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Lunar resource evaluation and mine site selection

Two scenarios in this evaluation of lunar mineral resources and the selection of possible mining and processing sites are considered. The first scenario assumes that no new surface or near-surface data will be available before site selection (presumably one of the Apollo sites). The second scenario assumes that additional surface geology data will have been obtained by a lunar orbiter mission, an unmanned sample return mission (or missions), and followup manned missions. Regardless of the scenario, once a potentially favorable mine site has been identified, a minimum amount of fundamental data is needed to assess the resources at that site and to evaluate its suitability for mining and downstream processing. Since much of the required data depends on the target mineral(s), information on the resource, its beneficiation, and the refining, smelting, and fabricating processes must be factored into the evaluation. The annual capacity and producing lifetime of the mine and its associated processing plant must be estimated before the resource reserves can be assessed. The available market for the product largely determines the capacity and lifetime of the mine. The Apollo 17 site is described as a possible mining site. The use of new sites is briefly addressed.

Bence, A. Edward↗

Site Selection for Mars Exopaleontology in 2001

The microbial fossil record encompasses a wide range of information, including cellular remains, stromatolites, biofabrics, trace fossils, biominerals and chemofossils. The preservation of fossils is strongly influenced by the physical, chemical and biological factors of the environment which, acting together, ultimately determine the types of information that will be captured and retained in the rock record. The critical factor in assessing the suitability of a site for a microbial fossil record is the paleoenvironment. The reconstruction of ancient sedimentary environments usually requires the integration of a wide variety of geological information, including the shape, geometry and internal structure of sedimentary deposits, their mineralogy, and geochemistry. For Mars, much of our knowledge about past environments is based on orbital imaging of geomorphic features. This evidence provides an important context and starting point for site selection. However, our knowledge of the martian surface is quite limited, and a major goal of the upcoming exploration effort is to reconstruct the history of Martian volatiles, climate, and hydrology as a context for the exploration for past or present life. Mineralogical mapping from orbit will be an important key in this effort. In exploring for evidence of past life, terrestrial experience suggests that the long-term preservation of biological information as fossils occurs under a fairly narrow range of geological conditions that are well known to paleontologists (1). In detrital sedimentary systems, microbial fossilization is favored by rapid burial in fine-grained, clay-rich sediments. In chemical sedimentary systems, preservation is enhanced by rapid entombment in fine-grained chemical precipitates. For long term preservation, host rocks must be composed of stable minerals that resist chemical weathering, and which form an impermeable matrix and closed chemical system that can protect biosignatures from alteration during subsequent diagenetic change or metamorphism. In this context, host rocks composed of highly ordered, chemically-stable mineral phases, like silica (forming cherts) or phosphate (forming phosphorites), are especially favored. Such lithologies tend to have very long crustal residence times and (along with carbonates and shales), are the most common host rocks for the Precambrian microfossil record on Earth. If we assume that a subsurface hydrosphere has been present throughout martian history, then life could have originated there at any time, perhaps emerging at the surface periodically when climate changes, induced by external forcing or endogenous processes (e.g. volcanism), allowed liquid water to exist at the surface. The recent discovery of subsurface chemolithoautotrophic organisms which are capable of synthesizing organic substrates from C02 and H2 liberated from the aqueous weathering of basalt, is especially. relevant as a model for martian life. While a subsurface habitable zone may yet exist on Mars, access to such environments will likely require drilling to depths of several kilometers. Given the technological challenge of deep drilling, this is unlikely to occur prior to human missions. So, even if there is extant life on Mars today in subsurface habitats, it may be much easier to find its fossil counterparts in ancient deposits exposed at the surface. In exploring for a fossil record in subsurface environments on Mars there are several geological situations that may provide access to the appropriate materials. These include 1) ejecta from impact craters, 2) talus slopes, debris flows or alluvial fans developed below the walls of deep canyons, and 3) the deposits of outflood channels. Examples of aqueous mineral deposits of formed in subsurface environments that could harbor a microbial fossil record include such things as cements in detrital sedimentary rocks, low temperature diagenetic minerals deposited in veins, or filling vesicles in volcanic rocks, and hydrothermal deposits formed