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At least 595 records · Page 33

The Search for Chiral Asymmetry as a Potential Biosignature in Samples from Mars

The search for evidence of extraterrestrial life in our solar system has been guided by our under-standing of terrestrial biology and its associated biosignatures. The observed homochirality in all life on Earth, that is, the predominance of “left-handed” or L-amino acids and “right-handed” or D-sugars, is a unique property of life that is crucial for molecular recognition, enzymatic function, information storage and structure, and is thought to be a prerequisite for the origin or early evolution of life. Therefore, the detection of L- or D-excesses of chiral amino acids or sugars could be a powerful indicator of extant or extinct life on Mars or other habitable environments in our solar system. However, studies of primitive meteorites have revealed that they contain extraterrestrial amino acids and sugar acids with large enantiomeric excesses (60% and higher) that resulted from non-biological processes [1], complicating the use of chiral asymmetry by itself as a definitive biosignature. The exploration of habitable environments on Mars, including an assessment of the preservation potential for complex organics of either abiotic or biological origin, is an objective of both current and future Mars missions. Now with the unambiguous detection of indigenous organic matter in sedimentary rocks by the Sample Analysis at Mars (SAM) instrument suite on Mars [2-5], NASA’s Curiosity rover has found evidence of the preservation of potential chemical biosignatures in the martian near surface. Although amino acids have not yet been identified by in situ measurements on Mars [5], indigenous achiral amino acids have been identified in one martian meteorite [6]. It is expected that amino acid racemization would be very slow and any chiral or isotopic signatures from an extinct martian biota could be preserved for billions of years, given the extremely cold and dry surface conditions [7]. The ESA/Roscosmos ExoMars mission scheduled for launch next year includes the Rosalind Franklin rover designed to acquire samples from a depth of ~2 m and deliver them to a suite of instruments, including the Mars Organic Molecule Analyzer (MOMA). The MOMA instrument contains a wet chemistry experiment designed specifically for the detection of amino acids and measurement of their enantiomeric compositions [8]. The complexity and limited duration of spaceflight operations, and the known analytical challenges associated with in situ extraction and characterization of trace reduced organic com-pounds in ancient rocks, make it challenging to determine the origins of martian organic matter found to date. Coordinated state-of-the-art laboratory measurements of returned samples from Mars that include spatially resolved chemical, mineralogical, bulk and molecule-specific isotopic, and enantiomeric measurements will be required to firmly establish whether the complex organic matter detected on Mars derives from bio-tic or abiotic processes. Ultimately, Mars Sample Return of rock cores collected by NASA’s Perseverance rover may be our best chance of identifying chemical biosignatures, including any chiral amino acid asymmetry resulting from a past or present martian biota, if one ever existed on Mars. Here we review our current knowledge of the distributions, and enantiomeric and isotopic com-positions of amino acids found in meteorites compared to terrestrial biochemistry. We also propose a set of measurement criteria that should be used to help establish the sources of any amino acids detected in samples returned from Mars using state-of-the-art gas and liquid chromatography mass spectrometry techniques [1].

D P Glavin↗

COLDArm Pressure-Sinkage Testing: Implications for Assessing Lunar Trafficability

The ability for regolith to support the movement of vehicles, known as trafficability, is commonly assessed using pressure-sinkage relationships. Trafficability on the lunar surface is controlled by the site-specific physical properties of the regolith and the geometry and mass of the roving vehicle. Lunar regolith pressure-sinkage testing can be performed with standard exploration hardware (e.g., robotic arms with scoops) and will help define exploration routes and hazard zones for rovers and astronauts, as knowledge of the sinkage of a wheel in regolith helps constrain viable operating conditions for rovers. The objective of this study is to demonstrate the necessity of in situ testing and characterization of lunar regolith physical properties for exploration and infrastructure development activities.

