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At least 235 records · Page 13

Subsurface Sampling and Sensing Using Burrowing Moles

Finding evidence for life on Mars will likely require accessing the subsurface since the Martian surface is both hostile to life and to preservation of biosignatures due to the cold dry conditions, the strong W environment, and the presence of strong oxidants. Systems are needed to probe beneath the sun and oxidant baked surface of Mars and return samples to the surface for analysis or to bring the instrument sensing underground. Recognizing this need, the European Space Agency incorporated a small subsurface penetrometer or Mole onto the Beagle 2 Mars lander. Had the 2003 landing been successful, the Mole would have collected samples from 1-1.5 m depth and delivered them to an organic analysis instrument on the surface. The de- vice called the Planetary Underground Tool (PLUTO), also measured soil mechanical and thermophysical properties. Constrained by the small mass and volume allowance of the Beagle lander, the PLUTO mole was a slender cylinder only 2 cm diameter and 28 cm long equipped with a small sampling device designed to collect samples and bring them to the surface for analysis by other instrument. The mass of the entire system including deployment mechanism and tether was 1/2 kg. sensor package underground to make in situ measurements. The Mars Underground Mole (MUM) is a larger Mole based on the PLUTO design but incorporating light collection optics that interface to a fiber optic cable in the tether that transmits light to a combined stimulated emission Raman Spectrometer and Short Wave Infrared (SWIR) reflectance Spectrometer with sensitivity from 0.7 to 2.5 micrometers. This instrument is called the Dual Spectral Sensor and uses a Digital Array Scanning Interferometer as the sensor technology, a type of fourier transform interferometer that uses fixed element prisms and thus is highly rugged compared to a Michaelson interferometer. Due to the size limitations of an on-Mole instrument compartment, and the availability of a tether, the sensor head, light sources, and control electronics for the instrument are on the surface. The DSS sensor is capable of sensing a wide range of minerals relevant to Mars Astrobiology objectives including hydrated minerals, clays, carbonates, sulfates, and ice. Additionally, Raman spectroscopy is effective for detecting organics. The MUM is designed to achieve a maximum depth of penetration of 5 m in Mars regolith and can be repeatedly deployed and retrieved. The ability to perform repeated sampling, combined with the low mass and power requirements, means that Moles could be incorporated into a rover mission as well as used on a stationary platform. The Mole mechanism is a pointed slender cylinder that advances into soil by way of an internal sliding hammer mechanism. Part of the energy released by the spring-loaded hammer with each shock is transferred to the Mole casing and from there to the soil, resulting in penetration by displacing and compressing the surrounding soil. A backwards-directed impulse as a re- action to each forward shock is transferred via a suppressor mass against a second weaker spring allowing forward motion without requiring reactive forces provided by the lander. The Mole tip can be opened to collect soil samples. The Mole casing is tethered to a supporting mechanism that supplies power. Components supporting the Mole on the surface include a launch tube, tether reel and winch for pulling in tether, in addition to the tether itself.

Stoker, C. R.↗

The in situ exobiological investigation of the Martian surface mineralogy during unmanned missions

An important goal of exobiological research is to determine if life arose on planets other than Earth. The only other planet known, to date, on which life may have arisen is Mars. The data suggest that the physical environment of early Mars (i.e., temperature, pressure, and radiation regimes) was suitable for life to arise. Thus far, the data also suggest that early Mars possessed sufficient quantities of the required building blocks and a number of the chemical compounds necessary for life to arise. It is not known, however, if water existed in the appropriate state (i.e., liquid) in sufficient quantities long enough for life to arise. Determining the mineralogy and components of the Martian soil through in situ analyses during missions to Mars will provide information from which an assessment can be made for the probability of the origin of life on Mars. Missions to Mars in the near future will be unmanned and capable of in situ analyses. Our studies have shown that differential thermal analysis coupled with gas chromatography (DTA/GC) is a more appropriate analytical technique than, x-ray fluorescence, x-ray diffraction, alpha-proton backscatter, gamma-ray spectrometry, differential scanning calorimetry coupled with mass spectrometry (DSC/MS), or DSC/GC to identify the mineralogy of the Martian surface material in situ. DTA/GC is an advancement over the pyrolytic techniques flown on previous missions that have supplied only limited mineralogical information (Biemann et al. 1977).