below the upper temperature limit for life (about 160 degrees C). There are many sites within the present latitudinal constraints for the 2001 mission (15 deg S to 30 deg N) that meet these requirements. But the practical problem with these kinds of deposits is that they tend to be disseminated, making up only a small percentage of a host rock. Even with mineralogical information provided by the Thermal Emission Spectrometer (TES) presently in orbit around Mars, predicting their occurrence ahead of time may be quite difficult. The deposits of surficial aqueous sedimentary systems are likely to provide the largest targets for site selection in 2001. Of these, the deposits of hydrothermal systems (subaerial and subaqueous thermal springs) have been discussed previously. It is likely that hydrothermal systems were widespread on Mars early in its history and a number of common geo-tectonic settings on Mars are likely to have hosted hydrothermal activity. Most of these are represented within the latitudinal constraints presently identified for 2001. However, the deposits of surface spring systems are likely to be difficult to find as well. On Earth, exposure areas for hydrothermal spring mounds are typically a few square kms, less than a single TES pixel. But such deposits may be quite abundant within some volcanic terrains, It is estimated, for example, that between 15-20% of the floor of Yellowstone caldera is covered by thermal spring deposits. In such abundances, subaerial sinters could well be detected by TES. Where exposed, the shallow subsurface portions of these systems may be quite a lot larger (perhaps tens of square kms), although (as noted above) mineralization may be finely disseminated in the basement rock, making remote detection more difficult. Paleolake Basins. There are a large number of potential paleolake basins on Mars (inclusive of impact craters and volcanic calderas) that have been previously identified using Viking images. Most of these lie in the southern highlands beyond the l5 deg S constraint for 2001. However, deposits of paleolakes may offer the largest and most easily identified exopaleontological targets from orbit. Based on a variety of arguments, some workers have suggested that there was once an ancient ocean on the northern plains, and some sites of interest (potential shoreline terraces) fall within the 30 deg N constraint. From a paleontological standpoint the most interesting places of this type are terminal paleolake basins which are likely to have been both saline and alkaline. Models by Schaefer suggest such environments could be widespread on Mars. The conditions in terminal lake basin settings favor widespread chemical sedimentation, an important condition for microbial fossilization. Important lithological targets for a microbial fossil record in terminal lake basins include spring-deposited carbonates, shoreline cements, a wide variety of evaporite minerals and fine-grained detrital sediments including shales, marls, and water-lain volcanic ash deposits. In developing a strategy to explore for ancient hydrothermal deposits on Mars, we can learn from the methods that have been developed by explorationists to explore for economic mineral deposits on Earth. Due to their simple mineralogy, hydrothermal deposits can often be detected using remote sensing methods. Common thermal spring mineral assemblages include silica, carbonate, and various metallic oxides and sulfides. But there are also a number of diagnostic silicate minerals, including clays, formed by the hydrothermal alteration of country rocks. These hydrothermal minerals have characteristic spectral signatures that could be detected from Mars orbit using high resolution infrared remote sensing methods. In playa lake settings, evaporite deposits often form a predictable "bull's eye" pattern with carbonates being deposited in marginal basin areas, and sulfates and halides occurring progressively more basinward. The floors of some impact craters on Mars, such as "White Rock" and Bequeral Crater (see Oxia Palus NE, Site 148), have floor deposits that could be evaporites, inclusive of carbonates. Evaporite minerals possess characteristic spectral signatures in the infrared and could similarly be identified from Mars orbit using high resolution remote sensing methods. Clearly, utilization of TES data will be important for optimizing site selection for Exopaleontology, and every effort should be made to benefit from that data before a final decision is made.

Farmer, Jack↗

Mechanistically Informed Strategies for Site-Selective Atomic Layer Deposition

While atomic layer deposition (ALD) processes from across the periodic table have been designed to deposit conformal thin films, an atomistic view of disparate substrate sites reveals the possibility of even greater synthetic control and precision. An understanding of the mechanism by which a particular ALD precursor reacts (or does not react) at myriad surface sites remains in its infancy. Here, in this Perspective, we summarize site-specific chemical reaction strategies that utilize ALD precursors and tailored surface chemistry to discriminate among potential deposition sites as well as describe techniques and tools that can be used to investigate site-selective ALD (SS-ALD). The Perspective is focused on the science of site-selective vapor-phase surface reactions but inevitably reveals the potential utility of such surface synthetic precision.

