon atom with two nonbridging oxygens ((≡SiO) 2 Zn 2+ O 2 Si=), anchored at 4-, 5-, and 6-membered siloxane rings. A minor fraction of surface ZnO x sites possessed Lewis acidity, and even fewer sites possessed a Bro̷nsted acidic Zn(OH) + Si moiety. Ethanol temperature-programmed surface reaction-mass spectrometry (TPSR-MS) with various oxidative or ethanol reaction pretreatments indicated that only sites with Lewis and Bro̷nsted acidic character (Zn(OH) + Si) were active for ethanol dehydrogenation, while the majority surface (≡SiO) 2 Zn 2+ O 2 Si= sites were inactive. Greater heterogeneity among all surface ZnO x sites, as assessed by in situ DR UV–vis spectroscopy, was associated with a greater number of ZnO x sites that were active for ethanol dehydrogenation as well as lower enthalpic barriers for acetaldehyde production among the most active surface ZnO x sites. Turnover frequencies and the apparent activation energy for ethanol dehydrogenation were determined from steady-state kinetics. Together, these findings suggested that anchoring inactive surface (≡SiO) 2 Zn 2+ O 2 Si= sites on the silica support caused a greater number of active surface ZnO x sites to adopt a more strained configuration, promoting ethanol dehydrogenation catalysis. Pretreatments and catalysts that promoted desorption of ethanol during TPSR, taken as a marker of surface dehydroxylation, were associated with an increased number of the most active surface (Zn(OH) + Si) sites. Such findings suggested that inactive surface ZnO x sites were activated for ethanol dehydrogenation by dehydroxylation of the support and/or decreased coordination to hemilabile siloxane ligands.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2020

Whose Gas is it anyway? Differentiating the Source of a Large Soil Vapor Plume beneath Two Adjacent Waste Sites - 20487

DOE contractor CH2M Hill Plateau Remediation Company is currently responsible for conducting groundwater contamination monitoring at several RCRA treatment, storage, and disposal units located on the Hanford Site in Richland, Washington State. The Nonradioactive Dangerous Waste Landfill treatment, storage, and disposal unit presents a distinct groundwater monitoring problem because of a large multi-contaminant soil vapor plume beneath it that is a likely source of low-level volatile organic compound groundwater contamination. Adjacent to Nonradioactive Dangerous Waste Landfill is the Solid Waste Landfill. Volatile organic compounds are inventory components of both the Nonradioactive Dangerous Waste Landfill and the Solid Waste Landfill. Therefore, it is possible that both sites could be contributing to the soil vapor plume. For regulatory purposes, it is important to differentiate which site is the primary contributor of volatile organic compounds to the plume. An approach was developed to identify the primary volatile organic compound source of the soil vapor plume beneath Nonradioactive Dangerous Waste Landfill and Solid Waste Landfill. The site conceptual model hypothesis of vapor-phase volatile organic compound transport to the dissolved phase in groundwater was tested by a simple mathematical model of vapor/liquid equilibrium concentrations at the groundwater/air interface. Once it was shown that vapor-phase volatile organic compound transport to groundwater was a valid conceptual model for Nonradioactive Dangerous Waste Landfill and Solid Waste Landfill, spatial and statistical methods were used to determine the primary site contributing to the majority of volatile organic compounds to the soil vapor plume. Average groundwater chloroform, tetrachloroethene, and trichloroethene concentrations from Nonradioactive Dangerous Waste Landfill and Solid Waste Landfill monitoring network wells were plotted on maps of the facilities and immediate vicinities and compared to soil vapor sampling probe locations. Principal component analysis and mixing ratios were used to identify source contributions of each treatment, storage, and disposal unit to the plume. Results of the vapor/liquid equilibrium concentrations mathematical model showed that transport phenomena outweigh steady-state equilibria. Estimated vapor/liquid equilibrium concentrations were considerably lower than soil vapor measurements. The results indicate that dynamic vadose zone and groundwater factors such as decreased vapor concentrations with depth, vapor dilution from dispersion in the vadose zone, and advective and diffusional volatile organic compound dilution in groundwater result in groundwater volatile organic compound concentrations much less than would be measured under steady-state equilibrium conditions. Site source contribution differentiation by principal component analysis and mixing ratios was inconclusive using actual soil gas data because of the similarity in concentration values in both datasets for Nonradioactive Dangerous Waste Landfill and Solid Waste Landfill. Similar data populations suggest mixing of the vapor contributions from both sites by dispersion through the soil matrix pore spaces. However, when groundwater volatile organic compound data were compared between the Nonradioactive Dangerous Waste Landfill and Solid Waste Landfill monitoring networks, Solid Waste Landfill mean concentrations were higher, suggesting more vapor-phase volatile organic compound transport to groundwater at those locations. Simulated volatile organic compound soil vapor and groundwater datasets created to test the methods developed for this study show that the method can be successful in source differentiation when significantly different datasets are compared. This paper will describe a method of testing a conceptual model for vapor-phase contaminant transport to groundwater and for differentiating site sources of contaminants comprising a mixed-constituent soil vapor plume. (authors)

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗
DOE OSTI2023

Plasmonic nanorod probes’ journey inside plant cells for in vivo SERS sensing and multimodal imaging

Nanoparticle-based platforms are gaining strong interest in plant biology and bioenergy research to monitor and control biological processes in whole plants. However, in vivo monitoring of biomolecules using nanoparticles inside plant cells remains challenging due to the impenetrability of the plant cell wall to nanoparticles beyond the exclusion limits (5-20 nm). To overcome this physical barrier, we have designed unique bimetallic silver-coated gold nanorods (AuNR@Ag) capable of entering plant cells, while conserving key plasmonic properties in the near-infrared (NIR). To demonstrate cellular internalization and tracking of the nanorods inside plant tissue, we used a comprehensive multimodal imaging approach that included transmission electron microscopy (TEM), confocal fluorescence microscopy, two-photon luminescence (TPL), X-ray fluorescence microscopy (XRF), and photoacoustics imaging (PAI). We successfully acquired SERS signals of nanorods in vivo inside plant cells of tobacco leaves. On the same leaf samples, we applied orthogonal imaging methods, TPL and PAI techniques for in vivo imaging of the nanorods. This study first demonstrates the intracellular internalization of AuNR@Ag inside whole plant systems for in vivo SERS analysis in tobacco cells. This work demonstrates the potential of this nanoplatform as a new nanotool for intracellular in vivo biosensing for plant biology.