Regolith↗

COLDArm Pressure-Sinkage Testing: Implications for Assessing Lunar Trafficability

The ability for regolith to support the movement of vehicles, known as trafficability, is commonly assessed using pressure-sinkage relationships [1]. Trafficability on the lunar surface is controlled by the site-specific physical properties of the regolith and the geometry and mass of the roving vehicle. Lunar regolith pressure-sinkage testing can be performed with standard exploration hardware (e.g., robotic arms with scoops) and will help define exploration routes and hazard zones for rovers and astronauts, as knowledge of the sinkage of a wheel in regolith helps constrain viable operating conditions for rovers. The objective of this study is to demonstrate the necessity of in situ testing and characterization of lunar regolith physical properties for exploration and infrastructure development activities.

Regolith↗

Influence of Cation Species on Thermal Expansion of Y2Si2O7–Gd2Si2O7 Solid Solutions

Mixtures of Y 2 Si 2 O 7 and Gd 2 Si 2 O 7 were synthesized by solid-state reaction at 1600°C and characterized via in situ x-ray diffraction (XRD) to determine their coefficients of thermal expansion (CTE). All solid solutions within the system exhibited the orthorhombic δ-RE 2 Si 2 O 7 (Pna2 1 ) structure. Thermal expansion measurements of Y 2 Si 2 O 7 and Gd 2 Si 2 O 7 correlated well with reported values in literature, and all synthesized solid solutions exhibited CTEs between Y 2 Si 2 O 7 and Gd 2 Si 2 O 7 . Generally, there was a slight decrease in CTE exhibited by the materials with increasing Gd 2 Si 2 O 7 content, with Gd 2 Si 2 O 7 having the lowest CTEs and Y 2 Si 2 O 7 the highest CTEs. The decrease in CTE was attributed to stronger bonds of Gd-O over Y-O, as determined by calculated crystal orbital Hamilton populations using density functional theory. However, such differences were very small and crystal structure was the dominating factor in CTE trends.

rare earth silicates↗

AERACEPT (AErosol Rapid Analysis Combined Entry Probe/sonde Technology) for the Nephele Venus Cloud Mission Concept

Nephele is a small atmospheric probe mission concept to determine whether the Venus clouds contain organic matter. Nephele complements larger missions that seek to conduct Venus atmospheric analyses, such as DAVINCI, Venera-D, and the Morning Star missions, by directly sampling and analyzing cloud and haze particles. AERACEPT is an aerosol sampling technology designed to minimize the mass, volume, and complexity required for in situ planetary atmosphere characterization. A single aeroshell functions as a combined entry vehicle, descent probe, and instrumented sonde, combining recent advances in thermal protection materials with heritage technology from planetary and airborne science. The velocity of descent drives aerosol through inlets embedded in the aeroshell’s thermal protection material; inertial separation isolates the particles from the gas stream; and the particle capture surface doubles as the analysis substrate. This method can work without heat shield separation, descent control, or active sample handling; these advantages trade against a smaller sample volume, higher risk of sample heating, and shorter time for analysis and data return. AERACEPT further benefits from modeling of the internal and external flow to understand the particle capture efficiency and bias for size and concentration distributions. AERACEPT is well suited for a Venus mission such as Nephele, where a passive descent trajectory is both subsonic over the altitudes of interest and provides sufficient velocity and pressure differential for the particle sizes of interest. A thermal and flow toolchain developed in-house (Traj→ DPLR→ PATO→ openFOAM) was used to model an 80-cm aeroshell with science operations 63–39 km. These models indicate that AERACEPT will provide ~24 µL accumulated sample of particles ≥ 0.2 µm, substantially above the 2 µL threshold requirement. The worst-case particle heating will be ~14 K above ambient, for the smallest particles at the lowest altitude; most particles will experience ≤ 1 K rise, at which almost all analytes of interest will be unaffected. Plasma jet testing of a small-scale aeroshell-material inlet was recently conducted to validate the thermal model parameters; wind tunnel testing to validate the flow model parameters is underway.