36 MATERIALS SCIENCE↗

The Viking landing sites - Selection and certification

During the past several years the Viking project developed plans to use Viking orbiter instruments and earth-based radar to certify the suitability of the landing sites selected as the safest and most scientifically rewarding using Mariner 9 data. During June and July 1976, the earth-based radar and orbital spacecraft observations of some of the prime and backup sites were completed. The results of these combined observations indicated that the Viking 1 prime landing area in the Chryse region of Mars is geologically varied and possibly more hazardous than expected, and was not certifiable as a site for the Viking 1 landing. Consequently, the site certification effort had to be drastically modified and lengthened to search for a site that might be safe enough to attempt to land. The selected site considered at 47.5 deg W, 22.4 deg N represented a compromise between desirable characteristics observed with visual images and those inferred from earth-based radar. It lies in the Chryse region about 900 kilometers northwest of the original site.

Masursky, H.↗

CoSn-type NiIn1–xSbx (0 ≤ x ≤ 0.17): Site-Selective Substitution, Electronic Structure, Chemical Bonding, and Structural Transformation

CoSn-type intermetallic compounds have emerged as a model platform for Kagome-derived flat-band physics, where subtle chemical perturbations can strongly influence electronic structure and phase stability. Here, we present a combined experimental and theoretical study of Sb-substitution in CoSn-type NiIn1–xSbx (0 ≤ x ≤ 0.17) to elucidate the interplay between site selectivity, solubility limit, chemical bonding, and electronic structure. Rietveld refinements on Neutron powder diffraction data confirmed the selective Sb-substitution at the electron-rich In2 (2d) site forming the honeycomb substructure, while the In1 (1a) site within the Kagome layer remains exclusively occupied by In. Density functional theory (DFT) calculations revealed that pristine CoSn-type NiIn hosts Ni 3d-dominated flat bands near the Fermi level (EF), originating from the Kagome-like Ni substructure. Partial replacement of In by Sb within the honeycomb layer alters these flat-band features below EF, reducing the density of states and suppressing the flat-band topology near the Fermi level. Orbital-resolved electronic structure and chemical-bonding analyses show that Sb-substitution enhances Ni-p-block (In/Sb) covalency and optimizes charge compensation, stabilizing the CoSn-type structure up to the solubility limit x ≈ 0.17. Beyond the limit, the higher-Sb compositions show satellite reflections consistent with an incommensurately modulated phase. These results establish a link between site-selective chemical substitution, bonding optimization, and flat-band electronic structure evolution, providing fundamental insights into how chemical substitution influences the electronic properties of Kagome-based intermetallic compounds.

Roy, Nilanjan [National Institute of Technology Si↗

Implications of high-spatial-resolution thermal infrared (Termoskan) data for Mars landing site selection

Thermal infrared observations of Mars from spacecraft provide physical information about the upper thermal skin depth of the surface, which is on the order of a few centimeters in depth and thus very significant for lander site selection. The Termoskan instrument onboard the Soviet Phobos '88 spacecraft acquired the highest spatial-resolution thermal infrared data obtained for Mars, ranging in resolution from 300 m to 3 km per pixel. It simultaneously obtained broadband reflected solar flux data. Although the 6 deg N - 30 deg S Termoskan coverage only slightly overlaps the nominal Mars Pathfinder target range, the implications of Termoskan data for that overlap region and the extrapolations that can be made to other regions give important clues for optimal landing site selection.