Mancinelli, Rocco L.↗

Nanopore Sequencing in Space: The Advancement of In Situ Microbiome Analysis for the International Space Station and Beyond

Introduction: Routine assessment of the International Space Station (ISS) microbiome has been performed through in-flight culture and Earth-based analysis. Through utilization of the ISS, significant progress toward in situ microbial identification has been achieved. In 2016, the molecular space age began when DNA-based, Earth-prepared samples were amplified within miniPCR (Genes in Space-1), and subsequent samples were sequenced with the MinION (Biomolecule Sequencer). The following year, these platforms were used collectively to yield the first off-Earth identification of unknown bacteria collected and cultured onboard the ISS (Genes in Space-3). Further advancement occurred in 2018 when a culture-independent, direct swab-to-sequencer method revealed a more thorough depiction of the ISS surface microbiome (BEST). As NASA looks towards Artemis and extended exploration missions, it is critical to continue to harness the ISS to expand in situ nanopore sequencing-based analysis in support of microbial-related crew health, planetary protection, and space research initiatives.

Christian G. Mena↗

Microwave-Driven Nonoxidative and Selective Conversion of Methane to Ethylene over Mn-Based Catalysts

Recent advancements in microwave-driven nonoxidative catalytic synthesis of C 2 H 4 from CH 4 coupling offer a promising, energy-efficient, and eco-friendly alternative to conventional methods, where selective heating under microwave irradiation enables comparable conversions at substantially lower bulk temperatures and shorter reaction times. This study explores the performance of an MnO X -based catalyst supported on CeO 2 and HY zeolite (silica-toalumina ratio = 5.1) for the nonoxidative coupling of CH 4 (NOCM) under microwave irradiation. Inspired by the well-established efficacy of MnO X catalyst in oxidative CH 4 coupling (OCM), their application in NOCM has also shown significant performance. The catalytic system achieved 15% CH 4 conversion and 99% selectivity toward C 2 hydrocarbons and maintained 64% selectivity toward C 2 H 4 surpassing the yields reported in the literature even at higher temperatures (700−1000 °C). Catalyst performance was correlated with measurements by in situ Raman spectroscopy, and additional characterizations were performed using H 2 −temperature programmed reduction , NH 3 −temperature programmed desorption, and BET surface area analysis to understand structural changes during the reactions. These findings suggested that Mn functions as active sites for CH 4 activation in nonoxidative environments while also promoting efficient C−C coupling under microwave irradiation.

Catalysts↗

Operando XPS in reactive plasmas: The importance of the wall reactions

In this article, advancements in differential pumping and electron optics over the past few decades have enabled x-ray photoelectron spectroscopy (XPS) measurements at (near-)ambient pressures, bridging the pressure gap for characterizing realistic sample chemistries. Recently, we have demonstrated the capabilities of an ambient pressure XPS setup for in situ plasma environment measurements, allowing plasma-surface interactions to be studied in operando rather than using the traditional before-and-after analysis approach. This new “plasma-XPS” technique facilitates the identification of reaction intermediates critical for understanding plasma-assisted surface processes relevant to semiconductor nanomanufacturing, such as physical vapor deposition, etching, atomic layer deposition, and many other plasma applications. In this paper, we apply the plasma-XPS approach to monitor real-time surface chemical changes on a model Ag(111) single crystal exposed to oxidizing and reducing plasmas. We correlate surface-sensitive data with concurrent gas-phase XPS measurements and residual gas mass-spectrum analysis of species generated during plasma exposure, highlighting the significant role of plasma-induced chamber wall reactions. Ultimately, we demonstrate that plasma-XPS provides comprehensive insights into both surface and gas-phase chemistry, establishing it as a versatile and dynamic characterization tool with broad applications in microelectronics research. Finally, we outline potential enhancements and future metrology directions to advance plasma-XPS investigations further.

