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Lunar and Planetary Science XXXVI, Part 13

Contents include the following: A Fast, Non-Destructive Method for Classifying Ordinary Chondrite Falls Using Density and Magnetic Susceptibility. An Update on Results from the Magnetic Properties Experiments on the Mars Exploration Rovers, Spirit and Opportunity. Measurement Protocols for In Situ Analysis of Organic Compounds at Mars and Comets. Piping Structures on Earth and Possibly Mars: Astrobiological Implications. Uranium and Lead in the Early Planetary Core Formation: New Insights Given by High Pressure and Temperature Experiments. The Mast Cameras and Mars Descent Imager (MARDI) for the 2009 Mars Science Laboratory. MGS MOC: First Views of Mars at Sub-Meter Resolution from Orbit. Analysis of Candor Chasma Interior Layered Deposits from OMEGA/MEX Spectra. Analysis of Valley Networks on Valles Marineris Plateau Using HRSC/MEX Data. Solar Abundance of Elements from Neutron-Capture Cross Sections. Preliminary Evaluation of the Secondary Ion/Accelerator Mass Spectrometer, MegaSIMS. Equilibrium Landforms in the Dry Valleys of Antarctica: Implications for Landscape Evolution and Climate Change on Mars. Continued Study of Ba Isotopic Compositions of Presolar Silicon Carbide Grains from Supernovae. Paleoenviromental Evolution of the Holden-Uzboi Area. Stability of Magnesium Sulfate Minerals in Martian Environments. Tungsten Isotopic Constraints on the Formation and Evolution of Iron Meteorite Parent Bodies. Migration of Dust Particles and Volatiles Delivery to the Inner Planets. On the Sitting of Trapped Noble Gases in Insoluble Organic Matter of Primitive Meteorites. Trapping of Xenon Upon Evaporation-Condensation of Organic Matter Under UV Irradiation: Isotopic Fractionation and Electron Paramagnetic Resonance Analysis. Stability of Water on Mars. A Didactic Activity. Analysis of Coronae in the Parga Chasma Region, Venus. Photometric and Compositional Surface Properties of the Gusev Crater Region, Mars, as Derived from Multi-Angle, Multi-Spectral Investigation of Mars Express HRSC Data. Mapping Compositional Diversity on Mars: Spatial Distribution and Geological Implications. A New Simulation Chamber for Studying Planetary Environments. Folded Structure in Terra Sirenum. Mars. Nitrogen-Noble Gas Static Mass Spectrometry of Genesis Collector Materials. Neon Isotope Heterogeneity in the Terrestrial Mantle: Implication for the Acquisition of Volatile Elements in Terrestrial Planets. The Cosmic Clock, the Cycle of Terrestrial Mass Extinctions.

Source record↗

Io - A surface evaporite deposit

A model is suggested for Io's surface composition involving evaporite salt deposits, rich in sodium and sulfur. According to this model, these deposits were produced as a result of the migration of salt-saturated aqueous solutions to Io's surface from a warm or hot interior followed by loss of the water to space. This model satisfies cosmochemical constraints based on Io's initial composition, current density, and thermal history. Salt-rich assemblages are easily derivable from the leaching of carbonaceous chondritic material. The chemical and optical properties of such deposits, after modification by irradiation, can be used to explain Io's overall albedo and spectral reflectance, its dark reddish poles, and the observed sodium emission as well as or better than other currently suggested materials.