Betts, Bruce H.↗

Chemoselective and Site-Selective Reductions Catalyzed by a Supramolecular Host and a Pyridine–Borane Cofactor

Supramolecular catalysts emulate the mechanism of enzymes to achieve large rate accelerations and precise selectivity under mild and aqueous conditions. While significant strides have been made in the supramolecular host-promoted synthesis of small molecules, applications of this reactivity to chemoselective and site-selective modification of complex biomolecules remain virtually unexplored. We report here a supramolecular system where coencapsulation of pyridine-borane with a variety of molecules including enones, ketones, aldehydes, oximes, hydrazones, and imines effects efficient reductions under basic aqueous conditions. Furthermore, upon subjecting unprotected lysine to the host-mediated reductive amination conditions, we observed excellent ε-selectivity, indicating that differential guest binding within the same molecule is possible without sacrificing reactivity. Inspired by the post-translational modification of complex biomolecules by enzymatic systems, we then applied this supramolecular reaction to the site-selective labeling of a single lysine residue in an 11-amino acid peptide chain and human insulin.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Modulating Mid-Gap Electronic States Through Site-Selective Modification in B-Pbx/B'-CuyV2O5/CdS Heterostructures for Photocatalytic Hydrogen Evolution

We interfaced ..beta..-Pbx/..beta..'-CuyV2O5 compounds, with varying stoichiometries of precisely positioned Pb-ions (x) and Cu-ions (y) in interstitial sites along a tunnel-structured ?-V2O5 framework, with cysteine-capped CdS (cysCdS) quantum dots (QDs) to yield heterostructured photocatalysts. ..beta..-Pbx/..beta..'-CuyV2O5 compounds exhibit midgap electronic states with orbital contributions from both Cu 3d and stereochemically active Pb 6s states that show distinctive light-initiated reactivity with photoexcited QDs. ..beta..-Pbx/..beta..'-CuyV2O5/CdS heterostructures were prepared by linker-assisted assembly (LAA). Scanning and transmission electron microscopy, energy-dispersive X-ray spectroscopy, and Raman spectroscopy revealed that cysCdS QDs were deposited onto surfaces of ..beta..-Pbx/..beta..'-CuyV2O5 via LAA. HAXPES revealed that the site-selective positioning of Pb-ions and Cu-ions promoted close energetic alignment of the midgap states of ..beta..-Pbx/..beta..'-CuyV2O5 compounds with the valence-band maximum of cysCdS QDs. Transient absorption spectroscopy revealed that photogenerated holes were transferred from CdS QDs to midgap states of ..beta..-Pbx/..beta..'-CuyV2O5 compounds on time scales <50 ps. Finally, photoelectrochemical and photochemical experiments revealed that ..beta..-Pbx/..beta..'-CuyV2O5/CdS heterostructures promoted the photocatalytic reduction of H+ to H2. In photoelectrochemical experiments, under oxidative conditions, for all ..beta..-Pbx/..beta..'-CuyV2O5/CdS heterostructures, H2 was evolved at a Pt counter electrode while a sacrificial donor was oxidized at the heterostructure-functionalized working electrode. In contrast, under reductive conditions, for ..beta..-Pb0.152V2O5/CdS and ..beta..-Pbx/..beta..'-CuyV2O5/CdS heterostructures, H2 was evolved at the working electrode. In photochemical experiments, dispersed ..beta..-Pbx/..beta..'-CuyV2O5/CdS heterostructures promoted the reduction of H+ to H2 under white-light illumination; ..beta..'-Cu0.55V2O5/CdS and ..beta..-Pbx/..beta..'-CuyV2O5/CdS heterostructures, for which midgap states have Cu 3d orbital character, generated 2-fold more H2 than ..beta..-Pb0.152V2O5/CdS heterostructures. Cu-ion insertion thus appends additional acceptor surface states that improve ligand-mediated hole transfer from photoexcited QDs, but such states are intrinsically limited in mediating hole transport to the substrate as a result of the low mobility of holes in narrow Cu 3d-states. Our results reveal that the density and orbital character of midgap states of ..beta..-Pbx/..beta..'-CuyV2O5 compounds, tunable through recently developed site-selective ion insertion strategies, determine efficiencies of charge-transfer and charge-transport mechanisms that underpin photocatalysis.