AERACEPT↗

In situ synchrotron X-ray imaging and mechanical properties characterization of additively manufactured high-entropy alloy composites

Laser beam directed energy deposition has become an increasingly popular advanced manufacturing technique for materials discovery as a result of the in situ alloying capability. In this study, we leverage an additive manufacturing enabled high throughput materials discovery approach to explore the composition space of a graded W x (CoCrFeMnNi) 100–x sample spanning 0 ≤ x ≤ 21 at%. In addition to microstructural and mechanical characterization, synchrotron high speed x-ray computer aided tomography was conducted on a W 20 (CoCrFeMnNi) 80 composition to visualize melting dynamics, powder-laser interactions, and remelting effects of previously consolidated material. Results reveal the formation of the Fe 7 W 6 intermetallic phase at W concentrations> 6 at%, despite the high configurational entropy. Unincorporated W particles also occurred at W concentrations> 10 at% accompanied by a dissolution band of Fe 7 W 6 at the W/matrix interface and hardness values greater than 400 HV. In this work, the primary strengthening mechanism is attributed to the reinforcement of the Fe 7 W 6 and W phases as a metal matrix composite. The in situ high speed x-ray imaging during remelting showed that an additional laser pass did not promote further mixing of the Fe 7 W 6 or W phases suggesting that, despite the dissolution of the W into the Fe 7 W 6 phase being thermodynamically favored, it is kinetically limited by the thickness/diffusivity of the intermetallic phase, and the rapid solidification of the laser-based process.

36 MATERIALS SCIENCE↗

In-situ TEM Holder for Ultrafast, Multimodal Imaging

This project developed a prototype in-situ specimen holder product to transmission electron microscope (TEM) users that drastically expand the usability of TEM by combining nanoscale laser excitation and optical signal collection. A commercial prototype has been constructed and a few nanoscale materials characterization experiments have been performed to validate its performance and demonstrate its utility in real scientific studies, for example, in-situ characterization and mapping of defects in the synthesis of nanostructures.

77 NANOSCIENCE AND NANOTECHNOLOGY↗

CO 2 Methanation on Cu-Cluster Decorated Zirconia Supports with Different Morphology: A Combined Experimental In Situ GIXANES/GISAXS, Ex Situ XPS and Theoretical DFT Study

We report that subnanometer copper tetramer-zirconia catalysts turn out to be highly efficient for CO 2 hydrogenation and its conversion to methane. The cluster size and substrate morphology are controlled to optimize the catalytic performance. The two types of zirconia supports investigated are prepared by atomic layer deposition (~ 3 nm thick film) and supersonic cluster beam deposition (nanostructured film, ~ 100 nm thick). The substrate plays a crucial role in determining the activity of the catalyst as well as its cyclability over repeated thermal ramps. A temperature-programmed reaction combined with in situ X-ray characterization reveals the correlation between the evolution in the oxidation state and catalytic activity. Ex situ photoelectron spectroscopy indicates Cu clusters with stronger interactions with the nanostructured film, which can be the cause for the higher activity of this catalyst. Density functional theory calculations based on the Cu 4 O 2 cluster supported on a ZrOx subunit reveal low activation barriers and provide mechanism for CO 2 hydrogenation and its conversion to methane. Altogether, the results show a new way to tune the catalytic activity of CO 2 hydrogenation catalysts through controlling the morphology of the support at the nanoscale.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Characterization of axolotl lampbrush chromosomes by fluorescence in situ hybridization and immunostaining

The lampbrush chromosomes (LBCs) in oocytes of the Mexican axolotl (Ambystoma mexicanum) were identified some time ago by their relative lengths and predicted centromeres, but they have never been associated completely with the mitotic karyotype, linkage maps or genome assembly. We identified 9 of the axolotl LBCs using RNAseq to identify actively transcribed genes and 13 BAC (bacterial artificial clone) probes containing pieces of active genes. Using read coverage analysis to find candidate centromere sequences, we developed a centromere probe that localizes to all 14 centromeres. Measurements of relative LBC arm lengths and polymerase III localization patterns enabled us to identify all LBCs. This study presents a relatively simple and reliable way to identify each axolotl LBC cytologically and to anchor chromosome-length sequences (from the axolotl genome assembly) to the physical LBCs by immunostaining and fluorescence in situ hybridization. Our data will facilitate a more detailed transcription analysis of individual LBC loops.