36 MATERIALS SCIENCE↗

Martian Chronology and Atmospheric Composition: In Situ Measurements versus Sample Return

I examine two significant issues of martian science from the point of view of in situ measurements by robotic spacecraft versus sample return and analysis in terrestrial labs. (1) To define martian history, ages of geological processes and surface features are required. Estimated ages from surface crater densities have limitations, and the ages measured for martian meteorites cannot be associated with specific martian locales. Whereas returned martian rocks could be accurately dated, some have suggested sending a robotic spacecraft to Mars to measure rock ages using the classical K- Ar-40 technique, considered the easiest to implement. (2) To understand the evolution of the martian atmosphere and its interactions with the surface, requires precise measurements of atmospheric composition. A significant amount of information has derived from measurements by Viking and of martian meteorites. Instrumentation on the Mars Science Lander (MSL) spacecraft to be launched in the near future promises to determine atmospheric composition even more precisely. If MSL is successful, which questions about atmospheric composition will remain and thus will require atmospheric sample return to answer?

Bogard, Donald D.↗

Using CubeSats to Monitor Debris Flux

Recent updates to NASA's Orbital Debris Engineering Model (ORDEM 3.0) include a population of small particles (1-2 mm in size) composed of high-density materials (e.g., steel) that drive much of the predicted risk for satellites in the 700-1000 km altitude regime. This modeled population was based on the analysis of returned surfaces of the Shuttle, which flew below 600 km altitude. The cessation of Shuttle missions, plus the lack of in situ data above 600 km means that a data source is being sought to either confirm or modify this high-density population. One possible data source would be a database of anomalous sporadic changes in spacecraft orbit/orientation that might be due to momentum transfer from small particles too small to seriously damage the spacecraft. Because the momentum imparted from an impact would be tiny, it would most likely show up in the orbital behavior of cubesats and other small satellites. While such small satellites were few in number, this was not a particularly attractive option, but now with the proliferation of cubesats in multiple orbit planes and altitudes, the possible collecting area has increased significantly. This presentation will discuss the physics of momentum-transferring impacts from hypervelocity collisions, and make predictions about rates, directions, and locations of such impacts. In addition, it will include recommendations for satellite users on what kind of data might be worth archiving and investigating.

Matney, Mark↗

Status and Plans for Reanalysis at NASA/GMAO

Reanalysis plays a critical role in GMAOs goal to enhance NASA's program of Earth observations, providing vital data sets for climate research and the development of future missions. As the breadth of NASAs observations expands to include multiple components of the Earth system, so does the need to assimilate observations from currently uncoupled components of the system in a more physically consistent manner. GMAOs most recent reanalysis of the satellite era, MERRA-2, has completed the period 1980-present, and is now running as a continuing global climate analysis with two- to three-week latency. MERRA-2 assimilates meteorological and aerosol observations as a weakly coupled assimilation system as a first step toward GMAOs longer term goal of developing an integrated Earth system analysis (IESA) capability that will couple assimilation systems for the atmosphere, ocean, land and chemistry. The GMAO strategy is to progress incrementally toward an IESA through an evolving combination of coupled systems and offline component reanalyses driven by, for example, MERRA-2 atmospheric forcing. Most recently, the GMAO has implemented a weakly coupled assimilation scheme for analyzing ocean skin temperature within the existing atmospheric analysis. The scheme uses background fields from a near-surface ocean diurnal layer model to assimilate surface-sensitive radiances plus in-situ observations along with all other observations in the atmospheric assimilation system. In addition, MERRA-2-driven simulations of the ocean (plus sea ice) and atmospheric chemistry (for the EOS period) are currently underway, as is the development of a coupled atmosphere-ocean assimilation system. This talk will describe the status of these ongoing efforts and the planned steps toward an IESA capability for climate research.

MERRA-2↗

Studying Interfacial Dark Reactions of Glyoxal and Hydrogen Peroxide Using Vacuum Ultraviolet Single Photon Ionization Mass Spectrometry