36 MATERIALS SCIENCE↗

Urban Climate Station Site Selection Through Combined Digital Surface Model and Sun Angle Calculations

Meteorological measurements within urban areas are becoming increasingly important due to the accentuating effects of climate change upon the Urban Heat Island (UHI). However, ensuring that such measurements are representative of the local area is often difficult due to the diversity of the urban environment. The evaluation of sites is important for both new sites and for the relocation of established sites to ensure that long term changes in the meteorological and climatological conditions continue to be faithfully recorded. Site selection is traditionally carried out in the field using both local knowledge and visual inspection. This paper exploits and assesses the use of lidar-derived digital surface models (DSMs) to quantitatively aid the site selection process. This is acheived by combining the DSM with a solar model, first to generate spatial maps of sky view factors and sun-hour potential and second, to generate site-specific views of the horizon. The results show that such a technique is a useful first-step approach to identify key sites that may be further evaluated for the location of meteorological stations within urban areas.

digital surface model↗

Site-Selective Modification of Lanthanum Oxychloride to Modulate Halide-Ion Conduction

Design principles for solid-state halide-ion conduction remain poorly defined despite the increasing importance of halide ions as charge carriers in a variety of energy storage and electrochemical computing technologies. Here, we employ a siteselective modification strategy in which aliovalent cations are preferentially introduced at the La 3+ crystallographic site of LaOCl in the 2c Wyckoff position, enabling controlled generation of chloride vacancies and modification of lattice dynamics to enhance chloride-ion conductivity. Aliovalent substitution of La 3+ with Mg 2+ , Ca 2+ , and Sr 2+ generates charge-compensating Cl vacancies while preserving the matlockite crystal structure. X-ray excited optical luminescence measurements with Dy 3+ as a reporter chromophore evidence vacancy-derived midgap electronic states and an extended energy range of radiation-less Auger electron emission corresponding to substantial modification of electronic structure and local electrostatic potentials. Ca alloying at 8−10 at. % increases the chloride-ion conductivity by three- to 4 orders of magnitude as compared to unalloyed LaOCl, whereas comparable amounts of Sr- and Mg-alloying in LaOCl imbue less pronounced conductivity enhancements. Temperature-dependent Raman spectroscopy measurements reveal that Ca- and Sr-alloying substantially soften the La−Cl sublattice and yield a more compliant crystal lattice that can deform to accommodate Cl-ion migration. Structure solutions derived from Rietveld refinements to powder Xray diffraction reveal larger O−La−Cl bond-angle deviations and enhanced out-of-plane cation displacements for Ca- and Sr-alloyed compositions as compared to Mg-alloyed LaOCl. Such local distortions enhance chloride-ion mobility by reshaping and flattening vacancy migration energy landscapes and by modulating lattice dynamics governing anion conduction. We further illustrate that coalloying of Ca with Mg and Sr induces a nonmonotonic conductivity−defect stoichiometry relationship that can be rationalized based on cooperative interactions. Together, these results establish site-selective aliovalent alloying of LaOCl as an effective route to halide-ion solid electrolytes and provide broadly generalizable design principles for site-selective modification to induce vacancy formation and lattice softening to engender facile anion transport

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Constraints, Approach, and Status of Mars Surveyor 2001 Landing Site Selection

There are many similarities between the Mars Surveyor '01 (MS '01) landing site selection process and that of Mars Pathfinder. The selection process includes two parallel activities in which engineers define and refine the capabilities of the spacecraft through design, testing and modeling and scientists define a set of landing site constraints based on the spacecraft design and landing scenario. As for Pathfinder, the safety of the site is without question the single most important factor, for the simple reason that failure to land safely yields no science and exposes the mission and program to considerable risk. The selection process must be thorough and defensible and capable of surviving multiple withering reviews similar to the Pathfinder decision. On Pathfinder, this was accomplished by attempting to understand the surface properties of sites using available remote sensing data sets and models based on them. Science objectives are factored into the selection process only after the safety of the site is validated. Finally, as for Pathfinder, the selection process is being done in an open environment with multiple opportunities for community involvement including open workshops, with education and outreach opportunities. Additional information is contained in the original extended abstract.