Fanale, F. P.↗

In Situ Studies of Copper-Zirconia-Zinc Oxide Model Catalysts for CO 2 Hydrogenation

A combination of in situ X-ray photoelectron spectroscopy (XPS) and infrared reflection absorption spectroscopy (IRAS) was used to investigate the formation of surface intermediates from CO 2 hydrogenation on copper-zirconia-zinc oxide model catalysts under reaction conditions. Copper clusters with different numbers of atoms (n = 1, 4, 13) were deposited onto bare and ZrO 2 -modified ZnO powder supports to systematically examine the effects of Cu cluster size and the synergy between metal and metal-oxide components. Under low pressure CO 2 hydrogenation conditions (CO 2 :H 2 = 1:9, 0.4 mbar, 300–600 K), XPS and IRAS identify the most prominent intermediates as carbonate (CO 3 *), formate (HCOO*) and methoxy (CH 3 O*), which is the final surface-bound intermediate leading to methanol. The temperature profiles are consistent with a mechanism in which CO 2 is adsorbed as carbonate species (HCO 3 *, CO 3 *) followed by hydrogenation reactions to formate (HCOO*) and methoxy (CH 3 O*), but the relative yields strongly depend on surface composition. Specifically, the presence of ZrO 2 promotes CO 2 adsorption and activation and improves the thermal stability of the Cu clusters against loss of surface area. Moreover, the ternary Cu 4 /ZrO 2 /ZnO surface is significantly more active than Cu 4 /ZnO and ZrO 2 /ZnO surfaces for the formation of methoxy (CH 3 O*), indicating that Cu–ZrO 2 interfaces promote the formation of key intermediates leading to methanol. Finally, the yields of intermediates are similar for all Cu cluster sizes (Cu 1 , Cu 4 and Cu 13 ), indicating that the primary role of Cu is to provide H atoms via H 2 dissociation and spillover. In conclusion, these molecular-level insights provide a fundamental understanding of the enhanced efficiency of ternary Cu–ZrO 2 –ZnO catalysts and establish design principles for developing improved catalysts for CO 2 conversion.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

The satellites of Jupiter and Saturn

The nature of the Jovian and Saturnian satellites as places, and their probable history, are discussed. Orbital data on the satellites are presented, including the radius, period, eccentricity, inclination, mass, density, albedo, and surface composition. The relationship between cratering and geologic time scales is reviewed. The major and intermediate satellites are categorized as giant, rocky, or icy, and their surface topography, internal heat sources, geologic activity, and impact crater density are discussed. The characteristics of Titan's atmosphere are covered. What is known of the small satellites of Saturn, the inner satellites of Jupiter, and the irregular outer satellites of Jupiter is assessed.

Morrison, D.↗

Surface analysis of space telescope material specimens

Surface analysis by electron spectroscopy for chemical analysis (ESCA) was used to characterize a number of the material samples for the space telescope. With ESCA, the sample is irradiated with monoenergetic soft X-rays and the resulting emitted electrons are energy analyzed to determine the binding energy of electrons to the surface atoms. The major peaks were used in the quantitative determination of the surface composition. The presence of trace elements (impurities below 1% atomic composition) was also detailed. Initially a survey scan was run for each sample to deduce the elemental composition. Then the major peaks of interest and those of the trace elements were individually examined. After this, the samples were argon sputtered to etch away surface layers, and then additional measurements were carried out in order to obtain depth profile information. In this way it was possible for those species present only on the surface to be distinguished from those having a significant depth distribution within the sample.

Fromhold, A. T.↗

Hayabusa2#’s Exploration to Asteroids 2001 CC21 and 1998 KY26 Provides Key Insights Into Planetary Defense