Aqueous secondary organic aerosol (aqSOA) formation from volatile and semivolatile organic compounds at the air–liquid interface is considered as an important source of fine particles in the atmosphere. However, due to the lack of in situ detecting techniques, the detailed interfacial reaction mechanism and dynamics still remain uncertain. In this study, synchrotron-based vacuum ultraviolet single-photon ionization mass spectrometry (VUV SPI-MS) was coupled with the System for Analysis at the Liquid Vacuum Interface (SALVI) to investigate glyoxal dark oxidation products at the aqueous surface. Mass spectral analysis and determination of appearance energies (AEs) suggest that the main products of glyoxal dark interfacial aging are carboxylic acid related oligomers. Furthermore, the VUV SPI-MS results were compared and validated against those of in situ liquid time-of-flight secondary ion mass spectrometry (ToF-SIMS). The reaction mechanisms of the dark glyoxal interfacial oxidation, obtained using two different approaches, indicate that differences in ionization and instrument operation principles could contribute to their abilities to detect different oligomers. Therefore, the mechanistic differences revealed between the VUV SPI-MS and ToF-SIMS indicate that more in situ and real-time techniques are needed to investigate the contribution of the air–liquid interfacial reactions leading to aqSOA formation.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Evolution of Metastable Phases During Mg Metal Corrosion: An In Situ Cryogenic X-ray Photoelectron Spectroscopy Study

Magnesium and its alloys are potential structural materials candidates for a wide variety of applications due to their high strength-to-weight ratio. However, ductility and poor corrosion resistance under ambient environmental conditions are the bottleneck for industrial deployment. Designing passivation layers and/or corrosion resistant alloys requires fundamental understanding of the corrosion process. The traditional ex-situ spectroscopic measurements of polycrystalline metal surface with ubiquitous surface impurities and grain boundaries only provided an indistinct view of the corrosion process. To clearly distinguish the mechanism and sequence of corrosion process, we employed in-situ cryo-based x-ray photoelectron spectroscopy (XPS) measurements on Mg single crystal surface exposed to aqueous salt solution. Clean Mg (0001) surfaces were exposed to pure D2O and NaCl aqueous solution (5 wt% NaCl+95 wt% D2O). The interfacial reactions were studied using multimodal analysis including XPS, x-ray diffraction (XRD) and scanning electron microscopy (SEM). In contrast to previous studies, our experiments demonstrated the formation of magnesium chloride hydroxide hydrate during aqueous salt corrosion processes. Evidence of metastable ClO* radicals were also found during the initial aqueous salt solution exposure.

Shutthanandan, Vaithiyalingam↗

Solid phase characterization and transformation of illite mineral with gas-phase ammonia treatment

In situ remediation applications of ammonia (NH 3 ) gas have potential for sequestration of subsurface contamination. Ammonia gas injections initially increase the pore water pH leading to mineral dissolution followed by formation of secondary precipitates as the pH is neutralized. However, there is a lack of understanding of fundamental alteration processes due to NH 3 treatment. In these batch studies, phyllosilicate minerals (illite and montmorillonite) were exposed to NH 3 gas with subsequent aeration to simulate in situ remediation. Following treatments, solids were characterized using a variety of techniques, including X-ray diffraction, N 2 adsorption-desorption analysis for surface area, Fourier transform infrared (FTIR) spectroscopy, nuclear magnetic resonance (NMR), and microscopy methods to investigate physicochemical transformations. The results of this study indicate that, at high pH, the clays are altered as observed by differences in morphology and particle size via microscopy. However, the two clays interact differently with NH 3 . While montmorillonite interlayers collapsed due to intercalation, illite layers were unaffected as confirmed by FTIR analysis. Further, structural changes in silicate ([SiO 4 ] n- ) and aluminol (Al-OH) groups were identified by NMR and FTIR. This research showed that mineral alteration processes occur during and after NH 3 gas treatment which may be used to remove radionuclides from the aqueous phase through sorption, co-precipitation, and coating with secondary phyllosilicate alteration products.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Structural Transformation and Degradation of Cu Oxide Nanocatalysts during Electrochemical CO 2 Reduction