Golombek, M.↗

Atmospheric Constraints on Landing Site Selection

The Martian atmosphere is a significant part of the environment that the Mars Exploration Rovers (MER) will encounter. As such, it imposes important constraints on where the rovers can and cannot land. Unfortunately, as there are no meteorological instruments on the rovers, there is little atmospheric science that can be accomplished, and no scientific preference for landing sites. The atmosphere constrains landing site selection in two main areas, the entry descent and landing (EDL) process and the survivability of the rovers on the surface. EDL is influenced by the density profile and boundary layer winds (up to altitudes of 5 to 10 km). Surface survivability involves atmospheric dust, temperatures and winds. During EDL, the atmosphere is used to slow the lander down, both ballistically and on the parachute. This limits the maximum elevation of the landing site to -1.3 km below the MOLA reference aeroid. The landers need to encounter a sufficiently dense atmosphere to be able to stop, and the deeper the landing site, the more column integrated atmosphere the lander can pass through before reaching the surface. The current limit was determined both by a desire to be able to reach the hematite region and by a set of atmosphere models we developed for EDL simulations. These are based on Thermal Emission Spectrometer (TES) atmospheric profile measurements, Ames Mars General Circulation Model (MGCM) results, and the 1-D Ames GCM radiative/convective model by J. Murphy. The latter is used for the near surface diurnal cycle. The current version of our model encompasses representative latitude bands, but we intend to make specific models for the final candidate landing sites to insure that they fall within the general envelope. The second constraint imposed on potential landing sites through the EDL process is the near surface wind. The wind in the lower approximately 5 km determines the horizontal velocity that the landers have when they land. Due to the mechanics of the landing process, the total velocity (including both the horizontal and vertical components) determines whether or not the landers are successful. Unfortunately, the landing system has no easy way to nullify any horizontal velocity imparted by the wind, so the landing sites selected need to have as little wind as possible. In addition to the mean wind velocity, the landing system is sensitive to vertical wind shear in the lowest kilometer or so. Wind shear can deflect the retro rockets (RADs) from their nominal vertical orientation producing unwanted horizontal spacecraft velocities. Both mean velocity and wind shear are dominated by the the local topography and other surface properties (in particular albedo and thermal inertia which control the surface temperature). This is seen even in simplified 2-D mesoscale models. The effects in a fully 3-D model are expected to he even more topographically dependent. In particular there is potential for wind channeling in canyons and other terrain features. Boundary layer winds and wind shear are currently being modeled based on terrestrial data and boundary layer scaling laws modified for Martian conditions. We hope to supplement this with mesoscale model results (from several sources) once the number of landing sites is reduced to a manageable number.

Kass, David M.↗

Mineralogy Considerations for 2003 MER Site Selection and the Importance for Astrobiology

Much of the discussion of site selection on Mars is based on interesting images of the surface combined with safety issues. I argue that the two rovers should be sent to mineralogically distinct regions. Compositional information is still poorly constrained on Mars; however, the instruments on the 2003 Mars Exploration Rovers (MERs) will provide a unique opportunity for detailed characterization including mineral identification. There is strong motivation for sending one rover to a "typical" region on Mars to be used as a ground truth for the Thermal Emission Spectrometer (TES), while the other rover should be sent to a site where water and chemical alteration are likely to have occurred. Determining the mineralogy of the Martian surface material provides information about the past and present environments on Mars which are an integral aspect of whether or not Mars was suitable for the origin of life. Understanding the mineralogy of terrestrial samples from potentially Mars-like environments is essential to this effort.

Bishop, J. L.↗

Strategy for Ranking the Science Value of the Surface of Asteroid 101955 Bennu for Sample Site Selection for Osiris-REx

OSRIS-REx is NASA's New Frontiers 3 sample return mission that will return at least 60 g of pristine surface material from near-Earth asteroid 101955 Bennu in September 2023. The scientific value of the sample increases enormously with the amount of knowledge captured about the geological context from which the sample is collected. The OSIRIS-REx spacecraft is highly maneuverable and capable of investigating the surface of Bennu at scales down to the sub-cm. The OSIRIS-REx instruments will characterize the overall surface geology including spectral properties, microtexture, and geochemistry of the regolith at the sampling site in exquisite detail for up to 505 days after encountering Bennu in August 2018. The mission requires at the very minimum one acceptable location on the asteroid where a touch-and-go (TAG) sample collection maneuver can be successfully per-formed. Sample site selection requires that the follow-ing maps be produced: Safety, Deliverability, Sampleability, and finally Science Value. If areas on the surface are designated as safe, navigation can fly to them, and they have ingestible regolith, then the scientific value of one site over another will guide site selection.

Nakamura-Messenger, K.↗