The Hayabusa2 extended mission, nicknamed Hayabusa2# (SHARP: Small Hazardous Asteroid Reconnaissance Probe), started its mission after the Hayabusa2 spacecraft successfully returned in December 2020 to the Earth with Ryugu's samples and released the Sample Return Capsule containing it. Hayabusa2#’s key operations include flying by Near Earth Asteroid (98943) 2001 CC21 and rendezvousing with Near-Earth Asteroid 1998 KY26. The flyby is planned to be in 2026, and the rendezvous will be in 2031. Detailed investigations of these targets enable maturing key knowledge and technologies necessary for planetary defense. This paper reviews the characteristics of these targets and strategies to maximize outcomes from the mission. The spacecraft will fly by 2001 CC21 at a speed of ~5 km/s in 2026. Given constraints on the spacecraft condition, not designed to perform a flyby operation, operational plans require careful assessments to maximize the proximity observations of this asteroid. The ~700 m diameter asteroid's shape is currently unknown, though lightcurve observations suggest the asteroid is elongated. While the spin pole is not constrained well, the spin period is about 5.02 h with uncertainties of 0.01 h [1]. The taxonomic class may be L-type, which implies the presence of Calcium-aluminum-rich inclusions (CAI), one of the primitive materials in the solar system [2], although there are studies suggesting an S-type. Therefore, this must be carefully examined. Photometric and spectroscopic observations will strongly constrain this asteroid’s properties. Our rendezvous target, 1998 KY26, is a ~30 m diameter roundish object spinning at a spin period of 10.7 min, which may represent one of the common groups of Near Earth Asteroids in size and composition that give a higher likelihood of threatening the Earth. Radar and optical observations reconstructed this asteroid's shape with high uncertainties and inferred that its surface composition might be similar to that of carbonaceous asteroids [3]. No spacecraft has ever visited such small bodies. Hayabusa2# visiting 1998 KY26 will be the first mission to document its geophysical properties, offering strong insights into what most frequent invaders look like [4].

Hayabusa2#↗

Capacitive deionization using carbon derived from an array of zeolitic-imidazolate frameworks

Capacitive deionization (CDI) represents one of the most thermodynamically efficient technologies for brackish water desalination. Its performance is highly reliant on the surface properties of carbon-based electrodes. Zeolitic-imidazolate framework (ZIF)-derived carbon materials have emerged among the most promising candidates owing to their high structural and compositional tuneability. However, the impacts of the precursory ZIF structure on the properties of the final carbon, and therefore, CDI capacity and efficiency remain to be further explored. In this work, four Zn-based ZIFs with different side-chain substitutions on the imidazolates were synthesized on a gram scale with high yields to produce N-doped carbons by pyrolysis. Next, the resulting carbons along with four commercial carbon blacks were characterized physically and electrochemically to explore the structure-performance relationship. We demonstrated that the imidazole side-chain substitution alters the ZIF's decomposition during pyrolysis, influencing the elemental compositions, surface properties, wettability and graphitization levels. The diverse carbon properties result in variable double layer capacitance and charge-transfer resistance, ultimately impacting the CDI performance. Among these carbons, Zn (4abIm)2-C afforded the greatest salt adsorption capacity of 14.19 mg NaCl $·g_C^{–1}$, while Zn (mIm) 2 -C showed the highest overall salt adsorption capacity and rate; both exceeded the performance of the commercial carbon blacks.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Quantifying oxygen induced surface enrichment of a dilute PdAu alloy catalyst

Dilute PdAu alloys are promising catalysts for selective oxidation and hydrogenation reactions. However, the surface composition and active site density of the minority metal, Pd, is unknown. Here, we quantitatively determine a three-fold increase in the Pd site density on the surface of a dilute Pd 0.08 Au 0.92 alloy catalyst after oxygen activation by titrating the oxidized surface with quantified pulses of CO.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Challenges in atomic layer etching of gallium nitride using surface oxidation and ligand-exchange

Two atomic layer etching (ALE) methods were studied for crystalline GaN, based on oxidation, fluorination, and ligand exchange. Etching was performed on unintentionally doped GaN grown by hydride vapor phase epitaxy. For the first step, the GaN surfaces were oxidized using either water vapor or remote O 2 -plasma exposure to produce a thin oxide layer. Removal of the surface oxide was addressed using alternating exposures of hydrogen fluoride (HF) and trimethylgallium (TMG) via fluorination and ligand exchange, respectively. Several HF and TMG super cycles were implemented to remove the surface oxide. Each ALE process was monitored in situ using multiwavelength ellipsometry. X-ray photoelectron spectroscopy was employed for the characterization of surface composition and impurity states. Additionally, the thermal and plasma-enhanced ALE methods were performed on patterned wafers and transmission electron microscopy (TEM) was used to measure the surface change. The x-ray photoelectron spectroscopy measurements indicated that F and O impurities remained on etched surfaces for both ALE processes. Ellipsometry indicated a slight reduction in thickness. TEM indicated a removal rate that was less than predicted. In conclusion, we suggest that the etch rates were reduced due to the ordered structure of the oxide formed on crystalline GaN surfaces.