The electrochemical CO 2 reduction reaction (CO 2 RR) holds enormous potential as a carbon-neutral route to the sustainable production of fuels and platform chemicals. The durability for long-term operation is currently inadequate for commercialization, however, and the underlying deactivation process remains elusive. A fundamental understanding of the degradation mechanism of electrocatalysts, which can dictate the overall device performance, is needed. In this work, we report the structural dynamics and degradation pathway of Cu oxide nanoparticles (CuO x NPs) during the CO 2 RR by using in situ small-angle X-ray scattering (SAXS) and X-ray absorption spectroscopy (XAS). The in situ SAXS reveals a reduction in the size of NPs when subjected to a potential at which no reaction products are detected. At potentials where the CO 2 RR starts to occur, CuO x NPs are agglomerated through a particle migration and coalescence process in the early stage of the reaction, followed by Ostwald ripening (OR) as the dominant degradation mechanism for the remainder of the reaction. As the applied potential becomes more negative, the OR process becomes more dominant, and for the most negative applied potential, OR dominates for the entire reaction time. The morphological changes are linked to a gradual decrease in the formation rate for multicarbon products (C 2 H 4 and ethanol). Other reaction parameters, including reaction intermediates and local high pH, induce changes in the agglomeration process and final morphology of the CuO x NPs electrode, supported by post-mortem ex situ microscopic analysis. The in situ XAS analysis suggests that the CuO x NPs reduced into the metallic state before the structural transformation was observed. The introduction of high surface area carbon supports with ionomer coating mitigates the degree of structural transformation and detachment of the CuO x NPs electrode. These findings show the dynamic nature of Cu nanocatalysts during the CO 2 RR and can serve as a rational guideline toward a stable catalyst system under electrochemical conditions.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Satellite detection of phytoplankton export from the mid-Atlantic Bight during the 1979 spring bloom

Analysis of Coastal Zone Color Scanner (CZCS) imagery confirms shipboard and in situ moored fluorometer observations of resuspension of near-bottom chlorophyll within surface waters (1 to 10 m) by northwesterly wind events in the mid-Atlantic Bight. As much as 8 to 16 micrograms chl/l are found during these wind events from March to May, with a seasonal increase of algal biomass until onset of stratification of the water column. Rapid sinking or downwelling apparently occurs after subsequent wind events, however, such that the predominant surface chlorophyll pattern is approx. 0.5 to 1.5 micrograms/l over the continental shelf during most of the spring bloom. Perhaps half of the chlorophyll increase observed by satellite during a wind resuspension event represents in-situ production during the 4 to 5 day interval, with the remainder attributed to accumulation of algal biomass previously produced and temporarily stored within near-bottom water. Present calculations suggest that about 10% of the primary production of the spring bloom may be exported as ungrazed phytoplankton carbon from mid-Atlantic shelf waters to those of the continental slope.

Walsh, J. J.↗

Variability in equatorial Pacific sea surface topography during the verification phase of the TOPEX/POSEIDON mission

As part of the verification phase of the TOPEX/POSEIDON mission, 10-day gridded fields of altimeter data derived from TOPEX geophysical data records are compared with 10-day gridded fields of dynamic height derived from more than 60 moorings of the Tropical Ocean and Global Atmosphere-Tropical Atmosphere Ocean (TOGA-TAO) array in the equatorial Pacific Ocean. Access to TAO data in real time permits the first 500 days of the TOPEX/POSEIDON mission to be placed in the context of complementary, in-situ measurements of surface winds, sea surface temperatures, and upper ocean thermal structure, as well as the time history of these variables prior to launch. Analysis of the space-time structure in the TOPEX and TAO surface topography data increases sea level variability primarily due to equatorial Kelvin wave activity generated by intense wind bursts west of the date line in association with the 1991-1993 El Nino. Cross correlations between the two data sets are generally greater than 0.7, with root mean square (RMS) differences less than 4 cm. However, for reasons not fully understood, correlations drop to less than 0.5 in certain regions off the equator in the eastern Pacific and RMS differences can be greater than 5 cm north of the equator in the central and eastern Pacific.

Busalacchi, Antonio J.↗

Assessing Hurricane Katrina Vegetation Damage at Stennis Space Center using IKONOS Image Classification Techniques

Hurricane Katrina inflicted widespread damage to vegetation in southwestern coastal Mississippi upon landfall on August 29, 2005. Storm damage to surface vegetation types at the NASA John C. Stennis Space Center (SSC) was mapped and quantified using IKONOS data originally acquired on September 2, 2005, and later obtained via a Department of Defense ClearView contract. NASA SSC management required an assessment of the hurricane s impact to the 125,000-acre buffer zone used to mitigate rocket engine testing noise and vibration impacts and to manage forestry and fire risk. This study employed ERDAS IMAGINE software to apply traditional classification techniques to the IKONOS data. Spectral signatures were collected from multiple ISODATA classifications of subset areas across the entire region and then appended to a master file representative of major targeted cover type conditions. The master file was subsequently used with the IKONOS data and with a maximum likelihood algorithm to produce a supervised classification later refined using GIS-based editing. The final results enabled mapped, quantitative areal estimates of hurricane-induced damage according to general surface cover type. The IKONOS classification accuracy was assessed using higher resolution aerial imagery and field survey data. In-situ data and GIS analysis indicate that the results compare well to FEMA maps of flooding extent. The IKONOS classification also mapped open areas with woody storm debris. The detection of such storm damage categories is potentially useful for government officials responsible for hurricane disaster mitigation.