Cupil-Garcia, Vanessa↗
NASA NTRSDate not supplied

An Overview of Experiments and Modeling of Polysiloxane-Coated Thermal Protection Systems for Missions to Mars, Titan, and Beyond.

Phenolic Impregnated Carbon Ablator (PICA) gained heritage during the historic Stardust mission, where it successfully returned samples from a comet’s tail and has since been instrumental in delivering payloads to the surface of Mars [1-3]. Most recently, PICA enabled the safe return of samples collected from asteroid Bennu as part of the OSIRIS-REx mission. This rich legacy underscores PICA’s critical role in allowing NASA’s most ambitious exploration missions. However, the friable nature of its phenolic phase presents challenges during handling and pre-launch activities. To mitigate this issue, PICA is coated with a polysiloxane resin system, which serves to suppress particulate dispersion and thereby safeguard spacecraft components. A comprehensive understanding of the polysiloxane resin’s behavior is imperative, as it profoundly shapes the material response of PICA during atmospheric entry by influencing its thermal and oxidative stability. This influence extends to thermocouple plugs embedded within thermal protection systems. These plugs have demonstrated their significance in missions such as Mars Science Laboratory (MSL) and Mars 2020, where the MEDLI and MEDLI2 instrumentation suites delivered in-valuable insights into the performance of thermal protection systems during entry into the Martian atmosphere [4]. Looking ahead, missions such as Dragonfly, set to descend into Titan’s dense atmosphere, aim to leverage advanced sensor technologies to further refine our understanding of thermal protection response [5]. Moreover, thermocouple plugs play an essential role in validating cutting-edge material response models, such as those pioneered under NASA’s Entry Systems Modeling Project (ESM), designed, in-part, to predict the operational integrity of thermal protection systems under the extreme stresses of atmospheric entry. To achieve these modeling goals, ground-based experiments are crucial to provide the foundational data necessary for developing and refining these predictive tools. To this end, an extensive test campaign was conducted at the Hypersonic Materials Environmental Test System (HyMETS) to investigate the high-temperature behavior of the polysiloxane resin in an air environment [6]. These experiments revealed critical phenomena, including the formation of a silicon oxycarbide layer that enhances oxidation resistance, moderates surface temperatures, and alters in-depth thermal response. Building on these findings, subsequent tests were designed to simulate atmospheric entry conditions in reactive gases, such as CO2 and N2, to mimic the environments of Mars and Titan, respectively, as well as non-reactive gases representing the atmospheres of the Ice Giants (Neptune and Uranus). A heating rate dependent decomposition mechanism has been identified for the polysiloxane resin under oxidizing conditions (Fig. 1). In the initial stage, the resin and the underlying thermal protection system undergo pyrolysis, rapidly generating a thin amorphous silicon oxycarbide interwoven with carbonaceous char and residual fibers from PICA. During the second stage, the nascent oxide layer establishes a robust, oxidation-resistant thermal barrier coating, which significantly impedes heat transfer to the underlying carbonaceous char, resulting in a stagnation of the surface temperature. A key factor contributing to this thermal resistance is the low recombination efficiency of atomic oxygen (γ), which further diminishes the heat load on the material’s interior layers [7]. Moreover, as the surface temperature stagnates, the silicon oxycarbide phase separates into distinct regions of silica and free graphite. Ultimately, when the heat flux reaches a critical threshold, a third stage is triggered, leading to the breakdown of the coating through carbothermal reduction, exposing the underlying char layer. This exposure leads to a dramatic surface temperature spike, driven by highly exothermic reactions between atomic oxygen and the char layer, further accelerating material degradation. A detailed mass and heat transfer model of PICA coated with polysiloxane resin was implemented in the Porous material Analysis Toolbox based on OpenFOAM, PATO [8]. The initial stage was considered negligible in this model because the resin decomposition occurs rapidly within a thin surface layer. Instead, the coating was directly considered as an oxygen-resistant thermal barrier coating. For the second stage, the thin amorphous silicon oxycarbide was treated as a pure silica surface to simplify the thermochemical behavior. The model ac-counts for surface equilibrium processes using representative elements of the coating-environment system. For the third stage, specific boundary conditions were developed to estimate the onset and progression of the coating removal. Two-dimensional material response simulations were conducted to compare uncoated and coated PICA using boundary conditions calibrated with HyMETS data. Fig. 2 illustrates that the simulations closely align with experimental data, successfully reproducing measured temperature profiles. This work will include the latest advancements in the coating model, including the calibration of recombination of atomic oxygen at the surface during the second phase. These simulated results will be further validated against additional CO2 data points from HyMETS, reinforcing the models’ predictive capabilities. These mechanisms and their effects on thermal protection systems, including thermochemical behavior and thermocouple probe performance in extreme environments, provide crucial insights for optimizing spacecraft designs that safeguard scientific payload and ensure mission success in future planetary exploration endeavors.

Active Oxidation↗