36 MATERIALS SCIENCE↗

Materials characterization: Can artificial intelligence be used to address reproducibility challenges?

Material characterization techniques are widely used to characterize the physical and chemical properties of materials at the nanoscale and, thus, play central roles in material scientific discoveries. However, the large and complex datasets generated by these techniques often require significant human effort to interpret and extract meaningful physicochemical insights. Artificial intelligence (AI) techniques such as machine learning (ML) have the potential to improve the efficiency and accuracy of surface analysis by automating data analysis and interpretation. In this perspective paper, we review the current role of AI in surface analysis and discuss its future potential to accelerate discoveries in surface science, materials science, and interface science. We highlight several applications where AI has already been used to analyze surface analysis data, including the identification of crystal structures from XRD data, analysis of XPS spectra for surface composition, and the interpretation of TEM and SEM images for particle morphology and size. We also discuss the challenges and opportunities associated with the integration of AI into surface analysis workflows. These include the need for large and diverse datasets for training ML models, the importance of feature selection and representation, and the potential for ML to enable new insights and discoveries by identifying patterns and relationships in complex datasets. Most importantly, AI analyzed data must not just find the best mathematical description of the data, but it must find the most physical and chemically meaningful results. In addition, the need for reproducibility in scientific research has become increasingly important in recent years. The advancement of AI, including both conventional and the increasing popular deep learning, is showing promise in addressing those challenges by enabling the execution and verification of scientific progress. By training models on large experimental datasets and providing automated analysis and data interpretation, AI can help to ensure that scientific results are reproducible and reliable. Although integration of knowledge and AI models must be considered for the transparency and interpretability of models, the incorporation of AI into the data collection and processing workflow will significantly enhance the efficiency and accuracy of various surface analysis techniques and deepen our understanding at an accelerated pace.

Materials Science↗

Experiments and Spectral Studies of Martian Volcanic Rocks: Implications for the Origin of Pathfinder Rocks and Soils

The composition and spectral properties of the Mars Pathfinder rocks and soils together with the identification of basaltic and andesitic Mars terrains based on Thermal Emission Spectrometer (TES) data raised interesting questions regarding the nature and origin of Mars surface rocks. We have investigated the following questions: (1) are the Pathfinder rocks igneous and is it possible these rocks could have formed by known igneous processes, such as equilibrium or fractional crystallization, operating within SNC magmas known to exist on Mars? If it is possible, what P (depth) and PH2O conditions are required? (2) whether TES-based interpretations of plagioclase-rich basalt and andesitic terrains in the south and north regions of Mars respectively are unique. Are the surface compositions of these regions plagioclase-rich, possibly indicating the presence of old AI-rich crust of Mars, or are the spectra being affected by something like surface weathering processes that might determine the spectral pyroxene to plagioclase ratio?

Rutherford, Malcolm J.↗

Lunar Reconnaissance Orbiter Camera Observations Relating to Science and Landing Site Selection in South Pole-Aitken Basin for a Robotic Sample Return Mission