Spruce, Joseph P.↗

OASIS: Organics Analyzer for Sampling Icy Surfaces

Liquid chromatography mass spectrometry (LC-MS) is a well established laboratory technique for detecting and analyzing organic molecules. This approach has been especially fruitful in the analysis of nucleobases, amino acids, and establishing chirol ratios [1 -3]. We are developing OASIS, Organics Analyzer for Sampling Icy Surfaces, for future in situ landed missions to astrochemically important icy bodies, such as asteroids, comets, and icy moons. The OASIS design employs a microfabricated, on-chip analytical column to chromatographically separate liquid ana1ytes using known LC stationary phase chemistries. The elution products are then interfaced through electrospray ionization (ESI) and analyzed by a time-of-flight mass spectrometer (TOF-MS). A particular advantage of this design is its suitability for microgravity environments, such as for a primitive small body.

Getty, S. A.↗

Instrument for Analysis of Organic Compounds on Other Planets

The goal of this project is to develop the Instrument for Solvent Extraction and Analysis of Extraterrestrial Bodies using In Situ Resources (ISEE). Specifically, ISEE will extract and characterize organic compounds from regolith which is found on the surface of other planets or asteroids. The techniques this instrument will use are supercritical fluid extraction (SFE) and supercritical fluid chromatography (SFC). ISEE aligns with NASA's goal to expand the frontiers of knowledge, capability, and opportunities in space in addition to supporting NASA's aim to search for life elsewhere by characterizing organic compounds. The outcome of this project will be conceptual designs of 2 components of the ISEE instrument as well as the completion of proof-of-concept extraction experiments to demonstrate the capabilities of SFE. The first conceptual design is a pressure vessel to be used for the extraction of the organic compounds from the regolith. This includes a comparison of different materials, geometry's, and a proposition of how to insert the regolith into the vessel. The second conceptual design identifies commercially available fluid pumps based on the requirements needed to generate supercritical CO2. The proof-of-concept extraction results show the percent mass lost during standard solvent extractions of regolith with organic compounds. This data will be compared to SFE results to demonstrate the capabilities of ISEE's approach.

supercritical fluids↗

Suppressing strain propagation in ultrahigh-Ni cathodes during fast charging via epitaxial entropy-assisted coating

Surface reconstruction and the associated severe strain propagation have long been reported as the major cause of cathode failure during fast charging and long-term cycling. Despite tremendous attempts, no known strategies can simultaneously address the electro-chemomechanical instability without sacrificing energy and power density. Here we report an epitaxial entropy-assisted coating strategy for ultrahigh-Ni LiNi x Co y Mn 1-x-y O 2 (x ≥ 0.9) cathodes via an oriented attachment-driven reaction between Wadsley-Roth phase-based oxides and the layered-oxide cathodes. Further, the high anti-cracking and anti-corrosion tolerances as well as the fast ionic transport of the entropy-assisted surface effectively improved the fast charging/discharging capability, wide temperature tolerance and thermal stability of the ultrahigh-Ni cathodes. Comprehensive analysis from the primary and secondary particle level to the electrode level using multi-scale in situ synchrotron X-ray probes reveals greatly reduced lattice dislocations, anisotropic lattice strain and oxygen release as well as improved bulk/local structural stability, even when charging beyond the threshold state of charge (75%) of layered cathodes. Layered Ni-rich oxide cathodes are susceptible to challenges with surface reconstruction and strain propagation, limiting their cyclability. The authors propose a solution involving oriented attachment-driven reactions, utilizing Wadsley-Roth nanocrystals and layered oxide to induce an epitaxial entropy-assisted coating, effectively addressing these issues.

25 ENERGY STORAGE↗