60 APPLIED LIFE SCIENCES↗

System and method using in-situ electromagnetic diagnostic for real-time projectile characterization

The present disclosure relates to a system for detecting characteristics of a moving element. The system may include a tubular housing having a tubular first portion having a first end and a second end, with the first end forming an input port and the second end forming an output port. A source of wireless electromagnetic energy projects a wireless electromagnetic energy signal, travelling in a first direction, into the input port and through an interior area defined by the tubular first portion. A signal processing subsystem detects at least one characteristic of the signal after the signal is reflected back to the first end after having interacted with the element as the element moves past the output port of the housing.

Chang, Tammy↗

Phase Doppler Interferometry for Efficient Cloud Drop Size Distribution, Number Density, and LWC Measurements

Threats to aviation safety as a result of super-cooled large drops (SLD) has been addressed by the FAA rules change (14 CFR Part 25) with the additional icing certification requirement. SLD clouds often consist of bi-modal drop size spectra leading to significant problems in simulating and characterizing these conditions in situ and in icing wind tunnels. Legacy instrumentation for measuring drop size distributions and liquid water content are challenged under these conditions. The large size range measurement problem is addressed with the development of the Phase Doppler Interferometer, Flight Probe Dual-Range (PDI FPDR). The method is described in this report along with the measurement capabilities including the dynamic measurement range and overall working size range. The PDI instrument bases drop size measurements on the light wavelength as the measurement length scale. The light wavelength is a much more robust scale, especially as compared to the light scattering intensity. Additionally, methods for accurately characterizing the sample volume in situ based on measured drop velocity and transit time are reviewed, given the importance of this parameter for merging results and measuring LWC. Droplet coincidence in the sample volume can be problematic so this condition is treated with an innovative signal parsing approach. Measurement examples acquired in the NASA IRT are provided. Measurements of LWC showed good agreement with the Artium Particle Imaging (PI) instrument but diverged from the tunnel calibration results for larger MVD values.

42 ENGINEERING↗

Airborne Ground Penetrating Radar (GPR) for peat analyses in the Canadian Northern wetlands study

The study was conducted as part of the NASA Biospherics Research on Emissions from Wetlands (BREW) program. An important aspect of the program is to investigate the terrestrial production and atmospheric distribution of methane and other gases contributing to global warming. Multi-kilometer transects of airborne (helicopter) Ground Penetrating Radar (GPR) data were collected periodically along the 100 km distance from the coast inland so as to obtain a regional trend in peat depth and related parameters. Global Positioning System (GPS) data were simultaneously collected from the helicopter to properly georeference the GPR data. Additional 50 m ground-based transects of GPR data were also collected as a source of ground truthing, as a calibration aid for the airborne data sets, and as a source of higher resolution data for characterizing the strata within the peat. In situ peat depth probing and soil characterizations from excavated soil pits were used to verify GPR findings. Results from the ground-based data are presented.

Pelletier-Travis, Ramona E.↗

In Situ Attenuated Total Reflectance Infrared Spectroelectrochemistry (ATR-IR-SEC) for the Characterization of Molecular Redox Processes on Surface-Proximal Doped Silicon ATR Crystal Working Electrodes