The Moon's South Pole-Aitken basin (SPA) is a high priority target for Solar System exploration, and sample return from SPA is a specific objective in NASA's New Frontiers program. Samples returned from SPA will improve our understanding of early lunar and Solar System events, mainly by placing firm timing constraints on SPA formation and the post-SPA late-heavy bombardment (LHB). Lunar Reconnaissance Orbiter Camera (LROC) images and topographic data, especially Narrow Angle Camera (NAC) scale (1-3 mpp) morphology and digital terrain model (DTM) data are critical for selecting landing sites and assessing landing hazards. Rock components in regolith at a given landing site should include (1) original SPA impact-melt rocks and breccia (to determine the age of the impact event and what materials were incorporated into the melt); (2) impact-melt rocks and breccia from large craters and basins (other than SPA) that represent the post-SPA LHB interval; (3) volcanic basalts derived from the sub-SPA mantle; and (4) older, "cryptomare" (ancient buried volcanics excavated by impact craters, to determine the volcanic history of SPA basin). All of these rock types are sought for sample return. The ancient SPA-derived impact-melt rocks and later-formed melt rocks are needed to determine chronology, and thus address questions of early Solar System dynamics, lunar history, and effects of giant impacts. Surface compositions from remote sensing are consistent with mixtures of SPA impactite and volcanic materials, and near infrared spectral data distinguish areas with variable volcanic contents vs. excavated SPA substrate. Estimating proportions of these rock types in the regolith requires knowledge of the surface deposits, evaluated via morphology, slopes, and terrain ruggedness. These data allow determination of mare-cryptomare-nonmare deposit interfaces in combination with compositional and mineralogical remote sensing to establish the types and relative proportions of materials expected at a given site. Remote sensing compositions, e.g., FeO, also constrain the relative abundances of components. Landing-site assessments use crater and boulder distributions, and slope and terrain rugge

Jolliff, B. L.↗

Surface engineering of MXenes for energy and environmental applications

We report MXenes, a new family of two-dimensional (2D) transition-metal carbides, nitrides, and carbonitrides, have received considerable attention in energy and environmental applications due to their intriguing electronic, electrochemical, optical, and chemical properties. Applications of MXenes have been witnessed in photocatalysis, electrocatalysis, thermocatalysis, sensing and biosensing, electrochemical energy storage, energy conversion and storage, rechargeable batteries, supercapacitors, and biomedicine. Notably, the tunable surface chemistry of MXenes plays an important role in their success in those applications. The surface composition of MXenes is considered to have a significant influence on their physicochemical properties and functionalities. In order to achieve a comprehensive understanding and rational design of MXenes by surface engineering, in this review, we highlight the application of several kinds of surface engineering approaches for MXenes, including tuning the surface termination groups, surface functionalization, surface defects, surface doping, surface oxidation, and the theoretical simulation of surface engineering of MXenes. Moreover, the relationship between the surface engineering and the physicochemical properties of MXenes is discussed. Finally, the ongoing challenges and opportunities for the future development of MXene surface engineering are also highlighted.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Comparison of Newly Acquired Lunar Spectra with the Titanium Abundance Maps Derived from Clementine

The Mercury Atmospheric and Surface Composition Spectrometer (MASCS) is one of seven science instruments onboard NASA's MESSENGER mission, currently en-route to the planet Mercury. One of MASCS s components, referred to as the Visible and Near Infrared Spectrograph (VIRS), will record reflectance spectra of the surface in order to characterize the mineralogy of the planet [1]. The lunar highlands and the average mercurian crust are proposed to be compositionally similar [i.e. 2]. In preparation to interpret VIRS reflectance spectra of Mercury to be first obtained in 2008, the Moon has been observed with an engineering model of the VIRS from a ground-based telescope. In this study, the ultraviolet and visible region of the spectrum is compared with titanium content in the lunar regolith.