In situ mid-infrared spectroscopy is a powerful technique for understanding the mechanism of CO 2 reduction (CO 2 R) catalysts because it enables the direct detection of catalytic intermediates and products. Moreover, spectroelectrochemistry (SEC), the coupling of spectroscopy with electrochemistry, allows spectroscopic changes to be correlated with applied potentials to reveal potential-dependent intermediates that are often relevant to photoelectrochemical reactions. Hybrid photoelectrodes, comprised of a narrow bandgap semiconductor, like silicon (Si), with a covalently-linked molecular catalyst, are a promising platform for sunlight-driven catalysis, but characterization of the catalytic mechanism(s) is challenging under photoelectrochemical conditions, particularly when the catalyst is present in monolayer or less concentrations. Here, we have developed a new strategy to use multiple-reflection attenuated total reflectance IR spectroscopy (ATR-IR) coupled with electrochemistry to characterize catalysts directly integrated with a semiconductor surface under applied potential. We show that by surface-proximal n-type or p-type doping of the top ~100-200 nm of the crystal surface, Si ATR crystals can be used simultaneously as the internal reflection element and semiconductor working electrode for ATR-IR-SEC measurements. The surface-proximal doping strategy yields a quasi-equipotential surface with excellent infrared transparency that would have been compromised by free carrier absorption if the crystal was uniformly doped. This approach permits the catalytically-active functionalized surface to be directly probed without modification and overcomes signal-to-noise limitations of other strategies that use separately deposited working electrodes on Si ATR crystals. Proof-of-concept ATR-IR-SEC spectra were collected during the reduction and oxidation of monolayers of Re- and Ru-based transition metal carbonyl complexes, respectively, verifying the viability of the technique to probe redox processes associated with CO 2 R catalysts on Si electrode surfaces with high sensitivity.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Characterizing Physical Properties of Streambed Interface Sediments Using In Situ Complex Electrical Conductivity Measurements

Streambed sediment physical properties such as surface area, are difficult to quantify in situ but exert a high-level control on a wide range of biogeochemical processes and sorption of contaminants. We introduce the use of complex electrical conductivity (CC) methods (also known as spectral-induced polarization (SIP)) that measure both real and imaginary conductivity to noninvasively and efficiently characterize shallow streambed sediments. We explore the method through synthetic modeling, laboratory, and field measurements to demonstrate the sensitivity of imaginary conductivity to sediment surface area, controlled in part by fine-grained iron oxides produced by anoxic groundwater discharge. Laboratory measurements verify expected relationships between CC parameters and sediment properties. Synthetic modeling using a 1D analytical model illustrates the influence of water layer depth and conductivity on the field CC measurements made at the streambed-stream water interface. Specifically, the inverted sediment imaginary conductivity is less impacted by uncertainty in the water layer depth and conductivity relative to the real conductivity and phase shift. Field CC measurements along a landfill-impacted river reveal discrete streambed zones with enhanced bulk surface area generally corresponding to anoxic groundwater discharge zones with high concentrations of fine-grained iron oxide precipitates.

54 ENVIRONMENTAL SCIENCES↗

Dislocation loop evolution in F/M steel T91 under in-situ ion irradiation: Influence of the presence of initial dislocations

Ferritic/Martensitic (F/M) steel T91 was irradiated in-situ to 4 and 10 dpa at 470 °C using 1 MeV Kr 2+ . Additionally, the microstructure evolution under irradiation was followed and characterized by in-situ Transmission Electron Microscopy (TEM), in terms of dislocation loop Burgers vector, average size and density as a function of dose. Furthermore, the influence of the presence of dislocations in the pre-irradiated matrix was investigated by comparing the radiation induced defect evolution in grains with and without initial dislocations.

36 MATERIALS SCIENCE↗

Direct measurement of the effective properties of an additively manufactured titanium octet truss unit cell using high energy X-ray diffraction

Additively manufactured lattice structures offer a high specific strength-to-density ratio in comparison to conventional, fully dense parts. The small feature size and intricate geometry of lattice structures make it challenging to directly characterize their mechanical properties. This study presents direct measurement of the elastic mechanical properties of an additively manufactured titanium alloy octet truss unit cell. Strut stress and strain were measured using high-energy X-ray diffraction during quasi-static compressive loading. The crystallographic stress-strain relationship was converted into the stress-strain relationship of the octet truss lattice unit cell using the known symmetry of the struts. The sample studied herein was best fit by an orthorhombic linear elastic stress-strain relationship. In conclusion, this technique shows promise for studying additively manufactured lattice structures at length scales not previously reported.

36 MATERIALS SCIENCE↗