Holsclaw, G. M.↗

Advanced Pt-Based Core–Shell Electrocatalysts for Fuel Cell Cathodes

Proton-exchange membrane fuel cells (PEMFCs) are highly efficient energy storage and conversion devices. Thus, the platinum group metal (PGM)-based catalysts which are the dominant choice for the PEMFCs have received extensive interest during the past couple of decades. However, the drawbacks in the existing PGM-based catalysts (i.e., high cost, slow kinetics, poor stability, etc.) still limit their applications in fuel cells. The Pt-based core–shell catalysts potentially alleviate these issues through the low Pt loading with the associated low cost and the high corrosion resistance and further improve the oxygen reduction reaction’s (ORR’s) activity and stability. This Account focuses on the synthetic strategies, catalytic mechanisms, factors influencing enhanced ORR performance, and applications in PEMFCs for the Pt-based core–shell catalysts. We first highlight the synthetic strategies for Pt-based core–shell catalysts including the galvanic displacement of an underpotentially deposited non-noble metal monolayer, thermal annealing, and dealloying methods, which can be scaled-up to meet the requirements of fuel cell operations. Subsequently, catalytic mechanisms such as the self-healing mechanism in the Pt monolayer on Pd core catalysts, the pinning effect of nitrogen (N) dopants in N-doped PtNi core–shell catalysts, and the ligand effect of the ordered intermetallic structure in L10-Pt/CoPt core–shell catalysts and their synergistic effects in N-doped L10-PtNi catalysts are described in detail. Additionally, the core–shell structure in the Pt-based catalysts have two main effects for enhanced ORR performance: (i) the interaction between Pt shells and core substrates can tune the electronic state of the surface Pt, thus boosting the ORR activity and stability, and (ii) the outer Pt shell with modest thickness can enhance the oxidation and dissolution resistance of the core, resulting in improved durability. We then review the recent attempts to optimize the ORR performance of the Pt-based core–shell catalysts by considering the shape, composition, surface orientation, and shell thickness. The factors influencing the ORR performance can be grouped into two categories: the effect of the core and the effect of the shell. In the former, PtM core–shell catalysts which use different non-PGM element cores (M) are summarized, and in the latter, Pt-based core–shell catalysts with different shell structures and compositions are described. The modifications of the core and/or shell structure can not only optimize the intermediate-binding energetics on the Pt surface through tuning the strain of the surface Pt, which increases the intrinsic activity and stability, but also offer a significantly decreased catalyst cost. Finally, we discuss the membrane electrode assembly performance of Pt-based core–shell catalysts in fuel cell cathodes and evaluate their potential in real PEMFCs for light-duty and heavy-duty vehicle applications. Even though some challenges to the activity and lifetime in the fuel cells remain, the Pt-based core–shell catalysts are expected to be promising for many practical PEMFC applications.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Correlation of Gear Surface Fatigue Lives to Lambda Ratio (Specific Film Thickness)

The effect of the lubrication regime on gear performance has been recognized, qualitatively, for decades. Often the lubrication regime is characterized by the specific film thickness being the ratio of lubricant film thickness to the composite surface roughness. Three studies done at NASA to investigate gearing pitting life are revisited in this work. All tests were done at a common load. In one study, ground gears were tested using a variety of lubricants that included a range of viscosities, and therefore the gears operated with differing film thicknesses. In a second and third study, the performance of gears with ground teeth and superfinished teeth were assessed. Thicker oil films provided longer lives as did improved surface finish. These datasets were combined into a common dataset using the concept of specific film thickness. This unique dataset of more 258 tests provides gear designers with some qualitative information to make gear design decisions.

gear↗

Surfaces and interfaces of glass and ceramics; Proceedings of the International Symposium on Special Topics in Ceramics, Alfred University, Alfred, N.Y., August 27-29, 1973

The characterization of surfaces and interfaces is considered along with the infrared spectra of several N-containing compounds absorbed on montmorillonites, applications of surface characterization techniques to glasses, the observation of electronic spectra in glass and ceramic surfaces, a method for determining the preferred orientation of crystallites normal to a surface, and the friction and wear behavior of glasses and ceramics. Attention is given to the wear behavior of cast surface composites, an experimental investigation of the dynamic and thermal characteristics of the ceramic stock removal process, a dynamic elastic model of ceramic stock removal, and the structure and properties of solid surfaces. Individual items are announced in this issue.

Frechette, V. D.↗